1336402157,1362 /wEPDwUKMTEw

/wEWBALo5JGxC

Home
Contact Us
MRS Press Room
Advertising and Exhibits
Sitemap
RSS Feeds
Search
Submit

Create Account Login

About MRS
o The Society
o MRS Mission, Vision and Values
o Contact Us
o Governance
o Elections
o Annual Reports
o Materials Research Society Foundation
o MRS Press Room
o Social Media
Meetings & Exhibits
o MRS Spring Meetings & Exhibits
o MRS Fall Meetings & Exhibits
o Technology Innovation Forum | iMatSci
o MRS Conference Services
o MRS Joint Meetings
o MRS Workshop Series
o Endorsements & Co-Sponsorships
o Additional Meeting Activities
o 8th International Workshop on Zinc Oxide and Related Materials (IWZnO 2014)
o 4th International Symposium on Graphene Devices (ISGD-4)
o 20th International Conference on Solid State Ionics (SSI-20)
o 18th International Conference on Metal Organic Vapor Phase Epitaxy
(ICMOVPE-XVIII)
o MRS OnDemand
o Meetings Calendar
o Meeting Scene
Publications & News
o Journals:
o MRS Communications
o MRS Bulletin
o Journal of Materials Research
o MRS Online Proceedings Library
o MRS Energy & Sustainability A Review Journal
o Books & Textbooks
o MRS Print Proceedings Series
o MRS Publishing
o News & Information:
o Materials360 Online
o Materials360 Newsletter
o Reports & Resources
o Meeting Scene
o MRS Bulletin Energy Quarterly
o MRS Innovation Source
o MRS OnDemand
o MRS OnDemand Webinar Series
Advocacy
o Congressional Fellows
o INTERSECTIONS Newsletter
o Materials Voice
o Resources
o Issues
Career Connections
o Job Postings
o Awards
o Career Centers
o University Chapters
o Women in Materials Science and Engineering
o Funding Resources
o Diversity
o MRS Mentoring Program
Membership
My MRS
Email
Print
Share
Home
Meetings & Exhibits
MRS Spring Meetings & Exhibits
MRS Fall Meetings & Exhibits
Technology Innovation Forum | iMatSci
MRS Conference Services
MRS Joint Meetings
MRS Workshop Series
Endorsements & Co-Sponsorships
Additional Meeting Activities
8th International Workshop on Zinc Oxide and Related Materials (IWZnO 2014)
4th International Symposium on Graphene Devices (ISGD-4)
20th International Conference on Solid State Ionics (SSI-20)
18th International Conference on Metal Organic Vapor Phase Epitaxy (ICMOVPE-
XVIII)
MRS OnDemand
Meetings Calendar
Meeting Scene
Symposium B: Concepts in Molecular and
Organic Electronics


Concepts in Molecular and Organic Electronics
April 13 - 17, 2009




Chairs
Norbert Koch
Institut fuer Physik
Humboldt-Universitaet zu Berlin
Newtonstr. 15
Berlin, 12489 Germany
49-30-2093-7819

Egbert Zojer
Institut fuer Festkoerperphysik
Technische Universitaet Graz
Petersgasse 16
Graz, 8010 Austria
43-316-873-8475
Saw-Wai Hla
Dept. of Physics and Astronomy
Ohio University

Xiaoyang Zhu
Dept. of Chemistry
University of Minnesota
Clippinger Lab 251B
Athens, OH 45701
740-593-1727
207 Pleasant St. SE
Minneapolis, MN 55455-0431
612-624-7849
Symposium Support
Air Force Research Laboratory

Proceedings to be published in both book form and online
(see MRS Online Proceedings Library at www.mrs.org/opl)
as volume 1154
of the Materials Research Society
Symposium Proceedings Series.

* Invited paper

SESSION B1: Molecular Scale Electronics I
Chair: Norbert Koch
Monday Morning, April 13, 2009
Room 2001 (Moscone West)

8:30 AM *B1.1
SAMs, the ``Liquid-Metal Junction, and the Study of Electron Transport through Organic
Monolayer Films." George Whitesides
1
, E. Weiss
1
, R. Chiechi
1
, C. Nihuis
1
, W. Reus
1
and M. A
Rampi
2
;
1
Chemistry, Harvard University, Cambridge, Massachusetts;
2
Chemistry, University of
Ferrara, Ferarra, Italy.

Self-assembled monolayers (SAMs) are now accepted as the most flexible system available for
use in studying the physical-organic chemistry of surfaces and monolayer films. Superficially,
the most widely studied classes of SAMsalkanethiolates on metals (Au, Ag, Pd, Pt) seem to be
relatively simple structurally: in essence, defective 2D organic crystals supported epitaxially on
the metal film. The underlying molecular reality is much more complicated, and SAMs have
many types of local irregularities and heterogeneities. In some types of experiments, those
irregularities may be relatively unimportant; in others, very important. This talk will describe
studies of electron transport across SAMs using liquid-metal drop junctionsthat is, junctions
of the form metal/SAM//SAM/liquid metal (optimally eutectic GaIn)--and the use of SAMs to
study the mechanisms of this process. Although improving the reproducibility, and defining the
mechanism of electron transport, in these (and related) systems is a challenging experimental
problem, the metal/SAM//SAM/liquid-metal junction (especially using so-called ultrasmooth
metals as supports for the SAM) is probably the most useful one now available for surveying the
relationship between organic structure, current density, and the parameter characterizing
attenuation of current distance with thickness (). For most SAMs, tunneling is probably the
most important contribution to electron transport. The talk will describe studies of the influence
of a number of other characteristics of the systemthe structure of the metal-organic interface,
the method of preparation of the SAM, and the structure of the organic molecules making it up--
on current density.


9:00 AM *B1.2
Electronic Processes in Organic Electronic and Photonic Devices: A Theoretical
DescriptionJean-Luc Bredas, School of Chemistry and Biochemistry, Georgia Tech, Atlanta,
Georgia.

Conjugated organic oligomer and polymer materials are now increasingly used as the active
semiconductor elements in devices such as photo-voltaic cells, light-emitting diodes, field-effects
transistors, electro-optic modulators, or all-optical signal processors. In this presentation, we will
discuss the progress we have recently achieved in the theoretical understanding of: (i) the
mechanisms for charge dissociation and charge separation at the donor/acceptor interface in
organic solar cells; and (ii) the linear and nonlinear optical properties of a new class of cyanine
molecules that present a strong bond-alternated geometric structure.


9:30 AM B1.3
Is a Molecular Electronics Technology Useful? - A Device Theorists Perspective.Avik
Ghosh, Electrical Engineering, University of Virginia, Charlottesville, Virginia.

Molecular electronics is often touted as a potential successor to silicon-based CMOS, due to the
advantages related to size, cheapness of fabrication, chemical tunability and bottom-up self-
assembly. However, progress has been stymied by difficulties of creating stable junctions and
reproducible measurements of molecular currents. The situation has improved considerably over
the last few years, as experiments from various groups seem to be in agreement. It is thus a good
opportunity to compare experiments with theoretical models, and perhaps look ahead at what
molecules may be good for. <P> I will start by describing a unified theory of current flow
through any nano- channel, from small organic molecules, all the way to larger molecules such
as silicon nanowires, carbon nanotubes and graphene nanoribbons. By coupling this method with
quantitative band-structure theory, we can quantitatively explain a wide variety of observed
molecular current-voltage characteristics. For insulating alkanethiols, we can explain the
magnitude and robustness of the decay constant and derive a modification to Simmons equation
that yields the current per molecule. For aromatic molecules, we can establish both the maximum
current and the zero-bias conductance - the latter requiring incorporation of self- interaction
correction to get the right barrier height. For hybrid devices, we can predict the influence of
bonding configuration and molecular dipole on the band- structure of the underlying
semiconducting substrate, capturing molecular resonant tunneling diodes, molecular sensing and
molecular rectifiers on silicon. For molecular quantum dots, we can accurately describe Coulomb
Blockade effects that require careful attention to many-body excitations. <P> While our model
provides excellent quantitative benchmarks with dozens of experiments, its prediction for
molecular transistors is grim - we expect moleFETs to underperform due to strong tunneling, low
mobility and poor electrostatics. The strength of molecules lies instead in its charging energy,
suggesting that they be used as scatterers rather than channel materials. In fact, molecular
chemistry and self-assembly could be utilized to engineer surface traps in a silicon transistor,
leading to a new class of devices that rely on the utilization rather than the elimination of
scattering at nano-micro interfaces, involving novel multi-trap correlation effects that are
observed experimentally.


9:45 AM B1.4
2D Molecular Networks for Organic and Molecular Electronics Dmitrii F. Perepichka,
Chemistry, McGill University, Montreal, Quebec, Canada.

The single greatest advantage of organic molecules vs inorganic materials for electronic
applications is their capacity to self-assemble into complex and, at times, functional
architectures. Yet, practical applications of this property in organic/molecular electronics is
essentially limited to self-assembled monolayers (SAMs, where the molecules are simply grafted
on a surface with very limited lateral order) or 3D crystals (where the molecular packing is
critical for charge transport phenomenon, but little or no rational control of this packing can yet
be achieved). I will present our achievements in synthesis and surface characterization (STM and
auxiliary techniques) of 2D pi-electron functional molecular networks, highlighting two major
approaches: (i) using weak interactions to create nanotemplates on which organic
semiconducting molecules can be assembled, and which symmetry and periodicity can be
rationally and predictably controlled by the structure of a building block,[1] and (ii) exploring
surface-confined reactivity to create pi-conjugated polymers through epitaxial polymerization
reactions.[2] The latest development of the second approach opens an opportunity for creating a
new class of electronic materials- two dimensional (2D) conjugated polymers. I will describe the
principles of molecular design, the templating and catalytic role of the surface in formation of
these ordered functional materials, and provide our view on implications for the future
development of molecular electronics. [1] K.Nath et al. JACS 2006, 128, 4212; K.Nath et al.
JPC-C 2007, 111, 16996; J.MacLeod et al. Nanotechn. 2007, 18, 424031; O.Ivasenko et al.,
submitted. [2] J.Lipton-Duffin et al. submitted; (see also L.Grill et al. Nature Nanotech. 2007, 2,
687)


10:30 AM *B1.5
Conductance of Single Molecule Circuits. Latha Venkataraman, Applied Physics, Columbia
University, New York, New York.

The field of molecular electronics involves probing, manipulation, and control of single
molecules as active elements in electrical circuits. The underlying focus is to fabricate single
molecule circuits, a molecule attached to two electrodes, with varied functionality, where the
circuit structure is potentially defined with atomic precision. An experimental prerequisite to
creating functional molecular devices is to fabricate single molecule junctions reliably and
understand their physical properties. This poses fundamental challenges to nanoscience. Building
single molecule junctions with atomic precision is beyond the capability of top-down fabrication
techniques; however, variations in the device anatomy at the single bond scale can significantly
affect the junction characteristics. A bottom-up approach based on synthetic chemical control is
required to enable reproducible junction formation with well defined metal-molecule bonding
motifs. From a fundamental physics perspective, we need to understand, both experimentally and
theoretically, the electronic properties of metal-molecule-metal junctions. This will be the
primary focus of my talk. In this talk, I will review the scanning tunneling microscope break-
juncion technique we use to measure electronic transport through single molecule junctions, and
focusing on electron transport in the linear response regime, I will show that junctions formed
with gold-thiol links have large variability in conductance which can be attributed to the atomic
structure of the single molecule junctions formed with Au-S bonds. I will then discuss our
measurements using using novel metal-molecule link chemistries including amine-gold, methyl
sulfide-gold and dimethyl phosphine-gold to overcome the inherent variability of the gold-thiol
bonds. I will show that low-bias conductance of single molecules can be measured reliably and
reproducibly using these link groups [1-3]. I will then discuss the influence of the intrinsic
molecular properties, including their length, conformation, the gap between the highest occupied
molecular orbital and the lowest unoccupied molecular orbital and the alignment of this gap to
the metal Fermi level on the measured conductance. For single molecule junctions, I will show
that conductance relates to molecular conformation a biphenyl, two benzene rings linked
together by a single C-C bond [2]. For substituted benzenes, the relation between measured
conductance and the calculated ionization potential will be discussed [4]. For fused benzene
rings, I will show that conductance depends on the location of the amine groups on the molecule
[5]. [1] L. Venkataraman, et al., Nano Lett. 6, 458 (2006). [2] L. Venkataraman, et al., Nature
442, 904 (2006). [3] Y. S. Park, et al., J. Am. Chem. Soc. 129, 15768 (2007). [4] L.
Venkataraman et al., Nano Letters 7, 502 (2007). [5] J. R. Quinn et al., J. Am. Chem. Soc. 129,
6714 (2007).


11:00 AM B1.6
Charge Transport and Vibronic Effect in Nanoscale Molecular Junctions. Hyunwook Song
and Takhee Lee; Department of Materials Science and Engineering, Gwangju Institute of
Science and Technology, Gwangju, Korea, South.

Study of charge transport in molecules has become an active area of experimental and theoretical
research with promise in a variety of applications including molecular electronics [1],
optoelectronics [2], and thermoelectric energy conversion [3]. In this presentation, we interrogate
critical aspects on charge transport and vibronic effect in molecular junctions (MJs) by using
three different prototypes of device test-beds where either individual molecules or an ensemble
of molecules form a bridge between metallic electrodes in nanometer-scale junction area to
measure charge transport characteristics and electron-vibration coupling in MJs. First, we report
on a statistical method for investigating charge transport through MJs exploiting mass-produced
nanowell device structures (~7,000 devices) [4], which provides an objective criterion to
determine the most probable transport characteristics including a dominant conduction
mechanism in MJs. In the second part of the presentation, we will discuss the observation of two
tunneling pathways possible in self-assembled alkanethiol monolayers, i.e., through -bond and
intermolecular chain-to-chain tunneling, using conducting atomic force microscopy [5]. Lastly,
we present a method to explore the energy band lineups in MJs using a single-molecule transistor
(SMT) technique where individual molecules are linked between source and drain electrodes
with a third gate electrode. Furthermore, inelastic electron tunneling spectroscopy (IETS) is used
to observe vibrational spectra in a SMT configuration as the position of electronic resonance
level shifts by adjusting the gate voltage. The IETS provides not only in situ characterization
technique to identify the molecules associated with charge transport, but also a valuable insight
into how the interaction of charge carriers with molecular vibrational modes influences the
overall charge transport characteristics in MJs. [1] M. Galperin, M. A. Ratner, A. Nitzan, and A.
Troisi, Science 319, 1056 (2008). [2] M. S. Gudiksen, K. N. Maher, L. Ouyang, and H. Park,
Nano Lett. 5, 2257 (2005). [3] P. Reddy, S. Y. Jang, R. A, Segalman, and A. Majumdar, Science,
315, 1568 (2007). [4] H. Song, T. Lee, N. -J. Choi, and H. Lee, Appl. Phys. Lett. 91, 253116
(2007). [5] H. Song, H. Lee, and T. Lee, J. Am. Chem. Soc. 129, 3806 (2007).


11:15 AM B1.7
Electron-Phonon Interactions in Single Molecule Junctions. Joshua Hihath
1
, Carols R
Arroyo
2
, Gabino Rubio-Bollinger
2
, Nongjian Tao
1
and Nicolas Agrait
2
;
1
Center for
Bioelectronics an Biosensors, Arizona State University, Tempe, Arizona;
2
Departamento Fisica
de la Materia Condensada CIII, Universidad Autonoma de Madrid, Madrid, Spain.

Although significant advances have been made in molecular electronics in recent years, a
complete understanding of how a molecule interacts with its environment when connected to two
electrodes is still lacking. To help alleviate this issue, spectroscopy is becoming an increasingly
important aspect molecular electronics research. And, Inelastic Electron Tunneling Spectroscopy
(IETS), which provides information about the vibration modes of the molecular junction, has
become one of the more commonly used tools for characterizing molecular systems by helping to
detail electron-phonon interactions and tunneling pathways. However, even more information
can be gained about molecular transport by applying these same principles at the single molecule
level. We have studied the electron-phonon interactions in a single molecule junction where the
molecule is covalently bound to two electrodes. In this study, the vibration modes in a single
molecule junction are measured while the strain in the junction is changed by separating the two
electrodes. This unique approach allows changes in the conductance to be compared to changes
in the configuration of a single molecule junction by recognizing changes in the vibration energy
of the junction bonds. This approach opens a new door for characterizing single molecule
junctions and better understanding of the relationship between molecular conductance, electron-
phonon interactions, and junction configuration.


11:30 AM B1.8
Reversible Conductance Switching in Molecular Devices. Auke Jisk Kronemeijer
1
, Hylke B
Akkerman
1
, Tibor Kudernac
2
, Bart J van Wees
1
, Ben L Feringa
2
, Paul W.M. Blom
1
and Bert de
Boer
1
;
1
Zernike Institute for Advanced Materials, University of Groningen, Groningen,
Netherlands;
2
Stratingh Institute for Chemistry, University of Groningen, Groningen,
Netherlands.

Since the theoretical study of Aviram and Ratner in 1974 predicting a single molecule
functioning as a diode, the field of Molecular Electronics has received increasing interest.
Methodologies and processing techniques have been investigated to measure the electrical
properties of (single) molecules, including breakjunction techniques and scanning probe
microscopy techniques. Our approach has been to produce molecular junctions in vertical
interconnects, predefined in an insulating photoresist matrix [1]. In the vias, a self-assembled
monolayer (SAM) is created on the underlying gold patterned substrate and the junctions are
finished with a conducting polymeric top contact. The formation of this top contact is the key
step in the processing since it has been shown that direct evaporation of metals on top of SAMs
results in penetration of the metal through the monolayer. Instead, the conducting polymer
PEDOT:PSS is spincoated on top of the monolayer. Because of this extra layer, direct
evaporation of the auxiliary top contact is possible, penetrating to some extent the polymer layer
but leaving the SAM intact. Reliable molecular junctions based on alkane(di)thiol molecules
demonstrated that the electronic properties of the molecules in the SAM are indeed measured [2].
Therefore, functionalities can now be incorporated into the molecules. Photochromic switches
are molecules which are stable in two different states and can be driven from one state into
another by applying light of specific wavelength. An interesting subgroup of switches are the
diarylethenes, because during the transition between the two states, the -conjugation between
both ends of the molecule is formed or disrupted. Supposedly, this change in conjugation will
change the conducting properties of the molecules in molecular junctions. Molecular devices
which show (non-volatile) conductance switching are interesting for memory applications.
Therefore, diarylethenes have been assembled in a monolayer in the molecular junctions. J-V
characteristics of the molecular junctions were obtained for the two different states of the
switches, resulting in a clear difference in conductance between both forms. In situ irradiation of
the devices results in reversible switching of the conductance of the devices [3]. Reference
devices exhibit no switching. Therefore, the bidirectional conductance switching can indeed be
attributed to the monolayer of molecular switches in the devices. [1] H.B. Akkerman, D.M. de
Leeuw, P.W.M. Blom and B. de Boer, Nature 441, 69-72 (2006) [2] P.A. van Hal, E.C.P. Smits,
T.C.T. Geuns, H.B. Akkerman, B.C. de Brito, S. Perissinotto, G. Lanzani, A.J. Kronemeijer, V.
Geskin, J. Cornil, P.W.M. Blom, B. de Boer and D.M. de Leeuw, Nature Nanotechnol.
Advanced Online Publication 2008 [3] A.J.Kronemeijer, H.B. Akkerman, T. Kudernac, B.J. van
Wees, B.L. Feringa, P.W.M. Blom and B. de Boer, Adv. Mat. 20, 1467-1473 (2008)


11:45 AM B1.9
Conjugated Molecular Junctions with Strong Electronic Coupling. Richard L McCreery
1
,
Adam J Bergren
1
, Ken Harris
1
and Sergio Jimenez
2
;
1
National Institute for Nanotechnology,
University of Alberta, Edmonton, Alberta, Canada;
2
Cinvestav Quertaro, Libramiento
Norponiente No 2000, Mexico.

A thin layer (1-5 nm thick) of organic molecules bonded covalently to a very flat (<0.5 nm rms)
graphitic carbon substrate comprise the active region of reproducible, large area molecular
electronic junctions. UV-Vis and Raman spectroscopy indicate strong electronic coupling
between the molecule and substrate, possibly due to the nearly symmetric C-C bond between
phenyl rings. Vapour deposition of copper as a top contact completes the molecular junction,
resulting in >90% device yield, and with current-voltage characteristics that strongly depend on
the structure of the molecular component(1,2). Current-voltage curves are repeatable for millions
of cycles, and absolute current densities vary by 10-20% for several devices made with a given
molecule. In some cases, a covalent bond between the Cu top contact and a functional group in
the molecule has been detected such that both molecular layer-contact interfaces involve
covalent bonds The observed current is dependent on temperature above ~250 K, but
independent of temperature between 200 K and 5 K. The linear (i.e. ohmic) current-voltage
behaviour observed at 5 K indicates that the molecular layer has orbitals at the Fermi energy of
the contacts, and that transport through the molecular layer is resonant. Although transport
appears to be of the on resonance type, it occurs through a small subset of the available
molecules in the devices examined to date. While the current junctions behave as nonlinear
conductors, related devices show promise as photonic interfaces(3) and non-volatile
memory(4,5). References (1) Bergren, A. J.; Harris, K. D.; Deng, F.; McCreery, R.; J. Phys.
Condens. Matter 2008, 20, 374117. (2) Anariba, F.; Steach, J.; McCreery, R.; J. Phys. Chem B
2005, 109, 11163. (3) Bonifas, A. P.; McCreery, R. L.; Chem. Mater. 2008, 20, 3849. (4)
Barman, S.; Deng, F.; McCreery, R.; J. Am Chem Soc 2008, 130, 11073. (5) Wu, J.; Mobley, K.;
McCreery, R.; J. Chem. Phys. 2007, 126, 24704.



SESSION B2: Molecular Scale Electronics II
Chairs: Saw-Wai Hla and Heike Riel
Monday Afternoon, April 13, 2009
Room 2001 (Moscone West)

1:30 PM *B2.1
Charge Transport through Single Molecules - Opportunities and Challenges. Emanuel
Loertscher, Raoul Scherwitzl, Marius Trouwborst and Heike Riel; IBM Research, Rueschlikon,
Switzerland.

As device dimensions continue to shrink into the nanometer length-scale regime, conventional
semiconductor technology will be approaching fundamental physical limits. New strategies,
including the use of novel materials, innovative device architectures, and smart integration
schemes need to be explored and assessed. In that respect, molecular electronics is aimed at the
use of individual or small ensembles of molecules as functional building blocks in electronic
circuits. However, in order for molecular electronics to become a viable technology a number of
fundamental scientific issues need to be addressed. We have investigated electronic transport
through individually contacted and addressed molecules in a two-terminal break-junction
configuration under ultra-high vacuum condition at various temperatures. In this talk I will
discuss in particular our investigations of the molecule-metal coupling which we studied using
an ideal molecular system by anchoring a phenyl ring either by thiol, isocyanide or alternative
linker groups to gold electrodes. Transport measurements have been performed by repeatedly
forming and breaking the molecular junction during simultaneously recording the conductance
(under a fixed bias) and the current-voltage characteristics. The molecule-metal coupling was
derived from the molecular level broadening in resonance on the single-molecule level and from
the off-resonance conductance averaged over many thousands of junctions. The level broadening
was found to be 50% larger in case of thiol compared with isocyanide coupling, which is in good
agreement with the off-resonant conductance determined to be 25% higher for thiol coupling.
Moreover, electrical transport studies using alternative linker groups with a larger number of
chemical bonds will be presented. The conductance of the metal-molecule-metal system is
compared with thiol and isocyanide linker groups in the in-resonance as well as in the off-
resonance case.


2:00 PM B2.2
A Bistable Poly[n]rotaxane-Based Solid-State Switch. Erica Deionno
1
, Wenyu Zhang
2
,
William Dichtel
3
and J. F Stoddart
4
;
1
Electronics and Photonics Laboratory, The Aerospace
Corporation, El Segundo, California;
2
Department of Chemistry and Biochemistry, University of
California, Los Angeles, Los Angeles, California;
3
Department of Chemistry and Chemical
Biology, Cornell University, Ithaca, New York;
4
Department of Chemistry, Northwestern
University, Evanston, Illinois.

Mechanically interlocked compounds, such as bistable [2]catenanes and [2]rotaxanes, have been
shown to exhibit switching behavior in both the solution phase and the solid-state. Bistable
poly[n]rotaxanes, a new class of materials containing mechanical bonds and donor-acceptor
interactions, have been synthesized, and these polymers might be capable of similar switching
behavior in the solid-state. We report in this paper the fabrication and electrical characterization
of solid-state devices incorporating a bistable poly[n]rotaxane. Preliminary device measurements
show that the electrical properties of the devices are dependent on the electrode materials.
Devices with metal electrodes did not exhibit any switching behavior, while devices with silicon
bottom electrodes displayed a hysteretic response with applied voltage, indicating that the
devices can be switched between two conductance states, on and off. The polymer films can be
spin-cast on the bottom electrodes and the thickness of the films can be easily tuned, providing
an advantage over other molecule switches in the ease of fabrication.


2:15 PM B2.3
Collective Reactivity of Molecular Chains Self-Assembled on a Surface Peter
Maksymovych
1,2
, Dan C Sorescu
3
, Kenneth D Jordan
2
and John T Yates, Jr.
4,2
;
1
Center for
Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee;
2
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania;
3
U. S.
Department of Energy, National Energy Technology Laboratory, Pittsburgh, Pennsylvania;
4
Department of Chemistry, University of Virginia, Charlottesville, Virginia.

Molecular self-assembly on surfaces is a route toward not only creating structures, but also
engineering new chemical reactivity afforded by the intermolecular interactions. We will
describe a new type of chemical reaction which occurs in linear chain-like molecular structures
spontaneously self-assembled from CH
3
SSCH
3
molecules on Au(111) and Au(100) surfaces [1]:
injecting low energy electrons from a scanning tunneling microscope tip into a molecule in the
chain initiates a chain reaction that propagates through as many as 10 molecules in a row before
being quenched. Nearly every aspect of the chain reaction, as revealed by scanning tunneling
microscopy (STM) at 5K, is unprecedented. From STM-kinetic measurements, the chain reaction
can be triggered by one or two electrons, depending on the energy of the tunneling electrons. In
conjunction with the DFT-calculations of the electronic structure of the adsorbed CH
3
SSCH
3

molecule, this identifies electron attachment to a CH
3
SSCH
3
molecule as the triggering stage of
the chain reaction. Subsequent dissociation of the CH
3
SSCH
3
molecule produces two hot CH
3
S
fragments, one or both of which then collide with neighbor CH
3
SSCH
3
molecules, causing their
S-S bond to dissociate with the ejection of another CH
3
S fragment, and so forth. The propagation
of the chain reaction is thus reminiscent of the operation of the Newtons cradle. The majority
reaction products turn out to be CH
3
SSCH
3
molecules that relate as mirror images to the original
CH
3
SSCH
3
molecules. This is a unique product, since exciting an isolated CH
3
SSCH
3
molecule
leads only to its dissociation or diffusion as a whole, but never to simultaneous rotation of both
methyl groups about the S-S bond. Self-assembly therefore provides a new reaction coordinate
for the CH
3
SSCH
3
molecules dissociating on gold surfaces. DFT calculations of the transition
states reveal a nearly barrierless sequence of elementary steps along the new reaction coordinate
involving CH
3
S intermediates stabilized by neighbor CH
3
SSCH
3
molecules. [1] P.
Maksymovych, D. C. Sorescu, K. D. Jordan, and J. T. Yates, Jr., Science (2008) in press. We
thank D. B. Dougherty for fruitful discussions. P. M. and J.T.Y: Supported by the W. M. Keck
Foundation and by the Army Research Office. K.D.J acknowledges support from the National
Science Foundation through grant CHE0518253. A grant of computer time at the Pittsburgh
Supercomputer Center is gratefully acknowledged. P.M.: Research performed in part as a
Eugene P. Wigner Fellow and staff member at the Oak Ridge National Laboratory, managed by
UT-Battelle, LLC, for the U.S. Department of Energy under Contract DE-AC05-00OR22725.


2:30 PM B2.4
Self-Assembled Monolayers of Various Conjugated Macrocycles Grafted on Silicon Oxide
for Memory Applications Virginie Gadenne
1
, Lionel Patrone
1
, Alexandre Merlen
2
, Mireille
Mossoyan-Deneux
3
and Louis Porte
3
;
1
Institut Suprieur de lElectronique et du Numrique,
IM2NP, CNRS, IM2NP (UMR 6242), Maison des Technologies, Place Georges Pompidou, F-
83000 Toulon, France;
2
Universit du Sud Toulon-Var, IM2NP, CNRS, IM2NP (UMR 6242),
Btiment R, BP 20132, F-83957 La Garde cedex, France;
3
Aix-Marseille Universit, IM2NP,
CNRS, IM2NP (UMR 6242), Facult des Sciences et Techniques, Campus de Saint-Jrme,
Avenue Escadrille Normandie Niemen - Case 142, F-13397 Marseille Cedex, France.

Today self-assembled monolayers (SAM) [1,2] constitute a promising strategy to build
molecular nano-devices. Beside many studied molecules, conjugated macrocycles such as
porphyrins and phthalocyanines are good candidates for charge storage, within molecular
memory cells [3]. However their correct operation strongly depends on both molecular order and
binding to the substrate. Thus it is very important to control the deposition of these macrocycles
to form spontaneously ordered monolayers grafted on silicon for applications compatible with
microelectronics technology. In this work, we studied SAMs of three conjugated macrocycles on
silicon oxide pre-functionalized by aminopropyltrimethoxysilane (APTMS) coupling agent.
Selected macrocycles are Zn and Fe protoporphyrins bearing two carboxylic acid functions,
ZnPP and FePP respectively, and a synthesized Zn phthalocyanine surrounded by height
carboxylic acid functions, ZnPc(COOH)
8
. Carboxylic functional groups on peripheral cycles
allow molecules anchoring on the surface by imino link formation with APTMS. The samples
were characterized by scanning probe microscopy, ellipsometry, contact angle measurements,
Fourier transform infrared (ATR-FTIR) and UV-visible spectroscopy. Using gold surfaces and
replacing APTMS by amino-thiol coupling moieties allowed us to perform complementary
analysis of the grafting and structure of macrocycles with scanning tunneling microscopy and
surface enhanced Raman spectroscopy on appropriate nanostructured substrates. From analysis
carried out all along ZnPc(COOH)
8
. SAM formation, we show UV-visible spectroscopy exhibits
both a blue shift suggesting a growing face to face orientation and a splitting of the Q-band (at
698 nm). These results suggest a dimerization, due to formation of hydrogen bonds between
peripheral carboxylic acid groups [4]. They show that a great number of carboxylic acid
functions surrounding the molecule allows promoting a -stacking arrangement interesting to
obtain a charge delocalization over a small memory cell. On the contrary, for ZnPP SAM, Soret
band (at 400 nm) is red-shifted during the growth, which is typical for an edge to edge
organization [5]. However no shift is observed for FePP, indicating these molecules assemble in
a different way. Furthermore FTIR spectroscopy together with ellipsometry and scanning probe
microscopy experiments indicate that ZnPc(COOH)
8
and ZnPP anchor perpendicular to the
surface via imino bonds whereas FePP is linked by axial ligand position owing to iron electronic
configuration, which is less favorable for memory applications. [1] A. Ulman, Chem. Rev. 1996,
96, 1533 [2] F. Schreiber, Progress in Surf. Sci. 2000, 65, 151 [3] C.M. Carcel, J.K. Laha, R.S.
Loewe, P. Thamyongkit, K.-H. Schweikart, V. Misra, D.F. Bocian, J.S. Lindsey, J.Org. Chem.
2004, 69, 6739 [4] H. Xia, M. Nogami, Opt. Mater. 2000, 15, 93 [5] S. Boeckl, A.L. Bramblett,
K.D. Hauch, T. Sasaki, B.D. Ratner, J.W. Rogers., Langmuir 2000, 16, 564.


2:45 PM B2.5
Three-terminal, Single Molecule Circuits with Carbon Nanotube Wiring. Philip G. Collins,
Vaikunth Khalap, Danny Wan and Alexander Kane; Physics and Astronomy, Univ. of
California, Irvine, Irvine, California.

The vision for molecular electronics extends well beyond miniaturation and scaling of digital
electronics to include new techniques for studying chemical bonding, biocatalysis, and molecular
recognition in real time. However, operational single molecule devices remain exceedingly
fragile and difficult to fabricate. We have demonstrated a promising new architecture for the
versatile study of single molecule interrogation based on "point functionalization" of single-
walled carbon nanotube circuits [1]. In this technique, single defects are created in the sidewall
of an electrically connected nanotube. The technique, free of precision lithography or mechanical
manipulation, produces single, carbon-based attachment sites in operational circuits. A wide
range of organic molecules and biomolecules may then be covalently attached with single
molecule precision. This presentation will overview these experimental techniques and
demonstrate the types of signals that have been observed. Various chemical processes including
oxidation, conjugation, recognition and binding have all been monitored in real time [2,3]. The
circuit conductance and its spectral power density provide a direct measure of these time-
dependent, dynamic processes. Besides this high amplification transduction, other advantageous
properties of this architecture include excellent electrical, mechanical, and chemical stabilities
and well-defined bonding to the molecules of interest. [1] B. R. Goldsmith et al, Science v315 77
(2007). [2] B. R. Goldsmith et al, Nano Lett. v8 189 (2008). [3] J. Coroneus et al,
ChemPhysChem v9 1053 (2008).


3:30 PM *B2.6
Self-assembled Monolayers on Graphene Surfaces: Prospects for Graphene-based
Molecular Electronics. Mark C. Hersam, Materials Science and Engineering, Northwestern
University, Evanston, Illinois.

Chemically functionalized semiconductor surfaces have been widely explored due to their
potential for enabling molecular electronic and sensing devices that are compatible with
conventional microelectronic technology. Thus far, the vast majority of work in this field has
focused on established semiconductors including silicon, germanium, and gallium arsenide.
Meanwhile, the condensed matter physics community has diverted substantial experimental and
theoretical effort to graphene, an emerging electronic material with superlative carrier mobility
and exotic charge transport phenomena such as the quantum Hall effect. In an attempt to unify
these two fields, this talk will describe our recent efforts to interrogate and exploit organic self-
assembled monolayers on graphene surfaces. In particular, we have recently demonstrated that
self-assembled monolayers of perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA)
can be formed on graphene surfaces via gas-phase deposition in ultra-high vacuum (UHV)
environments. Molecular-scale resolution scanning tunneling microscopy (STM) images reveal
long-range order in the PTCDA monolayers, while scanning tunneling spectroscopy (STS)
measurements yield the interplay between the electronic structure of the PTCDA molecules and
the underlying graphene substrate. These fundamental studies are expected to provide insight
into the prospects and opportunities for graphene-based molecular electronics.


4:00 PM B2.7
Non Destructive Metallic Contacts for Molecular Electronic Devices. Oliver Seitz
1
, Min Dai
2

and Yves J. Chabal
1
;
1
University of Texas at Dallas, Dallas, Texas;
2
Rutgers University,
Piscataway, New Jersey.

Making reliable metallic contacts to organic molecules probably remains one of the biggest
challenges. Various approaches for establishing electrical contacts on self assembled monolayers
(SAMs) have been investigated (non-metallic: conductive polymers; metallic: LOFO, PALO,
direct and indirect evaporation, liquid metal), but none of them can provide a reliable non-
destructive contact with atomic control necessary for microelectronic devices. Atomic Layer
Deposition (ALD) is being considered for such applications because it could in principle make it
possible to chemically bond metal atoms to organics in a non destructive fashion. Using a novel
liquid copper precursor--copper(I) di-sec-butylacetamidinate ([Cu(
s
Bu-amd)]
2
), which can react
with molecular hydrogen at moderate temperatures (~180
o
C), we have successfully deposited
metallic copper on top of a carboxylic terminated SAM that is covalently attached to the silicon
surface (Si-C bond). The successful intimate contact between the molecules and the Cu as well
as the integrity of the monolayer quality (no interfacial oxide growth during the process) has
been verified by in-situ Fourier transformed infrared spectroscopy (FTIR). X-ray photoelectron
spectroscopy (XPS) confirm the metallic state of the copper and the non oxidation of the Si
interface. Atomic force microscopy (AFM) was used to quantify the homogeneity of these
contacts and the ability to create/control them at the microscale. We are now in the process of
electrical measurements, using a mercury contact as a reference electrode.


4:15 PM B2.8
Simultaneous Opto-electronic Measurement of Metal Filament Formation in Molecular
Electronic Devices. Nazanin Davani
1
, Ken T Shimizu
2
and Nicholas A Melosh
2
;
1
Chemical
Engineering, Stanford University, Stanford, California;
2
Materials Science and Engineering,
Stanford University, Stanford, California.

The behavior of molecular devices is known to depend upon the electrodes, molecules, and
electrode-molecule contacts, and electrical switching in molecular junctions has been reported
for several molecules. However, it can be difficult to distinguish between molecular dependent
switching and metallic filament formation when investigating dynamic switching events, largely
because of the reliance on electrical characterization. Recently, we have demonstrated that it is
possible to measure the real-time optical absorption of the molecular layer in between metallic
contacts during voltage cycling using Surface Plasmon Resonance Spectroscopy (SPRS). SPRS
can provide detailed information about the optical variations in addition to electrical changes in
the junction. Here we report the opto-electronic properties of thin films of electrically inert poly
methylmethacrylate (PMMA). Surprisingly, PMMA films with Au electrodes show changes in
electrical conductivity and SPRS signal as a function of electrical bias. The observations are
consistent with electro-dissolution/deposition of Au ions within the junction. These phenomena
are characterized optically and electrically, and demonstrate that the number of filaments that
contributes to electrical conductivity is a small fraction of the total present in the junction.
Further, the optical and kinetic characteristics of the metal filaments are largely distinct from
molecular charges allowing the two processes to be separated. These results have significant
implications for stability and switching in thin molecular film devices.


4:30 PM B2.9
The Nature of Fluctuations in Molecular Heterojunction Electronics. Jonathan A Malen
1,5
,
Kanhayalal Baheti
3,5
, Peter Doak
3,5
, T. Don Tilley
3,5
, Rachel A Segalman
2,5
and Arun
Majumdar
1,4,5
;
1
Mechanical Engineering, UC Berkeley, Berkeley, California;
2
Chemical
Engineering, UC Berkeley, Berkeley, California;
3
Chemistry, UC Berkeley, Berkeley,
California;
4
Materials Science and Engineering, UC Berkeley, Berkeley, California;
5
Materials
Science Division, Lawrence Berkeley Laboratory, Berkeley, California.

Single molecule circuits represent a lower limit on the scalability of electronic devices and are
hence an ultimate goal of nanotechnology. A deeper understanding of electronic transport
through single molecules is of critical importance to molecular electronics and bears added value
to the wider field of organic-inorganic heterostructured materials. While important experimental
and theoretical advances over the last decade have yielded some insight into electron transport in
metal-molecule-metal junctions, a number of fundamental questions remain unresolved. One
area of rich debate is the origin of fluctuations and stochastic switching of conductance. In
particular, (i) Compared to the energy barrier height, how large are the fluctuations in the charge
transmission function? (ii) Are thermal fluctuations more important than that of the metal-
molecule contact, or are both equally important? (iii) Do these values change with the molecule
or is there some universal behavior? By measuring the thermopower of a series of
pheneylenedithiol molecules we herein answer these questions. Junction thermopower S, an
alternative transport property to conductance, was determined by measuring the voltage
difference across molecules trapped between two gold contacts held at different temperatures (S
= V/T). A modified scanning tunneling microscope (STM) was used to form a junction
between a gold STM tip and the molecule-coated gold substrate. An applied temperature bias T
between the tip and substrate generated a proportional voltage V, related to S by V=S*T. The
experiment was repeated 500-1000 times at each T, resulting in a histogram of measured
voltages. Transport variations were quantified by S/S, where S is the observed spread in S.
Statistical analysis of data from repeated measurements shows that S/S is dominated by
junction-to-junction differences rather than thermal fluctuations within a given junction. The
remarkably large Seebeck variation (S/S~1) implies that variation in the molecular transmission
barrier is similar in magnitude to the barrier height itself. Measurements of 1,4-benzenedithiol,
4,4-dibenzenedithiol and 4,4-tribenzenedithiol, show that increased degrees of freedom from
added benzene rings result in increased transport variations. These inherent sources of noise
represent a significant obstacle for single molecule electronics, but may be obscured when large
ensembles of molecules are present.


4:45 PM B2.10
Alignment of Molecular Energy Levels Between Two Biased Metallic Electrodes. Nikolai
Severin
1
, Daria Skuridina
1,2
, Christian Seifert
1
, Xie Dou
3
, Ragnar Stoll
1
, Stefan Hecht
1
, Igor M
Sokolov
1
, Klaus Mllen
3
and Juergen P Rabe
1
;
1
Humboldt University, Berlin, Germany;
2
Lomonosov University, Moscow, Russia;
3
Max-Planck-Institute for Polymer Research, Mainz,
Germany.

While originally Aviram and Ratner had proposed a molecular recifyer based on tunneling
through donor and acceptor moieties linked by a spacer, it has been argued later that rectification
may be also achieved with a single physisorbed donor or acceptor molecule located
asymmetrically between two electrodes. The latter was attributed to the dependence of the
potential at the position of the molecular orbitals in the tunneling gap on their relative position
within the gap. However, it has been also claimed that the potential of a molecular adsorbate is
not dependent on the tip-sample distance but rather equal to the substrate potential. Here we
report in-situ STM and STS data on mono- and bilayers of conjugated molecules self-assembled
at the interface between an organic solution and the basal plane of graphite, in order to resolve
this issue. They confirm that the electron potential drops gradually across the molecular
adsorbate. In a first set of experiments, bias dependent STM-imaging of a molecular bi-layer
revealed a dependence of their visibility on the applied bias as predicted by the model. In a
second experiment, the relative position of a conjugated molecule within the tunneling gap was
varied by controlling the tip-surface distance. The dependence of the current rectification ratio on
the relative position of different molecules between substrate and tip is also consistent with the
model. The results indicate that resonance enhanced tunneling through physisorbed conjugated
molecules between two biased metallic electrodes depends sensitively on the gap width and the
relative position of the electronic orbitals within the gap, thereby providing a means to precisely
control current-voltage characteristics through the geometry of the gap.



SESSION B3: Molecular Scale Electronics III
Chairs: Avik Ghosh and Latha Venkataraman
Tuesday Morning, April 14, 2009
Room 2001 (Moscone West)

8:30 AM *B3.1
Imaging the Local Properties of Graphene: a New Platform for Molecular Electronics.
Michael F. Crommie, Y. Zhang, V. Brar, C. Girit and A. Zettl; Physics Dept. and Materials
Science Division, LBNL, UC Berkeley, Berkeley, California.

Graphene, a single atomic layer of carbon, provides an exciting new platform for molecular
electronics due to its chemical and structural flexibility as well as its novel electrical,
mechanical, and magnetic properties. Scanning tunneling microscopy (STM) is an ideal tool to
study the properties of graphene at lengthscales necessary to evaluate its utility for molecule-
scale device applications. We have used STM to explore backgated graphene flakes, and we
observe surprisingly strong electron-phonon coupling in electronic tunneling spectra. We also
find that the graphene charge neutral point (the Dirac point) manifests itself as a clear feature in
tunnel spectra, and it can be shifted by applied gate voltage. By spatially mapping the Dirac point
we are able to map out electron density inhomogeneities in graphene with a spatial resolution at
the nm scale. Using this new technique we have observed molecule-induced charge
inhomogeneities that coexist with energy-dependent electronic interference patterns in graphene,
giving us new insight into the microscopic mechanisms that determine graphene electron
mobility.


9:00 AM B3.2
Metal/Insulator/Metal Thin Film Electrodes for Molecular Conduction. Bing Hu, Pawan
Tyagi and Bruce Jackson Hinds; Chemical and Materials Engineering, Univ. of Kentucky,
Lexington, Kentucky.

Producing reliable electrical contacts with gaps having the dimensions of molecular lengths is a
difficult challenge for molecular electronics. As a promising alternative to break-junctions, we
use conventional film deposition and photolithography to form an exposed edge of a thin film
multilayer structure (metal/insulator/metal). Molecules can self-assemble on the exposed edge
offering an alternative conduction path through the molecules with angstrom-scale dimensional
control. Critical to this approach is to have minimal background tunnel current through the
insulator layer sandwiched between metal layers. Robust electrodes with aluminum oxide
insulator layer are found on alloys of Al/Au and Ta/Au. The readily oxidized Al/Ta reduce
surface energy for a mechanically stable interface with oxide but allow molecular contact with
metallic gold at the pattern edge. Electrodes were successfully fabricated with this strategy with
current measured through a metal coordination compound cluster composed of a cube with
cyano linked Ni or Fe at the corners. Thiolacetate ligand tethers come off of the cluster core and
bind the complex to the metal leads, allowing the molecule to span the insulator gap on the
surface of the etched pattern. Molecules that do not bridge the gap are not electrically active.
Along the 10um pattern edge approximately 6000 molecules are involved in conduction. 10nA
per molecule is seen at 10mV bias. Tunnel current through the molecules is analyzed with
Simmons model and barrier height is found to be 1.1 eV and tunnel length of 1.2nm.


9:15 AM B3.3
Dipole Effects on Electron Transport through Helical Peptides Immobilized on Gold.
Shunsaku Kimura and Tomoyuki Morita; Dept. of Material Chemistry, Kyoto University, Kyoto,
Japan.

Electron injection or extraction from helical peptides to gold was studied to evaluate the dipole
effects of Au-S linkages and helical peptides. The helical lengths of the helical peptides exceeds
over 3 nm, where the electron hopping mechanism is prevailing. The molecular terminal has a
ferrocene group as a redox species, and the electron transfer from the ferrocene unit to gold was
evaluated by electrochemical methods. The electron transfer process comprises three regions; the
hopping through the helical peptide under the peptide dipole, through the linker, and through the
covalent connection between Au and the peptide under the Au-S dipole. Not only the dipoles but
also the physical properties of the helical peptide SAMs were found to influence the electron
transfer processes at the interface. Eventually, we try to extract the dipole effects on the electron
transport through the helical peptide SAMs.


9:30 AM B3.4
Creating and Characterizing Robust, Large Area Molecular Electronic Junctions. Michael
Preiner
1
and Nicholas Melosh
2
;
1
Applied Physics, Stanford University, Stanford, California;
2
Materials Science and Engineering, Stanford University, Stanford, California.

While recent years have seen numerous advances in creating single-molecule electronic
junctions, practical molecular electronic devices will almost certainly require junctions with
large numbers of molecules. We demonstrate a technique for creating large area, electrically
stable molecular junctions. We use atomic layer deposition to create nanometer thick passivating
layers of aluminum oxide on top of self-assembled organic monolayers with hydrophilic terminal
groups. This layer acts as a protective barrier and allows simple vapor deposition of the top
electrode without short circuits or molecular damage. This method allows nonshorting molecular
junctions of up to 9 mm
2
to be easily and reliably fabricated. The effect of passivation on
molecular monolayers is studied with Auger and x-ray spectroscopy, while electronic transport
measurements confirm molecular tunneling as the transport mechanism for these devices. Using
a similar processing method, we also demonstrate the ability to rapidly characterize (and
passivate) single defects on hydrophobic SAMs.


9:45 AM B3.5
Atomic Level Analysis of Polythiophene by the Scanning Atom Probe. Osamu - Nishikawa
1
,
Masahiro - Taniguchi
2
, Hitoshi - Kato
3
and Satoru - Tanemura
4
;
1
Chemistry & Biology,
Kanazawa Institute of Technology, Nonoichi, Japan;
2
Chemistry & Biology, Kanazawa Institute
of Technology, Nonoichi, Japan;
3
Physics of Materials, Kanto Gakuin University, Yokohama,
Japan;
4
Physics of Materials, Kanto Gakuin University, Yokohama, Japan.

The atom probe (AP) is known to be an ultimate micro mass analyzer that allows atom-by-atom
mass analysis. However, the analyzable area of the conventional AP is limited to a minute
hemispherical area at the apex of an extremely sharp and long tip because a high field required to
field evaporate surface atoms as positive ions can be generated by a relatively low voltage. The
fabrication of such a filamentary long tip is extraordinary difficult for many materials.
Accordingly, the preparation of the specimens, such as polymers, is another barrier for wide
range applications of the atom probe. In order to overcome this difficulty, a funnel-shaped micro-
extraction electrode is introduced in the conventional AP. Since this electrode scans over a
planar specimen surface, this atom probe is named as a scanning atom probe (SAP). The
extraction electrode confines the high field required for field evaporation of surface atoms into a
small space between an apex of a minute cusp on the planar surface and an open end of the
electrode. Thus, the SAP can analyze not only a sharp slender tip but also an apex area of the
cusp. Thin films of conductive polythiophene are fabricated by electrochemically polymerizing
thiophene monomers on an ITO substrate. Film thickness is about 10m-30m and the dopant is
BF4-. A small piece of the polythiophene films is peeled off from the substrate and inserted into
a narrow gap between two small Nichrome nails. Then the film is clipped by the nails. The
Nichrome holder is introduced in the SAP and placed in front of the electrode. DC voltages and
pulsed YAG laser beams are applied to the specimen. The pulse width of the pulsed laser is 5 ns
and its wavelength is 532 nm. The field evaporated ions pass through the open hole of the
electrode and enter the reflectron type mass analyzer. Mass resolution of the analyzer m/dm is
better than 1000. Mass spectra of the analyzed polythiophene exhibit a large mass peak of
SC4Hn2+, the radical of the polythiophene, and various singly charged fragment ions such as
C2H+ and C3Hn+. The doubly charged radical ions indicate that the radicals are strongly bound.
All sulphur atoms are detected as S-C clusters such as SC+, SC2+ and SC3Hn+. Although no
fluorine ions are detected, most boron atoms are detected as the cluster ions with S and C such as
SCB2+ and C4HB+. Presently the mass analysis of the polythiophene films containing C60
molecules are under progress. The distribution of C60 and dopants in the polythiophene films
will be discussed.


10:30 AM B3.6
Monitoring Dynamic Molecular Electronic Processes at Buried Interfaces with ngstrom
Resolution using X-Ray Reflectivity. Jason D. Fabbri, Michael F Toney, Nazanin Davani, Ken
T Shimizu and Nicholas A Melosh; Stanford University, Stanford, California.

Molecular electronics has been proposed as a successor to conventional CMOS technology as
device dimensions continue to shrink. Interesting electrical behavior has been observed in
molecular junctions and structural and spectroscopic probes are needed to understand and
improve upon it. We demonstrate the utility of X-ray reflectivity as an in-situ probe of molecular
electronic junctions under electrical bias. In the present study, we have examined chlorophyll
monolayers deposited on silicon bottom electrodes using the Langmuir-Blodgett technique. The
spot size of the X-ray beam necessitates large area junctions (~ cm^2) posing a formidable
fabrication challenge. Using a soft top contact deposition technique we have developed we
obtain functioning molecular junctions. From the X-ray reflectivity curves, we obtain precise
structural characterization of the junction. In addition, by applying a pulsed voltage sequence we
detect changes in reflected intensity as a function of applied electric field. Control experiments
and modeling show that these changes can be attributed to polarization of the molecular layer.
Further modeling allows us to extract the voltage drop across the monolayer, an important
parameter for molecular electronic devices. Finally, we will discuss the general utility of this
technique as a highly spatially sensitive probe of electronic changes in thin film devices.


10:45 AM B3.7
Single Nanometric Memory Unit Based On a Protein-Nanoparticle Hybrid. Izhar Medalsy
1
,
Arnon Heyman
2
, Or Dgany
2
, Oded Shoseyov
2
and Danny Porath
1
;
1
Physical Chemistry, The
Hebrew University, Jerusalem, Israel;
2
Agriculture, The Hebrew University, Jerusalem, Israel.

Protein as a versatile isolating template on one hand and a nanoparticle (NP) as an electric
storage component on the other hand have long been investigated as independent entities. The
ability to combine thsee two species to form a single addressable unit cell isolated from the
conductive surface and from adjacent NPs gives rise to a wide range of nanoelectronic device
applications. Here we demonstrate the means to achieve an ultra dense memory unit using
individual protein-NP hybrids by Conductive Atomic Force Microscopy (C-AFM). SP1 (Stable
Protein 1) is a boiling-stable (melting temperature, Tm~109 oC) ring-shaped protein complex, 11
nm in diameter. Mutants of SP1 were synthesized by means of genetic engineering, allowing its
selective attachment to gold or silica surfaces (SiO2). The SP1-gold affinity is controlled by the
cys-group at different positions on the protein structure. Furthermore a switchable silica binding
SP1 mutant was engineered. Thru solvent condition changes, silica-binding peptides (serving as
anchors) are gradually and controllably exposed, thus creating a tunable silica-binding scaffold
while significantly reducing nonspecific surface binding. The mutants and their corresponding
attachment to the surfaces were characterized by gel electrophoresis and AFM. In order to serve
as an addressable memory device, 2D arrays of the SP1 protein were formed using different
methods such as phospholipids trough and Langmuir Blodgett and characterized using TEM and
AFM. In addition to the capability of selectively attaching to different surfaces and forming
ordered 2D arrays, SP1 was connected to gold and Si-SiO2 NP. This setup of an isolating unit
connected to a chargeable NP over a conductive surface enables selective charging of the NP.
Each NP holds three charging states: natural, positive and negative. The charging of the
conjugated Si-SiO2 NP was induced and tested using C-AFM, revealing life times of the charged
states of 10 min in ambient and hours in vacuum. Using this setup, and the relative long charging
time, we were able to apply a read and write operations on individual 5nm Si-SiO2 NP
embedded in a stable protein. Having a stable and well ordered array of SP1-NP hybrids capable
of charge storage at a three state setup for long times will enable to implement ultra high density
memory array.


11:00 AM *B3.8
Transition from Tunneling to Hopping Transport in Long, Conjugated Molecular Wires C.
Daniel Frisbie, Chemical Eng & Materials Science, University of Minnesota, Minneapolis,
Minnesota.

In this talk I will describe a series of comprehensive electrical transport measurements on
conjugated molecular wires up to 10 nm in length, grown off of gold electrodes. The wires are
grown using stepwise imine-forming reactions; using this chemistry the length of the wires can
be precisely controlled from 1-10 nm. Electrical conduction of ~100 parallel wires is measured
using metal coated AFM tips to make the second contact. Both the temperature and length
dependence of the wire resistance indicates a transition from tunneling to hopping transport at
approximately 4 nm in wire length. In addition, the current-voltage characteristics reveal that
field emission can occur at higher bias voltages. An important benefit of the length dependent
transport measurements is that the role of contact resistance can be assessed directly and
separated from the wire resistance. Overall, these measurements combined with the synthesis
chemistry open unprecedented opportunities to probe the connection between tailored molecular
structure and charge conduction in small bundles of conjugated molecular wires.


11:30 AM B3.9
Formation of Conjugated Monolayers on Metallic Nanoparticles for Single-Molecule
Transport Studies. Alexander Benjamin Neuhausen
1
, David Goldhaber-Gordon
2
, Chris
Chidsey
3
and Zhenan Bao
4
;
1
Electrical Engineering, Stanford University, Palo Alto, California;
2
Physics, Stanford University, Palo Alto, California;
3
Chemistry, Stanford University, Palo Alto,
California;
4
Chemical Engineering, Stanford University, Palo Alto, California.

We present studies of the formation of monolayers of conjugated organic molecules on metallic
nanoparticles. After monolayer formation, we have used click chemistry to link azide-terminated
monolayers with dialkyne bridge molecules. With appropriate tuning of azide density and the
concentration of linking molecules, we make the case for single-molecule linking of metallic
nanoparticles to form a dimer or "dumbbell" structure, and propose using nanoscale lithography
to fabricate leads to the nanoparticles, allowing for single-molecule transport and surface-
enhanced Raman spectroscopy measurements.


11:45 AM B3.10
Sub-10 nm Nanoimprint Lithography for the Application to Molecular and Organic
Electronic Devices. Andrew Paul Bonifas
1,2
and Richard L McCreery
2,3
;
1
Materials Science and
Engineering, The Ohio State University, Columbus, Ohio;
2
National Institute for
Nanotechnology, Edmonton, Alberta, Canada;
3
Chemistry, University of Alberta, Edmonton,
Alberta, Canada.

As the fields of molecular and organic electronics mature, progression from fundamental
experiments to the incorporation of molecular/organic components into real world devices has
become of primary interest. Numerous methods have been proposed to facilitate this progression
which include, but are not limited to, top contact fabrication on a preassembled molecular layer
through direct or indirect metal evaporation, conducting polymer intermediate, and soft contact
methods. Although these methods incorporate standard semiconductor processes, the degree of
structural damage to the molecular layer is highly debatable. To circumnavigate damage to the
molecular layer, methods where both electronic contacts are fabricated prior to the molecular
layer formation can be employed. The limitation with this approach is the difficulty to fabricate
on the length scale of several aromatic molecules for molecular devices or the polaron
delocalization length in conducting polymer devices. This presentation will outline a novel
technique to fabricate sub-10 nm gaps with nanoimprint lithography (NIL) and its application to
molecular/organic electronic devices. The inherent 1:1 pattern transfer from the NIL mold to the
substrate limits NIL to the resolution of the mold fabrication process. A straight forward NIL
mold fabrication technique incorporates electron beam lithography (EBL) followed by reactive
ion etching (RIE) of the NIL mold. The resolution of this technique is limited by the EBL
process which is on the order of 15-20 nm. Our approach is an extension of the standard
EBL/RIE process where the RIE of a Si mold is followed by a controlled Si oxidation process.
The formation of SiO2 narrows the gap between the NIL molds features and provides a surface
to allow the attachment of a silane based anti-adhesion layer. Since the molds features are
fabricated from a Si single crystal, the oxidation process is highly uniform. This technique is
intended to make sub-10 nm nanoimprint lithography accessible to a large range of researchers.
To illustrate applications of this technique to molecular/organic electronic devices,
experimentally measured electronic properties of conduction polymers are presented as the gap
of the prefabricated contacts approaches the polaron delocalization length. Electronic differences
between spin-coated and direct-polymerized polymer layers are discussed as a function of the
contact gap dimension, fabrication method, and applied gate bias.



SESSION B4: Molecular Scale Electronics IV
Chairs: Michael Crommie and Daniel Frisbie
Tuesday Afternoon, April 14, 2009
Room 2001 (Moscone West)

1:30 PM B4.1
ATP-driven Ionic Transport in 1-D Lipid Bilayer Nano/bioelectronic Devices. Shih-Chieh
Huang
1,2
, Nipun Misra
1,3
, Alexander B Artyukhin
1
, Costas P Grigoropoulos
3
, Jiann-Wen Ju
2
and
Aleksandr Noy
1
;
1
Lawrence Livermore National Laboratory, Livermore, California;
2
Civil and
Environmental Engineering, UCLA, Los Angeles, California;
3
Mechanical Engineering, UC
Berkeley, Berkeley, California.

1-D lipid bilayers- protective lipid bilayer shells on the one-dimensional inorganic nanomaterials
such as nanotubes and nanowires could provide a versatile matrix for incorporating biological
molecules into nanoscale electronic devices. We have used this platform to show that a
biological ATP-driven ion pump can efficiently gate single carbon nanotube transistors. We
show that these hybrid bio/nanoelectronic devices respond to the specific ion pump inhibitors.
The device response to the ATP concentration increase is consistent with the Michaelis-Menten
kinetics and shows that the electrical signals observed in our experiments originate from the
activity of the membrane ion pump.


1:45 PM B4.2
Environmental Effects on the Single Molecule Conductance of
bis(thiahexyl)oligothiophenes. Simon J. Higgins
1
, Edmund Leary
1
, Harm van Zalinge
1
,
Wolfgang Haiss
1
, Richard J Nichols
1
, Christopher M Finch
2
, Iain Grace
2
and Colin Lambert
2
;
1
Department of Chemistry, University of Liverpool, LIVERPOOL, United Kingdom;
2
Department of Physics, University of Lancaster, LANCASTER, United Kingdom.

It is now possible to measure the electrical conductance of nanoscale junctions in which a small
integer number of molecules bridges two metal contacts. This has further stimulated research
into single molecules as electronic components. There have been surprisingly few reports of
significant solvent effects upon single molecule conductance. Simple alkanedithiols exhibit the
same molecular conductance whether measured in air, under vacuum or under liquids of different
polarity. Here, using an STM-based method, we show that the presence of water gates the
conductance of a family of bis(thiahexyl)oligothiophenes, and that the longer the oligothiophene,
the larger is the effect; for the longest example studied, the molecular conductance is over two
orders of magnitude larger in the presence of water. This is an unprecedented result, suggesting
that, depending upon molecular structure, ambient water may need to be taken into account when
measuring single molecule conductances, or in the design of future single molecule electronic
devices. Theoretical investigation of electron transport through the molecules, using the ab initio
non-equilibrium Greens function (SMEAGOL) method, suggests that water molecules interact
directly with the thiophene rings, significantly shifting the transport resonances and greatly
increasing conductance.


2:00 PM *B4.3
Designing, Measuring and Controlling Molecular- and Supramolecular-Scale Properties
for Molecular Devices. Paul Weiss, Departments of Chemistry and Physics, Pennsylvania State
University, University Park, Pennsylvania.

We use molecular design, tailored syntheses, intermolecular interactions and selective chemistry
to direct molecules into desired positions to create nanostructures, to connect functional
molecules to the outside world, and to serve as test structures for measurements of single or
bundled molecules. Interactions within and between molecules can be designed, directed,
measured, understood and exploited at unprecedented scales. We look at how these interactions
influence the chemistry, dynamics, structure, electronic function and other properties. Such
interactions can be used to advantage to form precise molecular assemblies, nanostructures, and
patterns, and to control and to stabilize function. These nanostructures can be taken all the way
down to atomic-scale precision or can be used at larger scales. We select and tailor molecules to
choose the intermolecular interaction strengths and the structures formed within the film. We
selectively test hypothesized mechanisms for electronic switching by varying molecular design,
chemical environment, and measurement conditions to enable or to disable functions and control
of these molecules with predictive and testable means. Critical to understanding these variations
has been developing the means to make tens to hundreds of thousands of independent single-
molecule measurements in order to develop sufficiently significant statistical distributions,
comparable to those found in ensemble-averaging measurements, while retaining the
heterogeneity of the measurements. We quantitatively compare the conductances of molecule-
substrate junctions. We demonstrate the importance of these junctions in conductance switching
of single molecules. We find that the contacts and substrate play critical roles in the switching.
Switching of rigid, conjugated molecules is due to changes the molecule-substrate bonds, which
involves motion of the molecules and also motion of substrate atoms. We are able to measure the
coupling of the electrons of the molecules to those of the substrate by measuring the
polarizabilities of the connected functional molecules in high and low conductance states. These
polarizabilities are compared to those of other families of molecules and to detailed calculations.


2:30 PM B4.4
Single Molecular Dopants in Pentacene and Corresponding Spatial Electronic Effects
Observed by Scanning Tunneling Microscopy/spectroscopy. Sieu D Ha and Antoine Kahn;
Electrical Engineering, Princeton University, Princeton, New Jersey.

The physics of doping in inorganic semiconductors has been studied extensively in the past half
century and is generally well understood. In particular, the standard hydrogenic model
sufficiently describes dopant atoms, and the Coulomb potential therein specified has been
observed by scanning tunneling microscopy (STM). In contrast, analogous experimental and
theoretical research for organic doping is not nearly as developed. We present here the first (to
the best of our knowledge) observation by STM of a single molecular dopant in an organic host
matrix. These observations at the molecular level are key to better understand the mechanisms of
charge release and doping in van der Waals-bonded systems. The investigated organic system is
pentacene grown on Si(111)/Bi(001) and p-doped with tetrafluoro-tetracyanoquinodimethane
(F4-TCNQ). Pentacene has been shown to grow in a near-bulk upright phase on Si(111)/Bi(001)
and is thus an ideal candidate for epitaxial multilayer film deposition. Multilayer films are
necessary to decouple the surface electronic structure of the molecular film from the metallic
substrate. Pristine pentacene films three to four monolayer thick are surface-doped with F4-
TCNQ, and molecular resolution is obtained by STM. The topographic effects of the surface
dopants are predominantly localized and are directly dependent on sample bias. As the applied
bias is varied, in particular for imaging filled and empty states, the appearance of the acceptor
molecules changes reversibly from bright clusters to dark vacancies. This effect is purely
electronic and is thus strong evidence of dopant observation. Upon deposition of an additional
monolayer of pentacene on the surface-doped film, the dopants appear more delocalized. As the
bias is varied, the subsurface dopant appearance correspondingly varies from bright hillock to
dark depression. The dopant feature extends over several molecular lattice sites depending on the
sample bias and is reminiscent of the Coulomb potential as observed in inorganic semiconductor
systems. Moreover, at low bias conditions the subsurface dopant cannot be observed. The
localized electronic effects of surface dopants are compared with the delocalized effects of
subsurface dopants. Defects in the pentacene film are easily distinguishable from proposed
dopants, as they appear as vacancies for all tunneling conditions with minimal bias dependence.
As an additional check, scanning tunneling spectroscopy measurements show reproducible
differences between the local density of states measured near dopant centers and far from the
outer extent of the Coulomb potential.


2:45 PM B4.5
Towards Single-Molecule Electronics: Synthesis of Single Organic molecule-Bis(long DNA)
Structures and their Characterizations.JungKyu Lee
1
, Frank Jaeckel
1,2
, Young Hwan Jung
3
,
Jeffrey B.-H. Tok
4
, William E Moerner
1
and Zhenan Bao
5
;
1
Chemistry, Stanford University,
Stanford, California;
2
Physics, Ludwig-Maximilians-Universitt Mnchen, Mnchen, Germany;
3
Bioinformatics, Korea Bio Polytechnic, Chungnam, Korea, South;
4
Micropoint Biosciences
Inc., Sunnyvale, California;
5
Chemical Engineering, Stanford University, Stanford, California.

Precise electrical contact of single organic molecules onto electrodes is a key step to study
single-molecule electronics and its applications, such as nanodevices. To realize a reliable
electric contact, we introduce DNA as a template in the field of nanoelectronics because DNA
can be easily tethered to a single organic molecule using coupling reactions as well as be used as
a conducting element after DNA metallization. Herein, we demonstrate that the reactivity
between ssDNA and single organic molecules using several coupling reactions to build triblock
molecules. Furthermore, we show that the DNA length of the triblock molecules can be readily
controlled using the PCR or DNA hybridization. Finally, We will discuss recent technique to
characterize a single organic molecule-bis(long DNA) triblock architecture using the gel
electrophoresis, atomic force microscope (AFM), and single-molecule fluorescence microscopy.


3:30 PM *B4.6
Spin Excitations in Single Molecule Electronics Ungdon Ham, Physics and Astronomy,
University of California, Irvine, Irvine, California.

Recent results with a high field, sub-Kelvin scanning tunneling microscope (STM) in ultrahigh
vacuum will be presented. Inelastic electron tunneling spectroscopy (IETS) through spin-flip
excitation makes it possible to study spin degrees of freedom within a single molecule on the
surface. The STM allows the determination of the relationship between spin excitation and the
electronic and geometric structures of single molecules. The high field, low temperature
capabilities of the STM enables it to probe the dependence of spin excitation on the coupling of
the molecule to the substrate for a wide range of molecules such as single atoms, organometallic
molecules, and molecular radicals. Similar to the electron-vibrational coupling, spin-flip
excitations should play a significant role in electron transport through molecules.


4:00 PM B4.7
Role of Labile Bonding in Stochastic Switching of Molecular Conductance. Lionel Patrone
1
,
Jeremie Soullier
1
, Pascal Martin
1
, Bruno Jousselme
2
and Fabrice Moggia
2
;
1
Institut Suprieur de
lElectronique et du Numrique, IM2NP, CNRS, IM2NP (UMR 6242), Maison des
Technologies, Place Georges Pompidou, F-83000 Toulon, France;
2
CEA/DSM/IRAMIS/SPCSI,
Bt. 466, CEA/Saclay, F-91191 Gif-sur-Yvette cedex, France.

Due to the miniaturization of CMOS devices new memory cells with high density and low-power
consumption are investigated. Molecular switches are likely to be among the most basic and
important components of future molecule-based electronic devices. In the literature, on-off
switching effect has been reported with phenylene-ethynylene oligomers bonded to gold via S-
Au, using nanopore junctions [1] and scanning tunneling microscopy (STM). In these STM
studies, molecules of interest have been inserted in an alkylthiol self-assembled monolayer
(SAM). The observed stochastic conductance switching has been explained by conformational
changes through aromatic ring rotation [2] or molecular hybridization changes at the interface
with gold [3]. However, independent STM studies on SAMs on gold have reported similar
stochastic switching effects for thiol molecules which cannot exhibit any conformational changes
[4]. A thiol bond breaking/reforming mechanism was invoked, due to the labile nature of thiol
bonding. Potential use of such conductance switching for molecular memory cells requires
determining whether it is intrinsic to specific molecules or due to a bond fluctuation mechanism.
For this purpose, comparative experiments need to be carried out on molecules more strongly
bonded to the substrate. In this work, we compare the influence of S-Au labile bond versus C-Si
stronger covalent one in obtaining a stochastic conductance switching of terthiophene molecules
(3T). First we prepared binary SAMs of small bundles of 3T dispersed in dodecyl (DD) matrix,
both on Au(111) using thiol-ended molecules and on hydrogenated silicon surface H-Si(111)
with molecules bearing a vinyl reactive head. For this purpose, terthiophene-thiol and
terthiophene-allyl molecules were synthesized. If obtaining binary SAMs on Au(111) is well
known [5], growth of binary SAMs on H-Si(111) was studied using ellipsometry, contact angle
measurements and scanning probe microscopy in order to obtain the right conditions giving
isolated 3T molecules in DD. Then, we performed STM experiments on these binary SAMs,
using the apparent molecular height of 3T above DD matrix as a measure of electronic
conductance. We observed stochastic switching events for S-Au bond as reported in the
literature. A statistical analysis of molecular blinking was carried out. However we show that
stochastic switching is hindered in the case of C-Si bond. These results allow attributing the
origin of published stochastic switching observations to a bond fluctuation mechanism.
Moreover this work shows silicon is a suitable substrate for developing molecular memory cells
both avoiding stochastic switching and being compatible with microelectronics technology. [1] J.
Chen et al., Science 1999, 286, 1550 [2] Z.J. Donhauser et al., Science 2001, 292, 2303 [3] A.M.
Moore et al., J. Am. Chem. Soc. 2006, 128, 1959 [4] G.K. Ramachandran at al., Science 2003,
300, 1413 [5] L. Patrone et al., Chem. Phys. 2002, 281, 325


4:15 PM B4.8
Random Telegraph Signal in Macroscopic Silicon/Alkyl chain/Metal Molecular Tunnel
Junctions. Dominique Vuillaume
1
, Nicolas Clement
1
, David Guerin
1
, Stephane Pleutin
1
and
David Cahen
2
;
1
IEMN-CNRS, Villeneuve d'Ascq, France;
2
Weizmann Institute of Science,
Rehovot, Israel.

Monolayers of organic molecules present one of the main systems studied in molecular
electronics. Recently, very high quality alkyl monolayers on oxide-free silicon were reported to
be a basic system, very reproducible to study the electrical transport through these molecules
(1,2). In a previous report, we have studied the low frequency tunnel current noise in these self-
assembled monolayers (3). We report here the observation and study of a particular type of noise
called Random Telegraph Signal (RTS) in Si/SiO2/Alkyl chain/(Hg or Al) and Si/Alkyl
chain/(Hg or Al) junctions.The 2 levels of current can be clearly distinguished. With a
sufficiently long recording time (> 500 events), statistics can be performed on the current level
and on the upper and lower times. The RTS amplitude is usually few % of the average current
and the process follows poissonian statistics. This RTS signal is also modulated by another RTS
with a much longer time constant. This allowed us evaluation of the change of noise in the
frequency domain from 1/f noise to Lorentzian like spectrum. In inorganic tunnel junctions, such
signal can only be observed in sub-micrometric junctions whereas we observe it in almost
millimetric junctions. This precludes mechanisms involving electron trapping / detrapping in
single isolated trap. We propose several hypotheses leading to long-range fluctuations including
molecular dynamics and relaxation processes. (1) A.Salomon, T.Boeking, C.K.Chan, F.Amy,
O.Girshevitz, D.Cahen and A.Kahn, Phys.Rev.Lett. 95, 266807 (2005) (2) O.Seitz, T.Bcking,
A.Salomon, J.J.Gooding and D.Cahen, Langmuir 22, 6915 (2006) (3) N.Clement, S.Pleutin,
O.Seitz, S.Lenfant, D.Cahen and D.Vuillaume, Phys. Rev.B. 76, 205407 (2007) (4) N.Clement,
S.Pleutin, D.Guerin, D.Cahen and D.Vuillaume, in preparation.



SESSION B5: Poster Session I
Chairs: Saw-Wai Hla, Norbert Koch, Xiaoyang Zhu and Egbert Zojer
Tuesday Evening, April 14, 2009
8:00 PM
Exhibition Hall (Moscone West)

B5.1
Charge Transfer Excitons on Organic Semiconductor Surfaces. Qingxin Yang, Matthias
Muntwiler and Xiaoyang Zhu; Department of Chemistry, University of Minnesota, Minneapolis,
Minnesota.

Charge transfer (CT) excitons across donor/acceptor interfaces are believed to be barriers to
charge separation in organic solar cells, but little is known about their physical characteristics.
Here we probe CT excitons on crystalline pentacene and tetracene surfaces using time-resolved
two-photon photoemission spectroscopy. We observe a series of atomic-hydrogen like CT
exciton states, with the 1s CT exciton state at a binding energy of ~0.5 eV. The large binding
energy of the 1s CT exciton excludes its participation in photovoltaic. Efficient charge separation
in organic hetero-junction solar cells must involve a series of hot CT excitons.


B5.2
Optical and Structural Properties of rrP3HT on Highly Dense Vertically Aligned
CNTs.Wei-Chao Chen
1,2
, Chien-Hung Lin
3
, Hsiang-Ting Lien
4
, Kuei-Hsien Chen
1
and Li-
Chyong Chen
2
;
1
Institute of Atomic and Molecular Science, Academia Sinica, Taipei, Taipei,
Taiwan;
2
Center for Condensed Matter Science, National Taiwan University, Taipei, Taipei,
Taiwan;
3
Graduate Institute of Photonics and Optoelectronics and Department of Electrical
Engineering, National Taiwan University, Taipei, Taipei, Taiwan;
4
Institute of Organic and
Polymeric Materials, National Taipei University of Technology, Taipei, Taipei, Taiwan.

Influence of interchain-interactions in rrP3HT/VACNTs (vertically aligned carbon nanotubes)
composites have been investigated via optical and structural analyses. The composite was
synthesised through dip coating in different concentration or deposition time. The interchain
coupling can strongly influence the electronic properties of polymer chains. On the surface of
highly dense VACNTs, it was observed the pristine rrP3HT [regioregular poly(3-
hexylthiophene)] naturally induces the self-assembling organization with high-symmetry cofacial
configurations, particularly stronger edge-on orientation. From Raman spectrum, the outmost
surfaces of CNTs possessing electron-rich property strongly induce the non-specific covalent
interactions (- or CH-) with rrP3HT. Via strong - interactions between polymer-backbone
and CNTs-surface, or the multiple CH- interactions between the alkyl side chains of conjugated
polymer and outmost graphene of CNTs, the high-symmetry cofacial orientation can be induced.
The organized structure, as observed by XRD, exhibits a highly lamellae orientation of P3HT in
parallel with VACNTs template on a-face [100] Photoluminescence excitation (PLE) mapping of
this solid structure of rrP3HT/VACNTs also reveals a blue shift of radiative emission from 0-1 to
0-0 transition, (or this 2-dimentional conjugated orientation of rrP3HT leads to the blue shift of
radiative emission at 0-1 and 0-0 transitions. These results suggest decreasing in the polaron-
binding energy of rrP3HT/VACNTs. The self-assembling 2-dimentional structure of rrP3HT is
naturally achieved on VACNTs, via highly cofacial orientation, without any requirement of
surface-treatment.


B5.3
Semiconductor Organic-Inorganic Nanocomposites at the Air/Water Interface and Their
Performance in Thin Film Photovoltaic Devices. Zhiqun Lin, Matthew Goodman, Jun Xu and
Jun Wang; Iowa State University, Ames, Iowa.

Organic-inorganic nanocomposites consisting of electroactive conjugated polymer, poly(3-
hexylthiophene) (P3HT) intimately tethered on the surface of semiconductor CdSe quantum dot
(i.e., P3HT-CdSe nanocomposites) at the air/water interface formed via Langmuir isotherms
were explored for the first time. The P3HT-CdSe nanocomposites displayed a high pressure
plateau in the Langmuir isotherm, illustrating their complex packing at the air/water interface.
Furthermore, photovoltaic devices fabricated from the LB depositions of the P3HT-CdSe
nanocomposites exhibited a relatively high short circuit current, I
SC
, while maintaining a thin
film profile. These studies provide insights into the fundamental behaviors of semiconductor
organic-inorganic nanocomposites confined at the air/water interface as well as in the active
layer of an organic-based photovoltaic device.


B5.4
Co-deposited Films of Rod-like Conjugated Molecules: Mixing versus Phase Separation.
Jrn-Oliver Vogel
1
, Ingo Salzmann
1
, Steffen Duhm
1
, Bert Nickel
2
, Juergen P Rabe
1
and Norbert
Koch
1
;
1
Institut fr Physik, Humboldt-Universitt zu Berlin, Berlin, Berlin, Germany;
2
Department fr Physik, Ludwig-Maximilians-Universitt, Munich, Bavaria, Germany.

The co-deposition of two conjugated molecular species can lead to novel materials with new
properties. The formation of well ordered mixed layers of two different molecules can be used to
continuously tune the material properties, e.g., similar to the doping of inorganic semiconductors
[1] On the other hand, phase separation of donor and acceptor material is desired for organic
hetero-junction solar cells. To assess the extent to which the molecular length determines either
phase separation or mixing in co-deposited thin films, we investigated pairs of five different rod-
like conjugated molecules: -quaterthiophene (4T), -sexithiophene (6T), ,-
dihexylsexithiophene (DH6T), p-sexiphenyl (6P), and pentacene (PEN). With these molecules
we realized pairs differing in length either via the size of the conjugated core (CC) alone, or
additionally through the end-termination by alkyl chains. Such films were characterized with
specular and in-plane X-Ray diffraction (XRD), infrared absorption spectroscopy (IR) and
scanning force microscopy (AFM). The co-deposition of molecules with similarly sized CC, i.e.,
{6T/6P} led to well ordered mixed structures. The co-deposition of molecules with different
molecular length but similarly sized CC, i.e., {6T/DH6T and 6P/DH6T} led also to ordered
mixed layers. A particularly appealing feature of these films is that the interlayer distance can be
controlled via the mixing ratio. The co-deposition of molecules with differently sized CC, e.g.,
{4T/6T} or {6P/PEN} led to pronounced phase separation of the two species in thin films. The
results of this work will be useful to tailor the morphology and structure of organic co-deposited
films, in particular for solar cell applications. [1] P. Cosseddu, J.-O. Vogel, B. Fraboni, J. P.
Rabe, N. Koch, A. Bonfiglio, Adv. Mater., in press.


B5.5
Dependence of Organic Thin-film Transistors with Polymer-blend Small Molecule
Semiconductors on Molecular Weights and Types of Polymers. Takahiro Ohe, Miki
Kuribayashi, Ryoichi Yasuda, Ami Tsuboi, Kotaro Satori, Masao Itabashi and Kazumasa
Nomoto; Advanced Materials Laboratories, sony, Atsugi, Kanagawa, Japan.

We will discuss how performance of solution-processed organic thin-film transistors (OTFTs)
with a polymer-blend 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-pentacene) channel are
affected by molecular weight (MW) and type of the polymers. It has been reported that spin-
coating of a solution of TIPS-pentacene and poly(alpha-methylstyrene) (PaMS) induces phase
separation, and results in a trilayer film: a TIPS-pentacene layer, a mixed layer of TIPS-
pentacene/PaMS, and a TIPS-pentacene layer[1,2]. The experiments with two different MW of
PaMSs[2] and with various types of polymer dielectrics[3] have been reported. It, however, has
not been clear the specific dependence of phase separation phenomena, and performance of
OTFTs on MW and types of polymers. In order to understand the relations among them, we have
performed systematic study. First, we investigated the dependence of the filed-effect mobility on
MW of polymer dielectric. The results showed that when MW of PaMS is around 20 k, 60 k, 100
k, and 800 k, the OTFTs exhibits higher mobility around 0.1 cm
2
/Vs. The OTFTs with PaMS
with lower MW ~2 k showed lower mobility around 110
-4
cm
2
/Vs. TOF-SIMS analysis with
sputtering the film revealed that when MW is ~100 k (~2 k), the active layer is the separated
trilayer film (a homogeneously mixed film). This structural difference can be attributed to the
difference in the performance of the OTFTs. Various types of polymers have been also
examined. When we use the solubility parameter of the polymer closer to that of TIPS-
pentacene, for example, poly(isobutyl methacrylate) is employed as a polymer, the OTFTs
showed only lower mobility and the active layer was a homogeneously distributed structure. In
order to explain our results, we applied the Flory-Huggins theory to the polymer-blend organic
semiconductor system. In this theory, the Gibbs free energy change G
m
for mixing a polymer
with a small molecule is given by G
m
= kN
T
T[(
12

2
) + (
1
ln
1
+ (
2
/x)ln
2
)] , which depends
on MW and type of polymer. The results have shown that experimentally obtained conditions for
the phase separation are reasonably explained in term of the Gibbs energy calculated with this
equation. This consideration will be useful to develop higher-performance OTFTs. [1] T. Ohe et
al., Appl. Phys. Lett. 93, 053303 (2008). [2] J. Kang et al., J. Am. Chem. Soc., 130, 12273
(2008). [3] M.-B. Mardec et al., J. Mater. Chem., 18, 3230 (2008).


B5.6
``Column-like" Structure of the Cross-Sectional Morphology of Bulk Heterojunction
Materials. Ji Sun Moon, Jae Kwan Lee and Alan J Heeger; Center for Polymers and Organic
Solids, University of California, Santa Barbara, Santa Barbara, California.

Transmission electron microscopy (TEM) through thin sections cut from films of the bulk
heterojunction (BHJ) material comprising rr-poly(3-hexylthiophene), rrP3HT, and [6,6]-Phenyl-
C61 butyric acid methyl ester (PCBM) provides information on the cross-sectional morphology.
Previous studies of the BHJ morphology mostly have been carried out on or through the top
surface of the film (with Atomic Force Microscopy or with TEM, respectively). However,
subsequent to photo-induced charge separation, the photogenerated carriers must move toward
the electrodes by traveling across the film thickness rather than parallel to the film surface. Thus,
there is limited information on direct correlation between the cross-sectional morphology of the
BHJ material and the solar cell device performance. We report here the observation of column-
like structures in the defocused cross-sectional TEM images. These column-like structures
provide the required pathways for charge transport across the film thickness. We calculate the
power spectral density and the autocorrelation function of the vertical pathways and thereby
obtain information on the length scale of the nanometer scale phase separation.


B5.7
Layer Cross-Fading at Organic/Organic Interfaces in OVPD-Processed Red
Phosphorescent Organic Light Emitting Diodes as a New Concept to Increase Current and
Luminous Efficacy. Florian Lindla
1
, Manuel Bosing
1
, Christoph Zimmermann
1
, Frank Jessen
1
,
Philipp van Gemmern
2
, Dietrich Bertram
2
, Dietmar Keiper
3
, Nico Meyer
3
, Michael Heuken
1,3
,
Holger Kalisch
1
and Rolf H. Jansen
1
;
1
Chair of Electromagnetic Theory, RWTH Aachen
University, Aachen, Germany;
2
Philips Technologie GmbH, Aachen, Germany;
3
AIXTRON AG,
Aachen, Germany.

Organic light emitting diodes (OLED) have the potential to play a dominant role in solid state
lighting. Most small molecule based OLEDs are at present processed either by vacuum thermal
evaporation or organic vapor phase deposition (OVPD), with the latter offering unique features.
Most important, several growth parameters (substrate temperature, deposition chamber pressure,
carrier gas flows) can be controlled individually and growth rates are stable over a long period of
time. These features make it possible to control the ratios in mixtures of organic materials during
the deposition process precisely by adjusting the carrier gas flows through different organic
sources. This is used to investigate the impact of an introduced layer cross-fading at
organic/organic interfaces on current and luminous efficacy of phosphorescent red OLEDs.
Layer cross-fading describes linearly decreasing the fraction in growth rate of an organic layer
during deposition over a certain period of time while increasing the fraction in growth rate of the
following layer. The result is a cross-fading zone of controlled thickness. The base structure of
the investigated OLED consists of an ITO anode with a 20 nm hole injection layer (HIL), a 20
nm hole transport layer (HTL), a 40 nm host/guest system as red emission layer (EL) and a 30
nm electron transport layer (ETL) followed by a LiF/Al cathode. Devices with cross-faded
interfaces are compared with the basic layer-by-layer processed structure with sharp interfaces
and OLEDs in which the cross-fading zone is replaced by a mixed interlayer with constant ratios
of organic materials. The layer-by-layer processed OLED shows a current and luminous efficacy
of 18.8 cd/A and 14.1 lm/W (at 1000 cd/m
2
). A cross-fading zone of 10 nm thickness from either
the HIL to HTL or the EL to ETL has no impact on the efficacies. Whereas with a rising cross-
fading zone thickness of 40 nm at the HTL to EL interface, 29.3 cd/A (+56%) and 25.9 lm/W
(+84%) can be measured, compared to a 40 nm mixed interlayer which shows 24.8 cd/A (+32%)
and 20.4 lm/W (+45%). Different cross-fading zone and mixed interlayer thicknesses are
compared. The efficacy of OLEDs with a layer cross-fading always exceeds the one with mixed
interlayers. As result, layer cross-fading significantly increases both efficacy figures. The
observation of a lower driving voltage will be discussed in terms of an interpenetrating network
created in the cross-fading zone, which might improve charge injection and transport. A better
mixing of charge carriers would broaden the recombination zone and increase the current
efficacy. With an OVPD-based process, it is possible to realize nearly any kind of cross-fading
profile. Different profiles will be studied in future. Furthermore, the lifetime of OLEDs with
cross-faded interfaces will be investigated. An improved charge injection and transport should
have a positive impact here as well.


B5.8
Solution Processed Low-Voltage Organic Field-Effect Transistors Paul H Woebkenberg,
James M Ball, Florian Colleaux, Donal D Bradley and Thomas D Anthopoulos; Blackett
Laboratory, Imperial College London, London, United Kingdom.

The field of organic microelectronics has evolved rapidly during the past twenty years and is
now producing the first commercial applications. While recent progress in the area has been
astonishing, some major technology bottlenecks still remain and hinder practical implementation
of organic microelectronics in large-volume, low-end applications. One such technology
bottleneck is the large operating voltages of state-of-the-art organic field-effect transistors
(OFETs) and the resulting high power consumption. For example, the majority of OFETs
reported in literature operate at voltages in excess of 20 V. This makes organic transistor
technology unsuitable for use in a wide range of future applications including portable, battery-
powered devices where organic microelectronics could potentially play a dominant role. A very
promising approach towards low-voltage operation is the use of self-assembled monolayer
(SAM) nanodielectrics. Unfortunately, the majority of SAM based organic transistors have so far
been restricted to device architectures incorporating evaporated organic semiconductors.
Demonstration of similar low-voltage devices fabricated via solution processing has also been
attempted with limited success. It is the aim of this work to address both low-voltage operation
and solution processing of OFETs that are suitable for use in integrated circuits. We present a
simple method for fabricating <5 nm thin gate dielectrics from solution at room temperature
utilising suitably designed phosphonic-acid SAMs. We previously demonstrated that solution
processing of organic semiconductors on methyl terminated octadecylphosphonic acid is
incompatible with most organic semiconductors due to the SAM's low surface energy
characteristics. By modifying the terminal group (i.e. end-group) of the alkyl chain in these
molecules we are able to tailor the SAMs surface properties, consequently enabling solution
processing of a much wider range of organic semiconductors. Based on this approach we have
successfully demonstrated solution-processed hole (p-channel) and electron transporting (n-
channel) OFETs operating at voltages below |1.5| V. To demonstrate the potential of the
technology for use in practical applications, the transistors are integrated to form low-voltage,
low-power logic circuits such as unipolar and complementary voltage inverters. Based on the
same approach we also realise ambipolar SAM transistors and complementary-like inverters
employing a single semiconductor material. The potential application of these low-voltage
ambipolar organic transistors in light-sensing applications is also discussed. This work is a
crucial step towards the production of solution processed low-voltage, low-power organic
circuits and sensor arrays utilising low manufacturing cost methodologies.


B5.9
Properties of Fluorenyl Silanes in Organic Light Emitting Diodes. Wei Wei, Peter Djurovich
and Mark E Thompson; Department of Chemistry, University of Southern California, Los
Angeles, California.

Fluorene derivatives have been developed as potential charge transporters for OLEDs because of
their high charge transport mobilities and thermal stabilities. Here, we have designed and
synthesized four different fluorene silicon derivatives (PhnSi(DMFL)4-n, DMFL= 9,9-
dimethylflouren-2-yl, n= 0, 1, 2 and 3) with increasing number of fluorene units, in order to
provide a systematic study for investigating the changes of the molecular as well as the device
properties when the fluorene ratio increases in the molecule. All of these compounds possess
high triplet energies, large HOMO-LUMO gaps and high glass transition temperatures. Both
glass transition and sublimation temperatures increase linearly as the fluorene ratio increases. In
contrast, there is no apparent change in their electrochemical or photophysical properties, which
indicates that fluorene moieties have been conjugatively isolated by the central silicon. These
molecules exhibit ambipolar transport characteristics in undoped OLED devices
(ITO/NPD/mCP/PhnSi(DMFL)4-n/Alq3/LiF/Al) and the conductivity of the device is enhanced
by the molecules with higher fluorene ratios. Hence, the Si(DMFL)4 was used as the host of
Ir(ppy)3 and PQIr phosphorescence devices, respectively, and high device external efficiencies
were achieved.


B5.10
Stabilizing Single Atom Contacts by Molecular Bridge Formation. Everardus Hendrik
Huisman
1
, Marius L Trouwborst
1
, Frank L Bakker
1
, Bert de Boer
1
, Bart J van Wees
1
and Sense
Jan van der Molen
2
;
1
Zernike Institute for Advanced Materials, University of Groningen,
Groningen, Netherlands;
2
Kamerlingh Onnes Laboratory, Leiden University, Leiden,
Netherlands.

A single molecule forms a potential electronic component, offering the perspective of true
bottom up engineering of nanodevices. However, the field of molecular electronics as been
troubled by difficulties in making reliable and well-defined contacts to single molecules.
Fortunately, recent times have seen a significant growth of independent techniques to contact
single molecules or small ensembles of molecules [1,2]. A popular way to form a single metal-
molecule-metal bridge is to carefully break a gold nanowire in a solution containing dithiolated
molecules [3]. Surprisingly, there is little understanding on the mechanical details of the bridge
formation process and specifically on the role that the dithiol molecules play themselves. We
demonstrate that alkanedithiol molecules have already formed bridges between the gold
electrodes before the atomic gold-gold junction is broken [4]. This leads to stabilization of the
single atomic gold junction, as observed experimentally. Our data can be understood within a
simple spring model. [1] Chen, F.; Hihath, J.; Huang, Z.; Li, X.; Tao, N. J. Annu. Rev.
Phys.Chem. 2007, 58, 535-564. [2] Akkerman, H. B.; de Boer, B. J. Phys.: Condens. Matter
2008, 20, 013001. [3] Xu, B.; Tao, N. Science 2003, 301, 1221-1223. [4] Huisman, E.H.;
Trouwborst, M.L.; Bakker, F.L.; de Boer, B.; van Wees, B. J.; van der Molen, S.J. Nano Lett.
2008, 8, 3381-3385.


B5.11
Carbon Nanotube Enabled Vertical Organic Field Effect and Light Emitting
Transistors.Mitchell McCarthy
1,2
, Bo Liu
2
, Youngki Yoon
3
, Do Young Kim
1
, Zhuangchun Wu
2
,
Franky So
1
, Paul H Holloway
1
, John R Reynolds
4
, Jing Guo
3
and Andrew G Rinzler
2
;
1
Materials
Science and Engineering, University of Florida, Gainesville, Florida;
2
Physics, University of
Florida, Gainesville, Florida;
3
Electrical and Computer Engineering, University of Florida,
Gainesville, Florida;
4
Chemistry, University of Florida, Gainesville, Florida.

Active matrix organic light emitting diode (AMOLED) displays are expected to compete with
liquid crystal displays in the coming years due to the promise of increased power efficiency,
larger contrast ratio, wider viewing angle and thinner design. Currently there are technological
limitations to the widespread use of AMOLED displays such as limited lifetime of the OLED as
well material limitations preventing further technological advances, such as making AMOLED
displays flexible. All-organic AMOLED displays are required for use on flexible substrates;
however, the low mobility of organic materials, while enabling flexibility, hinders the overall
device performance by the requirement of larger driving voltages and smaller aperture ratios
leading to reduced power efficiency and lifetime. In this study, nanoscale materials are shown to
provide a promising path forward in the realization of industrially feasible all-organic flexible
AMOLED displays. In this collaborative study between the Departments of Computer Science
and Engineering, Materials Science and Engineering, Chemistry and Physics at the University of
Florida, carbon nanotube enabled vertical organic light emitting transistors (VOLETs) are
fabricated and characterized. Single walled carbon nanotube (CNT) networks possess unique
properties which make the networks ideally suited for use in the VOLET architecture. The low
density of states of the CNTs allows significant modulation of their Fermi level, resulting in
transconductance due to modulation of the hole injection barrier between the CNTs and the
active layer. It is shown by experiment and simulation that the unique properties afforded by the
nanoscopic nature of carbon nanotubes are responsible for the transconductance observed.
Preliminary devices using CNT networks show superior performance when compared to
VOLETs fabricated from other materials.


B5.12
Atomic-Scale Scanning Tunneling Microscopy and Spectroscopy Studies of Nanometer-
Sized Graphene Flakes on Semiconducting Surfaces. Justin Charles Koepke
1,2
, Kevin He
1,2

and Joseph W Lyding
1,2
;
1
Electrical and Computer Engineering, University of Illinois at Urbana-
Champaign, Urbana, Illinois;
2
Beckman Institute for Advanced Science and Technology,
Urbana, Illinois.

We have used ultrahigh vacuum scanning tunneling microscopy to perform atomic level studies
of graphene on semiconducting surfaces. We used a dry contact transfer technique (DCT)
developed by Albrecht and Lyding [1] to deposit mechanically exfoliated graphene in-situ onto
atomically clean semiconducting surfaces [2]. The DCT technique deposits predominantly single
and double layers of atomically clean graphene with lateral dimensions ranging from 2 - 60 nm.
We observe varying degrees of transparency of the graphene monolayers depending on the
substrate. This is most pronounced for graphene on the cleaved InAs(110), GaAs(110), and
Si(111)-7x7 surfaces, where the substrate atomic structure is clearly seen through the graphene.
On the Si(111)-7x7 surface, the substrate atomic structure can also be seen through graphene
bilayers. We believe that electronic structure of a graphene monolayer on the InAs(110) and
GaAs(110) surfaces leads to the transparency of monolayers and the opacity of bilayers similar
to the findings of Rutter, et al [3]. We suspect that the transparency of graphene bilayers on the
Si(111)-7x7 surface is due to a similar effect, while the transparency of graphene monolayers on
the same surface also has a topographic component. Room-temperature scanning-tunneling
spectroscopy (STS) measurements of the graphene monolayers and bilayers on the Si(111)-7x7
surface show predominantly metallic behavior. STS measurements of graphene features on the
InAs(110) and GaAs(110) surfaces also show predominantly metallic behavior, but
Semiconducting behavior is observed for the smaller features. [1] P.M. Albrecht and J.W.
Lyding, Appl. Phys. Lett. 83, 5029 (2003). [2] K.A. Ritter and J.W. Lyding, Nanotechnology 19,
015704 (2008). [3] G.M. Rutter, et al, Phys. Rev. B 76, 235416 (2007).


B5.13
Gold Work Function Reduction by 2.2 eV with a Molecular Donor Layer. Benjamin
Broeker
1
, Ralf-Peter Blum
1
, Johannes Frisch
1
, Antje Vollmer
2
, Oliver T Hofmann
3
, Ralph
Rieger
4
, Klaus Muellen
4
, Juergen P Rabe
1
, Egbert Zojer
3
and Norbert Koch
1
;
1
Institut fr Physik,
Humboldt-Universitt zu Berlin, Berlin, Germany;
2
Berliner Elektronenspeicherring-Gesellschaft
fr Synchrotronstrahlung mbH, Berlin, Germany;
3
Institut of Solid State Physics, Graz
University of Technology, Graz, Austria;
4
Max Planck Institut fr Polymerforschung, Mainz,
Germany.

Ultraviolet photoelectron spectroscopy was used to investigate neutral methyl viologen (1,1'-
dimethyl-1H,1'H-[4,4']bipyridinylidene, MV0) deposited on Au(111) surfaces. As a result of
molecule-to-metal electron transfer, the work function of Au(111) was decreased from 5.5 eV to
3.3 eV. The energy levels of electron transport layers deposited on top of modified Au surfaces
were shifted to higher binding energy compared to layers on pristine Au, and the electron
injection barrier was reduced by 0.8 eV for tris(8-hydroxyquinoline)aluminum (Alq3) and by 0.7
eV for C60. The air-stable donor MV0 can thus be used to facilitate electron injection into
organic semiconductors even from high work function metals. This work is financially supported
by European Community project "IControl" (EC-STREP-033197).


B5.14
Electronic Properties at Gold/Conjugated Polyelectrolyte Interfaces. Jung Hwa Seo,
Renqiang Yang, Jasek Z. Brzezinski, Bright Walker, Thuc-Quyen Nguyen and Guillermo C.
Bazan; UC Santa Barbara, Santa Barbara, California.

The electronic properties of conjugated polyelectrolytes (CPEs) with poly(fluorene-co-
phenylene) backbones and different counterions and charges have been investigated using
absorption, x-ray photoemission (XPS) and ultraviolet photoelectron spectroscopy (UPS). The
optical energy band gap of CPEs depends mainly on their conjugated backbone and nearly
insensitive to the charges or counterions. XPS and UPS measurements reveal that electron
injection from Au to polymers with cationic groups is more efficient than for the neutral and
anionic counterparts. The vacuum levels of CPEs were also shifted toward higher or lower
binding energy, relative to that of Au depending on the charge and counterion presence, and
provide insight into the general alignment of dipoles at the metal/organic interface. This finding
shows that counterions and backbone charges enable control of the electronic and chemical
nature of critical device interfaces.


B5.15
Study of Solid/liquid Interfaces in Organic Field-effect Transistors with Ionic
Liquids.Shimpei Ono
1
, Kazumoto Miwa
1
, Shiro Seki
1
and Jun Takeya
2
;
1
Materials Science
Research Laboratory, Central Research Institute of Electric Power Industry, Tokyo, Japan;
2
Graduate School of Science, Osaka University, Osaka, Japan.

There has been significant interest to develop new kinds of organic transistors such as those
using electric double layers (EDLs) of electrolytes. It is reported that the EDL gating can be a
promising technology not only to realize high performance organic field-effect transistors
(OFETs) [1-4], but also to drive phase transitions in strongly correlated electron systems to a
metal [5] or a superconductor [6]. However, there is no detailed study of microscopic
mechanisms of the charge transport in the vicinity of the solid/liquid interfaces. In this work, we
report the two-dimensional charge transport at the interface with the use of various ionic liquids
as the electrolyte layer in OFETs. Since the use of ionic liquid electrolytes in OFETs enables
high-density carrier doping with minimum gate voltages without scarifying the carrier mobility
[7], higher performances are likely to emerge by elaborate search for compounds incorporated in
OFETs. We have formed a well structure of polydimethylsiloxan elastomer on which rubrene
single crystal is electrostatically attached and each ionic liquid is poured underneath a rubrene
single crystal by the capillary force, so the EDL in the ionic liquid can induce high-density
carriers at the surface of the crystal. The achieved reproducibility permits one to observe that the
mobility of the charge carriers systematically increases with decreasing the dielectric constant of
the ionic liquids and becomes as high as 9.5 cm2/Vs in 1-ethyl-3methylimidazolium
bis(fluorosulfonyl)imide, which is only half of the value of the air-gap transistors. These results
suggest that the mobility of carriers in OFETs is an intrinsic property of the solid/liquid interface
between organic semiconductors and the ionic liquids. [1] M. Panzer, C. D. Frisbie et al., Appl.
Phys. Lett. 88 203504 (2006). [2] J. Takeya et al., Appl. Phys. Lett. 88 112102 (2006). [3] H.
Shimotani et al., Appl. Phys. Lett. 89 203501 (2006). [4] J. Lee, C. D. Frisbie et al., J. Am.
Chem. Soc. 129 4532 (2007). [5] H. Shimotani, et al., Appl. Phys. Lett. 91 082106 (2007). [6] K.
Ueno et al., Nature Materials (2008) in press. [7] S. Ono et al., Appl. Phys. Lett. 92 103313
(2008).


B5.16
Liquid-crystalline Semiconducting Copolymers with Intramolecular Donor-acceptor
Building Blocks for High-stability Polymer Transistors. Do Hwan Kim
1
, Bang-Lin Lee
1
,
Hyunsik Moon
1
, Eun-Jeong Jeong
1
, Jeong-Il Park
1
, Kuk-Min Han
1
, Byung Wook Yoo
1
, Bon
Won Koo
1
, Joo Young Kim
1
, Wi Hyung Lee
2
, Kilwon Cho
2
, Hector A Becerril
3
, Zhenan Bao
3

and Sangyoon Lee
1
;
1
Display Laboratory, Samsung Advanced Institute of Technology, Samsung
Electronics Co., LTD., Yongin, Korea, South;
2
Department of Chemical Engineering, Pohang
University of Science and Technology, Pohang, Korea, South;
3
Department of Chemical
Engineering, Stanford University, Stanford, California.

Organic field-effect transistors (OFETs) based on -conjugated polymers have recently attracted
significant attention because of their potential use as soft channel materials in organic/printed
optoelectronic devices such as active-matrix flat panel displays (AMFPDs), electronic paper,
RFID tags, and chemical/bio-sensors. The solution-processability of -conjugated polymers has
also stimulated interest in their utilization in active electronic elements for low-cost, large-area,
and flexible active matrix display backplanes, with performances that are comparable to those of
hydrogenated amorphous silicon (a-Si:H)-based thin-film transistors. However, when OFETs
based on -conjugated polymers are fabricated and tested under ambient conditions, their
electrical performance decreases remarkably, which is primarily due to the sensitivity of the
polymer chains to atmospheric O2/H2O and structural defects. In particular, OFETs composed of
solution-processed -conjugated polymers commonly exhibit some electrical instability under
external bias stress due to the less-ordered molecular structure of their semiconductor films;
charge trapping instability under bias-stress and environmental stability are problems for these
materials. In order to be comparable to a-Si-based TFTs, OFETs should exhibit similar
performance with respect to electrical bias stress. Although there have been a few studies aimed
at enhancing the environmental/electrical stability of -conjugated polymers under external bias
stress, an adequate understanding of the relationship between crystalline nanostructure and bias
stress driven electrical instability on the microscopic scale still eludes us. Here we report a novel
charge-transfer type liquid-crystalline semiconducting copolymer,
poly(didodecylquaterthiophene-alt-didodecylbithiazole), which contains both electron-donating
quaterthiophene and electron-accepting 5,5-bithiazole units, and exhibits unprecedented
electrical characteristics such as field-effect mobilities as high as 0.33 cm2/Vs and good bias-
stress driven electrical stability that is comparable to that of amorphous silicon (a-Si). Liquid-
crystalline thin films with structural anisotropy form spontaneously through the self-organization
of the individual polymer chains as a result of intermolecular interactions in the liquid-crystalline
mesophase, and adopt preferential well-ordered inter-molecular - stacking parallel to the
molecular surface. This bottom-up assembly of the liquid-crystalline semiconducting copolymer
enables the facile fabrication of highly-ordered soft channel layers with a minimal concentration
of charge traps, as well as unidirectional and delocalized transport with hitherto unreported
electrical stability.


B5.17
Reversible Electro-optical Switch of Self Assembled Monolayers of azobenzene-derivatized
Oligothiophenes Grafted on Gold. Dominique Vuillaume
1
, Kacem Smaali
1
, Stephane Lenfant
1
,
Dominique Deresmes
1
, Sandrine Karpe
2
, Maitena Ocafrain
2
, Philippe Blanchard
2
and Jean
Roncali
2
;
1
IEMN-CNRS, Villeneuve d'Ascq, France;
2
CIMA-CNRS, Angers, France.

The grafting of azobenzene-based molecules on surfaces is an attractive approach for optical
switches [1;2], molecular machines [3] and biosensors [4]. Here, we report the preparation of a
self-assembled monolayer (SAM) on gold surface obtained by grafting molecules based on an
azobenzene moiety associated to a bithiophene unit (see inset below). The structure of the SAM
was characterized using various techniques such as ellipsometry, X-ray Photoelectron-
spectroscopy, cyclic voltammetry and contact angle measurement. This azobenzene moiety can
switch between two isomeric configurations (trans and cis) when irradiated by visible (480 nm)
and UV (360 nm) light respectively. The electrical properties of the SAM in each configuration
were studied by conducting-AFM and by eutectic drop contact (GaIn). We clearly observed the
effect of this photo-isomerization on the current, at the nano-scale by conducting-AFM and at
macroscopic scale using GaIn. The current (ION) measured by C-AFM at 1.5V for the cis isomer
was higher by a factor ~2000 compared to the current (IOFF) for the trans isomer. By measuring
with GaIn contact, the value of this ION/ IOFF ratio was 223 at 0.5V (see graph). These results
represent significant improvement compared to those reported by Mayor and coworkers namely
~ 30 at 0.3V by mercury drop contact [2] and ~ 20 at 0.5V by C-AFM [3]. Various hypotheses to
explain this conductivity variation will be discussed, in particular an I-V analysis (Fowler-
Nordheim plot) that suggests an injection barrier reduction (lowering LUMO). [1] Kumar A.S. et
al., Nanoletters 8(6), 1644-1648 (2008) [2] Mativetsky et al., JACS 130(29), 9192-9193 (2008)
[3] Ferri V. et al., Angew. Chem. Int. Ed. 47, 3407-3409 (2008) [4] Dietrich P. et al., Appl. Phys.
A 93, 285-292 (2008)


B5.19
Extended Lifetime of Organic Field-Effect Transistors Encapsulated with Titanium Sub-
Oxide as an `Active Passivation/Barrier Layer. Shinuk Cho
1
, Kwanghee Lee
2
and Alan J
Heeger
1
;
1
Center for Polymers and Organic Solids, University of California at Santa Barbara,
Santa Barbara, California;
2
Department of Materials Science and Engineering, Gwangju Institute
of Science and Technology, Gwangju, Korea, South.

Despite significant improvements in the performance of organic electronic devices, the operating
lifetimes are limited by the intrusion of oxygen (O2) and water vapor (H2O). High performance
encapsulation with low-cost is therefore required to achieve lifetimes sufficiently long to enable
commercialization of plastic electronics technology. We report that a thin capping layer of
titanium sub-oxide (TiOx), prepared by sol-gel synthesis from titanium alkoxides, extends the
lifetime of organic FETs. The TiOx layer functions as an active passivation/barrier layer that
actually removes oxygen and water vapor from the organic semiconductor. The results
demonstrate a significant improvement in the lifetime of organic field effect transistors when
exposed to air.


B5.20
peri-Xanthenoxanthene Thin-Film Transistors. Norihito Kobayashi, Mari Sasaki, Noriyuki
Kawashima and Kazumasa Nomoto; Advanced Materials Laboratories, Sony Corporation,
Atsugi, Japan.

We have synthesized and characterized stable organic semiconductors (OSCs), 3,9-diphenyl-
peri-xanthenoxanthene (Ph-PXX) and its soluble derivatives of 3,9-bis(p-alkylphenyl)-peri-
xanthenoxanthene (CnPh-PXX) for organic thin-film transistors (OTFTs). A -system is
stabilized against oxidation by introduction of hetero-atoms and phenyl groups into the reactive
sites in the -system. This strategy for stabilization does not suffer from the conventional trade-
off between environmental stability and efficient carrier injection, which appears when OSCs
with deeper highest occupied molecular orbitals (HOMOs) are applied. UV-Vis spectra of an air-
saturated solution of Ph-PXX were unchanged over 120 hours, indicating that the molecule has
great environmental stability. A HOMO level of Ph-PXX molecule was estimated to be only 5.1
eV below vacuum level, achieving efficient carrier injection from Au electrodes. In fact, OTFTs
with Ph-PXX showed high apparent mobility over 0.4 cm
2
/Vs without demonstrating nonlinear
behavior of source-drain ohmic contacts, and have been stable over five months under ambient
conditions. In addition, the OTFTs showed great thermal stability at temperatures up to 150C in
air. These characteristics have been also achieved with a solution-processed OTFT with a soluble
CnPh-PXX. In this presentation, we will talk about the molecular design with the passivation of
the reactive cites leading to stable molecules and the characteristics of its OTFTs with efficient
carrier injection between metal electrodes and OSCs.


B5.21
Self Assembly and Activation of Phosphonic Acid Monolayers on GaN and AlGaN for
Biosensing Applications. Soonwook Hong
2
, B. S Simpkins
1
, R. Stine
1
, M. A Mastro
1
, C. R
Eddy Jr.
1
and P. E Pehrsson
1
;
1
Naval Research Lab, Washington, District of Columbia;
2
Thomas
Jefferson High School, Alexandria, Virginia.

Self assembled monolayers of 6-phosphonohexanoic acid and n-octadecylphosphonic acid
(ODPA) were formed on silicon dioxide, gallium nitride (GaN) and aluminum gallium nitride
(AlGaN) surfaces. Deposition and long-term stability of these phosphonic acids was verified
through water contact angle and X-ray photoelectron spectroscopy (XPS) measurements. The
ODPA monolayers reduced the conductivity of AlGaN/GaN HFET structures by ~30%. This
effect was evaluated in the context of the dipole contribution due to the PO3 end group found on
ODPA. We also report a novel method to activate ODPA monolayers for biological applications
by forming active carbonyl groups through exposure to microwave oxygen plasma. This
activation enables immobilization of 2-mercaptoethylamine (MEA) on functionalized silicon
oxide substrates. This research is of direct relevance to the operation of field effect transistor-
based biochemical sensors, and provides a fundamental basis for further applications of Si, GaN
and AlGaN in biosensing and microelectronics technologies.


B5.22
Anomalous Tunneling in Carbon/Alkane/TiO2/Au Molecular Electronic Junctions: Energy
Level Alignment at the Metal/Semiconductor Interface. Haijun Yan
1,2
and Richard
McCreery
2,3
;
1
Department of Chemistry, The Ohio State University, Columbus, Ohio;
2
National
Institute for Nanotechnology, Edmonton, Alberta, Canada;
3
Department of Chemistry,
University of Alberta, Edmonton, Alberta, Canada.

Carbon/TiO2/Au electronic junctions show slightly asymmetric electronic behavior, with higher
current observed in current density (J)-voltage (V) curves when carbon is biased negative with
respect to the Au top contact. When a ~1 nm thick alkane film is deposited between the carbon
and TiO2, resulting in a carbon/alkane/TiO2/Au junction, the current increases significantly for
negative bias and decreases for positive bias, thus creating a much less symmetric J-V response.
Similar results were obtained when SiO2 was substituted for the alkane layer, but Al2O3 did not
produce the effect. The observation that by adding an insulating material between carbon and
TiO2, the junction becomes more conductive is unexpected and counterintuitive. Kelvin probe
measurements revealed that while the apparent work function of the PPF electrode is modulated
by surface dipoles of different surface-bound molecular layers, the anomalous effect is
independent of the direction of the surface dipole. We propose that by using a nanometer thick
film with a low dielectric constant as an insertion layer, most of the applied potential is dropped
across this thin film, thus permitting alignment between the carbon Fermi level and the TiO2
conduction band. Provided the alkane layer is sufficiently thin, electrons can directly tunnel from
carbon to the TiO2 conduction band. Therefore, the electron injection barrier at the carbon/TiO2
interface is effectively reduced by this energy level alignment, resulting in an increased current
when carbon is biased negative. The modulation of injection barriers by a low- molecular layer
should be generally applicable to a variety of materials used in micro- and nano-electronic
fabrication.


B5.23
Single and Mixed Self-Assembled Monolayers of Phenyl Species on Silicon with Various
Ring to Ring Interactions Virginie Gadenne, Simon Desbief and Lionel Patrone; Institut
Suprieur de lElectronique et du Numrique, IM2NP, CNRS, IM2NP (UMR 6242), Maison des
Technologies, Place Georges Pompidou, F-83000 Toulon, France.

Preparation of self-assembled monolayers (SAM) [1] of aromatic conjugated molecules is a key
point in molecular electronics [2]. Moreover, regarding potential applications, it is important to
be able to prepare nano-islands of such active molecules on silicon. Nevertheless few works
addressed this subject [3]. In a first part of our work, in order to control the formation of
conjugated molecular nano-domains on native oxide covered silicon, we studied how various tri-
functionalized silane molecules bearing a phenyl cycle, modified or not, interact during their
self-assembly [4]. For phenyl rings without alkyl chain, SAM growth is shown to occur in a
single step: chemisorption on the surface. This step is thermally activated and does not depend
on ring to ring interactions. We show that adding a short alkyl chain (3-4 carbon atoms) to the
phenyl ring gives the molecules enough flexibility to generate an additional second growth step.
The latter is independent from the deposition temperature and corresponds to the arrangement
between molecules. We found that this packing step is accelerated by replacing phenyl by
pentafluoro-phenyl rings, possibly due to quadrupolar interactions between fluorinated cycles.
Furthermore we demonstrate that mixing phenyl and pentafluoro-phenyl molecules leads to an
even faster packing step which is accounted for by hydrogen bonding CH...FC in a face to face
phenyl/pentafluoro-phenyl arrangement [5]. We believe these results allow improving charge
delocalization over conjugated molecular domains. In a second part, we studied the phase
separation between phenyl-alkylsilane and octadecyltrichlorosilane (OTS) molecules. Improving
the phase separation was studied using two parameters: ring to ring interactions afore-analyzed
and reactive heads with different grafting kinetics. Using the same trichlorosilane grafting
moiety for phenyl molecules as for OTS, we show that phase separation is improved and OTS
islands are smaller with phenyl species that involve stronger ring to ring interactions. The best
case is obtained with mixing phenyl and pentafluoro-phenyl rings using hydrogen bonds for
packing together the aromatic species of the SAM. Small phenyl species islands (40-100 nm in
diameter) could be obtained inside the OTS SAM using a less reactive grafting head for the
aromatic molecules. These two cases demonstrate an improved control of SAM composition and
morphology essential to further use the obtained islands for building molecular devices. [1] F.
Schreiber, Progress in Surf. Sci. 2000, 65, 151. [2] H.B. Akkerman et al., Nature 2006, 441, 69.
[3] F. Fan et al., Langmuir 2003, 19, 3254. [4] J. Moineau et al., Langmuir 2004, 20, 3202. [5]
V.R. Thalladi et al., J.Am.Chem.Soc. 1998, 120, 8702 ; J.D. Dunitz, ChemBioChem 2004, 5,
614; S. Zhu et al., Tetrahedr. Lett. 2005, 46, 2713.


B5.24
The Effects of Octanedithiol Additive on the Three-Dimensional Nanoscale Organization of
Highly Efficient Conjugated Polymer Bulk Heterojunction Solar Cells. Mark Dante, Andres
Garcia and Thuc-Quyen Nguyen; University of California, Santa Barbara, Santa Barbara,
California.

It was recently shown that the addition of a small percentage of 1,8-octanedithiol to the solution
from which polymer:fullerene bulk heterojunction films are spin-coated leads to solar cell power
conversion efficiencies of greater than 5%. This additive approach circumvents the need of
post-deposition processing that improve efficiencies, such as thermal or solvent annealing, and
thus has the potential to greatly simplify the fabrication methods; an important consideration
when comparing polymer solar cell devices versus their inorganic counterparts. This effect was
first observed in poly(3-hexylthiophene) and [6,6]-phenyl C61-butyric acid methyl ester
(P3HT:PCBM) bulk heterojunction solar cells. The increase in efficiency of these devices has
been attributed to an increase in the crystallinity of the polymer phase, resulting in a higher
charge carrier mobility. Although similar increases in efficiency have been observed when
incorporating additives into bulk heterojunction blends containing the amorphous conjugated
polymer poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b]-dithiopene)-alt-4,7-(2,1,3-
bezothiadiazole)], and [6,6]-phenyl C71-butyric acid methyl ester (PCPDTBT:C71-PCBM), the
lack of crystallinity of the polymer phase with or without additive treatment and no increase in
the charge mobility indicate a different mechanism is responsible for the performance
improvement. Scanning probe examination of cross sections of PCPDTBT:C71-PCBM bulk
heterojunctions reveal a structural change in the internal morphology of the hole and electron
transporting networks when the film is cast from a solution containing 2% by volume 1,8-
octanedithiol. Phase separation of the nanoscalar domains becomes more defined and the average
sizes of hole and electron transporting networks double upon addition of the additive. The
increase in the size of the domains likely gives rise to less charge recombination.


B5.25
Maskless Patterning of Active Layer for Organic Thin-Film Transistor by Transfer-
Printing Based Lift-Off Technique. Wonsuk Choi, Min-Hoi Kim, Won-Ho Kim, Kyungmo
Koo and Sin-Doo Lee; School of Electrical Engineering, Seoul National University, Seoul,
Korea, South.

Organic thin film transistors (OTFTs) have great potential to replace conventional silicon-based
inorganic semiconductor devices as a mainstream of ubiquitous flexible electronic applications.
Although there has been a tremendous progress in the device performance of OTFTs during the
past several years, there still remains a critical issue on the methods of precisely patterning
organic active materials. For instance, accurate patterning of active semiconducting material in
the OTFTs is inevitably required for the enhanced device performances. Here, we present a high-
resolution patterning method of organic materials using transfer-printing based lift-off (TPLO)
technique. The patterning processes using the TPLO are described as: (i) a fluoro-polymer layer
is coated on a patterned polydimethylsiloxane (PDMS) stamp, (ii) the fluoro-polymer patterns
are transfer-printed onto a substrate as a sacrificial lift-off layer, (iii) an organic material is
deposited on the entire substrate having the lift-off layer, and (iv) the pattern of organic material
is formed by lifting-off the organic material remaining on the fluoro-polymer using a fluoro-
solvent. The TPLO technique has two distinctive advantages over existing approaches. First, the
TPLO is a maskless process which is inherently suitable for large-area and high-resolution
patterning so that a feature resolution down to 3 um (the resolution of conventional shadow mask
technique is about 30 um) was achieved for various organic materials. Second, the TPLO has the
capability of patterning organic materials onto various types of substrates including plastic
substrates due to the chemical compatibility of the fluoro-solvent. As a demonstration, we
fabricated pentacene patterns on the polymeric gate insulator layer using the TPLO technique to
fabricate OTFT device arrays. The surface morphology and the electrical characteristics of our
OTFTs are found to be comparable to those of the OTFT fabricated by a conventional shadow
mask process. In summary, we developed a transfer-printing based lift-off technique (TPLO) as a
general and versatile platform for precise patterning of organic materials in high resolution of a
few micrometers. Our pattering process is expected to be widely used for fabricating various
plastic electronic devices including high-resolution organic light emitting diode (OLED) displays
and top-contact OTFTs with a very short channel length.


B5.26
Electrical and Friction Properties of Stilbene Based Self Assembled Monolayers on Au
(111): The Role of Molecular Ordering. Yabing Qi
1,2
, Bas Hendriksen
2
, Xiaosong Liu
3
,
Violeta Navarro
2
, Jeong Y Park
2
, Imma Ratera
2
, John Klopp
4
, Carine Edder
4
, Franz J Himpsel
3
,
Jean Frechet
4,5
and Miquel Salmeron
2,4,6
;
1
Applied Science and Technology Graduate Group,
University of California Berkeley, Berkeley, California;
2
Materials Sciences Division, Lawrence
Berkeley National Laboratory, Berkeley, California;
3
Department of Physics, University of
Wisconsin, Madison, Madison, Wisconsin;
4
The Molecular Foundry, Lawrence Berkeley
National Laboratory, Berkeley, California;
5
Department of Chemistry, University of California
Berkeley, Berkeley, California;
6
Department of Materials Science and Engineering, University of
California Berkeley, Berkeley, California.

We intend to understand charge transport mechanisms, responsible for organic/molecular
electronics, by studying the relation between the structure of self-assembled monolayers of
molecules that contain conjugated groups and their electrical conductivity. As an example, we
investigated the electrical and friction properties of -(trans-4-stilbene)alkylthiol self-assembled
monolayers (SAMs) on Au(111) using Atomic Force Microscopy (AFM). The sample surface
prior to heating was uniformly covered with a molecular film that comprises of very small
grains. Well-packed and flat islands were formed after the sample was heated in nitrogen at 120
C for 1 h. While the lattice resolved AFM images revealed an enhanced ordering in islands, the
substrate area between islands was covered with disordered molecules. The islands exhibit
substantial reduction (50%) in friction supporting the existence of good ordering. The islands
were 8 higher than the surrounding disordered phase in the AFM topographic image,
indicating that the molecules of islands stand more upright on the substrate. Near edge X-ray
absorption fine structure spectroscopy (NEXAFS) measurements revealed an almost upright
molecular orientation for samples both before and after heating, with substantial increase of
ordering after heating. Conductance-AFM measurements revealed a more than 2 orders of
magnitude higher conductivity on the large islands than that of the disordered phase on the
heated samples. The current level on the ordered islands is also much larger than that of the non-
annealed SAM. We propose that the conductance enhancement is a result of a better - stacking
between trans-stilbene units of neighboring molecules as a result of improved ordering in islands.


B5.27
High Mobility n-Channel Organic Field-Effect Transistors by Solution Process. Peng Wei,
Joon Hak Oh and Zhenan Bao; Chemical Engineering, Stanford University, Stanford, California.

The development of n-channel organic field-effect transistors (OFETs) by solution-process is
crucial for low-cost and flexible electronics. For n-channel OFETs, the moisture and hydroxyl
groups at the semiconductor-dielectric interface act as the trap sites during operation. In this
work, we used double-layer dielectric with hydroxyl-free divinyltetramethyldisiloxane-
bis(benzocyclobutene) (BCB) to eliminate the electron-trap. High mobility (0.1 cm2/Vs) n-
channel OFET was obtained based on [6,6]-phenyl-C61-butyric acid ester (PCBM) by solution
process, which is a commercial available n-channel semiconductor. In comparison with SiO2
dielectric, both the mobility and on/off ratio significantly increase with this double-layer
dielectric.


B5.28
Measurement and Modeling of Current in Hole-only Tandem Structures of N,N'-diphenyl-
N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB) and 4,4,4-tris (3-
methylphenylphenylamino)-triphenylamine (m-MTDATA)Christoph Zimmermann
1
, Manuel
Bosing
1
, Florian Lindla
1
, Frank Jessen
1
, Hans-Peter Loebl
2
, Dietrich Bertram
3
, Michael
Heuken
1,4
, Holger Kalisch
1
and Rolf H Jansen
1
;
1
Chair of Electromagnetic Theory, RWTH
Aachen University, Aachen, Germany;
2
Philips Technologie GmbH Forschungslaboratorien -
Philips Research Laboratories, Aachen, Germany;
3
Philips Technologie GmbH, Aachen,
Germany;
4
AIXTRON AG, Aachen, Germany.

Organic light emitting diodes (OLED) have the potential to replace present light sources. The
most advanced types of OLED are complex stacks of doped transport and emission layers
consisting of small molecules. One advantage of multilayer OLED is the possibility to confine
the recombination zone in an emission layer by proper choice of energy levels. Little effort has
been spent so far to examine the charge carrier transport over energy barriers between layers of
small organic molecules. We have examined the hole transport through the interface between
layers of 4,4,4-tris(3-methylphenylphenylamino)-triphenylamine (m-MTDATA) and N,N'-
diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), both common hole transport
materials used in OLED. Samples with different combinations of layer thicknesses were
produced by vacuum thermal evaporation. They were designed as hole-only diodes with a well
injecting anode of indium tin oxide and a non-injecting cathode of aluminium on top.
Temperature-dependent I-V curves were measured for all samples. Additionally, dark injection
measurements were performed on the diodes to analyze their transient behaviour. Comparison of
the I-V curves of the different samples showed clear evidence that the hole current is limited by
the energy barrier between the two layers. The propagation time of carriers from the anode to the
interface and their accumulation at the barrier could be recognized in the dark injection signals.
The transient and stationary results were modeled with a numerical algorithm solving the time-
dependent semiconductor device equations with arbitrary mobility models and boundary
conditions at internal interfaces. The empirical findings with respect to voltage and temperature
dependence of the current were compared to established theoretical assumptions about hopping
transport in amorphous organic materials. Qualitative agreements concerning the shape of the
transient currents and the temperature dependence of the I-V curves were found, quantitative
deviations will be discussed.


B5.29
Abstract Withdrawn


B5.30
Torsion Mode Conductive Atomic Force Microscopy Study on Polypyrrole Based
Polyelectrolyte.Ling Sun
1
, Jianjun Wang
1
, Elmar Bonaccurso
1
, Andreas Muehlebach
2
, Hans-
Juergen Butt
1
and Gerhard Wegner
1
;
1
Physics of polymers, Max-planck institute for polymer
research, Mainz, Germany;
2
Group Research, Ciba Inc., Basel, Switzerland.

It has been commonly understood that the properties of organic functional materials and the
devices using these materials are determined by their local structure/morphological features .
Conductive atomic force microscopy (c-AFM) is usually used to study the morphological and
electronic properties of organic functional materials, especially conductive polymers. It measures
topography of the sample surface and current flow through the bulk material with a nanometer
resolution. However, conventional c-AFM has to be operated with a contact mode, which is
usually destructive. This is not favored for soft materials, i.e. polymers. As an alternative, we use
a torsion mode c-AFM to image the topography and current. In torsion mode c-AFM, the
cantilever is oscillated at the first torsional resonance frequency by two piezos. The lateral forces
that act on the tip cause a change in the torsional resonance frequency, amplitude and/or phase of
the cantilever. The oscillation of the cantilever is maintained in a near-field region where
electronic interaction still exists. Therefore torsion mode c-AFM could non-destructively
measure the topography and current flow through the sample. Here we present the electronic
property study of a newly synthesized Polypyrrole (PPy) based conductive polymer, by torsion c-
AFM and Kelvin probe force microscopy (KPFM). PPy has a high conductivity and of neutral
pH when doped with polystyrene sulfonate (PSS) . Thin films cast from PPy water suspension
are conductive and transparent as proved in our previous study . However, the microscopic
structure of the conductive species, i.e. the conductive grains, is elusive. We use torsion C-AFM
to visualize the conductive grain structure. The difference in conductivity implies a phase
separation which is also proved by the difference in Kelvin potential. The results suggest us the
mesoscopic structure of PPy/PSS and help to correlate the material structure and its property.


B5.31
Fabrication of Light-Emitting Transistor Combined with ZnO thin-film Transistors.
Hiroshi Yamauchi
1
, Yasuyuki Watanabe
2
, Masaaki Iizuka
3
, Masakazu Nakamura
4
and Kazuhiro
Kudo
4
;
1
Faculty of Engineering, Chiba University, Chiba, Japan;
2
Center of Frontier Science,
Chiba University, Chiba, Japan;
3
Faculty of Education, Chiba University, Chiba, Japan;
4
Graduate school of Engineering, Chiba University, Chiba, Japan.

Organic light emitting diodes (OLEDs) have much attention for flexible, low cost, and ease of
processing. In this work, as one of the method for expanding effective light-emitting area for
active matrix displays, a new type active light-emitting device combined with ZnO transistor is
proposed. An OLED is fabricated on the transparent FET. A transparent ZnO FET has an
indium-tin-oxide gate and a silicon nitride gate insulator fabricated by plasma-enhanced
chemical vapor deposition. These transparent materials are expected to be promising components
of high-efficiency light-emitting devices. This light-emitting device has an advantage to fabricate
without the damage to organic layer by the electrode sputtering and oxidation of emitting layer
with oxygen in the atmosphere. The light-emitting devices proposed here are suitable for the
display element because these ZnO layers between light-emitting layer work high-transparent
electron injection, electrode, and active layer of FET, therefore the aperture ratio increases and
light-emitting occurs efficiently. We describe the basic characteristics of transparent FET using
thin-film ZnO. The ZnO works as the active channel, and Al-doped ZnO (AZO) is used as the
source/drain electrode. These films were deposited by radio frequency (rf) magnetron sputtering.
In an attempt to reduce the plasma damage, we studied a method for fabricating the AZO
source/drain electrode. AZO layers are fabricated by the stepped rf power deposition method.
There is a correlation between rf power and resistivity and the AZO film deposited at low rf
power is low conductivity We compare the static characteristics of ZnO FETs with AZO
electrode deposited by uniform power deposition and those with AZO electrode deposited by
stepped power deposition. The current at Vds = 60 V saturated below 3.5A. In this experiment,
Vg was varied from -10 V to +100 V with 10 V steps. Id of uniform power deposition FET
shows a current saturation at low Vds and the current remains at low value of around 20 nA. On
the other hand, Id of stepped power deposition increases two orders magnitude of around 3A.
These improvements are derived from low-damage and high-conductivity AZO films obtained
by the new deposition method. We fabricated the active light-emitting device with ZnO
transparent FET and reported on the electrical properties of ZnO FET. The low-temperature and
low-damage sputtering method improves the on current in two orders magnitude. Luminance of
the active light-emitting device driven by ZnO transparent FET was obtained. These
experimental results indicate that the active light-emitting device using transparent ZnO thin
films on a plastic substrate should be realized by optimizing the device design and the fabrication
process.


B5.32
Abstract Withdrawn


B5.33
Vertical-channel Organic Transistors using Step-edge Structure and its Application to
Pixel Circuits. Makoto Shirakawa, Gaku Harada, Toru Ishikawa, Miwa Ogawa, Takeshi Sano
and Kenichi Shibata; Sanyo Electric Co., Ltd., Hirakata, Osaka, Japan.

One of the possible applications of organic thin-film transistors (OTFTs) is presumed to be a
backplane for an active matrix organic light emitting diode display (AM- OLED), however, high
driving voltage and low output current of OTFTs are the problems. In this work, we have
introduced a step-edge structure to form a vertical-channel OTFT in order to improve driving
voltage and output current for the use of driving transistor in a pixel circuit. By optimizing the
structure and the fabrication process of our vertical-channel OTFT, we have obtained sufficient
current for OLED which is around I
d
= 500 A (@ W = 3 mm, V
d
, V
g
= -10 V) and high on/off
ratio of 10
5
at a test piece using pentacene for the organic semiconductor layer. Our vertical-
channel OTFT using a step-edge structure also has an advantage of a high-resolution patterning
due to its self-aligned process, which is different from other types of vertical-channel transistors
reported before. We successfully fabricated OTFT arrays which consist of a driving transistor (W
/ L = 240m / 2m) and a switching transistor (W / L = 120m / 2m) in the pixels (450m x
450m). A part of this work was performed under management of the OITDA supported by
NEDO.


B5.34
Logic Devices with p-channel Organic and n-channel Inorganic Transistors. Yasuyuki
Watanabe
1
, Hiroyuki Iechi
2
, Hiroshi Yamauchi
3
and Kazuhiro Kudo
4
;
1
Center for Frontier
Science, Chiba University, Chiba, Japan;
2
Tohoku R&D Center, Research and Development
Group, RICOH Co., Ltd, Miyagi, Japan;
3
Faculty of Engineering, Chiba University, Chiba,
Japan;
4
Graduate school of Engineering, Chiba University, Chiba, Japan.

Flexible electronic devices have been strongly attracted much attention to the potential
application for the flexible displays, radio-frequency identification cards (RFIDs), etc.
Especially, it is required that the high-performance organic field-effect transistors (OFETs)
which are indispensable for the more advancing flexible displays because it realized the flat-
panel television using organic light-emitting diodes (OLEDs) on last year. Therefore, it is
important to study the characteristics of logic circuits based on p-type and n-type
semiconductors. We have already reported on the characteristics of the logic devices using
pentacene and ZnO FETs [1] and pentacene organic static induction transistors (OSITs) [1, 2]. In
general, organic semiconductors such as pentacene show p-type properties with low-mobility and
high-resistivity compared with inorganic semiconductors. In particular, it is difficult to control
the electrical properties such as the mobility of organic semiconductors because the doping
technology has not been established in organic semiconductors. On the other hand, ZnO
materials show the wide-range properties from insulator to low conductive n-type
semiconductor. In this study, we focus on the organic semiconductors with p-type properties and
the inorganic semiconductors with n-type properties for the fabrication of flexible logic devices.
First, the charge transport characteristics both ZnO and pentacene thin films are investigated.
Next, the performances of the CMOS inverter with pentacene and ZnO FETs are controlled by
matching the characteristics of ZnO to those of pentacene FETs. Finally, to improve the
characteristics of ZnO/pentacene logic devices, we propose new device structures of step-edge-
vertical-channel OFETs (SEVC-OFETs). The obtained results demonstrate that the hybrid
complementary inverters described here have potential for use as advancing flexible displays and
RFIDs. References [1] H. Iechi, Y. Watanabe and K. Kudo, Jpn. J. Appl. Phys. 46,4B, 2645
(2007). [2] Y. Watanabe, H. Iechi and K. Kudo, Thin Solid Films, 516, 2729 (2008).


B5.35
Study on the Spinodal Decomposition of P3HT:PCBM Layer with Different P3HT:PCBM
Ratio for High Performance Organic Solar Cells. Woon-Hyuk Baek
1
, Tae-Sik Yoon
1
, Hyun
Ho Lee
2
and Yong-Sang Kim
1,3
;
1
Nano Science & Engineering, Myongji University, Yongin,
Gyeonggi, Korea, South;
2
Chemical Engineering, Myongji University, Yongin, Gyeonggi,
Korea, South;
3
Electrical Engineering, Myongji University, Yongin, Gyeonggi, Korea, South.

In organic solar cells, composites of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-
butyric acid methyl ester (PCBM) are most widely used as an active layer and recorded to have
the highest power conversion efficiency. Since typical range of exciton diffusion length is 4~20
nm in polymer, nanoscale interpenetrating network morphology of donor (P3HT) and acceptor
(PCBM) is indispensable for efficient charge separation with extended interface and highly
efficient polymer solar cell. The relation between optical absorption and chemical properties of
P3HT is already well established. When P3HT has more ordered structure with longer chain
length and higher crystallinity, its UV/visible absorption is shown to be red-shifted, higher,
broader and more vibronic. And electro-optical and morphological characteristics of photovoltaic
cells with different P3HT:PCBM ratio were also reported. In this study, it is also observed that
the absorption of PCBM increases while that of P3HT decreases with increasing concentration of
PCBM in active layer. Moreover, the crystallinity of P3HT characterized by peak intensity of
XRD diffraction increases with increasing P3HT concentration. However, further increasing
P3HT concentration results in the reduced peak intensity. This anomalous observation of
crystallinity of P3HT layer depending on the ratio of P3HT and PCBM is discussed with the
behavior of spinodal decomposition of P3HT and PCBM. The P3HT:PCBM layers with varied
ratio are prepared on polyethylenedioxythiophene:polystyrenesulphonate (PEDOT:PSS) coated
indium tin oxide (ITO) substrate by spin-coating and subsequent annealing. The behavior of
spinodal decomposition is investigated by using atomic force microscopy (AFM) and
transmission electron microscopy (TEM).


B5.36
Transport Properties of Graphene Field-effect Transistors with Different Metal Electrodes.
Tatsuya Saito
1
, Ryo Nouchi
2
, Hiroki Watanabe
1
and Katsumi Tanigaki
1,2
;
1
Department of
Physics, Tohoku university, Sendai, Japan;
2
WPI Advanced Institute for Materials Research,
Tohoku university, Sendai, Japan.

A single-layer carbon sheet, graphene, has many interesting physical properties resulting from a
zero-gap band structure with the linear energy dispersion around the Fermi energy. In addition,
the highest mobility at room temperature among all materials makes graphene a major candidate
for future high-speed electronic devices. On the other hand, graphene is easily affected by
environment; the influences of metal contact on the electronic transport have been pointed out to
be large [1]. In fact, with Co contacts, the conducting property of graphene shows an anomalous
behavior [2]. In this study, we investigate the contact effect by employing field-effect transistors
(FETs) with different metal electrode, where the material for the source electrode is different
from that for the drain electrode (Au/Ca etc). We acquired graphene by the mechanical
exfoliation method [3], and patterned electrodes onto it by using electron beam lithography and
lift-off techniques. The fabricated FETs were measured in an inert atmosphere to avoid oxidation
of low work function metals. In this presentation, we report on the contact doping to the
graphene FETs from the view point of work function. Especially, p-n junctions formed by the
contact doping are discussed.[1] G. Giovannetti et al., Phys. Rev. Lett. 101, 026803 (2008). [2]
R. Nouchi et al., Appl Phys Lett. 93, 152104 (2008). [3] K. S. Novoselov et al., Proc. Natl. Acad.
Sci. U.S.A. 102,10453 (2008).


B5.37
Formation of Composite Organic Thin Film Transistors with One-Dimensional
Nanomaterials Gen-Wen Hsieh
1
, Flora M Li
2
, Sharvari Dalal
1
, Husnu Emrah Unalan
1
, Massimo
Spina
1
, Pritesh Hiralal
1
, Arokia Nathan
3
, Paul Beecher
4
, James E Stott
3
, Andrew J Flewitt
1
,
Gehan Amaratunga
1
and William I Milne
1
;
1
Engineering Department, University of Cambridge,
Cambridge, United Kingdom;
2
Electrical and Computer Eng., University of Waterloo, Waterloo,
Ontario, Canada;
3
London Centre for Nanotechnology, University College London, London,
United Kingdom;
4
Nokia Research Centre, Cambridge, United Kingdom.

Large area and flexible electronics is a rapidly expanding research area, which opens our eyes
into a new version of future electronics and is expected to revolutionise the electronics industry.
In this area, organic semiconductors and organic thin film transistors (OTFTs) have attracted
much interest by virtue of their solution processibility, low temperature processing, and
potentially low cost fabrication, with the advantage of lightweight, bendable features. Despite
ongoing advancements in material functionality and processing technologies, OTFTs are
somewhat limited in terms of device lifetime and mobility, which hinder their adoption on a
wider scale. Here, the purpose of this study is to develop augmentative material and fabrication
systems in the quest for higher performance transistors for large area and flexible applications.
One-dimensional (1-D) nanomaterials, such as nanotubes and nanowires, are of interest in view
of their unique optoelectronics properties, high aspect-ratio structures, high mobility and
conductivity. These nanostructures that present feasible alternatives can be used as the sole
material in a device structure, or can be implemented as a complement to organic materials. To
combine the advantages of 1-D nanostructures with the ease of processibility offered by organic
semiconducting materials, we aim to investigate means of incorporating 1-D nanomaterials into
organic devices by different techniques, such as ink-jet printing, contact printing, and spin
coating. A variety of carbon nanotubes (CNTs), and metallic and semiconducting nanowires
(NWs) are utilised as a prospective booster to p-type or n-type organic semiconductors. The first
is the fabrication of p-type OTFTs comprised of CNTs and semiconducting polymer by means of
ink-jet printing. Results show that low density ink-jet printed CNT networks can enhance the
performance of polythiophene-based OTFTs. For instance, the field effect mobility exhibited by
composite CNT-OTFT devices is seven times higher than that of pristine organic devices.
Secondly, a facile technique for large-scale parallel assembly of 1-D nanostructures by a dry
shear-sliding concept is demonstrated. Parallel arrays of silicon (Si) nanowires are employed in
the fabrication of bilayer composite Si-OTFTs. The electrical measurements of these p-type
OTFTs show that the relative direction of aligned NWs corresponding to the current flow
direction influences the field effect mobility and ON/OFF current ratio. The third strand of this
work features the use of n-type semiconducting zinc oxide (ZnO) nanowires as the mobility
enhancer in n-type OTFTs which represents a remarkable increase in field effect mobility by as
much as a factor of 40 over OTFTs comprising pristine organics.


B5.38
Self Organization of Regioregular Poly(3-Hexyl Thiophene)-Poly(-Caprolactone) Block
Copolymers Obtained by a Novel Controlled Synthesis Method. Mathieu Surin
1
, Khoa Tran
2
,
Olivier Coulembier
2
, Philippe Dubois
2
, Roberto Lazzaroni
1
and Philippe Leclere
1
;
1
Chemistry
for Novel Materials, University of Mons-Hainaut, Mons, Belgium;
2
Laboratory of Polymeric and
Composite Materials, University of Mons-Hainaut, Mons, Belgium.

Since the initial discovery of conductive organic polymers, tremendous efforts have been
devoted to the synthesis of processable compounds exhibiting high electrical conductivity or
charge mobility. Among these, polythiophene-based materials have received particular attention,
with applications ranging from field-effect transistors (FETs) to optical and electronic sensors,
photovoltaic diodes and non-linear optical materials. Substitution at the 3-and/or 4-position of
the thiophene ring not only improves the solubility and processability of poly(thiophene)s but
also strongly influences the macromolecular ordering by interdigitation of the alkyl side chains
between the lamellar structures of -stacked conjugated backbones. Regioregular poly(3-
alkylthiophene)s (rr-P3ATs) have been initially obtained by Mc Cullough and Rieke, who
discovered that transition metal-catalyzed polycondensation lead to head-to-tail P3ATs. While
side-chain functionalization has been demonstrated to be an effective way to modulate the
optoelectronic properties of rr-P3ATs, the synthesis of block copolymers containing a -
conjugated polymer segment can generate unique self-assembled electronic materials with
enhanced mechanical properties displaying phase separation and yielding discrete
microstructures. Here we propose an original, well-controlled synthesis method, based on the
association of the GRIM approach with the ring-opening polymerization (ROP) of lactones, for
the design of poly(3-hexyl thiophene) (P3HT) block copolymers with poly(-caprolactone)
(PCL) segments. This would lead to a new type of material, since PCL is: (i) crystallizable (in
contrast to other segments copolymerized with P3HT, such as poly(methacrylate)s).; (ii)
removable by hydrolysis, and ; (iii) biocompatible. The present communication reports on the
stepwise synthesis of new P3HT-PCL di- and triblock copolymers by controlled ROP of CL
from hydroxyl-terminated P3HT. Thin deposits of P3HT homopolymer compounds onto various
surfaces show a fibrillar morphology, as observed with Atomic Force Microscopy (AFM). Since
these deposits are formed from a good solvent for both blocks (i.e., tetrahydrofuran), the
observed morphology arises from the self-assembly of the P3HT segments into -stacked
assemblies, as observed for other poly(thiophene)s and conjugated (co)polymers systems. For the
P3HT-PCL block copolymers, they also self-assemble into fibrillar structures, with
semiconducting nanoribbons separated by removable, insulating domains of PCL. We investigate
the electrical properties of the P3HT-PCL fibrillar assemblies at the local scale via conducting
probe AFM techniques. Finally, since P3HT can be chemically doped after self-assembly process
and the lateral dimensions can be tuned by controlled synthesis of the polymer segments, this
could lead to an elegant way for fabricating nanowires for organic electronics.


B5.39
Temperature and Coverage Dependent Dewetting of Ultra-thin Films of Discoid Organic
Molecules on Au(111) and Ag(111). Paul Frank
1
, Norbert Koch
2
, Ralph Rieger
3
, Klaus
Muellen
3
and Adolf Winkler
1
;
1
Institute of Solid State Physics, Graz University of Technology,
Graz, Austria;
2
Institut fr Physik, Humboldt-Universitt zu Berlin, Berlin, Germany;
3
Max
Planck Institute of Polymer Research, Mainz, Germany.

Ultra-thin films of hexaazatriphenylene-hexacarbonitrile (HAT-CN) were prepared on a
gold(111) single crystal and on a silver(111) single crystal utilizing organic molecular beam
deposition (OMBD) under well defined ultra high vacuum (UHV) conditions. The thin films
were investigated by thermal desorption spectroscopy (TDS), X-ray photoelectron spectroscopy
(XPS) and atomic force microscopy (AFM). XPS in combination with TDS was applied to reveal
the kinetics of the layer growth. Additionally, the HAT-CN growth characteristics were studied
as a function of substrate temperature. From TDS, the pre-exponential factors and the heats of
evaporation for the individual layers could be determined experimentally. Ex-situ AFM was used
to determine the film morphology. A Kelvin probe (KP) was used to follow the change in the
work function with increasing film thickness. The HAT-CN molecules exhibit a quite unusual
layer growth behaviour and thermal stability. On the gold single crystal, the first two layers of
flat lying molecules wet the surface and they are stable up to 400 K and 500 K, respectively.
With increasing coverage islands form on the wetting layer, which induce a destabilisation of
these layers. As a function of coverage and temperature first the 2nd and then the 1st monolayer
are incorporated into the islands, as determined by thermal desorption spectroscopy. On the
silver single crystal, HAT-CN shows a similar layer growth and desorption behaviour, except
that the molecules in the 1st monolayer are bound more strongly and dissociate upon heating.


B5.40
Surface Plasmon and Semiconducting Polymer Luminescent Solar Concentrators. Michael
Griffo and Sue A Carter; Physics, University of California, Santa Cruz, California.

Luminescent solar concentrators use fluorescing materials with large Stokes shifts to absorb
incident sunlight and waveguide the emitted light to photovoltaic cells. Although the idea behind
luminescent solar concentrators is not new, they have recently been of great interest. Advances in
polymer and other fluorescent organic materials have enabled some increases in efficiency;
however, further improvement in the outcoupling and PL efficiency, especially of near-IR
emitting materials, is needed. We use tuned surface plasmons on silver nanoparticles to enhance
the fluorescence of semiconducting polymers and to increase coupling between the incident light
and glass to waveguide light for luminescent solar concentrator applications. We have
demonstrated a 5.6 fold increase in photoluminescence efficiency with this device structure and
enhancement in collection efficiency. We analyze the collected emission spectra as a function of
distance from the point the incident light is absorbed to the point the light exits the concentrator.
Comparing this with a control, the incident spectra, and the absorption spectra we gain insight
into the factors affecting the optical efficiencies of the structure.


B5.41
Abstract Withdrawn


B5.43
The Use of Tailored Host and Hole Blocking Materials for Improved Power Efficiencies of
Blue OLEDs.Asanga B Padmaperuma, Philip K Koech, Eugene Polikarpov, Amber L Von
Ruden, James S Swensen, Lelia Cosimbescu and Daniel J Gaspar; Pacific Northwest National
Laboratory, Richland, Washington.

The development of stable and efficient blue OLEDs is essential in the development of organic
solid state white lighting with 50% power conversion efficiency. Nationwide adoption of high-
efficiency OLED lighting instead of incandescent lighting would result in significant energy
savings. The simplest and lowest cost method of generating white light is to convert part of the
emission from a blue light source to white light using a system of phosphors external to the light
generating region. State of the art OLEDs are based on organometallic phosphors doped into
wide bandgap host materials. However, poor hole injection in these materials has limited
measured efficiencies, and in most cases the emitter is implicated in charge trapping. A direct
consequence of emitter charge trapping is a decrease in the operating voltage with increased
dopant concentration, but also reduced device efficiency at higher current densities. We have
demonstrated high efficiencies at lower operational voltages by using lower dopant
concentrations (~ 2% wt) in an ambipolar host material. Here we discuss the use of ambipolar
charge-transporting PO host materials and hole blocking materials for blue OLEDs. Ambiploar
host materials were developed by combining hole-transporting moieties with PO-based electron-
transporting moieties (ETm). The use of the same ETm as in the host in designing the hole
blocking materials gave rise to hosts and blocking materials with improved energy matching.
Design principles, physical properties, and electronic properties of these materials will be
discussed. Furthermore, we show the correlation of OLED current density and emission
efficiency results to the structure of the materials.


B5.44
Solution Processable n-Channel Semiconductors for Thin-Film Transistors Based on the
Pyromellitic Diimide Core. Qingdong Zheng
1
, Jia Huang
1
, Amy Sarjeant
2
and Howard E Katz
1
;
1
Department of Materials Science & Engineering, The Johns Hopkins University, Baltimore,
Maryland;
2
Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland.

In the past decade, there has been extensive effort toward developing new organic
semiconductors for thin film transistors due to their applications in complementary circuits, flat-
panel displays and sensors. Pyromellitic dimides (benzenetetracarboxylic diimides) are best
known as segments of highly insulating polyimide dielectrics. However, the authors report here
that this simple structure can be a sufficiently conjugated core for the construction of n-channel
organic semiconductors. Several pyromellitic diimides with fluorinated side chains were
synthesized by a one-step reaction. The field effect devices can be easily fabricated from the
synthesized pyromellitic diimides through vacuum sublimation or solution deposition. For the
vacuum sublimed materials, the electron mobility is found to be as high as 0.136 cm2/Vs and the
on/off ratios can reach a high value of 1000000. The electron mobility is found to be ~0.01
cm2/Vs for the solution deposited materials. We also report on the effects of deposition
temperature, surface treatment and chemical structure on the electron mobility of the fabricated
devices. An attempt to synthesize soluble polymers based on some functionalized pyromellitic
dimides is made, and the electron carrying properties of the resulting polymers are investigated
and discussed. Pyromellitic dimides are more readily available than the higher rylenes (such as
naphthalene or perylene tetracarboxylic diimides) already investigated, are highly transparent
and chemically stable, and lead to processable and electronically tunable derivatives. These
derivatives offer great opportunity for both scientific exploration and utilization in organic and
polymer-based devices.


B5.45
N-type and P-type Controlled Molecular Doping of MEH-PPV with all Solution-processed
Method Yuan Zhang, Mingtao Lu, Bert de Boer and Paul Blom; Zernike Institute for Advanced
Materials, University of Groningen, Groningen, Netherlands.

In organic light-emitting diodes (OLEDs) based on evaporated small molecules it has been
demonstrated that doping of the hole- and electron transport layers strongly reduces their
operation voltage.
1
Furthermore, the use of doped layers makes the OLEDs less sensitive to the
workfunctions of the anode and cathode. For solution-processed LEDs based on conjugated
polymers, however, doped charge transport layers are hardly applied. Here we present controlled
p-type and n-type doping of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]
(MEH-PPV) deposited from solution. Tetrafluoro-tetracyanoquinodimethane (F4-TCNQ) and
bis(pentamethylcyclopentadienyl)cobalt(II) (DMCO) are used for the p- and n-type dopants
respectively. By choosing the appropriate dopant solvents and adjusting the polarity of the
solution aggregation can be prevented and doped films can be deposited with a controlled carrier
density. Upon the p-type doping the low voltage part of the J-V characteristics of MEH-PPV
based hole-only devices is increased by several orders of magnitude and a clear Ohmic behavior
appears. We find that a doping concentration of 1.0wt.% leads to a free carrier density of 210
22

m
-3
. For the n-type doping it is observed that the electron transport greatly improves. The
electrons from the DMCO donor fill the trap states lying below the LUMO of the MEH-PPV.
For sufficiently high n-type doping trap-free electron transport is observed in PPV-based diodes.
We for the first time demonstrate that in MEH-PPV the free electron mobility is equal to the hole
mobility. Finally, we demonstrate the first working example of light-emitting polymer-based p-n
junctions from solution processing. References:
1
M. Pfeiffer et al., Organic Electronics, 4, 89-
103 (2003)


B5.46
Exciton Diffusion in Organic Semiconductors. Paul E Shaw, Arvydas Ruseckas and Ifor D.
W. Samuel; School of Physics and Astronomy, University of St Andrews, St Andrews, United
Kingdom.

The transport of charge has been extensively and elegantly studied in organic semiconductors.
However, the transport of excitons has received much less attention even though it is important
in a wide range of organic optoelectronic devices. In OLEDs it determines whether confinement
layers are needed and the roll-off at high brightness. In lasers exciton-exciton annihilation can be
a major loss mechanism. In polymer solar cells, the need for bulk heterojunctions is due in large
part to the limited exciton diffusion length. Furthermore exciton diffusion determines the
distance over which interfaces will strongly affect materials photophysics and device operation.
Estimates of exciton diffusion lengths in organic semiconductors range from nanometres to
microns, making it urgent to develop improved measurements that can guide the development of
improved materials. We show that time-resolved photoluminescence (PL) measurements provide
a powerful way of studying exciton diffusion. We have explored three approaches. In the first,
organic semiconductor layers of a range of thicknesses are deposited on an inorganic quencher
such as TiO2. Faster decay of the PL is seen for thinner samples, and the results are fitted to a
one-dimensional diffusion equation. For the widely studied solar cell material, poly(3-
hexylthiophene) we find that PL decays for film thicknesses ranging from 6 to 32 nm can be
fitted by a single fitting parameter - the diffusion constant and we obtain a value (1.80.3)x10-3
cm2/s which corresponds to a diffusion length of 8.50.7 nm. The second method for
investigating exciton diffusivity involves studying exciton-exciton annihilation. At high exciton
densities the PL decays faster and this change in behaviour can be modelled as a bimolecular
process, linked to the exciton diffusivity. For P3HT the results can be combined with the first
method to give an estimate for the distance apart at which two excitons annihilate of 1.80.4 nm.
In the third method, the decay of fluorescence anisotropy is used to study exciton diffusion: as
excitons diffuse they move to conjugated segments of different orientation and polarisation
memory is lost. These powerful techniques enable us to study how structure and processing
influence exciton diffusion in organic semiconductors. For example, we have demonstrated a
large reduction in exciton diffusivity in dilute copolymers. We also find that exciton diffusivity
is higher in MEH-PPV than P3HT, underlining the differences between charge transport and
exciton transport.


B5.47
Reduced Graphene Oxide Electrodes For Organic Thin-film Transistors. Hector Alejandro
Becerril-Garcia
1
, Randall M Stoltenberg
2
, Ming Lee Tang
2
, Mark E Roberts
1
, Zunfeng Liu
3
,
Yosheng Chen
3
and Zhenan Bao
1
;
1
Chemical Engineering, Stanford University, Stanford,
California;
2
Chemistry, Stanford University, Stanford, California;
3
Key Laboratory for
Functional Polymer Materials and Center for Nanoscale Science and Technology, Nankai
University, Nankai, Nankai, China.

Graphene oxide (GO) is a water-soluble nanomaterial that can be prepared in large quantities
from graphite and solution-processed into conformal thin-films on diverse substrates. GO thin-
films are electrically insulating, but become conductive upon removal of oxygenated
functionalities from the material. We previously reported the dependence of the conductivity of
reduced GO (RGO) on the reduction conditions, and the successful application of RGO films as
transparent electrodes for organic solar cells. We now present our evaluation of the use of
micropatterned RGO films as electrodes for organic thin-film transistors made with well
characterized p- and n-channel materials. Patterning techniques will be discussed. We show that
RGO films can inject electrons or holes into organic semiconductor layers. Furthermore, organic
semiconductors deposited on RGO show different morphology from that observed on metal
electrodes, leading to improved transistor performance. These findings illustrate the potential
benefits of using carbon electrodes for carbon-based electronics.


B5.48
Pendant Polymers in Light Emitting and Organic Photovoltaic Applications. Akhil Gupta
1
,
Scott Watkins
2
, Katalin Hegedus
3
, Melissa Skidmore
4
, Lynn Rozanski
5
, Gerard J Wilson
6
and
Richard A Evans
7
;
1
Molecular and Health Technologies, CSIRO, Melbourne, Victoria, Australia;
2
Molecular and Health Technologies, CSIRO, Melbourne, Victoria, Australia;
3
Molecular and
Health Technologies, CSIRO, Melbourne, Victoria, Australia;
4
Molecular and Health
Technologies, CSIRO, Melbourne, Victoria, Australia;
5
Energy Technology, CSIRO,
NewCastle, New South Wales, Australia;
6
Molecular and Health Technologies, CSIRO,
Melbourne, Victoria, Australia;
7
Molecular and Health Technologies, CSIRO, Melbourne,
Victoria, Australia.

Plastic solar cells produced from organic semiconductors offer the potential to deliver efficient
solar energy conversion with low-cost fabrication. The challenge is to develop materials for
efficient charge separation and charge transport. We are examining the potential of using free
radically synthesized polymers to replace conventional conjugated polymers such as
poly(alkylthiophenes) or poly(dialkylfluorenes) in polymeric light emitting diode (PLED) and
organic photovoltaic (OPV) applications. The use of free radically synthesized polymers has the
potential of cheap synthesis together with the opportunity of controlling polymer structure living
radical polymerization techniques such as RAFT and ATRP in order to probe structure property
relationships. Our starting point was to examine conventional cyano-PPV type polymers and by
using retro-synthetic analysis to make free radically polymerizable monomers with Cyano-PPV
functionality as pendant substituents. A variety of analogues were prepared by the condensation
of the appropriate aldehyde with p-cyanomethylstyrene. They were polymerized (uncontrolled)
and their HOMO and LUMO energy levels were determined by cyclic voltametry and UV-vis
spectroscopy. It was found that the incorporation of a triaryl amine group in the molecule (AG-1-
78 monomer: AG1-80 polymer) allowed hole transport in PLED and OPV applications. The new
material AG1-80 was evaluated in a hetero-junction organic photovoltaic device where AG1-80
replaced poly(3-hexylthiophene) (P3HT). AG1-80 is colored due to the acceptor donor nature of
the molecule which induces an internal dipole. Thus AG1-80 acts as absorbing chromophore and
hole transport material. An optimized device of AG1-80 and PCBM provided efficiencies of
0.2% across the entire solar spectrum. This modest efficiency would be largely due to the limited
absorption of the visible spectrum of AG1-80 (max 406 nm). However efficiency at its
absorption maxima was 10.5%. This suggests that the pendant nature of the AG1-80 was not a
significant problem for actual charge transportation. Thus, we have shown free radical polymers
with pendant electro-active moieties that combine charge transport and chromophore
functionalities may compete with conjugated polymers although an increased absorption of the
solar spectrum is essential for photovoltaic devices. This presentation will provide an overview
of this research from the design, synthesis, characterization and device evaluation of these
cyano-PPV derived materials within the Electro-active Nanomaterials Theme of CSIROs Niche
Manufacturing Flagship. Acknowledgements: Australian Department of Innovation, Industry,
Science and Research. International Science Linkage, CG100059 Victorian Department of
Primary Industries, Sustainable Energy Research and Development Grant and Merck Speciality
Chemicals for the generous donation of poly(3-hexylthiophene


B5.49
FET Characteristic of Chemically-Modified CNT Ryotaro Kumashiro
1
, Yan Wang
1
, Naoya
Komatsu
1
and Katsumi Tanigaki
2,1
;
1
Department of Physics, Graduate School of Science,
Tohoku University, Sendai, Japan;
2
World Premier International Research Center, Tohoku
University, Sendai, Japan.

Semiconducting carbon nanotubes (CNT) have shown promising applications as electronic
materials for nano-scale devices in the future. It is well known that the field effect transistors
(FET) fabricated by CNT show high performance. Semiconducting CNT have hole- and
electron-carrier type, therefore, CNT-FET usually exhibit ambipolar charge transport. In recent
years, the FET structure has attracted intense research interest as a light emitting device, and the
research related to organic light-emitting FET are of fundamental and practical significance. In
this study, we will report the light emission properties of CNT-FET with organic light emitter.
1,3,6,8-tetraphenylpyrene (TPPy) was used as a light-emitting organic-material. TPPy/CNT-FET
devices were fabricated by drop-cast method on SiO2/Si substrate. From the experimental
results, it was shown that the light emission in visible-light region can be observed in FET
operation and the state of light emission is changed by VG. The mechanism of light emission in
TPPy/CNT-FET will also be discussed.


B5.50
Controlling the Temperature Dependent Electronic Properties of Organic Thin Film
Transistors by Self Assembled Monolayers. Marco Marchl
1
, Peter Pacher
1
, Andrej Golubkov
1
,
Anja Haase
3
, Barbara Stadlober
3
, Stefan Possaner
2
, Ferdinand Schuerrer
2
, Karin Zojer
2
, Lucas
Hauser
4
, Christian Slugovc
4
, Gregor Trimmel
4
and Egbert Zojer
1
;
1
Institute of Solid State
Physics, TU Graz, Graz, Austria;
2
Institute of Theoretical Physics/Computational Physics, TU
Graz, Graz, Austria;
3
Institut fr Nanostrukturierte Materialien und Photonik, Joanneum
Research, Weiz, Austria;
4
Institute for Chemistry and Technology of Materials, Tu Graz, Graz,
Austria.

Manipulating the properties of the interface between the gate dielectric and the active layer in
Organic Thin Film Transistors (OTFTs) is of particular interest as this allows controlling the
charge carrier mobility and the threshold voltage. One possibility to tune the properties of this
interface is the insertion of covalently linked functional layers. We demonstrated recently that [2-
[4-(chlorosulfonyl)phenyl]ethyl]trichlorosilane and its sulfonic acid analogue (T-SC/SA) in
combination with exposure to ammonia can be used to shift the threshold voltage in
poly(thiophene) (rr-P3HT) based devices over more than 60 V exploiting acid/base chemistry. In
this work, we compare the results for rr-P3HT based transistors with data on transistors with
vacuum deposited pentacene as the active layer. To gain deeper insight into the mechanisms of
carrier transport and the origin of the threshold voltage shift, the devices were studied at
temperatures down to 77 Kelvin. The temperature dependent mobility could be described on the
basis of the multiple trapping and release model (MTR). Furthermore a drift-diffusion based
modelling has been performed to understand temperature dependent threshold voltage shifts.


B5.51
Regio-regular Pentacene Containing Polymers for Organic Photovoltaic Cells. Sanghyun
Hong, Joon Hak Oh, Ying Jiang, Rajib Mondal, Hector A Becerril, Toshihiro Okamoto,
Nobuyuki Miyaki and Zhenan Bao; Chemical Engineering, Stanford University, Stanford,
California.

The development of solar energy sources is necessary to decrease our dependency on fossil fuels
which are contributing to climate change and the polluting our environments. To make solar
energy sources inexpensive, many research groups have studied polymer photovoltaic cells.
Pentacene can be a good moiety for polymer photovoltaic cells due to its good hole mobility and
low bandgap property. However, pentacene containing polymers have not been widely
investigated for photovoltaic cells. Recently, our group developed the synthetic methodology to
make regio-regular pentacene moiety which can be easily polymerized with other co-monomers.
Pentacene-dithiophene conjugated polymers and pentacene- cyclopenta[2,1-b:3,4-b']dithiophene
conjugated polymers were prepared by this method. Regio-regular pentacene containing
polymers showed the good hole mobility up to 10
-3
cm
2
/Vs and below 1.7 eV bandgap properties
on solid state. Their power conversion efficiency will also be discussed in this presentation.


B5.52
Ion-induced Charge Screening and Significant Conductivity Enhancement of Conducting
Polymers.Yijie Xia and Jianyong Ouyang; Materials Science and Engineering, National
University of Singapore, Singapore, Singapore.

A novel approach will be reported to significantly enhance the conductivity of conducting
polymers. The approach is based on a new concept by considering conducting polymers as
complexes of polyions. Our novel approach is to reduce the Coulombic interaction between the
positive charge on the polymer chain and the counter anion by ion-induced charge screening.
The conducting polymer films by this approach can be used as the electrode of optoelectronic
devices.


B5.53
Determining the Optimum Pentacene Channel Thickness on Hydrophobic and Hydrophilic
Dielectric Surface.Sung-jin Mun, Seongil Im, Jeong-M. Choi, Kwang H. Lee and Kimoon Lee;
Physics, Yonsei University, Seoul, Korea, South.

Pentacene thin-film transistors (TFTs) are extensively studied for more than a decade due to its
potential advantages to replace amorphous Si TFTs: high mobility exceeding that of amorphous
Si TFTs, low channel deposition temperature, and accessibility to flexible plastic substrate.
Characterization of pentacene crystalline growth on various dielectric surfaces was one of the
important studies, as a fundamental intrinsic study to achieve high field effect mobility from
pentacene channel. Inorganic oxide dielectrics, self-assembled-monolayer (SAM)-coated oxide
dielectrics, and organic polymer dielectrics were studied for finding an enhanced mobility
pentacene TFT. As an extrinsic geometrical factor, optimum channel thickness in pentacene-
based TFTs was also discussed but only in adopting the case of inorganic dielectrics which have
generally hydrophilic surface. Now we report that the optimum pentacene channel thickness is
dependent on the surface energy state of its dielectric substrate. Pentacene TFT with hydrophobic
substrate displays a peak mobility at an optimum channel thickness of 50 nm, below or above
which the linear mobility decreases. In contrast, the linear mobility of the TFT with hydrophilic
substrate monotonically increases until the channel thickness decreases to 15 nm. According to
atomic force microscopy of 15 nm-thin pentacene grown on the SiO
2
and PVP dielectrics, the
pentacene islands on poly-4-vinyphenol (PVP) are not perfectly interconnected unlike the case
on SiO
2
. We briefly conclude that the pentacene TFT with hydrophobic PVP dielectric clearly
has an optimum channel thickness of 50 nm for a peak mobility while the TFT with hydrophilic
SiO
2
would show such peak mobility at even less than 15 nm of pentacene thickness. More
quantitative details on the channel thickness will be discussed in the conference.


B5.54
Epitaxially Grown Pentacene on h-BN Nanomesh. May Ling Ng
1,2
, Alexei B Preobrajenski
2
,
Alexei Zakharov
2
, Alexander S Vinogradov
3
, Sergey A Krasnikov
4
, John P Beggan
4
, Anthony A
Cafolla
4
and Nils Martensson
1,2
;
1
Department of Physics, Uppsala University, Uppsala, Sweden;
2
MAX-lab, Lund University, Lund, Sweden;
3
Institute of Physics, St.-Petersburg State
University, St. Petersburg, Russia;
4
School of Physical Sciences, Dublin City University, Dublin,
Ireland.

The advancement of lithography and imprinting technology is gradually approaching saturation
while the needs for faster and smaller electronics continue to grow exponentially. Therefore, it is
interesting, if not necessary, to explore alternative opportunities in organic and hybrid organic-
inorganic electronics. Pentacene is an interesting organic molecule because it crystallizes in a
well-ordered structure, resulting in high charge carrier mobility (comparable to amorphous
silicon). However, the very first challenge in realizing the concept of pentacene organic thin film
transistors or photovoltaic cells is to find an insulating substrate for the long range epitaxial
growth of structurally perfect pentacene. Hexagonal boron nitride (h-BN) can be a good choice
for such substrate due to its 2D nature, i.e. high surface mobility, insulating property and ease of
preparation by CVD. In the present study, we have investigated the structure of pentacene grown
by thermal evaporation on h-BN/Rh(111), alternatively known as h-BN nanomesh, at RT. Each
deposition step (from 0.06 ML to 4 ML) is characterized by recording the C 1s spectra at grazing
(20) and normal incidence (90), and C 1s PE spectra at normal emission. In addition, we have
used LEEM and micro-LEED to reveal the influence of the h-BN monolayer on the pentacene
growth mode. We have also checked the structure of the multilayer pentacene/nanomesh with
STM. For a small amount of pentacene (up to 0.3 ML), the pentacene molecules first fill the
pores of the nanomesh because the pores act as physical traps for the molecules that have only
weak bonding to h-BN (PES C 1s profile resembles the one of free pentacene molecule). These
molecules are lying flat due to the lack of pentacene neighbours to form crystal structure. On the
contrary, for 0.8 ML and above, pentacene molecules start to re-arrange among the neighbouring
pentacene molecules with hydrogen bonding and become more vertically aligned, i.e. imitating
its natural herringbone crystalline structure. With LEEM we observe pentacene grows in large
2D islands on h-BN while on clean rhodium it grows randomly with high nucleation due to the
strong bonding between pentacene and Rh. The lateral profile of the 2D pentacene crystals on h-
BN/Rh is modulated by the nanomesh buckling, as reflected in the micro-LEED patterns.


B5.55
Tuning the Ionization Energy of Organic-semiconductor Films: The Role of Intramolecular
Polar Bonds.Ingo Salzmann
1
, Steffen Duhm
1
, Georg Heimel
1
, Martin Oehzelt
2
, Rolf Kniprath
1
,
Robert L Johnson
3
, Juergen P Rabe
1
and Norbert Koch
1
;
1
Institut fr Physik, Humboldt-
Universitt zu Berlin, Berlin, Germany;
2
Institut fr Experimentalphysik, Johannes Kepler
Universitt, Linz, Austria;
3
Institut fr Experimentalphysik, Universitt Hamburg, Hamburg,
Germany.

For the prototypical conjugated organic molecules pentacene and perfluoropentacene, we
demonstrate that the surface termination of ordered organic thin films with intramolecular polar
bonds (e.g., -H versus -F) can be used to tune the ionization energy. The collective electrostatics
of these oriented bonds also explains the pronounced orientation dependence of the ionization
energy. Furthermore, mixing of differently terminated molecules on a molecular length scale
allows continuously tuning the ionization energy of thin organic films between the limiting
values of the two pure materials. Our study shows that surface engineering of organic
semiconductors via adjusting the polarity of intramolecular bonds represents a generally viable
alternative to the surface modification of substrates to control the energetics at
organic/(in)organic interfaces.


B5.56
Metal-contact Induced Anomaly in Transfer Characteristics of Graphene Field-effect
Transistors. Ryo Nouchi
1
, Tatsuya Saito
2
, Hiroki Watanabe
2
and Katsumi Tanigaki
1,2
;
1
WPI
Advanced Institute for Materials Research, Tohoku University, Sendai, Japan;
2
Department of
Physics, Tohoku University, Sendai, Japan.

Graphene is a name given to a one-atomic carbon sheet which forms a honeycomb structure.
This material shows a charge carrier mobility of higher than 200,000 cm2 V-1 s-1 at room
temperature and is regarded as a major candidate for the future high-speed electronics. In
addition to the strikingly high mobility, a weak spin-orbit interaction in graphene makes it a
pivotal material in the field of molecular spin electronics. In order to construct such electronic
devices, metallic materials should make a contact with graphene. When a molecule comes into
contact with a metal, the electronic structure of the molecule should be affected by a chemical
interaction with the metal. Recently, we observed anomalous distorted transfer characteristics in
Co-contacted graphene devices [1]. The present study aims at clarifying the microscopic
mechanism of the anomaly in the carrier transport properties. Graphene layers were formed onto
a highly doped Si substrate with a 300 nm thick thermal oxide layer using conventional
mechanical exfoliation [2]. These layers were confirmed to be single layer graphene from the
optical contrast. Metal electrodes were fabricated onto the graphene layers by electron beam
lithography and lift-off techniques. While graphene devices with inert metals (e.g. Au) displayed
conventional transfer characteristics, those with more reactive metals (e.g. Ni) showed distorted
characteristics. The distortion appeared only in short channel devices, suggesting that it is a
consequence of the metal contact. Carrier conduction through short graphene channels can be
ballistic [3]. Possible mechanisms of the anomaly, including one based on ballistic conduction,
will be presented. [1] R. Nouchi et al.: Appl. Phys. Lett. 93 (2008) 152104. [2] K. S. Novoselov
et al.: Proc. Natl. Acad. Sci. U.S.A. 102 (2005) 10451. [3] F. Miao et al.: Science 317 (2007)
1530.


B5.57
Abstract Withdrawn

B5.58
Abstract Withdrawn


B5.59
Ultrasensitive Solution Processed Polymer Photodetectors Xiong Gong, Alan J Heeger,
Minghong Tong and Yong Cao; UCSB and CBrite, UCSB and CBrite, Santa Barbara, California.

Semiconducting polymeric optoelectronic and electric devices have evolved as a promising cost-
effective alternative to silicon-based devices. Organic photodetectors have been the subject due
to several inherent advantages. Some of the important advantages of these so-called plastic
electronics include large-area detection, low cost of fabrication, ease of processing, mechanical
flexibility and versatility of chemical structure due to the advancements in organic chemistry.
Full-color, fast-response and positive sensitivity organic photodetectors have been reported.
However, there are few reports on organic photodetectors whose performances are comparable
with inorganic countparts. will report ultrasensitive solution processed photodetectors fabricated
by different semiconducting polymers as the electron donors and various fullerences derivatives
and/or inorganic quantum dots as the electron acceptors. Polymer photodetectors with different
photo-response and detectivity were demonstrated. One example is that polymer photodetectors
have photo-response from 300nm to 1450nm, the detectivity larger than 1012 cm Hz1/2/W, and
linear dynamic range larger than 120 dB. All these values are comparable to or even better than
their inorganic counterparts.


B5.60
Photo-crosslinkable Polythiophenes for Efficient Thermally Stable Organic
Photovoltaics.Yoshikazu Miyamoto
1,2
, Bumjoon J Kim
3
, Biwu Ma
2
and Jean Frechet
1,2
;
1
Department of Chemistry and Chemical Engineering, University of California, Berkeley,
California;
2
The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley,
California;
3
Department of Chemical and Biomolecular Engineering, Korea Advanced Institute
of Science and Technology, Daejeon, Korea, South.

Polymer based organic photovoltaics have attracted a great deal of attention due to their potential
as cost-effective, light-weight and flexible solar cells. Here we report a series of photo-
crosslinkable poly(3-hexylthiophene-co-3-(6-bromohexyl)thiophene) (P3HT-Br) for use in
solution processed organic photovoltaics. P3HT-Br copolymers were synthesized from two
different monomers, 2-bromo-3-hexylthiophene and 2-bromo-3-(6-bromohexyl)thiophene, where
the ratio of the two monomers was carefully controlled to achieve a UV photo-crosslinkable
layer while leaving the - stacking feature of conjugated polymers unchanged. We demonstrate
efficient thermally stable organic photovoltaics by using P3HT-Br copolymers as electron donors
in both bulk heterojunction (BHJ) and bilayer type devices. Our photo-crosslinking approach
stabilizes the nanophase separated morphology in the crosslinked P3HT-Br:PCBM BHJ with the
minimum disturbance in - stacking, which leads to photovoltaics with comparable power
conversion efficiency as compared to those of P3HT:PCBM and remarkably enhanced thermal
stability (over 2 days at 150C). We have further applied these photo-crosslinkable P3HT-Br
copolymers to making efficient solution processed bilayer devices. Benefited from the little
disturbance in - stacking by crosslinkable units, P3HT-Br/PCBM bilayer devices show high
power conversion efficiency of over 2.2% and excellent thermal stability (over 3 days at 150C),
which represents one of the highest performing bilayer devices fabricated by solution processing.


B5.61
Solution Processing of Small Molecules for Efficient Organic Photovoltaics Biwu Ma
1
,
Claire Woo
2
, Yoshikazu Miyamoto
2,1
and Jean Frechet
2,1
;
1
The Molecular Foundry, Lawrence
Berkeley National Laboratory, Berkeley, California;
2
Department of Chemistry and Chemical
Engineering, University of California, Berkeley, Berkeley, California.

Thin film organic photovoltaics (OPVs) based on polymeric materials or small molecules have
attracted tremendous research attention due to their potential application as low cost solar energy
conversion devices. Efficient OPVs have been fabricated by either solution processing of
polymeric materials or vapor deposition of thermally stable small molecules. To date, there has
not been much success in solution processing of small molecules for OPVs due to several
factors, such as limited solubility and poor film formation. Here I present our research efforts on
solution processing of small molecules for efficient OPVs. The materials of interest are soluble
conjugated organic subphthalocyanines. Due to their unique structural and photophysical
properties, including high solubility, low tendency of aggregation and strong light absorption, we
have been able to prepare amorphous thin films with high charge transporting and light
harvesting properties via simply solution casting. By using these materials as donor and
fullerenes as acceptor, we have demonstrated simple planar heterojunction OVPs with power
conversion efficiencies over 1.5 %, which represent the highest performing OPVs based on
solution processable small molecules to date. Our work clearly shows that solution processing of
light harvesting small molecules has great potential in low cost thin film organic photovoltaics.


B5.63
Energy Level Alignment of Model Molecular Electronic Systems on Silicon 111 7x7
Surfaces Conan Weiland
1
, Liu Yang
2
, Dimitri Skliar
3
, Brian Willis
3
, Doug Doren
2
and Robert
Opila
1
;
1
Department of Materials Science and Engineering, University of Delaware, Newark,
DE, Delaware;
2
Department of Chemistry and Biochemistry, University of Delaware, Newark,
Delaware;
3
Department of Chemical Engineering, University of Delaware, Newark, Delaware.

Molecular electronics promises great advances in device technology. With specialized chemical
functionalizations, molecular devices offer the prospect of novel device properties, while
promising reduced power consumption, inexpensive manufacturing and integration into everyday
products. Electron transport through single molecules has been well studied; however, the role of
the interface in charge transport in molecular electronic/substrate systems is not yet well
understood. This talk will focus on understanding the role of energy level alignment and hence
charge transfer at the molecule/silicon (111) 7x7 interface. Phenylacetylene and styrene were
used in this study as model molecular electronic systems as both molecules are conjugated over
the full molecule and are similar to the oligo-phenylene-vinylene moieties used in many
molecular electronics studies. Bonding between the molecule and surface was verified using X-
ray and UV photoelectron spectroscopy (XPS, UPS) as well as scanning tunneling microscopy
(STM). These measurements were also compared with density functional theory calculations.
Both molecules are seen to bind in a similar configuration - between the 2 carbon atoms of the
substituent and a silicon surface adatom-rest atom pair. Energy level alignment between
molecule and substrate was measured with UPS and bias dependent STM. The highest occupied
molecular orbital of both phenylacetylene and styrene were found to lie 0.7 eV below the silicon
Fermi level. The lowest unoccupied molecular orbital (LUMO) of phenylacetylene was found to
be about 0.7 eV above the silicon Fermi level, while the styrene LUMO was greater than 2 eV
above. This result shows that the specific chemical bond between molecule and substrate plays a
large role in the energy level alignment and hence charge transfer between molecule and
substrate.


B5.64
Enhanced Performance of Inverted Bulk-heterojunction Photovoltaic Cells by Interface
Modification with Self Assembled Monolayers Steven Hau
1
, Hin-Lap Yip
1,3
, Kevin O'Malley
2
,
Kung-shih Chen
1
, Jingyu Zou
1
, Hong Ma
1,3
and Alex K.-Y. Jen
1,2,3
;
1
Materials Science and
Engineering, University of Washington, Seattle, Washington;
2
Department of Chemistry,
University of Washington, Seattle, Washington;
3
Institute of Advanced Materials and
Technology, University of Washington, Seattle, Washington.

Compared to the conventional photovoltaic architecture which uses low work function metals,
inverted bulk-heterojunction photovoltaic cells have the advantage of using a more air stable
high work function metal (Au, Ag) as the hole collecting back electrode and a thin n-type metal
oxide (ZnO, TiO
2
) layer at the ITO interface as the electron selective contact. However, inverted
structures have had lower photocurrent density and fill factor compared to the normal device
structures due to the poor electrical coherence between the inorganic metal oxide and organic
active layers. Self-assembled monolayers (SAMs) have been shown to significantly change the
interfacial properties of various oxide and metallic surfaces. The adhesion, compatibility,
morphology and electrical coherence at the inorganic/organic interface can be tuned by
assembling different functional SAMs. Modifying the interface of the electron selective ZnO
nanoparticles layer with a C
60
functionalized SAM in inverted bulk-heterojunction photovoltaic
cells lead to an improvement in photocurrent density and fill factor. This monolayer can serve
multiple functions including the passivation of inorganic surface traps, enhancing interfacial
exciton dissociation efficiency, optimizing the upper organic layer morphology and stabilizing
the interface against dewetting.
1
In addition, these unencapsulated inverted devices have
excellent ambient stability retaining over 80% of its original conversion efficiency after 40 days
of exposure.
2
1. Hau, S., Yip, H.-L., Acton, O., Baek, N. S., Ma, H., Jen, A.K-Y., J. of Mater.
Chem. 18, 5113 (2008). 2. Hau, S., Yip, H.-L., Baek, N. S., Jen, A.K-Y., Appl. Phys. Lett. 92,
253301 (2008).


B5.65
Investigation on Optical and Optoelectronic properties of Blue Emission Conjugated
Polymer Optical Gain Media Cora E. C. Cheung, Boon Kar Yap, Ruidong Xia, Xuhua Wang,
Colin R. Belton, Paul N. Stavrinou and Donal D. C. Bradley; Department of Physics, Imperial
College London, London, United Kingdom.

Conjugated polymer semiconductors combine the processing and mechanical characteristics of
plastics with the desirable optical and electronic properties of semiconductors. A broad range of
devices including LEDs, field effect transistors, photodiodes and optical amplifiers and lasers are
under development with application potential in displays, lighting, RFID, display driver circuits,
imaging, solar energy conversion and data communications. Our focus here is on gain media,
where conjugated polymers are of interest for laser and optical amplifier development, with
visible spectrum emission, wavelength tunability and polymer optical fibre compatibility.
Extensive research has been undertaken on laser design and performance and it has become
evident that not all of the conjugated polymers optimised for LED operation are good gain
media. This presentation focuses on an investigation of the optical and optoelectronic properties
of a series of blue emission conjugated polymers, motivated by a desire to establish an effective
means to optimise polymer chemical structure for optical gain. Nine different polyfluorenes have
been selected for comprehensive characterisation of their optical properties, including amplified
spontaneous emission (ASE) measurements on asymmetric slab waveguides. The chosen
materials are from two groups of polyfluorenes coded as the SCB group (SCB3, SCB9, SCB11
and SCB18) and the SC group (SC005, SC006, SC007, SC008 and SC010), both from
Sumitomo Chemical. The S
1
to S
0
0-1 vibronic peaks (where gain is typically maximised) in the
polymer photoluminescence spectra range from 450nm (SCB11) to 463nm (SC006) and their
refractive indices range from 1.75 to 1.96. Three of the nine polymers (SCB3, SCB11 and
SC006) were unable to generate ASE at low pump energy (<30J per pulse, 10ns, 10Hz). All
three of these non-ASE polymers have long singlet excited state lifetimes (0.32-1.7ns) whilst the
polyfluorenes that do give ASE have significantly shorter lifetimes (134-250ps). In addition, the
highest photoluminescence quantum efficiency (PLQE) polymer is SC006 (96%) and lowest
SCB18 (22% with an ASE threshold of 1.7J/pulse). It is therefore evident that high steady state
PLQE and long excited state lifetime are insufficient for good optical gain properties. SC006 is,
moreover, the best LED material (highest efficiency) in the SC family whilst SC007 (which does
give ASE) is the worst. Similar trends apply to the SCB group, evincing an anti-correlation
between optimised LED and optical gain characteristics. The optimised LED materials have low
charge carrier mobility (10
-8
cm
2
/Vs for holes in SC006 c.f. 10
-2
cm
2
/Vs for SC007) consistent
with charge trapping due to the incorporation of a fraction of relatively low ionisation potential
arylamine moieties within the polymer chain that also bestow an excited state charge transfer
character. The nature of the differences between LED and optical gain optimised polymers will
be discussed in detail.


B5.66
Ultrathin Self-Assembled Organophosphonic Acid Monolayers/Hafnium Oxide Hybrid
Dielectrics for Low-Voltage Organic Thin Film Transistors Orb Acton
1
, Hong Ma
1,2
, Guy
Ting
3
, Hin-Lap Yip
1,2
, Balaji Purushothaman
4
, Itaru Osaka
5
, Tomek Kowalewski
5
, Richard D
McCullough
5
, John E Anthony
4
and Alex K.-Y. Jen
1,2,3
;
1
Materials Science & Engineering,
University of Washington, Seattle, Washington;
2
Institute of Advanced Materials and
Technology, University of Washington, Seattle, Washington;
3
Department of Chemistry,
University of Washington, Seattle, Washington;
4
Department of Chemistry, University of
Kentucky, Lexington, Kentucky;
5
Department of Chemistry, Carnegie Mellon University,
Pittsburgh, Pennsylvania.

Organic thin film transistors (OTFTs) based on pi-conjugated materials are envisioned for use in
ubiquitous low-cost flexible electronic devices, such as displays, sensors and electronic barcodes.
A prerequisite for realizing practical applications lies on the development of stable gate
dielectrics with low leakage current, low interface trap density, and high capacitance that afford
low-voltage OTFT operation with high performance. However, standard OTFTs still require
rather high operating voltages, often exceeding 20 V. By using organophosphonic acid self-
assembled monolayers (SAMs) on low-temperature solution processed hafnium oxide (HfOx) as
ultrathin hybrid gate dielectrics, we have realized low-voltage high performance OTFTs with
low leakage currents, and high charge carrier mobilities. In the demonstrated OTFTs, the
following device characteristics have been achieved: 1) low leakage current density - down to 1
nA/cm2; 2) large capacitance density - up to 630 nF/cm2; 3) low operating voltage (<2 V); 4)
high charge carrier mobility - up to 2.5 cm2/(Vs); 5) small subthreshold slope - down to 100
mV/decade; 6) low-hysteresis device operation. This is achieved by using well-packed and dense
organophosphonic acid SAMs (<4 nm) on HfOx (<5 nm) as ultrathin hybrid dielectrics and
through interfacial engineering using an appropriate SAM to control the chemical, electrical, and
morphological structure at the semiconductor/dielectric interface. Furthermore, this hybrid
dielectric system is shown to be generally applicable for solution processed organic
semiconductors by achieving stable device operation for polymer and soluble acene
semiconductors with mobilities >0.1 cm2/(Vs). This work represents a major advancement
towards developing large-area low-cost solution-processed/printed, flexible organic electronic
devices.


B5.67
Abstract Withdrawn


B5.68
Structured Interfaces in the Assembly and Performance of Organic Field-Effect
Transistors Gregory L Whiting, Rene J Kist, Tse Nga Ng, Sanjiv Sambandan, Beverly Russo,
Brent S Krusor and Ana C Arias; Electronic Materials and Devices Laboratory, Palo Alto
Research Center (PARC), Palo Alto, California.

Interfaces play an important role in the operation of organic thin-film field-effect transistors
(FETs). For example, many reports have shown that the composition and quality of the
dielectric/semiconductor or electrode/semiconductor interface has a significant effect on the
overall device performance. Control over the chemistry of surfaces can also greatly aide the
fabrication of solution-processed devices and the patterning of larger arrays of these devices to
form electronic components. This control is particularly useful when deposition methods like
ink-jet printing are used, as parameters such as the placement and drying of a drop can be
influenced. This report will focus on both n- and p-type solution processed FETs. Ink-jet printing
is used to pattern small molecule organic semiconductors, as well as silver source, drain and gate
contacts. By careful modification of surface energy, particularly through the use of self-
assembled monolayers, well-defined metal contacts can be produced, and semiconductor
morphology can be controlled. Device parameters can also be strongly affected by these
interfaces. For example, electrode work functions can be tailored to achieve good contact
between the printed silver and organic semiconductor. Both top- and bottom-gate architectures
have been used for this study, which present different benefits and challenges for additive
solution processing. In addition, ink-jet printed complementary circuits using these materials and
methods will be described.


B5.69
Impact of Interfacial Modification on Polymer Morphology, Photoexcitation Dynamics,
and Device Performance in P3HT/ZnO Solar Cells. Matthew Thomas Lloyd
1
, Rohit P
Prasankumar
2
, Michael B Sinclair
3
, Alex C Mayer
4
and Julia W Hsu
1
;
1
Surface and Interface
Sciences, Sandia National Laboratories, Albuquerque, New Mexico;
2
Center for Integrated
Nanotechnologies, Los Alamos National Laboratory, Los Alamos, New Mexico;
3
Sandia
National Laboratories, Albuquerque, New Mexico;
4
Department of Materials Science and
Engineering, Stanford Univeristy, Stanford, California.

Short-circuit current, which is determined by interfacial charge separation and recombination, in
ZnO/poly 3-hexylthiophene (P3HT) solar cells is found to improve by intentional modification
of the heterojunction interface. To understand the origin of this enhancement, we investigate the
morphology of the interfacial polymer layer and decay dynamics of photoexcited species in
P3HT deposited on glass, bare ZnO, and ZnO modified with an alkanethiol monolayer. These
results are correlated with the characteristics of P3HT/ZnO and P3HT/alkanethiol-modified ZnO
bilayer photovoltaic devices. Synchrotron x-ray diffraction spectra of pristine P3HT and P3HT
on an alkanethiol-modified ZnO surface point to a more crystalline P3HT interfacial layer, while
an amorphous interfacial layer of P3HT is found on unmodified ZnO. To investigate the decay
dynamics of initial photoexcited states in the ZnO/P3HT system, the composite samples are
interrogated by pump-probe spectroscopy with sub-picosecond resolution. Transient
photoinduced absorption spectra are collected for photoexcited species in the range of 1090 nm
to 3034 nm after excitation with a 550 nm pump. Compared to P3HT/ZnO composite films, the
decay behavior for both polarons and excitons over a 500 ps time interval becomes significantly
slower with alkanethiol modification, indicating a reduction in of early-stage charge
recombination. Accompanying the decrease in recombination, we find an increase in the short-
circuit current in the alkanethiol-modified ZnO devices in spite of the electron tunneling barrier
presented by the alkanethiol monolayer. External quantum efficiency measurements in
alkanethiol-modified devices also exhibit a clear signature of crystalline P3HT within an exciton
diffusion length from the heterojunction interface. As these experiments demonstrate, charge
injection efficiency and device performance can be improved by control of the polymer
morphology at the heterojunction interface. Sandia is a multiprogram laboratory operated by
Sandia Corporation, a Lockheed Martin Company for the United States Department of Energys
National Nuclear Security Administration under contract DE-AC04-94AL85000.


B5.70
Shelf Lifetime Study of Unencapsulated Organic and Hybrid Photovoltaic Devices.
Matthew Thomas Lloyd
1
, Dana C Olson
2
, Matthew O Reese
2
, Erica Fang
1
, Diana L Moore
3
,
James A Voigt
3
and Julia W Hsu
1
;
1
Surface and Interface Sciences, Sandia National
Laboratories, Albuquerque, New Mexico;
2
National Renewable Energy Laboratory, Golden,
Colorado;
3
Sandia National Laboratories, Albuquerque, New Mexico.

As organic photovoltaics (OPVs) approach commercially viable power conversion efficiencies,
in depth investigation of degradation mechanisms and methods for their mitigation becomes
increasingly important. To address this issue, we monitored the difference in degradation rates
for polymer:fullerene bulk heterojunctions (BHJ) and polymer/ZnO hybrid devices. The device
performance was measured over the course of 6 weeks, storing the devices in the dark in ambient
atmosphere between measurements. We found that the performance of BHJ devices employing
silver electron-extracting contacts degraded rapidly (with a half-life of three days). BHJ devices
with calcium/aluminum electron-extracting electrodes also degrade, but at a slower rate. These
results are in contrast with the behavior of inverted BHJ and hybrid polymer/ZnO devices,
where an ITO/ZnO electrode serves as the electron-extracting contact and silver serves to extract
holes. Initially, the efficiency of these inverted devices increased; notably, the inverted BHJ
device improved by more than 50% at day nine and maintained an efficiency greater than the
initial value for the duration of the degradation study. These results indicate that the cause of
OPV shelf life degradation is not, as commonly believed, the instability of the active organic
materials. We find that the changes in the contact are a more important cause. Specifically, as
silver oxidizes in air, its work function increases and loses selectivity as an electron-accepting
electrode. A larger work function is found to advantageously increase open-circuit voltage and
short-circuit current in both inverted BHJ and hybrid devices where Ag functions as the hole-
collecting electrode. In addition, we have measured the change of many polymer/ZnO bilayer
and nanorod devices over a longer period of time and found that, over 450 days, the devices still
perform at 50% of their initial efficiency. In summary, we found that changes in the metal
contact have a larger effect than changes in the active material on the degradation of organic and
hybrid solar cells. Sandia is a multiprogram laboratory operated by Sandia Corporation, a
Lockheed Martin Company for the United States Department of Energys National Nuclear
Security Administration under contract DE-AC04-94AL85000.


B5.71
Abstract Withdrawn


B5.72
Nanotube Based High Current Transistor with Good on/off Ratios. Islamshah Amlani and
Rudy Emrick; Applied Research and Technology Center, Motorola, Tempe, Arizona.

Aligned and randomly networked ensembles of single-walled carbon nanotubes (SWNT)
represent a potentially powerful platform for developing thin film semiconductor technologies
such as flexible electronics, optoelectronics, RF electronics and sensing. Electrical characteristics
of SWNT based devices that contain ensemble of nanotubes in the channel exhibit a cumulative
effect of the characteristics due to varying chiralities of the constituent nanotubes. For instance,
in an aligned SNWT device the lower limit of the off state leakage current characteristics will
depend on the fraction of metallic SWNTs in the channel. One way to improve the on/off ratio
post-fabrication is by selective joule heating of metallic and high-leakage ambipolar
semiconducting nanotubes. A typical approach is to bias the semiconducting tubes in the off-
state by applying an appropriate gate bias and apply a sufficiently high drain current to
electrically stress and break the conducting nanotubes. If not properly configured however, on-
current can also diminish substantially in this process due to undesirable burning of
semiconducting nanotubes. Here, we present an automated electrical burning process that
preferentially breaks down both metallic and high-leakage semiconducting SWNTs in a
nanotube ensemble to obtain on/off ratios higher than three orders of magnitude. Typical on-state
current of our back gated devices with interdigitated source drain geometry is in the milliampere
range due to a large number of nanotubes in the channel and the reduction in on-state current at
the end of the electrical burning process is minimal (~ 30%) with on/off ratios of 1000 or greater.
These results are among the best that have been reported. However, we were not able to obtain
electrical burning results on top gated geometry with similar efficiency. We perform two
different experiments to elucidate that nanotubes break at the center when electrically stressed,
the main reason for only marginal success with top gated devices. In the first experiment, the
channel of the back gated devices are completely passivated by PMMA to purposely block off
oxygen at the nanotube interface. Electrical burning result in this case is rather poor as lack of
oxygen availability at the nanotube interface leads to non-preferential breakdown of both
metallic and semiconducting nanotubes. In the second experiment we expose the center portion
consisting of ~30-50% of the channel by performing electron beam lithography and developing
the PMMA resist. Electrical burning results on these devices yield similar to those without any
passivation. This indirectly suggests that breakdown indeed takes place in the center of the
nanotubes and good on/off ratios can be obtained using this approach as long as the middle of the
channel is exposed to air. This has important consequences for top-gated devices where the
center portion of the channel is passivated by gate dielectric and metal.


B5.73
Control of Pentacene Growth and Its Effects on Organic TFT Characteristics Jong Sun
Choi
1
, Jaehoon Park
1
, Jong Won Lee
1
, Dong Wook Kim
1
, Hyung Tak Kim
1
and Dong Myung
Shin
2
;
1
Dept. of Electrical, Information and Control Engineering, Hongik University, Seoul,
Korea, South;
2
Dept. of Chemical Engineering, Hongik University, Seoul, Korea, South.

Recently, organic semiconductor devices have been extensively investigated and steady
progresses in device performances are continuously being obtained with ever increasing range of
applications. One of the most promising organic semiconductors is pentacene, mainly due to the
high hole mobility in pentacene-based TFTs. And many researchers continue to develop high-
performance pentacene thin-film transistors (TFTs), focusing on improving the electrical
conduction in the pentacene active layer. In this study, we have fabricated blends of two different
polyimides with varying the composition ratio and investigated the growth of pentacene grains
on each blend film. It is observed that the pentacene grain size pronouncedly reduced with
increasing the content of hydrophobic polyimide in the blend film. This result can be explained
by the interaction between the adsorbed pentacene molecules and the protrusion of hydrophobic
component in the blend film. Indeed, atomic force microscopy images show that the surface
diffusion of pentacene molecules on the blend film was limited by the hydrophobic protrusions.
Accordingly, it is confirmed that the fabricated blend films can be applied to control the
pentacene grain growth. We extended these results to investigate the effects of pentacene grain
size on the TFT characteristics. Organic TFTs with larger pentacene grains exhibited improved
device performances, which might be attributed to less grain boundaries. And experimental
results show that grain boundaries act as trap sites during device operation and the trapped
charges at grain boundaries can be activated by increasing the gate-source field. However, the
threshold voltage shift upon a gate-voltage sweep direction was more pronounced for the device
with larger pentacene grains, even strongly depending on the delay time of gate-voltage step.
These results are considered to be attributed to a strong interaction between the pentacene layer
and the concomitant blend film owing to its polar feature. Of note, grain boundaries can be
identified as a limiting factor to the charge transport in organic TFTs and the interface between
the organic semiconductor and insulator layer plays a significant role in the operational stability.
Further investigations are focused on evaluating the activation energies of trapped charges at
grain boundaries as well as the interface. These results will be presented.


B5.74
Effects of Alignment Layers on Pentacene Molecular Orientation and Thin-Film Transistor
Characteristics Jae-Hoon Kim
1
, Jongseung Kim
1
, Hyunsuck Kim
1
, Jaehoon Park
2
, Jong Sun
Choi
2
and Dong Myoung Shin
3
;
1
Department of Electronics and Computer Engineering,
Hanyang University, Seoul, Korea, South;
2
Dept. of Electrical, Information and Control
Engineering, Hongik University, Seoul, Korea, South;
3
Dept. of Chemical Engieering, Hongik
University, Seoul, Korea, South.

Pentacene, a fused-ring polycyclic aromatic hydrocarbon, is one of the most intensively
investigated systems among various organic semiconductors due to great mobility and good
semiconducting behavior. The electrical conductivity in this material strongly depends on the
direction of applied electrical field to its long molecular axis. And also, it is known that the
vertical alignment of pentacene molecules to the gate insulator surface provides a strong -*
overlap and increases the electrical conductivity in the direction of perpendicular to the long-
axis. These have motivated several studies of the effects of pentacene molecular orientations on
the performance of organic thin-film transistors (OTFTs). In the present work, we use different
alignment layers to investigate their effects on pentacene molecular orientation and the
concomitant performance of organic TFTs. For the fabrication of morphological alignment layer,
polyimide films were formed by spin-coating and then rubbed in the parallel and vertical
directions to conducting channel in OTFTs. And also, liquid crystal (LC) material was used for
the fabrication of molecular alignment layer. LC molecules were aligned in the parallel and
vertical directions to channel direction. Experimental results show that the transistor
characteristics were dependent on the directions of alignment layers. The OTFTs with the
morphological alignment layer exhibited an increase in the drain current compared to the device
without rubbing treatment, independent on the rubbing directions. Dichroic ratio of the drain
current was about 1.2, which is defined as the ratio of current for the device with the parallel
alignment layer to that with the vertical alignment layer. On the other hand, the OTFTs with the
molecular alignment layer showed a significant dependence of drain current on the direction of
alignment layer: the drain current in the parallel direction increased compared with that for the
device with unaligned LC layer, but the drain current in the vertical direction even deteriorated.
In this case, dichroic ratio was about 2.1. These results indicate that the morphological effect on
the pentacene molecular orientation is intrinsically different from that of a prior molecular
orientation. We will report the detailed growth mechanism of pentacene molecule on these
alignment layers, combining with the electrical characteristics of OTFTs.


B5.75
Nanostructure-Assisted Hole Injection in Schottky Diodes and Application in Organic
TFTs Hyunsuck Kim
1
, Jongseung Kim
1
, Jae-Hoon Kim
1
, Jaehoon Park
2
and Jong Sun Choi
2
;
1
Department of Electronics and Computer Engineering, Hanyang University, Seoul, Korea,
South;
2
Dept. of Electrical, Information and Control Enigeering, Hongik University, Seoul,
Korea, South.

Organic thin-film transistors (OTFTs) have shown great promise for a variety of electronic
applications, including flexible displays, chemical sensors, and low-cost microelectronics. The
characteristics of OTFTs have been remarkably advanced and even surpass those of TFTs with
amorphous Si. Most of efforts for OTFTs have been mainly focused on the improvements of
electrical performance. But the basic study in the interfacial characteristics related with device
performance is not so much progressed, which is also necessary for understanding device physics
and further improvements in device characteristics. The interface between an organic material
and a metal is one of critical factors for the device performance. Recently, some groups have
investigated the importance of the interfacial characteristics and attempted to enhance the
interfacial characteristics. Therefore, the interfacial properties should be investigated and must
be improved in order to make OTFTs competitive with more conventional amorphous Si and
poly-Si TFTs. In this work, we have fabricated the conic-nanostructures on the Al-bottom
electrode and investigated the growth of pentacene molecules on the rough conic-nanostructures,
combing with the barrier heights for hole injection in Schottky diodes. For the fabrication of
conic-nanostructures, the H1 solution, in which polyurethane was dissolved into acetone solvent,
was spin-coated onto the Al-bottom electrode. X-ray diffraction results show that the conic-
nanostructures can contribute to the ordered growth pentacene molecules. And the barrier height
for hole injection from the top-Au electrode was calculated by Fowler-Nordheim theory and
found to be lowered for the Schottky diode with conic-nanostructures. This injection barrier
lowering can be explained by the ordered growth of pentacene molecules under the influence of
conic-nanostructures. We also introduced these structures into the interface bewteen the
pentacene layer and gate insulator of OTFTs. It is observed that the electrical characteristics of
the OTFT with conic-nanostructures were higher for the device without nanostructures. In
particular, the field-effect mobility was significantly improved by using conic-nanostructures,
calculated to be about 2.94 cm2/Vs. Consequently, we conclude that the nanostructure-assisted
hole injection facilitated the barrier lowering, thereby contributing to achieving high
performances in OTFTs. These results will be discussed.


B5.76
Structural Phase Transition and Molecular Electron Tunneling in Self-Assembled
Monolayers Kyoungja Seo and Hyoyoung Lee; ETRI, Daejeon, Korea, South.

The electrical and chemical nature of organic molecules in self-assembled monolayers (SAMs)
on metal or semiconductors have been studied for applications of molecular electronics[1]. As a
model system, alkanethiols have been studied extensively by current-voltage (I-V) characteristics
in molecular junctions (metal-molecule-metal). Electron transport across the alkanethiol
monolayers is influenced by a tunneling pathway through the -bonded alkyl chain (through-
bond tunneling) and through the intermolecular charge transport (through-space tunneling)[2].
Strong electronic coupling of a sulfur atom to a gold atom by chemisorption enhances the
electron transport via through-bond tunneling across the interfaces of alkanethiol and gold. A
molecular tilt in alkanethiol SAMs enhances contribution of through-space tunneling by the
intermolecular coupling, and molecular conductance across the SAM relatively decreases[3].
Molecular orientation on alkanethiol SAMs is changed with structural phase transition by
thermal annealing in the SAMs. Molecular electron transport characteristics will be varied by
different intermolecular coupling induced in each structural phase. However, tunneling
characteristics such as an electron tunneling barrier of molecular junctions has not been reported
with different structural phases, yet. In addition, it was reported that the thermal and electrostatic
effects influence conductance across molecular junctions, dependent of the local molecular
environment induced by neighboring molecules. Thus, we expect that the structural phase
transition-induced a difference in molecular electron tunneling characteristics will depend on
different intermolecular coupling effects created in a large molecular junction and an individual
molecular junction. In this study, we demonstrate structural phase dependency of conductance
across the thiolate (e.g., alkanethiol and alkanedithiol) SAMs, dependent of a junction area in
size. The molecular electron tunneling characteristics for each structural phase are compared
with I-V curves obtained in a scanning tunneling microscope (STM)-based individual molecular
junction and a micropore-based large molecular junction. A tunneling barrier is proved as a
measure of the intermolecular coupling on different structural phases of the thiolate SAMs. It is
the first examination of the molecular electron tunneling in different structural phases of the
thiolate SAMs and dependence of the molecular electron tunneling on a junction area in size. [1]
A. Salomon, D. Cahen, S. Lindsay, J. Tomfohr, V. B. Engelkes, C. D. Frisbie, Adv. Mater. 2003,
15, 1881-1890. [2] X. D. Cui, X. Zarate, J. Tomfohr, O. F. Sankey, A. Primak, A. L. Moore, T.
A. Moore, D. Gust, G. Harris, S. M. Lindsay, Nanotechnology 2002, 13, 5. [3] H. Song, H. Lee,
T. Lee, J. Am. Chem. Soc. 2007, 129, 3806-3807.


B5.77
Semi-transparent Flexible Photo-detector using Tetracene/ZnO hybrid p-n Junction. Aaron
Park, Seongil Im, Kimoon Lee and Kwang H. Lee; physics, Yonsei university, Seoul, Korea,
South.

Over the last few decades, organic thin-film devices, such as organic light-emitting diodes
(OLED), organic thin-film transistors (OTFT), solar cells, and photodetectors have made steady
progresses in their performances. Among organic materials polyacenes like tetracene, which is
one of the important organic molecules composed of four benzene rings, have been studied for
applying to optoelectronic devices due to their good optical properties. We report on the
fabrication of p-type organic/n-type ZnO hetero-junction diode and its applications. To construct
the organic/inorganic hetero-junction, 50 nm-thick ZnO was deposited on ITO-coated flexible
PET substrate at 100 C and then 100 nm-thick tetracene as a p-type organic semiconductor was
evaporated on the ZnO layer. Not only to make an ohmic contact with p-type organic layer but
also to investigate the photo-response properties of the p-n junction, we adopt the semi-
transparent NiO
x
electrode with large work-function value of ~5.1 eV and transmittance of ~30
%. Organic/inorganic hetero-junction of p-type tetracene/n-type ZnO showed rectifying behavior
with current-voltage (I-V) characteristic and exhibited quite a high current density under forward
bias. Also the tetracene/ZnO p-n diode has excellent photo-response properties under green,
blue, and weak UV illuminations. We actually fabricated pentacene/ZnO p-n diode using the
similar method, to compare with the tetracene/ZnO diode. Although the pentacene/ZnO diode
displayed a little higher forward current than that of the tetracene/ZnO, we now regard that our
p-tetracene/n-ZnO diode has clear advantages over pentacene/ZnO as an optoelectronic device
due to its excellent photodetecting potentials. More details on the comparison will be discussed
in the conference meeting.


B5.78
Characteristics of Organic Thin-Film Transistors with Anodized Aluminum Oxide as a
Gate Insulator.Jong Won Lee
1
, Dong Wook Kim
1
, Jaehoon Park
1
, Hyoung Tak Kim
1
, Dong
Myoung Shin
2
and Jong Sun Choi
1
;
1
Dept. of Electrical, Information and Control Engineering,
Hongik University, Seoul, Korea, South;
2
Dept. of Chemical Engineering, Hongik University,
Seoul, Korea, South.

Organic thin-film transistors (OTFTs) have been expected by switching devices for flexible
display. Aluminum gate electrode is usually adopted to reduce the delay time because of the
property of low resistivity. And anodized aluminum oxide film is considered as a good insulator
because it is resistant to various chemical solvent and has a high dielectric constant (high-k)
contributing to reduction of the threshold voltage. The reduction of threshold voltage can lead to
lowering supply voltage and thus resulting in lowering power dissipation. In general, anodized
oxide films form two types of morphology, i.e. barrier-type and porous-type films, by altering
the condition of electrolytes. Barrie-type films in the pH range of 5 to 7 are utilized as
electrolytic capacitors due to thin, compact, and non-porous structure, while porous-type films
are applied to nano-templates due to its thick and porous structure. In this work, we fabricated
two types of anodizing aluminum oxide films with varying the pH values of electrolyte. Atomic
force microscopy images of anodized aluminum oxide films show that the surface of film
forming the barrier-type structure grown at pH 6.3 is smoother than that for the porous-like
structure grown at pH 4.1. The difference in the height of these two films was about 10-30 nm.
And the OTFT with the barrier-type aluminum oxide insulator exhibited the mobility of 0.09
cm2/Vs, the subthreshold slope of 1.1 V/decade, and the on/off ratio of 10_4, which are superior
to those for the device with the porous-type insulator. It is thought that the smooth surface of the
barrier-type film might contribute to a long range hopping of charge carriers in the conducting
channel. Indeed, we found that the activation energy for device with the porous-like anodized
insulator was much larger than that for the barrier-type structure, which demonstrates that the
characteristic improvement in the device with the barrier-type structure was attributed to low
activation energy for carrier transport in the conducting channel. These results will be discussed.


B5.79
Scanning Probe Analysis of Poly(3-Hexylthiophene) Thin Films. Rajiv Giridharagopal and
Kevin Kelly; Electrical and Computer Engineering, Rice University, Houston, Texas.

The electronic behavior of conducting polymers at the polymer-electrode interface is of great
interest, both technologically and in terms of basic materials science. We have used scanning
tunneling microscopy (STM), including spectroscopic extensions such as work function imaging
and alternating current STM (ACSTM), to probe conducting polymer thin films and monolayers
with high spatial resolution in both ambient and ultrahigh vacuum environments. In our studies
we focus on poly(3-hexylthiophene) (P3HT) films, each approximately one to three monolayers
in thickness, deposited on highly-ordered pyrolytic graphite (HOPG) and molybdenum disulfide
(MoS
2
) substrates. P3HT is one of a number of conducting polymers, and STM reveals that
P3HT deposited on HOPG or MoS
2
self-assembles to form a highly-ordered structure with
symmetry commensurate with that of the underlying lattice. Additionally, we have used ACSTM
to analyze spatial variations in the charge carrier density in such layers, thus shedding light on
substrate-dependent charge transfer in P3HT films on different materials. Understanding such
effects is of great importance for improving P3HT devices and conducting polymer-metal
interfaces in general.


B5.80
Hybrid Nanostructures Semiconductor/Organic Dye J-Aggregate In Reverse Micelles.
Vladimir Razumov, Lubov Nikolenko and Sergey Brichkin; Institute of Problems of Chemical
Physics RAS, Chernogolovka, Russia.

Hybrid nanostructures such as molecular aggregate/semiconductor nanoparticle or core/shell
structures in which core is the semiconductor nanocrystal and shell is the organic dye are very
important for the charge separation at light absorption. These structures are useful for
development of light-emitting devices, thin-film transistors, and optical memory or solar cells.
Organic/inorganic semiconductor interfaces play an important role for effective charge
separation. There are different methods for design of hybrid nanostructures. One of these
methods is a self-assembly using of reverse micelles. The main procedure includes three stages.
The first is synthesis of semiconductor nanoparticles by chemical reaction controlled by
intermicellar exchange in water in oil microemulsions. The second stage is molecular dye
aggregation and the third stage is selfassembly of organic/inorganic nanostructures. Self-
assembly of hybrid nanocrystal/J-aggregate nanostructures after mixing two reverse micelle
AOT/water/hexane solutions: one containing J-aggregates of pyridinium salt of betaine 3,3'-di(-
sulfopropyl)-4,5,4',5'-dibenzo-9-ethylthiacarbocyanine and the other - AgI nanocrystals was
shown. During the hybrid nanostructure formation new dye absorption bands with max673
and 695 nm appeared, these belong to J-aggregates of different structures adsorbed on
nanocrystals. It was found that the excess of iodide ions during AgI nanocrystal synthesis is the
main factor influencing the hybrid nanostructures self-assembly, so AgI crystal lattice is of great
importance in this process. Taking into account that AgI nanocrystals synthesized in iodide
excess have hexagonal crystal lattice it can be concluded that J-aggregates effective absorb on -
AgI and do not absorb on -AgI. There occurs a symbiosis of the hybrid structure components:
nanocrystals raise the photostability of J-aggregates, and adsorbed J-aggregates efficiently
stabilize the nanocrystal size. It was shown that the stable hybrid nanostructures may be
extracted from micellar solution without further aggregation. Spectral and structure
investigations of these hybrid systems were carried out depending on average size of reverse
micelles using of light absorption and TEM techniques.


B5.81
Morphological Stabilization of Polymer Photovoltaic Cells by Using Cross-linkable
PolythiopheneShoji Miyanishi
1
, Keisuke Tajima
1
and Kazuhito Hashimoto
1,2
;
1
Enginnering,
Graduate School of The Univerity of Tokyo, Tokyo, Japan;
2
JST-ERATO, Tokyo, Japan.

Polymer photovoltaic cells draw considerable attention these days for their potential of low cost
fabrication of large area devices by simple means of painting or printing from the polymer
solutions. The most commonly used structure for the polymer photovoltaic cells now is a bulk
heterojunction, which is a physical mixture of donor and acceptor materials. Recent research has
suggested that control of the mixing morphology of the donor and the acceptor in films is of high
importance to achieve highly efficient charge separation and transport. Especially in the case of
the combination of poly(3-hexylthiophene) (P3HT) and (6,6)-phenyl C61 butyric acid methyl
ester (PCBM), thermal annealing of the films has been used to control this phase separation.
During the thermal annealing, both the polymer and PCBM crystallize to form an
interpenetrating network in nanoscale, resulting in drastic enhancement of the device
performance. However, even if such phase-separated nanostructure is constructed, this
morphology is not thermally stable and may gradually undergo changes during the device
operation since the polymer and the PCBM thermodynamically prefer to segregate from each
other. In fact, a prolonged thermal treatment of the device induces the formation of large
aggregations of PCBM in the films that lowered the device performance significantly. Therefore,
morphology control that only depends on thermal annealing might be insufficient for achieving a
stable and reliable mixing morphology of the donor and the acceptor. In this work a new cross-
linkable regioregular poly(3-(5-hexenyl)thiophene) (P3HNT) was synthesized for the purpose of
stabilizing the film morphology in polymer photovoltaic cells. The vinyl group at the side chains
of P3HNT is expected to conduct cross-linking reaction by thermal treatment. After the process
of cross-linking is complete, the diffusion of PCBM into the film can be lowered to suppress the
formation of large aggregations. As a result, the thermal stability of the cells is expected to
improved in comparison to non-cross-linkable P3HT:PCBM bulk heterojunction. P3HNT was
characterized by NMR, GPC, UV-vis absorption spectra, XRD spectra and DSC. XRD and UV-
vis spectra showed that P3HNT has similar crystallinity to P3HT. As a result, the performance of
the P3HNT:PCBM bulk heterojunction devices showed comparably high efficiency over 3%
similar to P3HT:PCBM cells. Furthermore, P3HNT was certainly cross-linked during thermal
treatment, confirmed by the insolubility of the films in organic solvents. This cross-linkability
was also confirmed even in the mixture films with PCBM. As the result, the formation of large
aggregations of PCBM was prevented in P3HNT:PCBM films even after prolonged thermal
annealing. In addition, the deterioration of the photoconversion performance at a high
temperature was suppressed in the polymer solar cells compared to the control cells with
P3HT:PCBM.


B5.82
Low-Voltage Self-Supported Ion Conductive Membrane Based Transistors Nikolai J.
Kaihovirta
1,3
, Carl-Johan Wikman
2
, Tapio Makela
1
, Carl-Eric Wilen
2
and Ronald Osterbacka
1
;
1
Center for Functional Materials and Department of Physics, bo Akademi University, Turku,
Finland;
2
Center for Functional Materials and Laboratory of Polymer Technology, bo Akademi
University, Turku, Finland;
3
Graduate School of Materials Research, Turku Universities, Turku,
Finland.

Ion enhanced organic transistors are promising candidates for large-scale fabrication of low-
voltage applications [1-3]. In the ion enhanced organic transistor, an ionic insulator replaces the
traditional dielectric insulator. Two types of ion enhanced polymer transistors have been
presented in the literature: Electrochemical transistors [1, 4] and electric double layer (EDL)
gated transistors [2, 3, 5, 6]. We present a novel EDL-gated transistor using a thick (> 50 m),
ion conducting membrane (MemFET) [7]. The membrane acts both as gate insulator and as
mechanical support. The fabrication of the membrane starts with a PVDF-film as base material.
The PVDF-film is functionalized by the roll-to-roll suitable electron beam irradiation induced
grafting technique [8]. For comparison, we have also used the commercially available, proton-
conducting Nafion-membrane, as received. The MemFETs are fabricated by standard
laboratory fabrication techniques using soluble polymers. As semiconductor we apply the
regioregular P3HT. The highly conducting polymers PANI or PEDOT:PSS are used for the gate
electrode, while evaporated gold is chosen, for convenience, for the source and drain electrodes.
The MemFETs operate at low voltages (1 V) with a high current throughput. By using the
electron beam irradiation induced grafting technique we can fabricate membranes to conduct
different ions and/or simply tailor-make membranes to be locally ion conducting in whatever
pattern needed. MemFETs fabricated on different membranes will be presented. Furthermore, the
ion conducting membrane allows for fabrication of two (or more) devices on the same membrane
in a simple and cost-effective matter. This will be shown by driving an electrochromic display
pixel with a MemFET, both fabricated on the same membrane. [1] R. Mannerbro, M. Ranlf, N.
Robinson, R. Forchheimer, Synth. Met. 158 (2008), 556-560. [2] D. Tobjrk, N. J. Kaihovirta, T.
Mkel, F. S. Pettersson, R. sterbacka, Org. Electron. 9 (2008), 931-935. [3] J. H. Cho, J. Lee,
Y. Xia, B. Kim, Y. He, M. J. Renn, T. P. Lodge, C. D. Frisbie, Nat. Mater. 7 (2008), 900-906.
[4] D. Nilsson, M. Chen, T. Kugler, T. Remonen, M. Armgarth, M. Berggren, Adv. Mater. 14
(2002), 51-54. [5] H. G. O. Sandberg, T. G. Bcklund, R. sterbacka, H. Stubb, Adv. Mater. 19
(2004), 1112-1115. [6] M. J. Panzer, C. D. Frisbie, Adv. Funct. Mater. 16 (2006), 1051-1056. [7]
N. J. Kaihovirta, C, -J. Wikman, T. Mkel, C. -E. Wiln, R. sterbacka, Adv. Mater. (2008) in
press. [8] T. Lehtinen, G. Sundholm, S. Holmberg, F. Sundholm, P. Bjrnbom, M. Bursell,
Electrochim. Acta 43 (1998), 1881-1890.


B5.83
Understanding Aminated Silane Monolayer Formation Kinetics for Use in Organic
Electronics Justin Opatkiewicz, Melbs C LeMieux and Zhenan Bao; Chemical Engineering,
Stanford University, Stanford, California.

Aminated silane films are being used in a wide variety of fields: from biological sciences to
semiconductor research. Amines with varying degrees of substitution are common in nature and
hence can be used to modify surfaces to interface with biological systems. 3-
aminopropyltriethoxysilane (APTES) is a very common silane and has been characterized in
many studies. It is generally accepted that the amine catalyzes monolayer formation by
electrostatic attraction of the amine to a hydrophilic surface. Silanes with very similar structures,
however, have not been analyzed in as much depth. Similar molecules varying simply by methyl-
substitutions, such as N-methylaminopropyltrimethoxysilane (MAPS) and (N,N-
dimethylaminopropyl)trimethoxysilane (DMAPS), can potentially be used alongside APTES in a
variety of applications such as biological linkages and carbon nanotube separation. Here, we
compare the kinetics of MAPS and DMAPS to APTES surface reactions and determine the
influence of the methyl substitution on monolayer formation. After the kinetics of the three
silanes are understood, their abilitly to separate carbon nanotubes (CNTs) are analyzed.


B5.84
Enhanced Performance of Organic Light Emitting Diodes Using LiF Buffer Layer. Omkar
Vyavahare
1
and Richard Hailstone
2
;
1
Materials Science and Engineering, Rochester Institute of
Technology, Rochester, New York;
2
Imaging Science, Rochester Institute of Technology,
Rochester, New York.

Since the invention of organic electroluminescent devices a great deal of effort has been made to
improve their performance. Reducing the barrier and optimizing charge injection is crucial for
efficient and bright Organic Light Emitting Diodes (OLEDs). We report improvement in the
performance of OLEDs with ITO/TPD/Alq3/Al structure by inserting LiF both at electrode-
organic interface and organic-organic interface. In this paper, we elucidate the mechanism of LiF
buffer layer inserted at different interfaces. These devices show improved luminescence and
steeper IV characteristics.


B5.85
Transparent Photo-stable Complementary Inverter with Organic-inorganic Nano-hybrid
Dielectrics.Min Suk Oh
1
, Yong Hoon Kim
1
, Sung Kyu Park
1
, Jeong In Han
1
, Byoung H. Lee
2
,
Myung M. Sung
2
, Kimoon Lee
3
, Kwang H Lee
3
, Sung Hoon Cha
3
and Seongil Im
3
;
1
Flexible
Display Research Center, Korea Electronics Technology Institute, Seongnam, Korea, South;
2
Department of Chemistry, Hanyang University, Seoul, Korea, South;
3
Institute of Physics and
Applied Physics, Yonsei University, Seoul, Korea, South.

Transparent electronics has been one of the key terminologies forecasting the ubiquitous
technology era. Several researchers have thus extensively developed transparent oxide-based
thin-film transistors (TFTs) on glass and plastic substrates although in general high voltage
operating devices have been mainly studied considering transparent display drivers. However,
low voltage operating oxide TFTs with transparent electrodes are very necessary if we are
aiming at logic circuit applications, for which transparent complementary or one-type channel
inverters are required. The most effective and low power consuming inverter should be a form of
complementary p-channel and n-channel transistors but real application of those complementary
TFT inverters also requires electrical- and even photo-stabilities. Since p-type oxide TFTs have
not been developed yet, we previously adopted organic pentacene TFTs for the p-channel while
ZnO TFTs were chosen for n-channel on sputter-deposited AlOx film. As a result, decent
inverting behavior was achieved but some electrical gate instability was unavoidable at the
ZnO/AlOx channel interface. Here, considering such gate instability issues we have designed a
unique transparent complementary TFT (CTFTs) inverter structure with top n-ZnO channel and
bottom p-pentacene channel based on 12 nm-thin nano-oxide/self assembled monolayer
laminated dielectric, which has a large dielectric strength comparable to that of thin film
amorphous Al2O3. Our transparent CTFT inverter well operate under 3 V, demonstrating a
maximum voltage gain of ~20, good electrical and even photoelectric stabilities. The device
transmittance was over 60 % and this type of transparent inverter has never been reported, to the
best of our limited knowledge.


B5.86
Pentacene- and Anthradithiophene-Containing Conjugated Polymers for Organic
Photovoltaics. Ying Jiang
1
, Toshihiro Okamoto
2,1
, Hector A Becerril
1
, Sanghyun Hong
1
and
Zhenan Bao
1
;
1
Chemical Engineering, Stanford University, Stanford, California;
2
Functional Soft
Matter Eng. Laboratory, The Institute of Physical and Chemical Research (RIKEN), Saitama,
Japan.

Material innovation is a key component of the research towards enhancing organic solar cells
performance. We have taken the new approach of incorporating acenes such as pentacene and
anthradithiophene into conjugated copolymers, based on their superior thin-film transistor
performance. In this work, we extend our research to report two classes of novel acene-
containing polymers. The first class consists of the regioregular 2,9- and 2,10-pentacene-
diethynylbenzene copolymers. The two polymers are observed. to differ in absorption properties
owing to foreseeably different conformations. The second class of materials consisting
anthradithiophene-cyclopentadithiophene copolymers shows excellent film absorption properties
as well as solubility in common organic solvents. High field effect mobilities of up to 10-3
cm2/Vs are measured for anthradithiophene-4,4-bis(2-ethylhexyl)cyclopentadithiophene
deposited in top-contact geometry on a silane treated silicon oxide surface. The material also
achieves a power conversion efficiency of 0.59% in preliminary solar cell devices.


B5.87
Synthesis and Optical properties of Perylene Bisimide Incorporated Low Bandgap
Polymers for Photovoltaics. Sivamurugan Vajiravelu and Valiyaveettil Suresh; Department of
Chemistry, National University of Singapore, Singapore, Singapore.

Synthesis and development of a broad range light absorbing molecules with high extinction
coefficient as suitable metarials to improve the solar cell efficiency is exciting due to the great
demand in energy for our day to day life. Perylene diimide (PDI) derivatives are most attractive
molecule owing to high charge mobility, greater electron affinity and act as good n-type
materials. In this investigation, we focused on the synthesis of alternative donor-acceptor
conjugated systems prepared using Suzuki polymerization of N,N-didodecyl 1,7-
dibromoperylene diimide (PDI) with diboronic acids of flurene and dithiophene respectively.
The polymers were designed to achieve molecular heterojunction through charge transfer from
donor to acceptor. The polymers were characterised using GPC, 1H, 13C NMR and elemental
analysis. TGA and DSC techniques were used to identify thermal stability and phase changes of
the polymers. The absorption spectra of polymers covered whole range of visible absorption
region from 300 to 800 nm in solution and the absorption maximum shifts to higher wavelength
in solid state.


B5.88
Multifunctional Organic Field-effect Transistor Based on Polydiacetylene. Jaehui Ahn, Doo
Ho Yang, Chunzhi Cui, Jihyun Kim and Dong June Ahn; Chemical & Biological Eng., Korea
Univ., Seoul, Korea, South.

Recently, the interest of low cost and reliable organic materials for multifunctional device is
increased. Organic field effect transistors (OFETs) are suitable for multifunctional devices
because of their potential applications. In our research, PCDA based FET was used. Among a lot
of conjugated polymer, the hole mobility of single crystal polydiacetylene is founded to be 1-10
cm2/V*s by time of flight method[1], it is good property as candidate of OFETs material.
Another unique property of PDA is electrical property to be varied as change of PDAs phase (so
called blue and red phase), which can be controllable by UV and external stimuli. We
demonstrated that the single device performed as both UV and gas sensor which shows that
PCDA based FET has potential application in multifunctional device. In this research, we
investigated electrical property of both red phase and blue phase PDA. First, we made thin film
of 10,12-pentacosadiynoic acid (PCDA) by the Langmuir-Blodgett (LB) deposition on SiO2/Si
substrate that has predefined source and drain metal. And then, we performed polymerization to
obtain PDA thin film, followed by thermal treatment to obtain red phase PCDA. Then, we
measured specific contact resistance by the transmission line modeling (TLM) method and the
characterization of Field Effect Transistor. We found that the red phase of PCDA can be
obtained by specific species by the surface modification to increase the selectivity. In our
experiment, the surface of PCDA was modified to have selectivity for NH3 over N2. The details
about the fabrication process and sensing mechanism will be presented.


B5.89
Abstract Withdrawn


B5.90
Doping of Perylene Diimide Derivatives n-type Semiconductor Layer and Interface
Modification for Organic Thin Film Transistor. Heng-Wen Ting and Tri-Rung Yew;
Department of Materials Science and Engineering, Nationl Tsing Hua University, Hsinchu,
Taiwan.

Doping of air-stable solution-processed tetrachloroperylene tetracarboxyldiimide based n-type
semiconductor (TC-PDI-F) layer by dipolar molecules and ionic compounds is demonstrated to
enhance the electrical properties of organic thin film transistors (OTFT). Besides, the interface
modifications between semiconductor and insulator layers by dipolar molecules with phenyl,
alcohol and fluoro-functional groups were applied to improve the molecules packing order and
the electrical performance of doped TC-PDI-F OTFTs. The electronic structures were
characterized by cyclic voltammetry (CV), UV-visible optical absorption spectroscopy (UV-Vis)
and photoluminescence spectroscopy (PL). The surface properties were also inspected by atomic
force microscope (AFM), contact angle system and X-ray diffraction spectroscopy (XRD). The
electrical properties of OTFTs were also measured. All processes were fabricated and measured
in air.


B5.91
Self-Assembled Hydrophobin Protein Membranes on Silicon Platforms Jouni Ahopelto
1
,
Markku Kainlauri
1
, Jani Kivioja
1
, Paivi Laaksonen
2
, Arja Paananen
2
and Markus Linder
2
;
1
Micro
and Nanoelectronics, VTT, Espoo, Finland;
2
Nanobiomaterials, VTT, Espoo, Finland.

We report on formation and characterisation of ordered single layer protein crystals formed by
directed self-assembly on hydrophobic substrates, such as graphite and silicon platforms. The
hydrophobin proteins form an ordered two-dimensional crystal at air-water interface with the
protein molecules all having a well defined orientation and position [1]. From the air-water
interface the crystal membranes are transferred onto surface of highly oriented pyrolytic graphite
or on patterned silicon substrates. The thickness of the membrane is about 3 nm and it has a
hexagonal-like lattice with lattice constant of about 6 nm. On silicon substrates selectivity can be
obtained between hydrophilic oxide and hydrophobic silicon areas, providing means to integrate
protein membranes with silicon microelectronics [2]. By decorating the proteins with Au
nanoparticles, nanoelectrodes for electrical measurements and, on the other hand, plasmonic
devices can be envisaged. The effect of nanoelectrodes, as measured by conducting AFM, can be
seen as largely enhanced conductivity through the protein membrane. Also, on glass slides made
hydrophobic by silanization, clear plasmon band absorption arising from the Au nanoparticles
can be seen. [1] G. Szilvay, A. Paananen, K. Laurikainen, E. Vuorimaa, H. Lemmetyinen, J.
Peltonen, M. Linder, Self-assembled hydrophobin protein films at the air-water interface:
structural analysis and molecular engineering, Biochemistry . Vol. 46 (2007) 2345 - 2354. [2] P.
Laaksonen, J. Kivioja, A. Paananen, M. Kainlauri, K. Kontturi, J. Ahopelto, M. B. Linder,
Selective nanopatterning using citrate stabilized Au nanoparticles and NCysHFBI fusion protein,
submitted 2008.


B5.92
A Self-patterned Polymer Dielectric for Low Voltage Pentacene Thin Film Transistor. Hui-
Chen Huang, Ting-Hsiang Huang and Zingway Pei; Graduate Institute of Optoelectronic
Engineering, Department of Electrical Engineering, National Chung Hsing University, Taichung,
Taiwan.

Organic thin-film transistors (OTFTs) based on pentacene has attract much attention due to low
temperature and low cost fabrication process. Although mobility of pentacene is comparable to
the a-Si:H having potential to replace a-Si:H TFT in display applications, the high driving
voltage is still a problem. Self-assembled monolayer (SAM) or ultra thin film are general
methods used to reduce the operation voltage to about 2~ 5 volts. However, SAM methods
require unique coating technique and the thickness of the ultra thin film is hard to control during
the coating process limit theses method only demonstrated by some very specific group. In this
work, a random copolymer, PS-r-PMMA, is used as dielectric material for a pentacene OTFT.
The PS-r-PMMA dielectric with 10 nm thick can be uniform coated on the surface with hydroxyl
groups in a very simple spin coating process. The PS-r-PMMA is initially coated in roughly 50
nm thick. After thermal annealing, a layer of PS-r-PMMA will connect to the OH- group
forming a 10nm thick layer no matter how thick of the initial layer. Besides the thickness control,
the PS-r-PMMA only coated on the surface having OH- groups, the self-patterning is possible to
prevent the chemical etching process during the organic circuit fabrication. The designed OTFT
is bottom gate and top contact structure. The substrate is glass and gate material is aluminum.
After the deposition of the Al, the UV/ozone process is performed to convert the surface of Al
into Al2O3 having OH- groups. After this, PS-r-PMMA is spin coated and heated sequentially.
Finally, pentacene and gold contact electrodes are deposited sequentially by thermal evaporation
to finish the OTFT. By using this self-patterning thin dielectric, the pentacene OTFT exhibits
operation voltage as low as 5V and an on/off ratio large than 105.


B5.93
Abstract Withdrawn


B5.94
Controlling the Electrical Properties of Molecule-Terminated, Non-Oxidized Silicone by
the C-C Bond Nearby the Surface Sreenivasa R Puniredd
1
, Ilia Platzman
1
and Hossam
Haick
1,2
;
1
Chemical Engineering, Technion- Israel Institute of Technology, Haifa, Israel;
2
Russell Berrie Nanotechnology Institute, Technion- Israel Institute of Technology, Haifa, Israel.

The ability to exert systematic control over the electronic properties of Si is an important factor
for the realization of nanoelectronic devices. Mostly, such controllability can be achieved by
placing molecules, whose dipole can be changed systematically, at the device surface and/or
interface. In this study, we present an approach for controlling the electrical properties of Si by
inducing deliberate interaction between the energy levels of organic molecules and Si, without
the need for a dipole modification. We illustrate this approach by functionalizing 502% of Si
atop sites of n- and p-type Si (111) oxide-free surfaces with various organic molecules having
similar (3C) backbone but different in their C-C bond close to the Si surface (i.e., C-C vs. C=C
vs. CC bonds). These molecules have nearly similar dipole moment (0.9-1.6 Debye). Electrical
characterizations of molecule/Si surfaces and Hg/molecule/Si junctions showed a systematic
control over the work function and Schottky barrier of the Si, respectively, in the range from 0.2
to 0.8 eV, as compared to H-terminated Si. Our results show that the control over the electrical
properties of n- and p-type Si is dominated by systematic electron transfer from the Si surface to
the organic monolayers. The results indicate that the extent of electron transfer depends on the
difference between the energy levels of the organic molecules and the Si surface. This finding,
for which we will present a detailed explanation, has very significant implications as it suggests
the ability to control the electrical properties of semiconductors with minimal depolarization
effects.


B5.95
Ultrathin and Printable Conjugated Films for Organic Electronics. Li Tan, Engineering
Mechanics and Nebraska Center for Materials and Nanoscience, University of Nebraska-Lincoln,
Lincoln, Nebraska.

Ultrathin organic films or self-assembled monolayers (SAMs) can provide molecular or organic
electronics unmatched processing convenience and some knowledge in device operation.
Conventional concepts often come from a head-tail molecular design, where the head carries the
function of charge transport and the tail is capable of self-assembly. Amorphous nature of the
monolayers and rather significant defects along grain boundaries, however, all inhibit their
device performances at high current density and high temperature conditions. Toward this end,
we are investigating a new family of ultrathin organic thin films, i.e., self-organized nanolayers.
This type of molecules enjoys a polymeric backbone, branched with an extended pi-pi system.
Rather rigid branches, plus the chain-chain cooperation allow the polymer form long-range
ordered lamellae in solution. Printed films have a super dense, multistack morphology over tens
of microns. Unprecedented thermal stability is also realized due to an enhanced molecular
interaction between the pi-pi units, plus a strong interlayer binding between the layers. Research
efforts with scientific and engineering importance are worth of reporting, including 1) strategy of
the molecular design and synthesis; 2) film casting and characterizations; and 3) molecular
modeling to interpret the structuring mechanism of the nanolayers. Merits of well-ordered
packing, plus easiness to chemically functionalize these nanolayers, all promise great
applications in molecular or organic electronics.


B5.96
Probing Nanoscale Electric Field Fluctuations: Towards a Local Measurement of Carrier
Mobility in Organic Semiconductors. Showkat Yazdanian
1
, Seppe Kuehn
2
, Nikolas Hoepker
1
,
Roger Loring
1
and John Marohn
1
;
1
Cornell University, Ithaca, New York;
2
Rockefeller
University, New York, New York.

A rich array of dynamic physical processes can be modelled as fluctuating electric fields. These
processes include electron transfer, enzyme kinetics, ionic motion in solution and the glass
transition. We have shown that cantilever friction can be used to study dielectric fluctuations in
the vicinity of the cantilever resonance frequency. Here we show that cantilever frequency
fluctuations (jitter) can be used to probe low frequency dielectric fluctuations over a much
broader frequency window. We present measurements of dielectric fluctuations in polymers in
tandem with a theory predicting the shape and magnitude of the effect. We also present our
progress towards employing this technique to measure the local carrier mobility in organic
semiconductor systems.


B5.97
Porphyrins and N-confused Porphyrins as Spectral Dopants in Organic Solar Cells.
Warwick J Belcher, Nathan Cooling and Paul Christopher Dastoor; Physics, University of
Newcastle, Callaghan, New South Wales, Australia.

Organic photovoltaic cells show immense promise as a new alternative for renewable energy.
However, one major problem with these devices is that the polymers typically employed in their
design absorb light in only a limited part of the solar spectrum (usually <600nm). One way to
further extend the spectral response of these devices is via the addition of complimentary
chromophores. It has been shown that the absorption of light by the Q-bands of porphyrins
incorporated into MEH-PPV/PCBM blends contributes up to 20% of the total photocurrent
generated by the device by utilising light that would not normally be absorbed [1]. Furthermore,
N-confused porphyrins could be used to extend the absorption spectra of these devices even
further, since they have Q-band absorptions extending well beyond the range of a standard
porphyrin. Despite this promise porphyrin aggregation within these ternary devices has been
observed to lead to disruption of the crucial morphology of the active layer and lowered device
efficiency. Porphyrin aggregation can be controlled by controlling the steric bulk of peripheral
substituents on the porphyrin. A series of substituted tetraphenylporphyrins and N-confused
tertraphenylporphyrins have been prepared in which the steric bulk of the peripheral substituents,
and thus the degree to which aggregation occurs, was varied. These materials have been used to
prepare a series of MEH-PPV/Porphyrin/PCBM and PPV/N-confused Porphyrin/PCBM ternary
organic photovoltaic devices. Furthermore, we have observed that the porphyrin molecules act as
hole traps within the devices due to the basicity of the pyrollic nitrogens, lowering device
efficiency. Reduction of this basicity has been achieved by metallation and alkylation of these
sites. The effect that these structural changes have on device performance will be presented.
References [1] P.C. Dastoor, C. R. McNeill. H. Frohne, C, J, Foster, B. Dean, C.J. Fell, W. J.
Belcher, W. M. Campbell, D.L. Officer, I. M. Blake, P. Thordarson, M.J. Crossley, N.S. Hush,
R. Jeffrey, J. Phys. Chem. 111(42) (2007), 15415-15426.


B5.98
Near Infrared Fluorescent and Phosphorescent Organic Light-Emitting Devices. Yixing
Yang
1
, Richard T Farley
2
, Timothy T Steckler
2
, Jonathan Sommer
2
, Sang-Hyun Eom
1
, John R
Reynolds
2
, Kirk S Schanze
2
and Jiangeng Xue
1
;
1
Department of Materials Science and
Engineering, University of Florida, Gainesville, Florida;
2
Department of Chemistry, Center for
Macromolecular Science and Engineering, University of Florida, Gainesville, Florida.

There has been a growing interest in the development of near-infrared (NIR) organic light-
emitting devices (OLEDs) due to their potential applications in defense, biomedical sectors, and
telecommunications. For example, NIR OLEDs can be used as illumination and signaling
sources for night vision and friend-foe identification, and have advantages in light weight, low
thermal signature, low power consumption, and compatibility with large area and flexible
substrates. Existing NIR OLEDs have been mostly based on lanthanide-based organometallic
complexes, which generally have low external quantum efficiencies (EQE) (<0.1%). Only
recently were high efficiency NIR OLEDs reported, in which peak emission at 770 nm and a
maximum EQE up to 8.5% were achieved using a phosphorescent Pt-porphyrin complex.
1

Nonetheless, alternative materials and devices that exhibit longer emission wavelengths (>800
nm) with high efficiencies are still needed. Here we report fluorescent and phosphorescent NIR
OLEDs with peak emission wavelengths up to 892 nm and EQE up to 3.8%. First, OLEDs based
on two NIR-emitting fluorescent donor-acceptor-donor (DAD) oligomers, BEDOT-TQMe
2
and
BEDOT-BBT, are demonstrated. In these molecules, the energies of the highest occupied and
lowest unoccupied molecular orbitals are controlled by the donor and the acceptor portion,
respectively. A maximum EQE of
EQE
= 1.6% and a maximum power efficiency of
P
= 7.0
mW/W are achieved in devices based on BEDOT-TQMe
2
, with the electroluminescence (EL)
peaked at 692 nm but extending to well above 800 nm. BEDOT-BBT based OLEDs show red-
shifted emission peaking at 815 nm (and extending to as far as 950 nm), although the maximum
efficiencies were reduced to
EQE
= 0.51% and
P
= 2.1 mW/W due to the significantly lower
fluorescent quantum yield of the NIR emitter. The efficiencies of these fluorescent OLEDs were
further increased by two to three times by incorporating a phosphorescent sensitizer in the
emissive layer to funnel the triplet excitons formed on the host molecules to the fluorescent
emitters, which are not utilized in fluorescent devices. Using this sensitized fluorescence
structure, we achieved maximum efficiencies of
EQE
= 3.1% and
P
= 12 mW/W for BEDOT-
TQMe
2
based devices, and
EQE
= 1.5% and
P
= 4.0 mW/W for BEDOT-BBT based devices.
Finally, a phosphorescent NIR emitter, platinum tetraphenyltetranaphtho[2,3]porphyrin (Pt-
TPTNP), was synthesized. The more extended conjugation on this molecule compared to the Pt-
porphyrin complex used in Ref. 1 leads to a red shift in the emissive wavelength by more than
100 nm. In the Pt-TPTNP-based OLEDs, we obtain peak emission at 892 nm, and maximum
efficiencies of
EQE
= 3.8% and
P
= 19 mW/W, much higher than those of the sensitized
fluorescence OLEDs based on DAD oligomers.
1
Y. Sun et al., Appl. Phys. Lett. 90, 213503
(2007)


B5.99
Non-Volatile Molecular Monolayer Memory. Sangkwan Kim
1,2
, Hojong Chang
1,2
, Junghyun
Lee
1
, Gyeong Sook Bang
1
and Hyoyoung Lee
1
;
1
Center for Smart Molecular Memory,
Electronics and Telecommunications Research Institute(ETRI), Deajeon, Korea, South;
2
Next
Generation Device Engineering, University of Science and Technology, Deajeon, Korea, South.

Molecular monolayer memory is considered to be one of the best solutions to the scaling limit
problem in the silicon industry. Organic self-assembled monolayers (SAMs) as active memory
elements in electronic devices are capable of highly integrated density in metal-molecule-metal
(MMM) types of devices. Newly designed dialkylthiolate-tethered metal complex SAMs
(RuII(tpy(CH2)nS)2) are introduced. These SAMs using a conducting polymer, PEDOT:PSS, as
a soft part of top electrode provide a stable and reproducible molecular monolayer memory
device that shows hysteretic I-V characteristics, write-multiple read-erase-multiple read pulse
cycles and good retention time. As alkyl chain lengths of metal complexes increase from 7 to 13,
molecular monolayer device yield improves up to 81% at a micro-scale well and simultaneously
its retention time increases from 200 to 390 seconds. The non-volatile molecular monolayer
memory is non-destructive for more than 300 write-multiple read-erase-multiple read cycles. A
conduction mechanism is direct tunneling with little temperature dependence


B5.100
Light Absorption and Charge Generation in Polymer-Fullerene Organic Photovoltaic
Devices. Paul Christopher Dastoor, Centre for Organic Electronics, University of Newcastle,
Callaghan, New South Wales, Australia.

Solar cells based on semiconducting polymer blends offer great potential for the development of
low-cost printable photovoltaic arrays. Organic photovoltaic (OPV) devices fabricated from
polymer-fullerene blends are of particular interest since they provide the greatest power
conversion efficiency. The conventional view of device operation is that the light photons are
absorbed primarily by the polymer component resulting in the generation of excitons that in turn
are separated at the many polymer-fullerene interfaces that are formed during the spin-coating of
these blended materials. The main role of the fullerene component is to provide the percolation
network for charge conduction [1-3]. In this paper we show that for some polymer-fullerene
blends this traditional paradigm of device operation needs to be reconsidered. We demonstrate
that ternary blends incorporating porphyrins can be fabricated with less than 10% polymer
composition and yet still exhibit full device functionality. By analysing the proportion of light
absorbed by each individual component it can be shown that the majority of the light is absorbed
by the fullerene component with over 50% of the photocurrent produced under AM 1.5
conditions occurring subsequent to C60-fullerene absorption [4]. New multi-wavelength near-
field scanning photocurrent microscopy studies show distinct differences in the distribution of
light absorbed by these devices at different wavelengths. These results provide for a consistent
understanding of the origin of primary charge separation in general polymer/C60-fullerene
blends.


B5.101
Nano-structured ITO Electrode Applied in Polymer Solar Cell Ming-Shin Su
1
, Kung-Hwa
Wei
1
, Chia-Hua Chang
2
and Prichen Yu
2
;
1
Department of Material Science and Engineering,
National Chiao Tung University, Hsinchu, Taiwan;
2
Institute of Electro-Optical Engineering,
National Chiao Tung University, Hsinchu, Taiwan.

Organic photovoltaic has become an emerging research subject recently because of their easy
and low-cost fabrication process as compared to their counter parts such as silicon or compound
semiconductor solar cells. In particular, bulk hetero-junction (BHJ) polymer solar cells that
typically consist of an active layer of about 100nm-thick film blends constituted by P-type
conjugated polymers and N-type fullerene derivatives sandwiched between two electrodes
appear to attract large attentions since they can provide large surface area with limited amount of
effort. Since the power conversion efficiency (PCE) of BHJ polymer solar cells still remains an
area where improvements are greatly needed. Many researchers have tried to optimize the
interface structures of these polymer solar cells by modifying the work function of the electrodes
or adopting other transparent metal oxides as electrode, for enhancing the PCE. Nanotechnology
has provided many researchers a new way to achieving this goal by applying nano-structure to
enhance the performance of these cells. In the present study, we would like to use a nano-
structured ITO electrode to enhance internal reflection of the incident light as well as to facilitate
the charge transport in the devices In this paper, we report the performance of polymer solar cell
devices that used the ITO electrodes with nanorods structures produced by an oblique-
evaporation deposition method. These ITO nanorods have a uniform shape with diameter
ranging from 120nm to 160nm and the inter-rod spacing between them is about 150nm to
300nm. The structures of the polymer solar cell device are composed of ITO glass substrate with
or without ITO nanorods, PEDOT:PSS, P3HT/PC61BM, and top Al electrode. The PCE of the
devices with ITO nanorods on the ITO electrode is about 3.3% under AM1.5G (100mW/cm2)
standard testing condition, as compared to 3% for the devices without ITO nanorods.
Additionally, we measured these two types of devices under 5 suns (500mW/cm2) incident light
intensity condition. The PCE of the devices with ITO nanorods reached about 4% as compared to
3.3% for the ones without ITO nanorods under 5 suns condition. Then, we make lifetime
measurement under 5 suns condition and all the tested devices are maintained at the short circuit
state under illumination. It takes almost 110 minutes to decay to 80% of their original PCE value
for the devices with ITO nanorods, whereas the ones without ITO nanorods takes 55 minutes to
decay to the same extent. The ITO glass substrate with ITO nanorod is a proper choice to
enhance polymer solar cell PCE. Polymer solar cell containing substrate with ITO nanorod has
better lifetime and the electrode with nano structure can sustain such high photo current
generation or high incident light intensity with lower degradation rate. The two benefits imply
that the polymer solar cell with ITO nanorod electrode has the potential to be developed into a
concentrator type for polymer solar cells.


B5.102
Electrochemical Characterization of Tyrosinase Nanoparticles Protected by Organic-
inorganic Network in Nano-biosensor. Woo Jin Lee, Dong-Hwa Yun, Jun-Hyoung Chang,
Keum-Ju Lee and Suk-In Hong; Biochemical engineering, Korea University, Seoul, Korea,
South.

Semiconductor techologies have become essential in various field of biosensors and bio-
microelectromechaniical systems. They provide miniaturization and mass production of silicon-
based sensors. However, the smaller the area of sensing electrode, the more and more problems,
i.g., depreciation of the whole performances including low sensitivity and stability,
embarrassment of enzyme or any kinds of bio-molecular immobilization occur. Tyrosinase also
known as polyphenol oxidase(PPO), is a copper containing enzyme. Nowdays mushroom
tyrosinase has become important because it is readily available and useful in a number of
applications which environment, food industry, and medical science. Therefore, many research
groups have developed tyrosinase enzzyme. Tyrosinase has a pair of copper ions with six
conserved histidine residues in the active site. But Tyrosinase stability has a connected with of
oxidation of cooper ions in the air. To overcome this problem, we approach to improve the
enzyme stability in various nanostructures such as nanoparticles, mesoporous materials and
single enzyme nanoparticles. In this works, tyrosinase nanoparticles surrounded by a polymeric
organic-inorganic network resulting in stabilization of enzyme activity. They were observed by
transmission electron microscope (TEM) and analyzed electrochemical properties using cycle
voltametry(CV) by VMP40 Multi-potentiostat.


B5.103
The Newly Designed p-type Polymer Containing alkyl-substituted Thiophene for Organic
Thin Film Transistors (OTFTs) Pengtao Kang
1
, JongWon Park
1
, SungJin Park
1
, JinUk Ju
1
,
Yunhi Kim
2
, DaeSung Jung
3
, ChanEon Park
3
and SoonKi Kwon
1
;
1
School of Nano & Advanced
Materials Science and Engineering and ERI, Gyeongsang National University, Jinju, Korea,
South;
2
Department of Chmistry, Gyeongsang National University, Jinju, Korea, South;
3
Department of Chmical Engineering, Pohang University of Science and Technology, Pohang,
Korea, South.

A new p-type polymer was synthesized by the oxidation coupling reaction. The monomers were
prepared with highly overall yields and the obtained polymer is confirmed by elemental analysis,
1H NMR, 13C NMR, FT-IR, UV absorption, photoluminescence (PL), and cyclic voltammetry
(CV). The polymer is having alkyl-substituted thiophene and we are expected to have a high
solubility by introducing the long alkyl-chain. Furthermore, the introduction of the alkyl chain
can increase the degree of orderness by self-assembly. The thermal property of polymer was
confirmed by using the thermogravimetric analysis (TGA) and differential scanning calorimetry
(DSC). The polymer was showed 5% weight losing temperature at 438 oC and the curve of alkyl
chain was showed around 80 oC. The number-, weight-average molecular weight of the
polymers were determined to be 10,820 and 15,663 gel permeation chromatography (GPC) using
polystyrene standards for calibration in the eluent THF. The solubility of the polymer was
showed a poor solubility in common solvents, such as chloroform, tetrahydrofuran (THF),
toluene. On the other hand, the polymer was showed a good solubility in chlorobenzene at room
temperature with 0.7 wt%.


B5.104
Formation of Nanopatterned Polymer Blends in Photovoltaic Devices. Ximin He
1,2
, David
Hasko
3
, Ullrich Steiner
3
, Richard Friend
3
, Sven Hunter
3
and Wilhelm Huck
1,2
;
1
Chemistry,
University of Cambridge, Cambridge, Canbridgeshire, United Kingdom;
2
The Nanoscience
Centre, University of Cambridge, Cambridge, United Kingdom;
3
Physics, University of
Cambridge, Cambridge, United Kingdom.

The ideal structure for polymer photovoltaic (PV) devices has been believed so far as an
interpenetrating nanoscale columnar architecture that maximizes the interface between electron
and hole transporting polymers, and thereby greatly improves exciton dissociation. Despite
attempts at achieving such structures via block copolymers, inorganic templates, columnar liquid
crystalline phases, no such structures have been achieved in efficient devices at the level of
practical applications. Instead, the best polymer photovoltaic devices, based on P3HT:PCBM,
rely on a complicated procedure of spincoating from the most suitable solvents and thermal or
solvent annealing steps to improve the nanoscale morphology and thereby the blend
performance. Here, we have developed a double nanoimprinting (NIL) process that allows the
formation of nanostructured polymer blends of any composition and morphology and
demonstrated how it approached the ideal polymer film architecture for PV devices. It has been
conceived that we could use a pre-patterned polymer film to imprint another polymer film
through NIL, with feature size down to 20 nm. The new and simple approach, which only
employ solution spin coating of polymer film and NIL, was basically established by successfully
obtaining very uniform and precise patterns, in quite complete large area, inside of a variety of
polymer blends, ranging from conventional and semiconductor polymers to organic-polymer
blend, as a photoactive layer in PV cell, including PS/PEO, PMMA/PEO, PVP/PS,
F8BT/PMMA and P3HT/PCBM. Evidenced by morphology studies through AFM and SEM, this
approach is able to create integrated polymer layer with controllably varied and precisely defined
interdigitated interface nano-geometric structures inside, which is the ideal structure of high-
efficiency PV cells, so called well-ordered bulk heterojunctions, benefiting high intersurface area
and straight carrier transport pathway. Conjugated polymer-based PV cells with both 1D and 2D
nanostructured donor-acceptor interface of well-ordered densely packed 20~200-nm-wide lines
and 25~200-nm-wide dots were fabricated by employing this double-NIL approach. Cell devices
performance enhancement was found in the nanostructured one over the conventional flat-
interface double-layer one, which was believed to result from well-ordered vertically oriented
heterojunction with precisely defined interdigitated nanostructured interface of electron donor
and acceptor components, which facilitated charge transport as well as charge separation,
ordering of conjugated polymer. Systematic study showed PV performance improved as domain
size decreased and interface area increased, especially pronouncedly with domain sizes closer to
carrier diffusion length, convincing the interdigitated structure as ideal polymer PV
configuration. This technique of producing nanostructured polymer or organic blends are
expected to be applied into more other device fabrications in the future.


B5.105
Numerical Modeling for Optical Property and Charge Transport in Bulk Heterojunction
Organic Solar Cells. Young Min Nam
1
, June Huh
2
and Won Ho Jo
1
;
1
Materials Science and
Engineering, Seoul National University, Seoul, Korea, South;
2
Active Polymer Center for Pattern
Integration, Yonsei University, Seoul, Korea, South.

Organic photovoltaic cells based on bulk heterojunction concept has been a promising alternative
for conventional silicon-based solar cells, mainly due to their potential for low cost, ease of
fabrication, and mechanical flexibility. However, the power conversion efficiencies of such
devices remain too low for commercialization, and thus a number of researchers have devoted to
improve the efficiency. Despite growing research efforts, the fundamental processes governing
the performance of organic photovoltaic cells are still poorly understood and therefore a
theoretical model, which deals with a whole process of optical-to-electric energy conversion, is
highly demanded. Such a model should take into account not only dynamic characteristics of
exciton and electron/hole transfer in the active layer but also optical interference between layers
of organic solar cell so as to cover the overall conversion process in the multilayered structure of
solar cell device. In this study, a device model accounting for the effect of morphology of active
layer as well as the effect of layer configuration of multilayer-structured device is established to
predict the current-voltage characteristics of polymer/fullerene bulk heterojunction solar cells.
The model morphologies of active layers were generated by using Cahn-Hilliard-Cook diffusion
dynamics which models the dynamics of phase separation between polymers and fullerenes,
varying the thickness of active layer, characteristic dimension of phase-separated morphology,
and long range order of phase-separated domains. The steady-state behavior of electron, hole and
exciton concentrations in phase-separated morphology is captured by the drift-diffusion model
for the generated morphologies of active layer, while the optical transfer matrix theory is used
for optical carrier generation to consider the effects of active layer thickness and layer
configuration on the light absorption efficiency in the active layer which ultimately affects the
power conversion efficiency of solar cells. The model was validated by comparing the simulation
results with the experimental data, such as J-V characteristics of solar cell and the thickness of
each layer. Simulation results show that the power conversion efficiencies of solar cells with
ideal active layer morphology are much higher than those of solar cells with randomly oriented
active layer morphology. Furthermore, the performance of solar cells with randomly oriented
active layer morphology changes dramatically with variation of the characteristic dimension of
phase-separated morphology, while the performance of solar cells with oriented active layer
morphology is less dependent to the characteristic dimension of phase-separated morphology. It
is also found that the optimum thickness of active layer with oriented morphology is much larger
than the optimum thickness of active layer with randomly oriented morphology.


B5.106
Abstract Withdrawn


B5.107
Effect of the Surface Characteristics of TCO Thin Films on the Performance of OLED
Devices.Yu Lim Lee and Kyu-Mann Lee; Materials Engineering, Korea University of
Technology and Education, Cheonan-city, Chungnam, Korea, South.

OLED device is one of the most attractive and alternative display components, which stems
primarily from the self-emission, large intrinsic viewing angle, and fast switching speed.
However, because of its relatively short history of development, much remains to be studied in
terms of its basic device physics, manufacturing processes, and reliability etc. Especially among
several issues, it should be noted that the device characteristics are very sensitive to the surface
properties of transparent conducting oxide (TCO) electrode materials. Sn-doped In2O3 (ITO)
thin films have been extensively studied for OLED devices because of transparency, high electric
conductivity, and large work function. However, indium has some problems such as rare raw
material, high cost, low stability in plasma, and toxicity. On the other hand, Al-doped ZnO
(AZO) thin films have a lot of advantages, such as low cost, good stability in plasma, non-
toxicity, optical transparency, and good electrical conductivity. As a result, AZO thin films are
actively studied as an alternative candidate for ITO substrates. In this study, we have investigated
the performance of OLED devices as a function of sheet resistance and surface roughness of
TCO thin films. For this purpose, ITO and AZO thin films were deposited by r. f. magnetron
sputtering under various ambient gases (Ar, Ar+O2 and Ar+H2, respectively). The micro-
structural observation and crystal orientation of the TCO thin films were evaluated using X-ray
diffraction and FESEM (field emission scanning electron microscope), respectively. The optical
transmittance and the film thickness were measured using ultraviolet spectrophotometer (Varian,
cary-500) and surface profile measurement system, respectively. The electrical properties such as
sheet resistance, charge carrier concentration, and mobility of TCO films were measured using
four point probe system and hall effect measurement (HMS-3000), respectively. In order to
control the surface roughness of TCO films, we have proceeded with photo-lithography and
reactive ion etching processes. The micro-size patterned mask was used and the etching depth
was regulated by changing etching time. The surface morphology of the TCO films was
observed by FESEM and atomic force microscopy (AFM). And then, organic materials and
cathode electrode were sequentially deposited on the TCO thin films. Device structure was
TCO/-NPD/DPVB/Alq3/LiF/Al. The DPVB was used as a blue emitting material. The
electrical characteristics such as current density vs. voltage and luminescence vs. voltage of
OLED devices were evaluated by using spectrometer (minolta CS-1000A).


B5.108
Substrate Effect on Energy Level Alignment at the CuPc-C60 Interface in Organic Solar
Cells.Zengtao Liu, City University of Hong Kong, Hong Kong, China.

The interface energy level alignment between copper phthalocyanine (CuPC) and fullerene
(C60) on indium-tin oxide (ITO) and Mg substrate was investigated. The CuPC/C60 interface
deposited on ITO shows a nearly common vacuum level, but a dipole and band-bending exist,
resulting in a 0.8 eV band offset at the same interface on Mg. Significantly, this observation
indicates that the energy difference between the highest occupied molecular orbital of CuPC and
the lowest unoccupied molecular orbital of C60, which dictates the open circuit voltage of the
CuPC/C60 OPV, can be tuned by the work function of the substrate. Furthermore, the substrate
effect on the energy alignment at the donor/acceptor interface can satisfactorily explain that a
device with an anode of a smaller work function would provide a higher open circuit voltage.


B5.109
New Multi-branched -conjugated Molecules bearing Benzothiadiazole-based Peripheral
Moieties and Their Electrical Properties Ki Won Lee
1
, Dae Cheol Kim
1
, Tae Wan Lee
1
,
Kyung Hwan Kim
1
, Min Ju Cho
1
, Dong Hoon Choi
1
and Jae-Woong Yu
2
;
1
chemistry, Korea
University, Seoul, Korea, South;
2
Korea Institute of Science and Technology, Seoul, Korea,
South.

Photovoltaic cells based on polymer semiconductors are of great interest as a low cost approach
to solar energy conversion. Although numerous polymers have to date been explored as the
donor in polymers / fullerene bulk heterojunction solar cells, not many new functional materials
were demonstrated for the efficient photovoltaic devices. For the development of ideal donor
material, -conjugated small molecules, dendrimers, oligomers, and polymers were employed
because of their strong potential applications to electronics and optoelectronics. We recently
reported the facile synthesis of new p-type multi-branched semiconducting molecules and their
organic photovoltaic cells applications including the device performance of organic thin film
transistors. For this presentation, new conjugated crystalline multi-branched molecules bearing
benzothiadiazole-based peripheral moieties have been synthesized through various cross-
coupling reactions. A good correlation between theoretical calculations performed on model
compounds and the experimental HOMO, LUMO, and band gap energies of the serial materials
has been obtained. These materials was characterized by UV-visible spectroscopy,
photoluminescence spectroscopy, cyclic voltammetry, thermogravimetric analysis and
differential scanning calorimetry. They also display a p-type semiconducting behavior and their
electrical properties are investigated in detail. We investigated the performance of bulk
heterojunction type photovoltaic device and capability of molecular heterojunction or
supramolecule through self-association in solution or in the bulk.


B5.110
Numerical Study for the Morphological Effect on the Performance of Organic Solar
Cells.Sungjun Kong and Dongchoul Kim; Mechanical Engineering, Sogang University, Seoul,
Korea, South.

The conversion of solar energy into electricity indicates the route to reduce the concern over
global warming and satisfy our global energy needs. Polymer solar cells have potential to be
alternative to silicon-based solar cells which are impractically expensive. To improve the
performance of polymer solar cells, significant efforts have been made to decrease energy loss
from the internal morphology in a bilayer system. Here, we present a three-dimensional model to
study the effect of device morphologies on photovoltaic performance. The diffuse interface
model is employed and incorporates photovoltaic mechanism. The semi-implicit Fourier spectral
method and preconditioned biconjugate-gradient method are applied for high efficiency and
numerical stability. The simulations demonstrate the improved performance of the organic solar
cells with designed morphologies.


B5.111
Conjugated Polymers Based on Pyridazine and Benzothiadiazole for Photovoltaic
Applications.Sangwon Ko
1
, Rajib Mondal
2
, Sanghyun Hong
2
, Hector A Becerril
2
and Zhenan
Bao
2
;
1
Chemistry, Stanford University, Stanford, California;
2
Chemical Engineering, Stanford
University, Stanford, California.

A new class of conjugated copolymers based on pyridazine and benzothiadiazole was designed
and synthesized for application in polymer solar cells (PSCs). The absorption spectra,
electrochemical, field effect carrier mobility, and photovoltaic properties of these polymers were
investigated. The broad absorptions (300-600 nm), and low band gaps (~ 2.0 eV), and high hole
mobility of the polymers make them promising for solar cell application. The changing
copolymerization units leaded further red-shifted (max) broadening of the wavelengths at which
high photoconversion efficiencies can be achieved. The results indicate that the polymers
consisting of further improved the absorption properties are promising polymer photovoltaic
materials.


B5.113
Predicting the Efficiency of Organic Photovoltaics Based on Optical Properties. Katherine
E. Hurst, Nathan A Tomlin and John H Lehman; National Institute of Standards and Technology,
Boulder, Colorado.

Improving the quantum efficiency of organic photovoltaics is a requirement for large-scale
commercial use. It has been established that doping of conjugated-polymer films with single
walled carbon nanotubes (SWCNTs) facilitates exciton dissociation and electron transport.
Accurate measurement of important intrinsic device properties such as absorbance with respect
to film thickness and SWCNT concentration is necessary for informing our expectations for
extrinsic photovoltaic efficiency. This is also the basis for modeling the role of the photoactive
layer and maximizing the efficiency of the device. In this work, we explicitly measured the
absolute absorbance of photoactive films by depositing them on a pyroelectric detector and
modeled the optical function of the doped films based on Kramers-Kronig analysis. Raman
spectroscopy, UV-VIS absorption and four-point probe measurements provide further
characterization of nanotube concentration and homogeneity of our films. Our study provides
direct quantitative measurements traceable to NIST standards, which demonstrates variations in
the intrinsic efficiency of the photoactive layer directly correlate to the extrinsic efficiency of the
SWCNT-polymer photovoltaics.


B5.114
Abstract Withdrawn


B5.115
N-type Semiconducting Organic Materials for High-Performance and Air-Stable Organic
Field-Effect Transistors and Circuits. Yoonyoung Chung
1
, Joon Hak Oh
2
, Boris Murmann
1

and Zhenan Bao
2
;
1
Electrical Engineering, Stanford University, Stanford, California;
2
Chemical
Engineering, Stanford University, Stanford, California.

Unlike inorganic electronic devices which have higher electron mobility than hole mobility,
organic electronic devices show superior performance in p-type where holes dominate the
current. Although p-type organic field-effect transistors (OFET) have been widely investigated,
air-stable and high-performance n-type OFETs have been less developed. A major drawback of
n-type materials is the existence of oxygen and water molecule which have high electron affinity.
Considering many advantages of complementary circuit design, there is no doubt about the
necessity of fast and reliable n-type OFETs. We report the fabrication of simple electronic
circuits, such as inverters and ring oscillators, using high performance air-stable n-type OFETs,
based on Perylene Diimides (PTCDI) derivatives and Naphthalene Diimides (NTCDI)
derivatives, together with p-type pentacene OFETs. Their electrical characteristics such as bias-
stress effect and air-stability have also been investigated. The field-effect mobility of the n-type
OFETs was close to 1 cm
2
/Vs in air.


B5.116
A Crystalline Dielectric Surface-modification Layer for High Performance Organic Thin-
film Transistors. Ajay Virkar
1
, Stefan Mannsfeld
1
, Yutaka Ito
1
, Michael Toney
2
and Zhenan
Bao
1
;
1
Stanford University, Stanford, California;
2
Stanford Synchrotron Radiation Lab, Menlo
Park, California.

In organic thin film transistors (OTFTs),the vast majority of the current flows within the first few
monolayers of the semiconductor at the dielectric interface. To improve performance it is very
common to modify the SiO2 dielectric with an octadecylsilane (OTS) monolayer. We found that
the phase (order) of the underlying OTS is a critical device parameter which must be controlled
in order to optimize OTFTs. We found a crystalline, dense octadecylsilane (OTS) surface
modification layer promotes two-dimensional growth in a variety of organic semiconductors.
Higher mobility is achieved for OTFTs with a crystalline OTS layer compared to a disordered
one, with mobilities as high as 5.3 cm2/Vs and 2.2 cm2/Vs for C60 and pentacene, respectively.
Moreover, we developed a simple, scalable spin-coating method to produce crystalline OTS.
This work demonstrates a significant step towards a general approach for morphological control
of organic semiconductors which is directly linked to their performance in OTFTs. Finally,
nucleation and thin film growth of semiconductors on the different OTS surfaces will be
discussed with particular attention to the relevant energetics which must be considered to design
ideal dielectric surfaces.


B5.117
Energetics and Stability of Pentacene Thin Films on Methyl Terminated Surfaces Ajay
Virkar, Stefan Manssfeld and Zhenan Bao; Stanford University, Stanford, California.

Increasingly there has been interest in analyzing the nucleation, growth, and morphology of
pentacene thin films on methyl terminated surfaces. We recently discovered that pentacene has a
high nucleation density and a 2D growth mode on dense methyl terminated surfaces compared to
loosely packed methyl surfaces. The desired 2D growth gave rise to much better performance
pentacene transistors. In this work we discuss the relevant energetics of pentacene nucleation and
thin film growth on methyl surfaces. We also demonstrate how to design the dielectric surface so
that pentacene thin films are stable. These findings are important for monolayer transistors and
ultrathin organic transistor based sensors.


B5.118
Three-dimensional Anisotropic Electronic Properties of Solution Grown Organic Single
Crystals Measured by Space-Charge Limited Current (SCLC). Beatrice Fraboni
1
, Fabio
Brigidi
1
, Anna Cavallini
1
and Alessandro Fraleoni-Morgera
2
;
1
Physics, University of Bologna,
Bologna, Italy;
2
Sincrotrone ScpA, Trieste, Italy.

Charge transport processes in organic materials are highly sensitive to the material deposition
and device fabrication conditions that, in turn, affect to a major extent the molecular packing and
interface defective states. In order to correlate the electrical properties of organic semiconductors
to their molecular functionality, it is necessary to control the effects of impurity and disorder
induced defects. It is has been shown that organic single crystals offer the possibility of studying
the intrinsic properties of organic molecules thanks to their high purity and molecular order, and
single crystal field effect transistors (SCFET) are a powerful tool in this respect. The observation
of anisotropic transport in single crystals, due to the anisotropic packing of the organic
molecules, provides an assessment of the occurrence of band-like transport processes.We studied
the three-dimensional anisotropic charge transport properties of solution-grown organic single
crystals based on a dipolar molecule 4HCB (4-hydroxy-cyanobenzene) by Space Charge Limited
Current (SCLC), by spectral photocurrent (PC) and by X-ray diffraction analyses. Most reports
on organic single crystals deal with crystals grown by vacuum deposition methods, while only a
few are available on high quality single crystals obtained by growth from solution [1,2]. We have
measured the charge carrier mobility along the three crystallographic axes of single crystals by
SCLC analyses obtaining highly reproducible and markedly anisotropic values (i.e. 5x10-2
cm2/Vs for the main axis a, 3x10-3 for the axis b and 3x10-6 cm2/Vs for the axis c, along the
crystal thickness). These results fully confirm values we have previously obtained by measuring
the carrier mobility using FET devices [2]. In addition, a modelization of the obtained data
allowed to evaluate the concentration and activation energy of the dominant deep traps along
each crystallographic direction. We observed how the exposure to visible light induced a
different effect on the transport properties along the two directions, that we have attributed to the
presence and alignment of the electron-attractor cyano group. We suggest that the presence of an
intrinsic molecular dipole differently affects the flow of charge carriers along the two main
planar crystal axes, thus altering the charge transport anisotropy induced by the molecular -
orbitals stacking. A band of electrically active deep traps was identified by PC analyses and we
suggest that this lattice structure may be ascribed to the intrinsic 4HCB molecular electric dipole
that may originate trapping centers that behave like deep donors and that are more efficient along
one of the two main planar axes. [1] S. C. B. Mannsfeld, J. Locklin, C. Reese, M. E. Roberts, A.
J. Lovinger, Z. Bao, Adv. Funct. Mater., 17, 1617 (2007) [2] B. Fraboni, R. DiPietro, A.
Castaldini, A. Cavallini, A. Fraleoni-Morgera, L. Setti, I. Mencarelli, C. Femoni, Organic
Electronics, 9, 974 (2008)


B5.119
Photocurrent Studies of Sexythiophene-based OFETs. Beatrice Fraboni
1
, Riccardo DiPietro
1
,
Anna Cavallini
1
, Piero Cosseddu
2
, Annalisa Bonfiglio
2
, Jorg Vogel
3
and Jurgen Rabe
3
;
1
Physics,
University of Bologna, Bologna, Italy;
2
Electrcal Engineering, University of Cagliari, Cagliari,
Italy;
3
Physics, Humboldt University, Berlin, Germany.

Photocurrent (PC) spectroscopy is proposed as a reliable tool in the investigation of the transport
properties of organic thin film transistors (OFETs). We have applied PC analyses to the study of
the electronic density of states distribution (DOS) of the OFETs with crystalline mixed films of
two derivatives of a conjugated molecule [-sexithiophene (6T), and its alkylated analogue ,-
dihexylsexithiophene (DH6T)] as the active semiconductor. The charge carrier mobility in
organic semiconducting materials depends on the effective charge carrier density, which can be
modulated, e.g., by gate voltage induced charge in a transistor geometry. We investigated the
modifications in the DOS distribution associated to variations in the carrier density in the OFET
channel and we detected the formation of deep electrically active states in the below-band-gap
region, associated to polaron states induced by a prolonged exposure of the device to
atmosphere. A clear correlation between the PC results and the electrical characteristics of the
corresponding FET devices has been observed


B5.120
Abstract Withdrawn


B5.121
Solution Processable Green Polymers for Use in Solar Cells Subbiah Jegadesan
1
, Pierre
Beaujuge
2
, Kaushik Roy Choudhury
1
, John Reynolds
2
and Franky So
1
;
1
Dept of Materials
Science and Engineering, University of Florida, Gainesville, Florida;
2
Department of Chemistry,
University of Florida, Gainesville, Florida.

Polymer solar cells have attracted much attention in the last few years due to their promising
applications in clean and renewable energy sources. Over the years, the power conversion
efficiency of the polymer solar cells has steadily been improved with the use of new materials
and device architectures. Here, we report on bulk-heterojunction solar cells using a solution
processable neutral green conjugated polymer as the donor and PCBM as the acceptor. We have
found that the short-circuit current is very sensitive to the composition of the donor-acceptor
blend. The device with a donor-acceptor ratio of 1:8 gives the best performance with a power
efficiency of 1.9 %, a short-circuit current of 5.56 mA/cm2 and an open-circuit voltage of 0.77
V. The incident photon-to-current efficiency (IPCE) of the green solar cells shows two bands,
one with a maximum of 57% in the UV region corresponding to the absorption of PCBM and a
second one with a maximum of 42% in the visible-near IR region corresponding to the
absorption of the green polymer.



SESSION B6: Understanding Interfaces
Chairs: Antoine Kahn and Egbert Zojer
Wednesday Morning, April 15, 2009
Room 2001 (Moscone West)

8:30 AM *B6.1
Energetics of Organic-Electrode Interfaces: Polymer vs. Small Molecule FilmsAntoine
Kahn, Electrical Engineering, Princeton University, Princeton, New Jersey.

This talk reviews fundamental work on interfaces involving small molecule and polymer films,
which illuminates the commonality between the electronic structures, e.g. charge injection
barriers, of these two types of interfaces. The early work on small molecule-metal systems was
performed on ultra-clean interfaces, i.e. UHV deposition on ultra-clean substrate surfaces, in
order to identify intrinsic mechanisms that control the interface electronic structure, e.g.
chemistry or induced density of interface states. Results pointed out critical differences between
small molecule and polymer interfaces, the former displaying evidence of strong deviation from
the Schottky-Mott limit, and the latter following closely that limit. Recent work moved
increasingly toward realistic interfaces involving electrode surfaces exposed to ambient
conditions, much closer to future viable organic device fabrication conditions. This work show
that the nature of the interface is strongly related to the environmental conditions and processing
sequence used during interface formation. For example, the Schottky-Mott limit is (nearly)
achieved with small molecule interfaces formed on surfaces of contaminated (or otherwise
treated) or non-metallic electrodes, whereas a departure from the Schottky-Mott limit is observed
on polymer interfaces formed by vacuum evaporation of top contacts. The issue of Fermi level
pinning near the edges of the organic semiconductor transport gap, when using low or high work
function electrodes, is also discussed and results compared for polymer and small molecule
films.


9:00 AM B6.2
Polymer Solar Cells: Non-Conjugated Polymers and PESA Studies of Semiconductor
Energy LevelsScott E. Watkins, Ming Chen, Richard A Evans, Akhil Gupta, Matthias
Haeussler, Katalin Hegedus, Y. Phei Lok, Graeme Moad, Ezio Rizzardo, Gerard J Wilson and
Kevin Winzenberg; Molecular and Health Technologies, CSIRO, Melbourne, Victoria, Australia.

Plastic solar cells produced from organic semiconductors offer the potential to deliver efficient
solar energy conversion with low-cost fabrication. The challenge is to develop materials for
efficient charge separation and charge transport. Well-defined block-copolymers consisting of
organic conjugated chromophores are advantageous as their energy levels can be tuned relatively
easily through a structural engineering approach. In this contribution, we will discuss device and
characterisation results for new polymer building blocks including the use of bilayer devices to
study polymer fragments. Finally, we will present work on determining the energy levels of
known and novel materials by Photo Electron Spectroscopy in Air (PESA) and compare these
results with Ultraviolet Photoelectron Spectroscopy (UPS) and electrochemistry studies.


9:15 AM B6.3
Interface Engineering Concepts for Highly Efficient Inverted Organic Photovoltaics.
Roland Steim
1,2
, Stelios A Choulis
3
, Pavel Schilinsky
1
and Christoph J Brabec
1
;
1
Konarka
Technologies GmbH, D-90443 Nrnberg, Germany;
2
Light Technology Institute, Universitt
Karlsruhe (TH), D-76131 Karlsruhe, Germany;
3
Department of Mechanical Engineering and
Materials Science and Engineering, Cyprus University of Technology, 3603 Limassol, Cyprus.

For organic photovoltaics interface materials with high selectivity are needed to prevent
recombination losses, limit leakage currents and enable carrier extraction of one sort. Thus
beside the transport properties of the active layer, interface materials determine the fill-factor and
thus the efficiency of organic solar cells. Especially for low light applications but also for the
stability of devices under reverse bias, which is of importance for module applications, low
leakage current devices are needed [1]. We present data that stacking of solution processed
organic and metal oxide interfacial layers give highly charge selective low ohmic cathodes. We
present data that the incorporation of a polyoxyethylene tridecyl ether (PTE) interfacial layer
between ITO and solution processed titanium oxide (TiOx) raised the fill factor and power
conversion efficiency of inverted polymer:fullerene bulk heterojunction solar cells to 3.6 % of
efficiency. This is an improvement of around 15% in their performance over devices without the
organic interfacial layer [2]. We investigated the origin of this improvement in detail and present
morphological and surface energetically measurements. [1] R.Steim, P. Schilinsky, S.A. Choulis,
U. Lemmer and C.J. Brabec, manuscript submitted to APL [2] R. Steim, S.A. Choulis, P.
Schilinsky and C.J. Brabec, Interface modification for highly efficient organic photovoltaics,
Appl. Phys. Lett. 92 (2008), p. 093303-1-3


9:30 AM B6.4
Surface-Segregated Monolayers: A New Type of Ordered Molecular Monolayer for
Surface Modification of Organic SemiconductorsKazuhito Hashimoto
1,4
, Qingshuo Wei
1
,
Keisuke Tajima
1
, Yujin Tong
2
and Shen Ye
2,3
;
1
Department of Applied Chemistry, The
University of Tokyo, Tokyo, Japan;
2
Catalysis Research Center, Hokkaido University,
Hokkaido, Japan;
3
Precursory Research for Embryonic Science and Technology (PRESTO),
Japan Science and Technology Agency (JST), Hokkaido, Japan;
4
HASHIMOTO Light Energy
Conversion Project, Exploratory Research for Advanced Technology (ERATO), Japan Science
Technology Agency (JST), Tokyo, Japan.

Well-ordered ultrathin films of organic molecules have been extensively investigated due to their
potential applications in various fields, such as the molecular electronics, nonlinear optics and
biological sensors. Langmuir-Blodgett (LB) films and self-assembled monolayers (SAMs) are
two important classes of such films and frequently used for surface modification of metals, metal
oxides and inorganic semiconductors to control their chemical and physical properties of the
surfaces. However, the surface modifications of the organic semiconductors by using LB films
and SAMs are challenging because of the instability of the organic substrates in solutions and the
lack of the specific interaction between the functional head groups of SAMs or LB molecules
and the organic surfaces. Recently, we have reported a self-organized layer formation on organic
semiconducting materials by utilizing the phenomenon of surface segregation.6 A novel
fullerene derivative with a fluorocarbon chain (FC7) was designed and synthesized. When a
small amount of FC7 was mixed in the solution of [6,6]-phenyl-C61-butyric acid methyl ester
(PCBM), it spontaneously migrated to the air/solvent interface during spin-coating owing to the
low surface energy of the fluorocarbon, and forms a very thin FC7 layer on the PCBM surface in
a single step. As a buffer layer, the top FC7 layer resulted in the improvement of the
performance in bulk-heterojunction photovoltaic devices. Interestingly, the FC7 layer on PCBM
film showed a large shift of the ionization potential, suggesting the alignment of the molecular
dipole moment at the surface. This observation gave us a notion that the layer of FC7 could have
a well-oriented, ordered structure on the surface, despite the easiness of the procedure. In this
contribution, we have synthesized a series of the fullerene derivative with different lengths of
fluorocarbon chains (FCn) and further studied the structure of the surface segregated FCn thin
layer by X-ray photoelectron spectroscopy (XPS) and sum-frequency generation (SFG) vibration
spectroscopy. SFG spectra clearly revealed the uniform monolayer formation with high
molecular orientations on the PCBM surface. Remarkably, the intensity of the SFG signals
showed a clear odd-even effect when the length of fluorocarbon chain was changed. It indicates
that these surface-segregated monolayers have a closely packed and well-ordered structure on the
surface. This new class of monolayer can be a facile and versatile approach to modify the surface
of the organic semiconductors and applicable to various organic devices. [1] Wei, Q.S.;
Nishizawa, T.; Tajima, K.; Hashimoto, K., Self-Organized Buffer Layers in Organic Solar Cells.
Advanced Materials 2008, 20, (11), 2211-2216.


9:45 AM B6.5
''Soft" Metallic Contact to Isolated C
60
Molecules. Hendrik Glowatzki
1
, Benjamin Broeker
1
,
Ralf-Peter Blum
1
, Oliver T Hofmann
2
, Antje Vollmer
3
, Ralph Rieger
4
, Klaus Muellen
4
, Egbert
Zojer
2
, Juergen P Rabe
1
and Norbert Koch
1
;
1
Institut fr Physik, Humboldt Universitt zu Berlin,
Berlin, Germany;
2
Institut fr Festkrperphysik, Technische Universitt Graz, Graz, Austria;
3
Berliner Elektronenspeicherring-Gesellschaft fr Synchrotronstrahlung m.b.H., Berlin,
Germany;
4
Max Planck Institute for Polymer Research, Mainz, Germany.

We investigated the electronic as well as the structural properties of Hexaazatriphenylene-
hexanitrile (HATCN) and C
60
on Ag(111) by using ultraviolet photoelectron spectroscopy (UPS)
and scanning tunneling microscopy (STM) accordingly. HATCN was used as buffer layer to
decouple the test-molecule C
60
from the metal substrate. Photoemission revealed metallic
behavior of HATCN on Ag(111) which calculations confirmed to be due to partial filling the
LUMO of chemisorbed HATCN. From STM a regular honeycomb-structure was found. Using
C
60
as test-molecule on top of this layer the holes within the honeycombs were acting as
adsorption centers leading to laterally spacing between C
60
molecules as observed by STM. At
the same time UPS revealed virtually bulk like electronic properties of C
60
on metallic
HATCN/Ag(111) which is in strong contrast to the bare C
60
-Ag(111) interface being
significantly altered by charge transfer. This opens up new possibilities in probing the
undisturbed properties of individual molecules on metal substrates. This work is financially
supported by European Community project "IControl" (EC-STREP-033197).


10:30 AM B6.6
An Investigation of the Barrier Height, Morphology and Overlayer Lattice Structure of
Perylene Deposited on Au(111), Ag(111) and Cu(111). Kedar Manandhar
1,2
, Justin Sambur
3

and Bruce A Parkinson
1,2
;
1
Chemistry, University of Wyoming, Laramie, Wyoming;
2
School of
Energy Resources, University of Wyoming, Laramie, Wyoming;
3
Chemistry, Colorado State
University, Fort Collins, Colorado.

In situ deposited perylene films, with thicknesses from sub-monolayer to 1024 , deposited on
Au, Ag, Cu (111) surfaces were investigated using photoelectron-spectroscopy (UPS and XPS)
and scanning tunneling microscopy (STM). The analysis of the core level and the valence band
spectra showed no band bending at the perylene/metal interfaces. A Stranski-Krastanov type
growth mode of the films was revealed from the intensity analysis of metal core level and carbon
1s emission as a function of film thickness. A band energy diagram for these systems, the slope
of barrier height vs metal work function and the overlayer lattice structures and the morphology
of thin films will be presented and discussed.


10:45 AM B6.7
Formation and Electrical Interfacing of Nanocrystal-Molecule Nanostructures. Aidan
Quinn and Claire Barrett; Nanotechnology Group, Tyndall National Institute, Cork, Ireland.

Recent developments in the design and synthesis of nanoscale building blocks as active elements
for information storage, biosensing and photoconductive devices have the potential to
revolutionise several emerging technology markets across multiple sectors including healthcare,
printable electronics, security and energy conversion. Functional organic molecules and
biomolecules (~1-5 nm length scale) are attractive candidates as building blocks due to their
composition-, size- and structure-dependent electronic properties, the ability to design and
manipulate these properties via low-cost chemical synthesis, and finally the potential for
formation of ordered structures through (bio)-molecular recognition and self-assembly. Ligand-
stabilised inorganic nanocrystals (~1.6 - 30 nm core diameter) also represent attractive
candidates, both as building blocks with novel functionality (e.g., single charge tunnelling or
quantum confinement) and also as terminals or nodes to bridge the gap between length scales
accessible via top-down lithography (~ 25 nm) and molecular length scales. We present recent
results on solution-based formation of nanocrystal-molecule-nanocrystal n-mer nanostructures,
directed assembly of n-mers at contact nanoelectrodes and initial investigations of charge
transport in these few-molecule devices. For these studies, we have employed gold
nanocrystals with core diameters, d = 20 nm, and bifunctional organic linker molecules. The
novel plasmonic properties of these nanostructures can be used for in situ monitoring of the
nanostructure formation process. We have developed a rigorous nanovisulisation process based
on scanning electron microscopy to quantify the distributions of dimers, trimers and higher order
n-mers formed in solution, in order to investigate relationships between the distribution of
nanocrystal-molecule nanostructures formed and measured optical properties. Very recently, we
have demonstrated that UV-visible absorbance data reveals a characteristic response close to 600
nm upon formation of dimer nanostructures. Simulations based on the generalized multiparticle
Mie method are currently under development to gain further insight into this novel plasmonic
response. Directed assembly processes based on dielectrophoretic trapping have also been
developed for electrical interfacing of these nanostructures between top-down nanoelectrode
pairs (~25 nm interelectrode gaps). Initial current-voltage characterisation reveals contact
formation with ~10% yield, comparable to contacting yields for larger self-assembled networks
of metal nanocrystals. These contacting strategies are being iteratively optimized via a
combination of directed assembly and electrode functionalisation processes.


11:00 AM *B6.8
Theoretical Spectroscopy of Organic Semiconductors. Leeor Kronik, Materials and
Interfaces, Weizmann Institute of Science, Rehovoth, Israel.

The combination of density functional theory (DFT) with powerful spectroscopic tools, e.g.,
photoemission spectroscopy or absorption spectroscopy, is an important approach to elucidating
the electronic structure of materials. In recent years, it has become a particularly popular tool for
studying organic semiconductors and their interfaces with (metallic or semiconducting) inorganic
substrates - topics of great importance in organic electronics. In this talk, I review our recent
progress in understanding the strengths, limitations, and true predictive power of such analyses,
and our advances in accurate calculations of systems usually believed to be "too difficult for
DFT". In particular, the consequences of self-interaction and derivative discontinuity errors and
the role of dispersive interactions are addressed. The pros and cons of different functionals,
including standard and novel range-split hybrid functionals, as well as other orbital-dependent
approaches, are discussed. The role of post-DFT methods, especially many-body perturbation
theory, is also examined. Perhaps most importantly, general criteria for a priori selection of the
best-suited theoretical approach and evaluation of its accuracy are suggested. The new
approaches are demonstrated through a judicious comparison of DFT and related approaches
with concrete experimental results for a variety of prototypical semiconducting organic
molecules and organic/inorganic interfaces.


11:30 AM B6.9
Energy-Level Alignment at Metal/SAM/Organic Contacts. Ferdinand Rissner
1
, Gerold M
Rangger
1
, Oliver T Hofmann
1
, Anna M Track
1
, Georg Heimel
2
and Egbert Zojer
1
;
1
Institut fr
Festkrperphysik, Technische Universitt Graz, Graz, Austria;
2
Institut fr Physik, Humboldt-
Universitt zu Berlin, Berlin, Germany.

In the field of organic electronics, self-assembled monolayers (SAMs) are commonly applied to
enhance the performance of (opto)electronic devices. Over the past years considerable efforts
have been made to better understand the influence of SAMs on surface properties. In particular,
it has been shown that the deposition of SAMs on metals can cause significant work function
modifications. It is essential to understand to what extent a modification of the electrode work
function can be directly translated into a change of the electron and hole injection barriers into an
organic semiconductor (OSC) on top of the SAM, i.e., it needs to be tested under which
conditions the simple Schottky-Mott limit applies. In this contribution, density functional
theory based slab-type band-structure calculations are performed, adopting the VASP code. In
order to model metal/SAM/organic interfaces, we investigate three-component systems,
consisting of a metal surface, a SAM and a monolayer of a prototypical organic semiconductor
on top of the SAM. By varying the nature of the SAM interlayer, we can distinguish between
regions of Fermi level pinning and vacuum level alignment, where the former is found to be a
consequence of polarization of the SAM in addition to significant charge transfer at the
SAM/OSC interface. Support by the European Commission through the STREP project
ICONTROL (EC-STREP-033197) and by the FWF through project P20972-N20 is gratefully
acknowledged.


11:45 AM B6.10
Nanomagnetism at Organic/inorganic Interfaces.Jian-Bin Xu
1,2
, Xiao-Qing Tian
1,2
and Rong
Zhang
3
;
1
Dept. of Electronic Engineering, The Chinese University of Hong Kong, Hong Kong
SAR, China;
2
Materials Science and Technology Research Center, The Chinese University of
Hong Kong, Hong Kong SAR, China;
3
Physics Dept., Nanjing University, Nanjing, Jiang Su,
China.

Nanomagnetism at CoPc/Au(111) and CoPc/graphene interfaces are investigated by ab initio
calculations and Anderson localized magnetic impurity model. The strong coupling between Co
and Au(111) substrate causes the magnetic impurity d orbital redistribution. This results in
magnetic-nonmagnetic transition of the magnetic impurity. The graphene substrate has no
effective impact on the electronic structure of magnetic impurity, and thus there is no magnetic-
nonmagnetic transition at CoPc/graphene interface.



SESSION B7: Charges & Transport I
Chairs: Leeor Kronik and Xiaoyang Zhu
Wednesday Afternoon, April 15, 2009
Room 2001 (Moscone West)

1:30 PM B7.1
In Situ Optical Spectroscopy of Organic Electronics and Optoelectronics. Travis Mills,
Loren G Kaake and Xiaoyang Zhu; Chemistry, University of Minnesota, Minneapolis,
Minnesota.

Organic electronics and optoelectronics are commonly characterized from device perspectives,
such as I-V characteristics in organic thin film transistors (OTFTs) and photo-to-electric
conversion efficiencies in organic photovoltaics (OPVs). Little is known at the molecular and
quantitative levels regarding charge carriers in operating organic electronic and optoelectronic
devices. We apply attenuated total internal reflection Fourier transform infrared and near-
infrared spectroscopy (ATR-FTIR or FTNIR) to directly probe OTFTs and OPVs under
operational conditions. These measurements have been enabled by the fabrication of devices on
optical waveguides. We use this approach to quantify charge separation and collection
efficiencies in bilayer OPVs from molecular and polymeric semiconductors. This measure fills a
critical gap in current understanding of the efficiencies of OPVs. We also apply this
spectroscopic approach to quantify charge carriers in OTFTs gated with polymer electrolyte
dielectrics and show the limits in switching speed due to carrier and ion movements.


1:45 PM B7.2
Gating Conductance of Metal-organic Semiconductor Contacts: a Macro-scale Device
Reflecting Molecular-scale Switching. Jun Takeya
1
, K. Nakayama
1
, T. Uemura
1
, M.
Yamagishi
1
and M. Uno
1,2
;
1
Osaka University, Toyonaka, Japan;
2
TRI-Osaka, Izumi, Japan.

It is argued on one hand that an advantage of organic electronics is in large-scale application
utilizing a low-temperature roll-to-roll printing process whereas it is also addressed that organic
molecules can form ultimate nanoscale devices, on the other hand, when each molecular state is
independently controlled. It appears that the extreme multi-scalability is a pronounced feature of
organic materials that overwhelms that of inorganics. In fact, charge transport in organic
transistors, which are regarded as representative of the macro-scale devices, consists of
conductance with two very different length scales; i.e. carrier diffusion in the semiconductor
channels typically of m scales and carrier injection from metal electrodes to the organic
semiconductors governed by nanometer-scale physics. In this presentation, we disclose a device
of controlling the conductance of metal-organic semiconductor contacts, in contrast to usual
organic transistors where that of the semiconductor channels is modified. The present device
possesses potential advantages in 1) effective integration of the nano-scale active components, 2)
higher current-amplification performance due to the mechanism of controlling chemical potential
of the interface instead of electrostatic charging, and 3) high-speed response as the result of very
small amount of charge necessary for the operation. Prototypical switching devices were
prepared based on macro-scale organic top-contact single crystal transistors, in which thin
platelets of rubrene single crystals with the typical thickness of 2 m were laminated on SiO
2
/
doped Si substrates and two metal electrodes are deposited from the top. At this stage, the
devices worked as top-contact organic transistors where the charge amount was controlled at the
bottom surface with the application of gate electric field in the SiO
2
dielectrics. The top surfaces
of the single crystals were then coated with fluoro-silane molecular layers, which form a hole-
conducting layer at the top crystal surfaces as the result of mutual charge transfer between the
silane and rubrene molecules [1]. The structure ended up with normally-on transistors with the
sheet conductivity of 10
5
S which was little changed by the field effect. Interestingly, the device
suddenly switched to an off state with the application of positive gate voltage of a few volts,
which is far less than necessary to deplete the whole carriers in the top channel. Indeed, the result
of four-terminal-conductivity measurement did not show any sudden switching, meaning that
contacts are responsible for the effect. The conductance of the molecular-scale contacts was
tuned by the chemical potentials in the vicinity of the electrodes, modified through weak band-
bending in clean rubrene crystals. In other words, the observed performance of the macro-scale
devices reflects switching occurring in the molecular scale. [1] M. F. Calhoun et al., Nature
Mater. 7, 15259 (2008).


2:00 PM *B7.3
Electrostatic Modulation of Charge Density in Polymers and Molecular Crystals: an
Infrared Study. Dmitri N Basov, UCSD, La Jolla, California.

Recent advances in infrared spectroscopy enabled experimental studies of the electromagnetic
response of charges in a single molecular monolayer [Li et al. Nature-Physics 4 532 (2008)].
These advances paved the way towards a systematic exploration of electronic excitations
associated with high density of charges in the accumulation layer of organic field effect
transistors (OFET) with both polymers and molecular crystals as active semiconductors. Infrared
data for rubrene-based OFETs indicate that transport properties of these transistors at room
temperature are governed by light quasiparticles in molecular orbital bands with the effective
masses m* comparable to free electron mass [Li et al. PRL 99, 016403 (2007)]. Infrared
microscopy results have uncovered giant length scales characteristic of charge injection in
polymers with high electronic mobility including P3HT and PBTTT [Li et al. Nano Letters 6,
224-228 (2006)].


2:30 PM B7.4
Scanning Potentiometry of ribbon-phase pBTTT Thin Film Transistors Toby Hallam
1
, Ni
Zhao
1
, Mi Jung Lee
1
, Iris Nandhakumar
3
, Martijn Kemerink
2
and Henning Sirringhaus
1
;
1
Physics, University of Cambridge, Cambridge, United Kingdom;
2
Physics, Eindhoven
University of Technology, Eindhoven, Netherlands;
3
Chemistry, University of Southampton,
Southampton, United Kingdom.

The polymer poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene), pBTTT has been shown
to exhibit a highly organized terrace structure with grain sizes several m across after
annealing to a liquid crystalline phase at 180C. Thin films of pBTTT in the terrace phase have
demonstrated large field effect mobilities comparable to that achieved with small molecules or
amorphous silicon. Upon annealing at 260C, pBTTT adopts a highly crystalline ribbon phase
where well-defined, ~80nm wide crystalline ribbons are observed within which the polymer
adopts an extended chain conformation. The ribbons are separated by similarly well-defined
grain boundary regions with more disordered chain conformation. Until recently, Scanning
Kelvin Probe Microscopy (SKPM) has been limited to mapping surface potential in Organic
Thin Film Transistors with a resolution >100nm. We demonstrate here <50nm lateral potential
resolution achieved through use of AFM tips with attached carbon nanotubes. This has allowed
resolving potential variations associated with individual nanoribbons and grain boundary regions
in the ribbon phase of pBTTT. Using SKPM we have directly observed hole trapping at the inter-
grain regions in ribbon-phase pBTTT. For an unstressed pBTTT film the surface potential is
found to exhibit a characteristic, normal distribution. Following a prolonged negative gate bias,
the distribution of surface potentials measured across the surface exhibited an additional tail
towards more positive surface potential, which we interpret as being due to trapping of hole
carriers in the channel. We have been able to correlate the spatial locations of the sites that
exhibit the more positive surface potential after bias stress with the grain boundary regions of the
ribbon phase. This provides direct evidence that charge trapping occurs preferentially within the
grain boundary regions and that these provide bottlenecks for charge transport. Hole
delocalization in the pi-pi stacking direction also plays a crucial role in electronic transport. By
applying a source-drain voltage we can identify preferential current paths which appear to be
influenced by a combination of the alignment of lamellar packing for adjacent crystallites and the
direction of the applied lateral field. We have also investigated the temperature dependence of
the surface potential along the channel in the ribbon phase. We are able to resolve potential
variations across the ribbons and across the grain boundary regions between them and we have
observed a characteristic change in the nanoscale potential profiles around ~200K. We will
discuss these results in terms of the nanoscale charge transport properties of the polymer.


2:45 PM B7.5
Capacitance-Voltage Analysis for Interface Trap Density between Pentacene and
Insulators Seung-Hyeon Jeong and Chung-Kun Song; Electronics Engineering, Dong-A
University, Busan, Korea, South.

The study of interface trap density between semiconductor and dielectric is the important issue to
improve the performance of organic thin film transistors. In this study, we analyzed the interface
trap density between pentacene organic semiconductor and gate dielectrics such as poly-4-
vinylphenol (PVP) and SiO2 by using the combined high-low frequency C-V characteristics. In
capacitor consisting of organic semiconductor and organic dielectric, it is difficult to extract the
reliable low frequency C-V curve because of the slow responding interface traps. By varying
step delay time and frequency of small signal we extracted the measurement conditions for the
reliable low frequency C-V curve. From the reliable low and high frequency C-V curves we
obtained interface trap density between pentacene-PVP and pentacene-SiO2. The former
exhibited the large shallow trap density of 1013 [#/cm2 ev] and the small deep trap density of
109 [#/cm2 ev] meanwhile the later the large shallow trap density of 1013 [#/cm2 ev] and the
large deep trap of 1012 [#/cm2 ev] as well. The organic-organic interface produced the better
properties than the organic-inorganic interface in terms of trap density. *This research was
supported by a grant(F0004020-2008-31) from Information Display R&D Center, one of 21st
Century Frontier R&D Program funded by the Ministry of Knowledge Economy of Korean
government.


3:30 PM *B7.6
Organic Thin-Film Transistors and Circuits with Low Operating Voltage. Hagen Klauk,
Max Planck Institute for Solid State Research, Stuttgart, Germany.

Organic thin-film transistors (TFTs) often employ relatively thick gate dielectrics with small
capacitance (usually between 20 and 100 nF/cm2) und thus typically require operating voltages
in the range of 10 to 50 V. For certain applications, organic TFTs that can be operated with
voltages between 2 and 3 V will be beneficial. For example, state-of-the-art organic light-
emitting diodes (OLEDs) that employ doped transport layers require supply voltages between 2.5
and 3 V, reaching efficiencies between 10 cd/A (red and blue) and more than 70 cd/A (green)
[1]. To realize flexible active-matrix displays with such OLEDs, low-voltage organic TFTs will
be required. A second example for applications that will benefit from low-voltage organic TFTs
are hybrid systems in which flexible large-area TFT arrays share signals and power with silicon-
based processor units, which are typically designed to operate with a supply voltage of 2 or 3 V
[2]. To realize flexible organic TFTs that can be operated with voltages of 3 V or less, a low-
temperature-processed gate dielectric with a capacitance above about 0.5 F/cm2 is required. A
promising approach are hybrid dielectrics based on a thin, plasma-grown metal oxide in
combination with an organic self-assembled monolayer (SAM). The metal oxide is obtained by
exposing the metal gate electrode to an oxygen plasma; in the case of aluminum gate electrodes
this forms an AlOx layer with a thickness of 3 to 4 nm, depending on the plasma power. This
oxide layer alone is a poor dielectric characterized by substantial leakage currents. However, the
plasma-grown oxide provides an excellent surface for the self-assembly of a molecular
monolayer of an aliphatic phosphonic acid. This monolayer is obtained either by immersing the
substrate in a solution of the phosphonic acid or by transferring the monolayer from an
elastomeric stamp. The self-assembled monolayer has a thickness of about 1.5 to 2 nm, giving a
total oxide/SAM dielectric thickness of about 5 to 6 nm and a gate dielectric capacitance of 0.7
to 1 F/cm2. Despite its small thickness and the low process temperature, the oxide/SAM
dielectric provides leakage currents of less than 10 A/cm2 at 3 V. This allows p-channel and n-
channel organic TFTs on glass and on flexible polymeric substrates to operate with voltages
between 1.5 and 3 V and with excellent static and dynamic characteristics, including large carrier
mobility, large on/off current ratio, steep subthreshold slope, small gate leakage currents, and
large cut-off frequency. [1] P. Wellmamm et al., J. Soc. Inf. Display, vol. 13, p. 393, 2005 (see
also: www.novaled.com). [2] T. Sekitani et al., Int. Solid-State Circuits Conf. (San Francisco,
February 2009).


4:00 PM B7.7
High Performance N-type Organic Thin-Film Transistors with Inert Contact Metals. Sarah
Schols
1,2,5
, Lucas Van Willigenburg
1
, Robert Muller
1
, Dieter Bode
1,2
, Maarten Debucquoy
1,2
, Jan
Genoe
1
, Paul Heremans
1,2
, Shaofeng Lu
3
and Antonio Facchetti
3,4
;
1
SOLO/PME, IMEC, Leuven,
Belgium;
2
Electrical Engineering Department, Katholieke Universiteit Leuven, Leuven,
Belgium;
3
Polyera Corporation, Skokie, Illinois;
4
Department of Chemistry and the Material
Research Center, Northwestern University, Evanston, Illinois;
5
Aspirant at the FWO Vlaanderen,
Brussel, Belgium.

Driven by potential applications of complementary logic, the field of electron-channel (n-type)
organic thin-film transistors (n-OTFT) and corresponding n-type materials has gained a lot of
attention. 5,5'''-diperfluorohexylcarbonyl-2,2':5',2'':5'',2'''-quaterthiophene (DFHCO-4T) is an
example of such a promising electron-conducting organic semiconductor. Recently, high electron
field-effect mobilities were reported for DFHCO-4T.[1,2] While most n-OTFTs need low-
workfunction metal contacts such as Mg, Ca or LiF/Al for efficient electron injection into the
semiconductor lowest unoccupied molecular orbital (LUMO), DFHCO-4T-based n-OTFTs
function properly with high-workfunction source and drain Au contacts.[1] This fact is of high
technological relevance because for use in complementary logic it is preferable to use a single
type of source and drain metal for both the p-type and the n-type OTFTs. Here, we discuss the
optimization of DFHCO-4T growth and compare the performance of DFHCO-4T transistors
with different top contact metals. Thin film growth by high vacuum evaporation of the n-type
organic semiconductor DFHCO-4T on poly-(-methylstyrene)-coated n
++
-Si/SiO
2
substrates is
investigated at various deposition fluxes and substrate temperatures. Film characterization by
atomic force microscopy reveals typical Stransky-Krastanov growth. Transistors with Au source-
drain top contacts and optimized DFHCO-4T deposition conditions exhibit an apparent
saturation field-effect mobility of 4.6 cm
2
/Vs, whereas this parameter is 100x lower for similar
transistors fabricated with LiF/Al or Yb top contacts. We explain this reduced performance of
transistors with easily oxidizable top-contact metals such as Al by the formation of a thin
interfacial layer with poor injection properties resulting from an electron-transfer reaction
between the metal and DFHCO-4T. [1] M. Yoon, C. Kim, A. Facchetti, and T. J. Marks, J. Am.
Chem. Soc. 128, 12851 (2006). [2] M. Yoon, S. A. DiBenedetto, M. T. Russell, A. Facchetti, and
T. J. Marks, Chem. Mater. 19, 4864 (2007).


4:15 PM B7.8
Self-Assembly in Organic LEDs and FETs Simon Mathijssen
1,2
, Edsger Smits
3,2
, Paul van
Hal
2
, Ton van den Biggelaar
2
, Monja Kaiser
2
, Bert de Boer
3
, Sergei Ponomarenko
4
, Martijn
Kemerink
1
, Rene Janssen
1
and Dago de Leeuw
2,3
;
1
Applied Physics, Eindhoven University of
Technology, Eindhoven, Netherlands;
2
Philips Research Laboratories, Eindhoven, Netherlands;
3
University of Groningen, Groningen, Netherlands;
4
Enikolopov Institute of Synthetic Polymer
Materials of Russian Academy of Sciences, Moscow, Russia.

Self assembly, the autonomous organisation of components into patterns and structures without
human intervention is the ultimate technology for mass production of large area electronics. First
we demonstrate SAMFETs, field-effect transistors where the semiconductor is a monolayer
spontaneously formed on the gate dielectric. In order to form a conducting path in between the
source and drain electrode, the molecules in the self-assembled monolayer (SAM) should be
intimately connected. Any structural imperfection as voids or grain boundaries leads to potential
barriers and, hence, to a deteriorated charge carrier mobility. In addition the nature of the
electrical contact is crucial. Formation of an effective injecting electrode to a single layer of
molecules has proven to be a historical challenge. Here we show that the SAMFET consists of a
semiconducting monolayer. The electrical connectivity between the molecules is inferred from
electrical transport measurements as well as the local surface potential as determined from
scanning Kelvin probe microscopy (SKPM) measurements. To elucidate the efficient injection of
charge carriers in the SAM, the critical region where the SAM meets the edges of the electrode
was imaged with transmission electron microscopy. Morphological studies and SKPM
measurements substantiate that the prerequisites for efficient charge transport in a field-effect
transistor are fulfilled; we observe long-range connectivity together with an intimate contact
between the semiconductor and electrodes. The small parameter variation between transistors
allowed integration into a functional 15-bit code generator. Furthermore we applied self-
assembly to produce patterned OLEDs with micro-contact printed self-assembled monolayers.
Here SAMs with opposite dipole moments change the local work function and hence the
injection, which results in a patterned light emission. The local work function is analyzed using
scanning Kelvin probe microscopy. The scanning probe measurements together with optical
micrograph images of the patterned OLEDs demonstrate a direct correlation between the local
work function and light emission. In summary, we show the incorporation of SAMs in organic
field-effect transistors and light-emitting diodes. In the first case, the monolayer is acting as the
semiconductor, in the latter as an injection modifier.


4:30 PM B7.9
An Organic-nanoparticle Transistor Behaving as a Spiking Synapse.Dominique Vuillaume
1
,
Fabien Alibart
1
, David Guerin
1
, Stephane Pleutin
1
, Kamal Lmimouni
1
, Christophe Novembre
2

and Christian Gamrat
2
;
1
IEMN-CNRS, Villeneuve d'Ascq, France;
2
CEA-LIST, Gif-sur-Yvette,
France.

We demonstrate that an organic transistor, made of metal nanoparticles (NP) embedded into an
organic semiconductor channel, behaves as a spiking synapse (hereafter called an organic-
nanoparticle transistor-synapse - ONTS for short). We demonstrate that this ONTS device
exhibits the main behavior of a biological synapse. For instance, the ONTS can be programmed
to work as a facilitating or depressing synapse; it exhibits short-term plasticity as well as spike
timing dependent plasticity. This behavior is obtained by virtue of the combination of two
properties of the ONTS: the transconductance gain of the transistor and the memory effect due to
charges stored in the NP. We previously demonstrated that this type of device works as a non-
volatile memory (1) but with a leaky behavior. This behavior is used here to implement the
synapic weight wij with a possible dynamic behavior, a mandatory condition to obtain the
training/learning of a spiking neural network (2). The gold NP are immobilized into the source-
drain channel by using surface chemistry (self-assembled monolayers) and they were
subsequently covered by a thin film of pentacene. In a biological synapse, the facilitating
behavior means that an incoming signal with a given frequency and duty cycle induces a post-
synaptic signal having an increasing trend, whereas in the case of an depressing synapse, the
post-synaptic signal tends to decrease (3). This behavior is exactly what we demonstrated for the
ONTS. Our results also compare qualitatively well with a simulation model (4). (1) C.
Novembre, D. Gurin, K. Lmimouni, C. Gamrat, D. Vuillaume, Appl. Phys. Lett. 92, 103314
(2008). (2) S. Haykin, Neural networks. A comprehensive foundation., (Macmillian, NewYork,
1994). (3) H. Markram, Y. Wang, M. Tsodyks, Proc. Natl. Acad. Sci. USA 95, 5323 (1998). (4)
M. Tsodyks, K. Pawelzik, H. Markram, Neural Computation 10, 821 (1998)


4:45 PM B7.10
Light-emitting Ambipolar Field-effect Transistors using Organic Single Crystals. Hajime
Nakantani and Chihaya Adachi; Center for Future Chemistry, Kyushu University, Fukuoka,
Japan.

An ambipolar light-emitting organic field-effect transistor (LE-OFET) based on a 1,4-Bis(4-
methylstyryl)benzene (BSP-Me) single crystal was developed. The BSP-Me single crystal has
very high photoluminescence quantum efficiency (Fai(PL)) of 89%, while Fai(PL) of the BSP-
Me vapor-deposited film is limited to a much lower value of 54%. Ambipolar operation with
successive blue electroluminescence from the FETs based on the BSP-Me single crystals was
demonstrated by realizing nearly equal electron and hole mobilities (about 0.005 cm2/Vs) with
asymmetric gold-calcium contacts. Since BSP-Me single crystals can perform light
amplification, the BSP-Me-based ambipolar LE-OFET is a promising candidate for future
electrically driven organic blue-emitting solid-state lasers. We also mention organic/inorganic
hybrid FET structures for aiming efficient carrier recombination.



SESSION B8: Charges & Transport II
Chairs: Hagen Klauk and Nobuo Ueno
Thursday Morning, April 16, 2009
Room 2001 (Moscone West)

8:30 AM *B8.1
The first principles measurement of charge mobility of organic semiconductors with UPS.
Satoshi Kera
1
, Hiroyuki Yamane
2
, Shunsuke Hosoumi
1
, Shin-ichi Nagamatsu
1
and Nobuo
Ueno
1
;
1
Graduate School of Advanced Integration Science, Chiba University, Chiba, Japan;
2
Institute for Molecular Science, Okazaki, Japan.

Most of the over 86 million registered materials are organic materials, and many of them form
solid by weak intermolecular interaction. Organic semiconductor is the representative of
electronic function brought by the weak intermolecular interaction coupled with individual
molecular characteristics, and has been increasingly studied for device application. As organic
semiconductor films show various faces depending on molecular packing structure as well as
on individual molecular structure, many mysteries exist to be elusive. A key issue of organic
FET devises is how one can improve the carrier mobility () of organic thin films. As the
electrical conductivity () is given by =nq, where n is the carrier concentration and q is the
charge of the carrier concerned, one must know principal mechanism which dominates , namely
coherent band conduction or incoherent hopping conduction. In relation to organic transistors,
many electrical measurements have been performed to investigate the charge mobility.
Unfortunately, however, most of the works have directed to obtain phenomenological from I-V
measurements. The coherent conduction is dominated by the band dispersion with a mean free
path of the carrier much longer than intermolecular distance, and the hopping conduction is
specified by two physical parameters, the transfer integral (t) and the charge reorganization
energy (). t is the measure of the intermolecular interaction, and is related to charge-vibration
coupling. To go into the mobility, one needs to measure t and experimentally. t is given by
observing the energy band dispersion or the energy level splitting in finite molecular stacks, and
is obtained by measuring hole- or electron-vibration coupling in organic systems at low
temperature (namely not in gas phase but in a film). UPS can in principle measure these two
targets. At this conference we will present our recent challenges on UPS of the thin films that
give (1) the energy level splitting and the band dispersion, both of which offer the value of t, and
(2) obtained directly from the measurement of the HOMO hole-vibration coupling in various
organic semiconductor films. From these we can obtain the ultimate hole mobility for the
coherent band conduction and the hopping conduction.


9:00 AM B8.2
Charge Transport and Microstructure Correlations using Anisotropic Polythiophene Thin
Films Fabricated via Directional Crystallization. Leslie Hendrix Jimison and Alberto H
Salleo; Materials Science and Engineering, Stanford University, Stanford, California.

In recent years much research has been devoted to the improved fabrication and understanding
macroelectronics: a category of devices that include thin film transistors, photovoltaics and light
emitting diodes. Polymeric semiconductors have great potential as the active layer for such large
scale systems, with a key attribute being their ability to be dissolved in solvents to make
printable semiconducting inks. While polymer semiconductors are beginning to reach
performance levels that enable them to be competitive in low-cost electronics, what is lacking is
an understanding of the fundamental charge transport processes in relation to microstructure. We
have used a means of controlling the orientation and size of crystallites in the plane of the
substrate to produce films with well-known grain-boundary types. As a result we are able to
explore the relationship between trap density within grain boundaries and charge transport.
Regioregular poly-3-hexylthiophene (P3HT) is the material under investigation. We have
fabricated anisotropic films on glass and silicon substrates via directional solidification, using
1,3,5-trichlorobenzene first as a solvent and then as a substrate for epitaxy. The technique
enables us to create films consisting of large (mm
2
) domains of uniform extinction under crossed
polarizers, suggesting long range orientation of the polymer chain axis. Using a film lift-off
technique, atomic force microscopy reveals the lamellar microstructure at both the polymer/air
interface and polymer/substrate interface. Film microstructure was further characterized at the
Stanford Synchrotron Radiation Laboratory (SSRL). We have collected 2D diffraction patterns,
specular diffraction patterns, and grazing incidence diffraction patterns, confirming the unique
in-plane and out-of-plane texture of the polymer films. Charge transport in the directionally
crystallized films was probed by measuring temperature-dependent mobilities using thin film
transistors with the oriented film as the active layer. Devices were made with different relative
orientations between the channel and the polymer film. Transport measurements as a function of
charge density and temperature for different orientations of our film confirm mobility anisotropy
but no activation energy anisotropy. Temperature dependent transport measurements also reveal
increased effect of bias stress between 220-280C. Furthermore, there is marked anisotropy of
the bias stress effect between the different device orientations. Because our films are anisotropic
in the type of grain boundary present, this strongly suggests that bias stress in semicrystalline
organic thin films is dependent on the microstructure at the grain boundaries.


9:15 AM B8.3
Scanning Kelvin Probe Measurements on Pentacene based Field-Effect Transistors with
UV-modified Gate Dielectric Christopher Siol, Niels Benson, Christian Melzer and Heinz von
Seggern; Institute of Material Science, Technische Universitaet Darmstadt, Darmstadt, Germany.

The use of organic field-effect transistors (OFETs) in organic electronics is often hampered by
the fact that solely unipolar logic is implemented. In view of a performance improvement, it is
aspired to use complementary metal oxide semiconductor (CMOS) -like techniques to benefit
from the efficiency of complementary logic circuits. In recent publications we have
demonstrated a CMOS-like inverter based on pentacene n- and p-type OFETs that comprise
identical device layouts thus facilitating the production of CMOS-like elements. Solely the
treatment of the used PMMA gate dielectric with UV light prior to the pentacene deposition
allowed for an inversion of the operation mode from the usual n-type to a unipolar p-type
behaviour. Even though the stable device performance of the thus produced inverter
demonstrates the potential of the proposed UV treatment the exact mechanism allowing for the
polarity change is not known in detail. In this contribution, we try to reveal this mechanism by
discussing the results of Scanning Kelvin Probe Measurements (SKPM) performed in the
channel of UV-treated OFETs in combination with the analysis of the OFET performance. From
the current-voltage characteristics it is supposed that the UV treatment itself results in the
formation of electronic trap states, in particular in electron traps. Since the establishment of the
p-type behaviour requires, besides the UV treatment, a precedent operation of the transistor in
electron accumulation, it is speculated that the electron traps have to be negatively charged.
Indeed, SKPM disclose that the accumulation of negative charge carriers at the PMMA /
pentacene interface results in a distinct and stable trapping of electrons, which proves the
existence of efficient electron traps in UV-modified PMMA. In what way this charging helps to
convert the n-type transistor to a p-type transistor, in particular to inject holes from the employed
low workfunction metal Ca, will be discussed in detail. The stably trapped negative areal charge
density leads to a gate-field enhancement at the contacts. It is supposed that this field
enhancement is sufficient to inject holes from Ca into the channel. Under current flow, the
channel in the vicinity of the source will again partly deplete from the compensating holes
allowing anew for a field-enhanced hole injection from Ca.


9:30 AM B8.4
Trap-Dominated Charge Transport in Organic Transistors as Investigated by Field-
Induced ESR Spectroscopy. Hiroyuki Matsui
1,2
and Tatsuo Hasegawa
1
;
1
PRI, AIST, Tsukuba,
Japan;
2
Department of Advanced Materials Science, University of Tokyo, Tokyo, Japan.

Recently we reported that motional narrowing effect can be observed in field-induced electron
spin resonance (ESR) spectra of high-mobility pentacene thin-film transistors (TFTs). We found
that the methods are quite useful in elucidating the carrier dynamics in organic TFTs since the
narrowed linewidth allows us to estimate the average residence time of carriers at respective
sites. In particular the analyses afford a clear evidence for the considerably long trap residence
time or the trap-dominated conduction in pentacene TFTs. Meanwhile, motional narrowing
effect is directly evidenced by temperature-dependent and gate-field-dependent single-
Lorentzian ESR spectra. However, the temperature-dependent feature deviates from the simple
motional narrowing regime in high (T > 200 K) and low (T < 50 K) temperature ranges. Here we
discuss the whole picture of field-induced ESR spectra in the temperature range of 300 - 20 K on
the basis of continuous wave saturation experiments. The method enables us to check the
homogeneity of ESR spectra as well as to estimate spin-lattice relaxation time T1. It is found
from the temperature dependence of ESR linewidth that the linewidth increases as temperature
decreases with activation energy of about 15 meV at 50 K < T < 200 K, while it deviates from
the feature at higher and lower temperature ranges. First we examined the saturation behavior of
ESR signals, which allows us to separate the contribution of spin-lattice relaxation from
motionally-narrowed inhomogeneous linewidth. The motionally-narrowed and the spin-lattice
relaxation components compete with each other at around 200 K. From this we conclude that the
small increase of linewidth at higher than 200 K with increasing tempeature should be attributed
to the spin-lattice relaxation. At the temperature lower than 50 K, on the other hand, the
linewidth tends to converge at about 0.18 mT. The ESR spectra do not show broadening under
saturation at high microwave power, demonstrating the inhomogeneity of the ESR absorption. It
means that motional narrowing is no longer effective in the low temperature range because of
long residence time at trap states. Transport and localization of field-induced carriers will be
discussed on the basis of these experimental results.


9:45 AM B8.5
Electrochemical Transistors: New Platforms to Study Interfaces in Liquids. Fabio Cicoira
1,2
,
Sang Yang Yoon
1
, DeFranco A John
1
and George G Malliaras
1
;
1
MSE, Cornell UNiversity,
Ithaca, New York;
2
Institute of Photonics and Nanotechnology, CNR, Trento, Italy.

The considerable research efforts in organic electronics have led to the development of a number
of devices like organic light emitting diodes, solar cells and organic thin film transistors that are
nowadays in production or prototype stage. Along with these well-established fields, exciting
emerging applications are taking advantage of the mixed ionic/electronic transport in organic
electronics devices [1]. Along this line, the application of organic semiconductor devices to
chemical and biological sensors seems to be a great fit. A promising approach towards organic-
based sensors involves the use of organic electrochemical transistors (OECTs). OECTs consist of
source and drain electrodes, and a channel containing the organic active material in ionic contact
with a gate electrode via an electrolyte solution. These devices can be operated in aqueous
environment as efficient ion-to-electron converters, thus providing an interface between the
worlds of biology and electronics and also a unique platform for the study of organic/organic and
organic/metal interfaces in liquids. Although electrochemical transistors have been known since
long time [3], they received little attention in the scientific community until the recent resurgence
due to their application in biosensors. Therefore a great deal of work is needed to understand the
fundamental processes that take place in these devices, essential for their use in sensing
applications. In this presentation we intend to address this important issue. Using
photolithography, surface engineering and micro fluidics we have developed several technique to
fabricate OECTs having different geometries. This allows us to study the basic electronic
properties and the sensing response of devices in order to understand their mechanism of
operation [4] [5]. We studied how the dimensions of the transistors (in particular on the
gate/channel area ratio) and the gate electrode material (metal or polymer) can be used to tune
the device response. The effect of the electrolyte on device response was evaluated studying
transistors in aqueous electrolytes and ionic liquids. The detection limit of OECTs based sensors
having different geometry, was analyzed for glucose and hydrogen peroxide (a species involved
in glucose sensing). [1] J. M. Leger, Adv. Mater. 2008, 20, 837. [2] M. J. Panzer, C. D. Frisbie,
Adv. Mater. 2008, 20, 3177. [3] D. Vanmaekelberg, A. J. Houtepen, J. J. Kelly, Electrochem.
Acta 2007, 53, 1140. [4] D. A. Bernards, G. G. Malliaras, Adv. Funct. Mater. 2007, 17, 3538. [5]
D.A. Bernards, G. G., Malliaras, D. J. Macaya, M. Nikolu, J. A. DeFranco, S. Takamatsu, G. G.
Malliaras, J. Mater. Chem. 2008, 18, 116.


10:30 AM *B8.6
Electronic Structure of Organic Heterointerfaces. Henning Sirringhaus, University of
Cambridge, Cambridge, United Kingdom.

Charge injection at metal-semiconductor interfaces as well as transport in the accumulation layer
of organic FETs is critically determined by the electronic structure at these interfaces. In this
presentation we will review our current understanding of the factors that determine the molecular
structure, energetic disorder and polaronic relaxation processes at interfaces and discuss recent
experiments that have yielded information about such processes with high interfacial sensitivity.
A thorough understanding of interfacial electronic structure is needed in order to identify the
factors that limit performance of state-of-the-art organic FETs.


11:00 AM B8.7
Morphology and Energy Levels in Conjugated Polymers: A Theoretical View on P3HT.
Georg Heimel and Juergen P Rabe; Insitut fr Physik, Humboldt-Universitt zu Berlin, Berlin,
Germany.

In the field of organic electronics, -conjugated polymers bear great promise for solution-
processible, flexible applications such as organic light-emitting devices (OLEDs), organic field-
effect transistors (OFETs), or organic photovoltaics. In addition to the bulk material properties of
the active organic part, the interfaces between organic and inorganic components are well
acknowledged to be of paramount importance for device performance and functionality. Most
importantly, the energetic position of the conducting states in the organic material crucially
impacts the energy barriers for charge injection into the device. These barriers not only limit the
overall injection rates but also give rise to often undesirably high onset voltages below which the
device remains inactive. Preparation conditions are know to crucially impact the thin-film
morphology of the prototypical -conjugated polymer region-regular poly(3-hexylthiophene)
and, consequently, also the device characteristics of, e.g., OFETs based on this material (rr-
P3HT). In such devices, it has been shown that an edge-on configuration of highly ordered
polymer chains favorably impacts transistor performance while a face-on morphology proved
detrimental; in the former, the preferential direction for charge transport in these systems, the -
stacking direction in co-facial polymer chains, is aligned with the direction of current flow in an
OFET device geometry. In our contribution, we present density-functional theory (DFT) based
band-structure calculations on highly ordered rr-P3HT monolayers of different morphology, i.e.,
edge-on, face-on, and intermediate regimes. Supported by electrostatic modeling, we find that
the backbone orientation importantly influences the energy-level positions in these thin films due
to intra-molecular surface dipoles. As a consequence, also the hole-injection barriers (HIB) can
be expected to depend critically on thin-film morphology. Our calculations suggest that the HIB
into rr-P3Ht films with edge-on morphology can be up to 0.5 eV lower than into films of face-on
orientation. In addition to underlining the importance of morphology control in polymer-based
organic electronic devices, understanding the impact of intra-molecular surface dipoles also
paves the way towards novel strategies for material design. To that end, we extend our
investigations towards rr-P3HT with end-fluorinated alkyl side-chains. Our calculations reveal
that, due to the strongly negative surface termination in such films, the energy levels in the
polymer could be lowered by as much as 1.5 eV in the edge-on configuration compared to face-
on. This scenario would lead to significantly reduced electron injection-barriers and, thus, favor
device operation involving negative charge-carriers. Consequently, our results imply that such
materials, together with improved control over morphology and electron traps, could potentially
serve as active organic components in n-type polymer OFETs.


11:15 AM B8.8
Influence of Contact Effects on the Switching Behavior of Organic Transistors Arne
Hoppe
1
, Dietmar Knipp
2
, Benedikt Gburek
1
, Marko Marinkovic
2
and Veit Wagner
1
;
1
Molecular
and Nanoelectronics Laboratory, Jacobs University Bremen, Bremen, Germany;
2
Electronic
Devices and Nanophotonics Laboratory, Jacobs University Bremen, Bremen, Germany.

The influence of contact effects on the switching behavior of organic transistors was studied.
High switching frequencies can be achieved by using short channel transistors with high charge
carrier mobilities. However, most of the short channel transistors exhibit a distinct drop of the
device charge carrier mobility. The reduced device mobility is caused by the influence of contact
effects. In this study the influence of the drain/source contacts and the device geometry on the
switching frequency of high mobility dihexyl-7-thiophene (DH7T) oligothiophene thin film
transistors was investigated. The transistors were realized with channel lengths ranging from 50
nm to 50 m. The transistors exhibit high charge charier mobilities of 0.1 cm
2
/Vs and high
switching frequencies between 200 kHz and 2 MHz at low operating voltages of 5 V. The
maximum of the switching frequency is limited by the specific contact resistance and the overlap
capacitance between drain/source and gate electrodes. The normalized contact resistance of the
oligothiophene transistor was determined to be 3.5 kcm. An upper limit of the switching
frequency for organic thin film transistors was derived, which is determined by the specific
contact resistance between the drain and source electrodes and the organic channel material. The
charge carrier mobility does not affect the upper limit of the switching frequency. Different
strategies will be discussed to maximize the cut-off frequency.


11:30 AM B8.9
Polymer-Small Molecule Semiconductor Blends for Integrated Circuits with a 712 ns
Single Stage Delay. Jeremy Smith
1
, Richard Hamilton
2
, Donal D Bradley
1
, Iain McCulloch
2
,
Martin Heeney
3
, Dago de Leeuw
4
, John E Anthony
5
and Thomas D Anthopoulos
1
;
1
Physics,
Imperial College London, London, United Kingdom;
2
Chemistry, Imperial College London,
London, United Kingdom;
3
Materials, Queen Mary University of London, London, United
Kingdom;
4
Philips High-Tech Campus, Eindhoven, Netherlands;
5
Chemistry, University of
Kentucky, Lexington, Kentucky.

Solution processed semiconducting blends of acene based small molecules with amorphous
polymers provide a means of combining the high mobility of the former with the ease of
processing and thin-film uniformity of the latter. We have demonstrated organic field-effect
transistor (OFET) mobilities of up to 2.4 cm2/Vs with low device-to-device variation[1]. This
level of performance qualifies the system for use in integrated circuits with the possibility of
future applications such as organic radio frequency identification tags and electronic paper. High
mobility and optimal device architecture is required to attain a high operation frequency. In this
work logic inverters and ring oscillators have been used to evaluate the dynamic performance of
difluorinated triethylsilylethynyl anthradithiophene blended with a poly(triarylamine) and to
demonstrate that the technology can be transferred from single transistors to multi-transistor
circuits such as ring oscillators. The latter are often used as prototype circuits for the evaluation
of new semiconductors and deposition processes. They allow the determination of an inverter
stage delay, t (i.e. the switching time between a high and a low state) using the equation
t=1/(2nf), where n is the number of inverting stages and f the oscillation frequency. This delay is
proportional to the time taken for charging or discharging at the inverter input/output node and is
in turn determined by the charge carrier mobility, the supply voltage used and the transistor
channel length. Stage delay thus provides a useful indication of the speed of integrated circuit
operation. Ring oscillators were measured with a variety of design rules, specifically channel
lengths, and over a range of supply voltages resulting in the expected trends for oscillation
frequency. To obtain high performance circuits, an understanding of these effects and the ability
to control film morphology within the transistor channels are very important. The highest
mobility transistors employ a top-gate design due to vertical phase separation of the acene
molecule to the semiconductor-dielectric interface[1]. However, a bottom-gate, bottom-contact
circuit architecture is much easier to construct[2]. Hence surface energies and thin film formation
become critical to maintaining a high enough mobility for low t devices. By using short channel
transistors employing gold source-drain contacts functionalised with a self-assembled monolayer
(SAM) as hole injecting electrodes, we have fabricated 7-stage ring oscillators with a single
stage delay of less than 800 ns which, to our knowledge, is one of the fastest organic integrated
circuits to date[3]. This level of performance makes the polymer-small molecule blend an
excellent candidate for use in a wide range of low-end organic electronic applications. [1]
Hamilton, R. et al., Adv. Mater., (2008) in press. [2] Gelinck, G. H. et al., Nature Mater. 3 (2004)
106. [3] Smith, J. et al., (2008) submitted.


11:45 AM B8.10
Charge Transport in Organic Transistors Based on Interconnected Polythiophene
Nanofibrillar Network Embedded in Insulating Polymer Kilwon Cho
1,2
, Longzhen Qiu
1
,
Jung Ah Lim
1
, Juhyun Kim
2
and Wi Hyoung Lee
1
;
1
Chemical Engineering, Pohang University of
Science and Technology, Pohang, Korea, South;
2
School of Environmental Science and
Engineering, Pohang University of Science and Technology, Pohang, Kyungbuk, Korea, South.

Semiconducting and insulating polymer blends has brought a new way to tune the electronic
properties of devices and combine the electronic properties of semiconducting polymers with the
low-cost and excellent mechanical characteristics of insulating polymers. However, the presence
of the insulating component tends to degrade the device performance by diluting the current
density of the film. In this study, we demonstrated that organic field-effect transistors (OFETs)
with excellent electronic performance can be achieved in blends of poly(3-hexylthiophene)
(P3HT) and amorphous polystyrene (a-PS) at very low P3HT content by controlling the
solubility of solvent using a marginal solvent or solvent mixture. The controlled solubility allows
the P3HT chain in blends to form highly crystalline, interconnected nanowire networks
embedded in PS matrix. In particular, the precise control of solvent composition of P3HT/PS
blend by using solvent mixture causes the inkjet-printed blend deposits to form a uniform film-
thickness and highly ordered P3HT nanowire structure in PS matrix. The transistors based on
inkjet-printed P3HT/PS blends exhibits the improved electrical performance even though a
single droplet deposit with super-low content of P3HT (tens of pictogram) is used as an active
material. This finding may offer a excellent route to the direct-write fabrication of OFETs with
low semiconductor cost, high environmental stability, and good mechanical properties.
Acknowledgement. This work was supported by a grant (F0004021-2008-31) from the
Information Display R&D Center under the 21st Century Frontier R&D Program, and Creative
Research Initiative(CRI)-Acceleration Research (R17-2008-029-01000-0).



SESSION B9: Photovoltaics
Chairs: Emil List and Henning Sirringhaus
Thursday Afternoon, April 16, 2009
Room 2001 (Moscone West)

1:30 PM B9.1
Charge Extraction in Planar Heterojunction Organic Photovoltaics. Cody W Schlenker and
Mark E Thompson; Chemistry, University of Southern California, Los Angeles, California.

The buffer layer between the acceptor and cathode in multi-heterojunction organic photovoltaic
(PV) devices has the potential to act as powerful light management tool. However, conventional
buffer materials rely on metal mediated charge transport that is generally limited to ~10 nm,
precluding their use as versatile optical spacers. The complex tris(-diketonato)ruthenium(III)
has shown promising thickness tolerance resulting from reciprocal carrier transport in the
archetypical device anode/CuPC/C60/buffer/cathode. We examined the energetic constraints on
reciprocal carrier transport in the following series of 6 ruthenium diketonate complexes: 1,3-CH3
(acac); 1,3-C6H5; 1-CF2H,3-C6H5; 1-CF3,3-C4H3S; 1-CF3,3-C10H7; 1-CF3,3-C6H5. These
compounds were selected to adjust the carrier injection barriers as their oxidation and reduction
potentials vary by 680 mV and 830 mV respectively. The current density-voltage (J-V)
characteristics of PV devices were recorded in the dark, and under both white and
monochromatic illumination. The fill factor and maximum power output correlate with the
oxidation potential of the Ru complex. Due to concavity changes in the J-V trace, we attribute
this to an interfacial contact resistance arising from an increased hole injection barrier at the
buffer/cathode interface. Charge carrier injection, energy level alignment, and electrical contacts
to organic semiconductors will be discussed, as well as prospects for further study.


1:45 PM B9.2
Energy Level and Morphology Optimization of Small Band Gap Polymers for
Photovoltaics. Arjan Pieter Zoombelt
1,2
, Jan Gilot
1
and Rene Janssen
1,2
;
1
Eindhoven University
of Technology, Eindhoven, Netherlands;
2
Dutch Polymer Institute, Eindhoven, Netherlands.

Many small band gap polymers have been synthesized over the past few years to be utilized in
bulk heterojunction solar cells. The small band gap, in the range of 1.8-1.3 eV, would lead to an
improved overlap of the polymer absorption with the solar emission spectrum, which peaks
around 700 nm (1.77 eV), leading to an increase of absorbed photons and therefore would
enhance the efficiency of solar cells. A successful and flexible strategy to achieve small band gap
conjugated polymers involves the alternation of electron-rich (Donor) and electron-deficient
(Acceptor) units in the polymer chain. The chemical nature of the building blocks and side
chains determines energy level positions. These need to be judiciously positioned with respect to
those of phenyl-C61 butyric acid methyl ester (PCBM), the most commonly used acceptor, to
enable efficient charge separation and maintain the highest possible open-circuit voltage (Voc).
Furthermore, the polymers solubility, molecular weight, crystallization behavior, and miscibility
with the acceptor are key factors in determining photovoltaic performance. A series of new
conjugated polymers will be presented with band gaps ranging from 1.8 to 1.3 eV and energy
levels that are well matched for optimal performance. The focus will be on the effect of side
chain position, head-to-head and head-to-tail coupling, on Voc and short circuit currents (Jsc)
and the influence of solubility and aggregation behavior upon the processing conditions of the
active layer. We will show that a more planar backbone results in a lower Voc, but increases Jsc
due to a slightly improved absorption and hole mobility. In addition, we will present the
optimization of morphology of the active layer for a variety of polymers and show how different
polymers having a different solubility require distinct processing conditions.


2:00 PM B9.3
A Systematic Approach to the Design and Synthesis of New Acceptors for Organic
Photovoltaics. John E. Anthony
1
, Ying Shu
1
, Sean Parkin
1
, Yee-Fun Lim
2
and George G
Malliaras
2
;
1
Chemistry, University of Kentucky, Lexington, Kentucky;
2
Materials Science and
Engineering, Cornell University, Ithaca, New York.

High-performance organic photovoltaic reports are dominated by bulk-heterojunction structures
where semiconducting polymers are blended with the fullerene derivative PCBM (or higher-
order fullerene derivatives of this molecule). We wondered whether the fullerene-based acceptor
could be modified to yield improved open-circuit voltage and short-circuit current. Using an
approach similar to that used to engineer the solid-state order of pentacene, we have found a
simple route to a series of crystalline fullerene derivatives that can be prepared quickly and in
high yield. Our initial studies have shown that changes in the aromatic portion of the substituent
on the fullerene can yield significant changes in open-circuit voltage, arising from changes to the
fullerene LUMO arising from close contact with these pendant aromatic groups. Alternatively,
changes to the hydrocarbon portion of the substituent on the fullerene lead to alteration of the
crystal packing of the fullerene, which profoundly influences the short-circuit current of these
devices. The ability to independently tune both voltage and current is allowing us to explore
wide substitution space in preparing design rules for this class of fullerene-based acceptors. The
high energy requirements for fullerene synthesis may make these materials less desirable as
components of green energy sources. We are concurrently exploring alternative acceptors
based on nitrile-functionalized pentacenes. Here again, functionalization can be used to tune both
photovoltage and photocurrent, and our current best-performing material yields power
conversion efficiency > 1% in photovoltaic cells using poly(3-hexylthiophene) as donor. Our
progress in this material class will also be discussed.


2:15 PM B9.4
Morphological Model of Polymer:Fullerene Solar Cells. Klara Maturova
1
, Martijn Kemerink
1
,
Svetlana S van Bavel
2
and Rene A.J. Janssen
1
;
1
Dept. of Applied Physics, Eindhoven University
of Technology, Eindhvoen, Netherlands;
2
Laboratory of Polymer Technology, Eindhoven
University of Technology, Eindhoven, Netherlands.

Research on organic bulk heterojunction solar cells, which are promising candidates for low cost
energy harvesting, leads to yearly improvements in efficiency. Further improvement requires
better understanding of limiting factors of current devices. It is widely accepted that for
polymer:polymer or polymer:fullerene solar cells the morphology and phase separation are of
high importance. Most of the current device models treat the organic solar cells as homogeneous
devices. Moreover, it is commonly accepted that field dependent exciton dissociation is
responsible for features in high field regime of I-V curves. Here we present results from 1D as
well as 2D modeling of organic solar cells which are based on solving the coupled drift-
diffusion, continuity and Poisson equations. We are able to predict the I-V curves in the
operational and the high field regime. We have chosen three systems: MDMO-PPV:PCBM,
P3HT:PCBM and PF10TBT:PCBM, which represent the improvement in the field of organic
solar cells in going from an efficiency of 1% to 4%. Depending on spincoating conditions,
solvent and composition, and thus on morphology, two distinct situations can be distinguished:
one that can be described by a 1D model, i.e. one where phase separation is irrelevant and one
that requires a 2D model, i.e. inclusion of phase separation. A typical representative of a 2D
structure is MDMO-PPV:PCBM spincoated from toluene on glass/ITO/PEDOT:PSS substrates It
has a coarse phase separation consisting of 500 nm large PCBM clusters surrounded by a blend
of MDMO-PPV and PCBM. We have found that in this type of systems the short circuit current
Jsc and the characteristic linear part at intermediate bias in a double-log I-V curve are
determined by the length scale of the phase separation. The latter feature was previously
assigned to field-dependent exciton dissociation. The coarse phase separation and high electron
mobility in the PCBM cause that lateral charge transport at low fields remarkably contributes to
device current. Also the unannealed 1:1 (mass ratio) P3HT:PCBM and 1:4 PF10TBT:PCBM
cells fall in this 2D category. On the other hand, the annealed 1:1 P3HT:PCBM and the
PF10TBT:PCBM in weight ratio 4:1 (both spincoated from chlorobenzene) have very fine phase
separation and are found to behave mostly 1D-like. P3HT:PCBM after annealing at 130C has
20 nm large nanocrystals of P3HT surrounded by the blend of P3HT and PCBM, and can be
modeled by a 1D model. However to be able to determine the Jsc 2D model has to applied.


2:30 PM B9.5
Polymer Solar Cells using Self-Assembled Monolayers Modified Metal oxide/Metal as
Electron Collecting Electrode Hin-Lap Yip, Steve K. Hau, Hong Ma and Alex K.-Y. Jen;
Materials Science and Engineering, University of Washington, Seattle, Washington.

For efficient electron collection in polymer solar cells, thin films of low work-function metals
such as Ca/Al and LiF/Al are commonly used as the cathode. However, the performance of those
devices is limited by their poor stability due to the vulnerable contact between the polymeric
layer and the reactive metals. Here a simple method was developed to tune the interface of the
cathode in polymer solar cells. This was achieved by inserting a layer of metal oxide/self-
assembled monolayer (SAM) between the active poly(3-hexylthiophene) (P3HT) : [6,6]-phenyl-
C61 butyric acid methyl ester (PCBM) bulk-heterojunction film and the top metal cathode. We
found that the device performance could be significantly altered depending on the magnitude and
direction of dipole, and chemical bonding between the SAM and metals. With appropriate choice
of SAMs, devices showed dramatically improved efficiencies and even high work-function
metals such as Ag and Au could be used as electron collecting electrodes. This finding provides
an efficient method for interface engineering in organic-based optoelectronic devices.


2:45 PM B9.6
Charge-transfer Excitons in Strongly Coupled Supramolecular Semiconductors. Carlos
Silva, Department of Physics, Universit de Montral, Montreal, Quebec, Canada.

Time-resolved and temperature-dependent photoluminescence measurements on one-
dimensional sexithiophene lattices reveal intrinsic branching of photoexcitations to two distinct
species: self-trapped excitons and dark charge-transfer excitons (CTX; 5% yield), with radii
spanning 2-3 sites. The significant CTX yield results from the strong charge-transfer character of
the Frenkel exciton band due to the large free exciton bandwidth ( 400 meV) in these
supramolecular nanostructures.


3:30 PM B9.7
Dye Sensitized Solar Cells Fabricated Using Transparent Vertically Aligned Titania
Nanotube Arrays up to 18 m in Length Grown on FTO Coated Glass. Maggie Paulose
1
,
Oomman K Varghese
1
and Craig A Grimes
2,1
;
1
Materials Research Institute, The Pennsylvania
State University, University Park, Pennsylvania;
2
Department of Electrical Engineering, The
Pennsylvania State University, University Park, Pennsylvania.

Films comprised of a random interpenetrating network of titania nanoparticles, approximately
10-15 m thick, have been the foundation of dye sensitized solar cells since the potential of such
films were revealed by Graetzel and co-workers. Our research efforts to obtain ordered nano-
architectures of titania with superior light transmission and charge transport characteristics
yielded highly ordered nanotube arrays on titanium foils up to several hundred microns in length.
However the opaque Ti substrate necessitates a reversal in the solar cell illumination geometry,
which limits the solar cell efficiency due to loss of light at the counter electrode and electrolyte.
Fabrication of transparent nanotube array films, several microns thick, on FTO-coated glass has
been difficult to achieve. Requirements include the necessity of a thick and well-adhered starting
Ti film on the FTO glass substrate, obtaining suitable transparency in the anodized film, and
achieving a film robust enough to withstand various thermal, physical and chemical processes
during the solar cell fabrication. We have successfully fabricated robust, highly ordered
vertically aligned transparent nanotube array films on FTO glass by anodizing titanium films of
up to 20 m thickness sputter deposited onto FTO glass. The transparent films consist of
nanotube arrays up to about 18 m in length. We will discuss the effects of anodization
chemistry as well as physical and chemical surface treatments on the performance of dye
sensitized solar cells fabricated using these transparent nanotube array films.


3:45 PM B9.8
Carbon Nanotube Based Near-Infrared Photodetectors with >1% External Quantum
Efficiency. Jeramy D. Zimmerman
1
, Michael S Arnold
2
, Xin Xu
3
, Christopher K Renshaw
4
,
Christine M Austin
1
, Richard R Lunt
5
and Stephen R Forrest
1,2,6
;
1
Physics, University of
Michigan, Ann Arbor, Michigan;
2
Electrical Engineering and Computer Science, University of
Michigan, Ann Arbor, Michigan;
3
Electrical Engineering, Princeton, Princeton, New Jersey;
4
Applied Physics, University of Michigan, Ann Arbor, Michigan;
5
Chemical Engineering,
Princeton, Princeton, New Jersey;
6
Materials Science and Engineering, University of Michigan,
Ann Arbor, Michigan.

Organic photodetectors have seen limited success in the near infrared (NIR) region where
detection has had limited success beyond 1000 nm.
i
Carbon nanotubes (CNT) hold great promise
for extending the NIR sensitivity because they can be readily produced with diameters that
absorb between 1000 and 2000 nm and have carrier mobilities exceeding 10
5
cm
2
-V
-1
s
-1
.
ii
Due to
the inherent presence of metallic tubes and difficulties in processing, successful demonstrations
of photovoltaic action have been limited to single CNT devices.
iii
The CNTs are wrapped in the
polymer MDMO-PPV. Films are then doctor bladed onto indium tin oxide coated glass, and
followed by deposition of a compound acceptor/cathode structure by vacuum thermal
evaporation. These devices show CNT based photovoltaic response up to wavelengths of 1450
nm with external quantum efficiencies of over 1.5% at 1155 nm and 1300nm. By adjusting the
processing conditions, dark current rectification ratios of over four orders of magnitude are
achieved. A spectrally resolved specific detectivity of >10
10
cm-Hz
1/2
W
-1
from 400 nm to 1400
nm is realized. These devices significantly extend the detection capabilities of existing organics
into the NIR and indicate a promising new direction for CNT based optoelectronics.
i
R. Kroon
et al., Polym. Rev. 48, 531 (2008)
ii
T. Durkop et al., J. Phys.-Condes. Matter 16, R553 (2004)
iii

P. Avouris et al., Nat. Photonics 2, 341 (2008)


4:00 PM B9.9
Template-Assisted Fabrication of Free-Standing Nanorod Arrays of Semi-Conducting
Polymers for the Preparation of Organic Solar Cells. Niko Haberkorn and Patrick Theato;
Johannes Gutenberg University, Institute of Organic Chemistry, Mainz, Germany.

Arrays of free-standing nanorods are of great interest for the fabrication of high efficient bulk
heterojunction organic solar cells. The ideal structure that has been proposed for organic solar
cells is a bicontinuous and interpenetrating network of donor and acceptor phase, with the
interfacial distance being smaller than the exciton diffusion length in the polymer (~ 10-20 nm).
Such a nanostructured interdigitated network should result in an efficient exciton separation at
the interface between the donor and acceptor phase and the perculated pathways would ensure a
high mobility charge carrier transport to the electrodes. [1][2] In this study, we present a
template-assisted approach to pattern semi-conducting polymers to build up a photoactive layer
with a well-defined morphology that would fulfill the above mentioned requirements for
photovoltaic devices. Anodized aluminum oxide (AAO) membranes with a highly ordered
nanoporous structure were fabricated by a controlled anodization process and used as
templates.[3] [4] These membranes with pore diameters down to 20 nm and pore lengths of
several hundred nanometers were filled with cross-linkable triarylamines by a solution wetting
process. Thermal curing and selective etching of the AAO template resulted in free-standing
nanorod arrays of the cross-linked triarylamines attached to a conductive substrate. To overcome
aggregation and collapse of the nanorods after removal of the template, their aspect ratio was
optimized and a freeze-drying technique was applied after the etching step. Afterwards, an
electron-conducting material, e.g. perylene bisimide derivative, was used to fill the void between
the hole-conducting nanorods, which resulted in a bicontinuous photoactive layer with a large
donor-acceptor interface. The polymeric interpenetrating network was analyzed by cross-
sectional transmission electron microscopy (TEM). Further measurements concerning the
performance of organic photovoltaic devices that have been prepared by this template assisted
approach will be discussed. References [1] X. Yang, and J. Loos, Macromolecules, 2007, 40,
1354. [2] S. Gnes, H. Neugebauer and N. S. Sariciftci, Chem. Rev., 2007, 10, 1324. [3] M.
Masuda, and K. Fukuda, Science, 1995, 268, 1466. [4] M. Steinhart, J. H. Wendorff, A. Greiner,
R. B. Wehrspohn, K. Nielsch, J. Schilling, J. Choi and U. Gosele, Science, 2002, 296, 1997.


4:15 PM B9.10
Vertical Phase-Separation Due to Differences in Surface Energies in Bulk Heterojunction
Polymer Solar Cells. Sarah R. Mednick
2,1
, Anshuman Roy
2
, Ji Sun Moon
2,1
, Sung Heum Park
2

and Alan J Heeger
2
;
1
Materials Science & Engineering, University of California, Santa Barbara,
Santa Barbara, California;
2
Center for Polymers and Organic Solids, University of California,
Santa Barbara, Santa Barbara, California.

The synthesis and testing of new photoactive polymers is steadily improving the light conversion
efficiencies of organic bulk heterojunction (BHJ) solar cells. Understanding the physical
interactions between the polymer donor material and the electron acceptor is critical in
controlling and optimizing the morphology of the blend. While interactions between the donor
and acceptor in the blend determine the scale and stability of lateral phase separation,
interactions between the constituents of the blend and the neighboring device layers are equally
important. In this work, we demonstrate that bulk heterojunction constituents in a polymer solar
cell, i.e. the electron donating material and the electron accepting material, tend to vertically
phase-separate due to differences in surface energies. Using a combination of cross-sectional
transmission electron microscopy (TEM), variable angle spectroscopic ellipsometry (VASE),
and a contact angle study, we probe the vertical phase separation in poly(3-hexylthiophene) :
[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) and poly[N-9-heptadecanyl-2,7-
carbazole-alt-5,5-(4,7-di-2-thienyl-2,1,3-benzothiadiazole)] : [6,6]-phenyl-C71-butyric acid
methyl ester (PCDTBT:PC70BM). Finally, we demonstrate the relevance of vertical phase
separation in understanding the device level physics of bulk heterojunction polymer solar cells.


4:30 PM B9.11
Hybrid Organic/Quantum Dot Photodetector. Tim Osedach
1,3
, Scott M Geyer
2
, John C Ho
1
,
Alexi C Arango
1
, Moungi G Bawendi
2
and Vladimir Bulovic
1
;
1
Department of Electrical and
Computer Engineering, MIT, Cambridge, Massachusetts;
2
Department of Chemistry, MIT,
Cambridge, Massachusetts;
3
School of Engineering and Applied Sciences, Harvard University,
Cambridge, Massachusetts.

We describe a heterojunction photodetector of lateral geometry that consists of molecular
organic and colloidal quantum dot (QD) films. The interface between the organic and QD films
creates a type-II heterojunction that dissociates photo-generated excitons. Carriers are collected
at lateral in-plane electrodes in the presence of an applied electric field on the order of 10^5
V/cm. In contrast to organic photodetectors (PDs) and photovoltaics (PVs) of the more familiar
sandwich geometry, this unique device structure allows for independent optimization of optical
absorption and charge transport through the selection of the heterojunction materials. Optical
sensitivity can be controlled via the selection and sizing of the colloidal QDs and electronic
transport is dominated by the choice of organic film. We present numerical modeling results to
elucidate device operation as well as experimental data characterizing performance for devices
consisting of CdSe QDs and a variety of organic hole-transporting materials including Spiro-
TPD, NPD and MEO-TPD. Current is found to follow Child's Law for space-charge-limited
conduction and high photon-to-electron conversion efficiencies are measured under illumination.


4:45 PM B9.12
Molecular Semiconductor Blends: Microstructure, Charge Carrier Transport and
Application in Photovoltaic Cells. Andreas Opitz
1
, Julia Wagner
1
, Bernhard Ecker
1
, Marcel
Goetzenbrugger
1
, Ulrich Hoermann
1
, Markus Bronner
1
, Michael Kraus
1
, Wolfgang Bruetting
1
,
Alexander Hinderhofer
2
and Frank Schreiber
2
;
1
Institute of Physics, University of Augsburg,
Augsburg, Germany;
2
Institute of Applied Physics, University of Tbingen, Tbingen, Germany.

Blends of organic electron and hole conductive materials are widely used for ambipolar charge
carrier transport and photovoltaic cells. Many investigations have reported an increase of the
solar cell efficiency by optimizing the balance between charge carrier transport in phase-
separated structures and exciton dissociation at the interface between these phases. Here we
show the implications of blending molecular materials for structural, optical and electrical
properties in two model systems. These are (i) fullerene C
60
combined with copper-
phthalocyanine (CuPc) and (ii) CuPc in combination with fluorinated CuPc. The analysis of X-
ray diffraction measurements shows the formation of phase-separated nanocrystals for blends
from C
60
/CuPc and indicates the formation of mixed crystals for the CuPc/F
16
CuPc blends. The
absorption spectra for the nano-phase separated blends scale with the concentration of the
individual components whereas the absorption spectra for the mixed crystals show a decreasing
interaction between the F
16
CuPc molecules. The formation of mixed crystals is a new feature for
organic blends, which has not yet been explored in organic solar cells. Additionally the charge
carrier transport and the electronic structure were analyzed for the C
60
/CuPc blends. The
exponential decrease of the mobility by dilution of the respective transport material indicates that
percolation is a crucial feature in mixtures. Photoelectron spectroscopy measurements show that
mixing of the organic materials reduces the intermolecular gap between the highest occupied
molecular orbital of the donor and the lowest unoccupied molecular orbital of the acceptor. The
C
60
/CuPc system was analyzed also in solar cells. The comparison between bilayered and
blended cells shows a higher open circuit voltage of bilayered cells, which is related to the higher
intermolecular gap in this system. Nevertheless, the blended solar cells reach higher short circuit
currents based on the larger donor/acceptor interface even though the mobility in the mixed
system is much lower. This indicates that other solar cell geometries might be required to
combine a high open circuit voltage and a high short circuit current.



SESSION B10: Poster Session II
Chairs: Saw-Wai Hla, Norbert Koch, Xiaoyang Zhu and Egbert Zojer
Thursday Evening, April 16, 2009
8:00 PM
Salon Level (Marriott)

B10.1
Micro-cavity Effect on Light Extraction Efficiency of Blue Phosphorescent Organic Light
Emitting Devices. Jaewon Lee, Neetu Chopra and Franky So; Dept of Materials Science and
Engineering, University of Florida, Gainesville, Florida.

Recently we reported high efficiency blue phosphorescent organic light emitting devices
(PHOLEDs) (49 cd/A, 23% EQE) by controlling the device charge balance. In this paper we
demonstrated a Iridium(III)bis [(4,6-di-fluorophenyl)-pyridinato-N,C2] picolinate (FIrpic) based
blue emitting micro-cavity PHOLEDs . Our results show that in addition to a slightly blue shift
with spectral narrowing resulting in a more saturated blue color, there is also an enhancement in
current efficiency. Micro-cavity blue PHOLEDs were fabricated on two different dielectric
mirror substrates: two-layer quarter wave stacks (2QWS) with reflectivity of 0.39, and 4-layer
quarter wave stacks (4QWS) with reflectivity of 0.7 at 475nm. The design of the dielectric stacks
is to maximize the micro-cavity effect at 475nm. The devices have the following structure: glass
substrate (1mm)/SiO2 (79nm)/TiO2 (48nm) or SiO2 (79nm)/TiO2 (48nm)/SiO2 (79nm)/TiO2
(48nm)/ITO (50nm)/ 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC) (45nm)/mCP
(10nm)/ [1,4-bis(triphenylsilyl)benzene] (UGH-2) (20nm) doped with 20 wt % FIrpic/ tris[3-(3-
pyridyl)-mesityl]borane (3TPYMB) (40nm)/LiF (1nm)/Aluminum (100nm). Non-cavity devices
were also fabricated on ITO coated substrates without the SiO2/TiO2 dielectric stacks. We found
that the micro-cavity devices show enhancement in current efficiency (61 cd/A compared with
49 cd/A in non-cavity device) in addition to a more saturated blue color in micro-cavity devices
(CIE coordinates of x=0.12 and y=0.26 for the cavity device compared with x=0.15 and y=0.32
for non-cavity device). Furthermore, we also measured the amount of substrate guided modes
and found that the 4QWS cavity device has the strongest substrate modes compared with the
2QWS cavity device and the non-cavity device. Simulation results also confirmed the
experimental data and the substrate modes are coming from the secondary cavity mode at higher
angles.


B10.2
High Efficiency Blue Phosphorescent OLEDs by Tuning Charge Transport in the Emitting
Layer. Neetu Chopra, Jaewon Lee and Franky So; Dept of Materials Science and Engineering,
University of Florida, Gainesville, Florida.

Organic light-emitting diode (OLED) is a promising candidate for solid state lighting and display
applications. While high efficiency green phosphorescent OLEDs (PHOLEDs) have been
demonstrated, the efficiency of blue PHOLED is still low. Hereby, we demonstrate a high
efficiency iridium (III) bis[(4,6-di-fluorophenyl)-pyridinate-N,C2`]picolinate (FIrpic) PHOLED
by enhancing the carrier transport properties of the emitting layer. Charge transport and balance
in OLEDs are very important for achieving high device efficiency. Apart from charge transport
and balance in the charge transporting layers, charge transport in the emitting layer also plays an
important role determining the device performance. In this study we investigate and tune the
charge transport in the emitting layer to achieve high efficiency PHOLEDs. Wide gap materials
are required as the host in blue PHOLEDs. For some wide band gap materials such as p-bis
(triphenylsilyly) benzene (UGH2), they are poor carrier transporters and electro-
phosphorescence occurs by charge trapping on dopant molecules. Thus, the carrier transport
properties of the emitting layer can be tuned by controlling the dopant concentration in the
UGH2 host. In this work, we have fabricated PHOLED devices with different FIrpic
concentrations and found that the carrier transport property of the emitting layer is a strong
function of FIrpic concentration. As the dopant concentration is increased, the current density of
the devices increases and the turn-on voltage decreases. Furthermore, we also found that the
device efficiency increases with increasing FIrpic concentration. A maximum external quantum
efficiency of 25.6% (corresponding to 56 cd/A current efficiency and 40 lm/W luminous
efficiency) was achieved with 20% FIrpic doping concentration. This is one of the highest
efficiencies reported for blue PHOLEDs. Further increase in doping concentration decreases the
device efficiency due to concentration quenching. In addition to OLED devices, single carrier
devices with different FIrpic concentrations were also fabricated and the device data confirmed
the enhanced carrier transport due to doping.


B10.3
Enhanced Performance in Organic Solar Cells using Thermally-evaporated Tungsten
Oxide Interlayer and its Application to ITO-free Organic Solar Cells. Seungchan Han
1
, Won
Suk Shin
2
, Myungsoo Seo
1
, Dipti Gupta
1
and Seunghyup Yoo
1
;
1
Department of Electrical
Engineering and Computer Science, KAIST, Daejeon, Korea, South;
2
Energy Materials Research
Center, Korea Research Institute on Chemical Technology (KRICT), Daejeon, Korea, South.

In line with the recent trend that various metal oxide layers are used as an interfacial buffer layer
in organic solar cells to enhance their photovoltaic (PV) performance [1,2] we explore the effect
of insertion of tungsten oxide (WO3) films on the performance of organic solar cells based on
poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM-60).
Experimental results show that the insertion of thermally evaporated WO3 layer in between ITO
and photoactive layers renders fill factor (FF) and open-circuit voltage (VOC) of P3HT:PCBM
cells get significantly improved from 0.60 and 0.441 V of reference cells to 0.69 and 0.600 V
with the short-circuit current density (JSC) virtually unchanged, resulting in a net improvement
in power conversion efficiency by +67%. X-ray diffraction results consistently indicate that
P3HT films grown on WO3 layers have a higher degree of ordering than those grown on ITO or
on PEDOT:PSS layers. Such difference in growth behavior and PV performance improvement
are discussed in conjunction with the contact-angle measurement which revealed the relatively
low surface energy of WO3 films when compared to those of ITO and PEDOT:PSS surfaces.
Finally, we demonstrate the versatility of WO3 interlayers by presenting ITO-free organic solar
cells that employ a multilayer electrode in which WO3 layers play a key role in terms of both
optical and electrical properties. References [1] M. D. Irwin, B. Buchholz, A. W. Hains, R. P. H.
Chang, and T. J. Marks, PNAS 105, 0711990105 (2008) [2] V. Shrotriya, G. Li, C.-W. Chu, and
Y. Yang, Appl. Phys. Lett. 88, 073508 (2006)


B10.4
A New Physical and Electrical Model of Capacitor Consisting of Organic Semiconductor
and Organic Dielectric.Seung-Hyeon Jeong and Chung-Kun Song; Electronics Engineering,
Dong-A University, Busan, Korea, South.

In this study, we proposed a new physical and electrical model of capacitor consisting of
pentacene organic semiconductor and PVP dielectric. The measured capacitances in the
depletion region for low and high frequency mode as well as the capacitance in accumulation
region for high frequency were identical to the theoretical values. However, for low frequency
the measured capacitance in accumulation region was 40 nF/cm2 much larger than 8.6 nF/cm2 of
the theoretical one. For SiO2 dielectric with pentacene this was not true. The accumulation
capacitance for low frequency was identical to dielectric capacitance of 95 nF/cm2, which
satisfied the theory of MOS capacitor. The reasons of the large accumulation capacitance for low
frequency can be estimated from the two causes. The first one is due to the residual OH- ions in
PVP, and the other on is due to the surface roughness of PVP dielectric layer. Both factors
contributed to the parallel circuit effect of interface capacitance Cit to dielectric capacitance
CPVP instead of serial circuit in the case of pentacene-PVP capacitor. This model was confirmed
by the capacitor with PVP dielectric containing more OH- ions and rougher surface, which
exhibited 55 nF/cm2 in accumulation region for low frequency mode. *This research was
supported by a grant(F0004020-2008-31) from Information Display R&D Center, one of 21st
Century Frontier R&D Program funded by the Ministry of Knowledge Economy of Korean
government.


B10.6
Vertically Phase-separated Conjugated Molecules / Dielectric Bilayer Structure for High
Performance Organic Transistors. Wi Hyoung Lee, Jung Ah Lim, Donghoon Kwak and
Kilwon Cho; Chemical Engineering, POSTECH, Pohang, Kyungbuk, Korea, South.

We report on the structural development and phase separation behavior of spin-cast
triethylsilylethynyl anthradithiophene (TES-ADT) and poly(methyl methacrylate) (PMMA)
blends and their application in field-effect transistors (FETs). The difference of surface energy
between TES-ADT and PMMA causes TES-ADT-the phase with lower surface energy-
segregating at the air-film surface after spin-casting. Furthermore, TES-ADT molecules in
blended films can move toward the air-film surface after solvent-vapor annealing by the
minimization of surface energy, and large crystals of TES-ADT are formed at the surface. The
use of these phase-separated blended film as semiconducting (TES-ADT) and dielectric
(PMMA) layers leads to high performance FETs (i.e., field-effect mobility as high as 0.6 cm2V-
1s-1 and nearly zero hysteresis) because conducting channel is formed at the molecular interface
of phase-separated TES-ADT crystals and PMMA dielectric in a one step-process. In addition,
all organic FETs onto flexible substrates using phase-separated films of TES-ADT and PMMA
are successfully demonstrated using all solution process. Acknowledgement. This work was
supported by a grant (F0004021-2008-31) from the Information Display R&D Center under the
21st Century Frontier R&D Program, Creative Research Initiative(CRI)-Acceleration Research
(R17-2008-029-01000-0), and a Grant (RTI04-01-04) from the Regional Technology Innovation
Program of the MOCIE.


B10.7
Control of Morphology and Crystalline Microstructure of Inkjet-Printed Functionalized
Pentacene via Evaporation-Induced Flows in a Drying Droplet Jung Ah Lim, Wi Hyoung
Lee, Donghoon Kwak and Kilwon Cho; Chemical Engineering, POSTECH, Pohang, Korea,
South.

The evaporation of inkjet-printed droplets on solid surfaces has received special attention as a
key technology for controlling the morphology of dried deposits. The evaporation behavior of
droplets is a function of the liquid composition of the ink, the surface properties of substrate, and
the environmental conditions (i.e., temperature, moisture, and ambient pressure). Since the
surface properties of gate dielectrics in organic transistors significantly influence the
performance of the devices, understanding how the surface wettability of the dielectric layer
influences the evaporation behavior and the distribution of molecules is very important in inkjet
printing of organic semiconductors for the fabrication of organic transistors. In this study, we
systematically studied the self-organization phenomena of an inkjet-printed organic
semiconductor on a dielectric surface with controlled surface wettability through self-assembled
monolayers (SAMs). We used 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS_PEN), which
is a promising organic semiconductor due to its solution processability, and has a significantly
greater -orbital overlap and a smaller interplanar spacing than un-substituted pentacene. As a
result, the different types of evaporation, induced by the various surface wettabilities of the
dielectric substrates, lead to significantly different morphologies and crystalline microstructures
of the deposits. Interestingly, self-aligned TIPS_PEN crystals with highly ordered crystalline
structure were successfully produced on the hydrophilic surface when the contact line was
pinned upon drying. Our study indicates that a control of both contact line dynamics and the
evaporation behavior of inkjet-printed droplets on dielectric surfaces could become a key
technology for inkjet printing of organic semiconductors. Acknowledgement. This work was
supported by a grant (F0004021-2008-31) from the Information Display R&D Center under the
21st Century Frontier R&D Program, Creative Research Initiative(CRI)-Acceleration Research
(R17-2008-029-01000-0), and the ERC Program of MOST/KOSEF (R11-2003-006-06004-0).


B10.8
Effect of the Phase States of Self-Assembled Monolayers on Pentacene Growth and Thin-
Film Transistor Characteristics Hwa Sung Lee, Do Hwan Kim, Jeong Ho Cho and Kilwon
Cho; Chemical Engineering, POSTEH, Pohang, Korea, South.

To investigate the effects of the phase state (ordered or disordered) of self-assembled monolayers
(SAMs) on the growth mode of pentacene films and the performance of organic thin-film
transistors (OTFTs), we deposited pentacene molecules on SAMs of octadecyltrichlorosilane
(ODTS) with different alkyl-chain orientations at various substrate temperatures (30, 60, and
90C). We found that the SAM phase state played an important role in both cases. Pentacene
films grown on relatively highly ordered SAMs were found to have a higher crystallinity and a
better interconnectivity between the pentacene domains, which directly serves to enhance the
field-effect mobility, than those grown on disordered SAMs. Furthermore, the differences in
crystallinity and field-effect mobility between pentacene films grown on ordered and disordered
substrates increased with increasing substrate temperature. These results can be possibly
explained by (1) a quasi-epitaxy growth of the pentacene film on the ordered ODTS monolayer,
and (2) the temperature-dependent alkyl chain mobility of the ODTS monolayers.
Acknowledgement. This work was supported by a grant (F0004021-2008-31) from the
Information Display R&D Center under the 21st Century Frontier R&D Program, Creative
Research Initiative(CRI)-Acceleration Research (R17-2008-029-01000-0), and a Grant (RTI04-
01-04) from the Regional Technology Innovation Program of the MOCIE.


B10.9
Tuning the Threshold Voltage in Organic Field Effect Transistors by Space Charge
Polarization of Gate Dielectrics Heisuke Sakai, Koudai Konno and Hideyuki Murata; Japan
Advanced Institute of Science and Technology, Nomi, Japan.

Studies of gate dielectrics in organic field effect transistors (OFETs) have been attractive
because the electric properties of OFETs are susceptibly affected by the choice of the gate
dielectrics. Here, we demonstrate a tunable threshold voltage in an organic field effect transistor
(OFET) using an ion-dispersed gate dielectrics. By applying external electric field (Vex) to the
gate dielectrics, the dispersed ions in the gate dielectrics are separated by electrophoresis and
form space charge polarization. The drain current of the OFET increased over 1.9 times and the
threshold voltage (Vth) decreased 22 V (from -35.1 V to -13.1 V). The shift direction of Vth was
easily tuned by the polarity of the external voltage. The dielectric permittivity of the gate
dielectrics and mobility of the active layer were unchanged after the polarization of the gate
dielectrics. The UV-VIS differential absorption spectra of the OFETs indicate that there is no
chemical doping in the active layer of the OFETs. These results indicated the shifts of threshold
voltages were originated from the polarization of gate dielectrics.


B10.10
Spin Transport and Magnetoresistance in Organic Semiconductors. Mohammad Yunus
1
,
Paul P Ruden
1
and Darryl L Smith
2
;
1
Electrical and Compueter Engineering, University of
Minnesota, Minneapolis, Minnesota;
2
Los Alamos National Laboratory, Los Alamos, New
Mexico.

Small molecules and polymers of -conjugated organic semiconductors are of interest for the
fabrication of spintronic devices, primarily because the charge carrier spin relaxation times are
expected to be long and integration with extremely spin polarized (half-metallic) materials is
feasible. Half-metallic contacts (or ferromagnetic contacts with spin selective tunnel barriers) can
inject spin polarized charge carriers into organic semiconductors. Detection of the resulting spin
polarization of the current is, in principle, possible through the measurement of the magneto-
resistance of a spin valve device. Indeed, evidence for large MR effects in organic spin valves
has been reported in the literature.[1,2] However, the absence of MR, spin injection, and
transport in organic semiconductors has also been reported.[3] In this work, we model spin
injection, transport, and magneto-resistance (MR) in structures consisting of an organic
semiconductor layer sandwiched between two ferromagnetic contacts. We explore the different
regimes of diffusion dominated and drift dominated current, the effects of contact polarization
ranging from that of conventional ferromagnetic metals to half-metals, and the effectiveness of
spin polarized tunnel injection and extraction for the observation of MR. Carrier transport in
organic semiconductors is modeled with spin dependent device transport equations in drift-
diffusion approximation. We find that half-metallic contacts can inject strongly polarized charge
carriers, but that the resulting spin current does not necessarily manifest itself in a measureable
MR. Small MR effects may be observable at low bias. Furthermore, even in the case of
conventional ferromagnetic metal contacts, spin injection can be greatly enhanced if (spin
dependent) tunneling is the limiting process for carrier injection. However, the spin current by
itself does not give rise to measurable MR. In order to obtain a strong MR effect, we find that a
second tunnel barrier at the extracting contact is necessary. * This work was supported in part by
NSF-ECCS. [1] Z. H. Xiong, Di Wu, Z. Valy Vardeny, and J. Shi, Nature 427, 821 (2004). [2] S.
Majumdar, H. Huhtinen, H. S. Majumdar, R. Laiho, and R. sterbacka, J. Appl. Phys. 104,
033910 (2008). [3] J. S. Jiang, J. E. Pearson, and S. D. Bader, Phys. Rev. B 77, 035303 (2008).


B10.11
Novel Nanocomposites of Covalently Bonded Multi-Wall Carbon Nanotubes to Conducting
Polymers Yeong Joon Kim
1
, Changhyun Park
1
and Jae H Song
2
;
1
Chemistry, Chungnam
National University, Daejeon, Korea, South;
2
Chemistry, Sunchon National University, Sunchon,
Korea, South.

We describe here a synthesis of novel nanocomposites of covalently bonded multi-wall carbon
nanotubes (MW-CNT) to conducting polymers such as polypyrrole. The surface modification of
MW-CNT was done by the reaction with bis(2-picolyl)amine after oxidation. The Fe(III) ions
were able to coordinate to the surface functionalized MW-CNT and were used as in-situ catalysts
for the polymerization of pyrrole. According to TEM images, polymers cover the MW-CNT very
uniformly and the width of resulting nanocomposite can be controlled by the reaction conditions.
We will discuss the physical properties of novel nanocoposites.


B10.12
Self-assembled Nanostructured Molecular Memory Hyoyoung Lee, ETRI, Daejeon, Korea,
South.

For the realization of nano-structured molecular monolayer devices, it is essential to synthesize
and characterize active switching and memory materials that have hysteretic I-V characteristics
in the solid state, develop nano-sized conducting organic electrodes and patterning of active
memory materials on the nano-sized array electrodes. In this presentation, we like to introduce
thiol-terminated metal (Ru, Co, and Fe)-terpyridine, metal-to-ligand charge transfer (MLCT)
complexes for molecular switches and memory devices. Bis(terpyridine)-transition metal
complexes exhibit superior chemical and electronic stability toward redox reactions due to their
octahedral configuration in coordination.[1] We like to also introduce how to improve molecular
device yields using self-assembly technique.[2] For patterning-of organic electrodes, we like to
introduce a self-assembly process for an immobilization of the conducting polymer materials.[2]
Finally we like to present nano-patterning for molecular memory array devices using
nanoimprint lithography.[3] References 1. Seo, K., Konchenko, A. V., Lee, J., Bang, G. S., Lee,
H. Molecular Conductance Switch-On of Single Ruthenium Complex Molecules. Journal of the
American Chemical Society, 130, 2553-2559 (2008). 2. Bang, G. S., Chang, H., Koo, J.-R., Lee
T., Advincula R., Lee, H., The high-fidelity formation of molecular junction device using a
thickness controlled bilayer architecture, Small, 4, 1399-1405 (2008). 3. Jung, M.-H., Lee, H.,
Patterning of conducting polymers using charged self-assembled monolayers, Langmuir, 24,
9825-9831 (2008).


B10.13
Material Design of Triarylamine-Based Amorphous Polymers for Organic Field-effect
Transistors Takeshi Yasuda
1,2
, Takao Suzuki
3
, Mitsuru Takahashi
3
and Tetsuo Tsutsui
4
;
1
Innovative Materials Engineering Lab, National Institute for Materials Science, Tsukuba,
Ibaraki, Japan;
2
PRESTO-JST, Tokyo, Japan;
3
Nanyo Research Laboratories, Tosoh
Corporation, Syunan, Yamaguchi, Japan;
4
Institute for Materials Chemistry and Engineering,
Kyushu University, Kasuga, Fukuoka, Japan.

There has been a recent surge of interest in organic semiconductors with high carrier mobility
through ordering at the molecular level, as in single-crystalline, polycrystalline, and liquid-
crystalline films. However, thin films of organic semiconductors with an amorphous state have
some merits compared to those with the ordered state mentioned above. Most importantly,
morphological effects, which often lead to a poor reproducibility for the performance of organic
field-effect transistors (OFETs) using polycrystalline or liquid-crystalline films, are not a major
consideration. In this study, we have designed and synthesized twenty eight kinds of
polytriarylamine (PTAA)
1)
-based amorphous semiconductors for OFETs. The triarylamine-based
polymers which we developed in this study have different side-alkyl chain systems and
conjugated main-chain each. The molecular weights with polydispersity index, the glass
transition temperature, HOMO energy levels and the optical bandgap were estimated as the
physical and optical properties of polymers. Effects of the molecular design on the performance
of OFETs were also investigated. We fabricated OFETs having a top contact geometry using
amorphous polymers. The polymers as organic semiconductors were spin coated from toluene
solution onto a gate insulator of poly-chloro-p-xylylene (Parylene-C). A shadow mask was
attached onto the film to form Au source-drain electrodes. The field-effect mobility was
calculated from the saturation drain currents. All triarylamine-based polymers in this study
exhibited p-channel behaviors in OFETs and filed-effect hole mobilities were ranging from 10
-6

to 10
-3
cm
2
/Vs. For example, OFETs using a polymer with anthracene unit in the conjugated
main-chain showed a field-effect hole mobility of 6.110
-6
cm
2
/Vs. On the other hand, a
compound having naphthalene unit in the conjugated main-chain exhibited 1.610
-4
cm
2
/Vs. This
study on the field-effect hole mobilities in synthesized twenty eight kinds of triarylamine-based
polymers provides a good start point for molecular design of amorphous organic semiconductors
for OFETs. 1) J. Veres, S. D. Ogier, S. W. Leeming, D. C. Cupertino and S. M. Khaffaf, Adv.
Funct. Mater. 13 (2003) 199


B10.14
Fabrication of Pentacene Organic Thin Film Transistor with a Trapezoid-Shaped Active
Layer for Large Driving Drain Current. Min-Hoi Kim, Jin-Hyuk Bae, Won-Ho Kim, Chang-
Min Keum and Sin-Doo Lee; Electrical Engineering, Seoul National University, Seoul, Korea,
South.

Over the last decade, organic thin-film transistors (OTFTs) have attracted much attention for a
variety of low cost and large area electronic applications including chemical sensors, flat panel
displays, and smart cards. Although a pentacene based top contact OTFT shows good carrier
mobility comparable to an amorphous silicon based TFT, a drain current is still low for realizing
practical applications. In order to enhance the drain current in the top contact OTFT, reduction of
the channel length is one of simple ways since the drain current is inversely proportional to the
channel length. In principle, for a top contact OTFT, it is known to be difficult to fabricate a
short channel without deteriorating the organic active layer during patterning the channel by
lithography. In this work, we fabricate a top contact OTFT with trapezoid-shaped active layer for
a large drain current by using a short channel. Our approach is to use a trapezoid-shaped
structure of the organic active layer tilted from the substrate. The channel length in our
trapezoid-shaped OTFT is reduced as short as 1.5 um, which is 30 times smaller than the channel
length (typically, about 50 um) in a shadow mask-processed top contact OTFT with the help of a
ladder support. Note that the channel in our trapezoid-shaped OTFT is self-patterned by slanted
deposition without a shadow mask. Due to the short channel, a drain current per channel width in
our trapezoid-shaped OTFT is found to reach at about 100 uA/mm, which is at least 10 times
larger than that of the conventional top contact OTFT. Furthermore, our trapezoid-shaped OTFT
is operated at a drain voltage as low as -3V. In conclusion, we fabricated a short channel
trapezoid-shaped OTFT for a large drain current. By slanted deposition, the short channel length
of our trapezoid-shaped OTFT was naturally produced. Our concept of using a ladder support in
the OTFT would be a viable platform for realizing active driving elements in a variety of organic
electronic systems that require large drain currents in a low voltage regime.


B10.15
In Depth Investigations of State of the Art Molecules used to Tune Surface Properties.
Gerold M. Rangger
1
, Oliver T Hofmann
1
, Anna M Track
1
, Ferdinant Rissner
1
, Lorenz
Romaner
1,2
, Benjamin Broeker
3
, Ralf-Peter Blum
3
, Norbert Koch
3
and Egbert Zojer
1
;
1
Institute
of Solid State Physics, University of Technology Graz, Graz, Austria;
2
Department of Materials
Physics, Montanuniversitt Leoben, Leoben, Austria;
3
Institut fr Physik, Humboldt-Universitt
zu Berlin, Berlin, Germany.

The deposition of organic (sub)monolayers on metals is of particularly interest for modifying
surface properties, such as carrier injection barriers, for applications like chemical sensing, and
in the field of molecular electronics. Here, we present a joint theoretical and experimental study
of a number of prototypical acceptor molecules, such as, for example, F4TCNQ. In the
experiments, pronounced changes in the UPS spectra and an increase of the surface work
functions are observed. Density-functional theory based band-structure calculations as well as X-
ray standing wave experiments reveal a heavily distorted adsorbate structure. The modeling
provides also additional information on the intrinsic properties of the interfaces. For example,
employing certain projection techniques reveals that the experimentally observed (partial) filling
of the molecular -LUMO is to a significant extent compensated by back-transfer from localized
sigma-states. With the help of the crystal orbital overlap population (COOP) we identify
especially favored substituents that act as docking groups and, thus, are of particular relevance
when designing new molecules for surface treatments. In addition to varying the adsorbate
molecules, the role of the substrate metal as well as the implications of different packing
densities are discussed relying on the modeling and, whenever possible, also on experimental
data. Support by the European Commission through the STREP project ICONTROL (EC-
STREP-033197) is gratefully acknowledged.


B10.16
Structure and Electronic Properties of Anthraceneselenole SAMs - a Joint Theoretical and
Experimental Study. Anna Maria Track
1,2
, Ferdinand Rissner
1
, Daniel Kaefer
3
, Asif Bashir
3
,
Georg Heimel
4
, Gerold M Rangger
1
, Oliver T Hofmann
1
, Tomas Bucko
5
, Lorenz Romaner
6
,
Gregor Witte
7
and Egbert Zojer
1
;
1
Institut fr Festkrperphysik, Technische Universitt Graz,
Graz, Austria;
2
Institut fr Physik, Karl-Franzes Universitt Graz, Graz, Austria;
3
Lehrstuhl fr
Physikalische Chemie I, Ruhr-Universitt Bochum, Bochum, Germany;
4
Insitut fr Physik,
Humbold-Universitt zu Berlin, Berlin, Germany;
5
Insitut fr Physik, Universitt Wien, Wien,
Austria;
6
Lehrstuhl fr Atomistic Modelling and Design of Materials, Montanuniversitt Leoben,
Leoben, Austria;
7
Molekulare Festkrperphysik, Philipps-Universitt Marburg, Marburg,
Germany.

Self-assembled monolayers (SAMs) provide a simple, flexible, highly ordered and convenient
system to tailor and functionalize surface and interface properties of metals, metal oxides and
semiconductors. In particular, SAMs of -conjugated organic molecules have attracted
significant interest in the field of molecular and organic electronics because of their considerable
conductivity and there ability to change the substrate work function. We performed density-
functional theory (DFT) based slab-type band-structure calculations - including geometry
optimization in internal coordinates - to gain deeper insight into the energetic, chemical, and
physical properties of the interface between a metallic substrate and a covalently bound organic
semiconductor. In particular, we studied SAMs of anthracene-2-selenol on Au(111), which have
been characterized in detail with various experimental methods including Scanning Tunneling
Microscopy (STM), Ultraviolet Photoemission Spectroscopy (UPS), and Low Energy Electron
Diffraction (LEED) [1]. Only the combination of experiments and theoretical calculations allows
an accurate understanding of the structural ordering of the SAM on the surface. After identifying
the correct structure, the electronic properties (such as the work-function modification, the
interfacial charge rearrangements and the energy-level alignment) can be provided theoretically.
The obtained values agree very well with the experimental data which, in turn, allow a
benchmarking of the employed theoretical methods. [1] A. Bashir, D. Kfer, J. Mller, C. Wll,
A. Terfort, G. Witte, Angew. Chem. Int. Ed. 2008, 47, 5250-5252


B10.17
Turning Gold into Lead - Reducing the Work Function by Charge Transfer Monolayers.
Oliver T. Hofmann, Gerold M Rangger, Ferdinand Rissner and Egbert Zojer; Institut fr
Festkrperphysik, Technical University of Graz, Graz, Austria.

Application of (sub)monolayers of organic molecules on metal electrodes in order to tune the
effective work function has become a field of significant interest. Particular electron poor or rich
molecules grow charge transfer layers, which form an infinite dipole layer across the electrode,
thus altering the vacuum potential above the surface and hence its effective work function. In this
contribution, we investigate the interaction between the electron donor viologen and an Au(111)
surface. Depending on the coverage of the monolayer, the work function of the metal can be
theoretically lowered to the value of pristine lead (ca. 4.0 eV) or even that of Mg (ca. 3.7 eV).
Using density functional theory, an in-depth analysis of the electronic structure at the interface is
presented and compared to that of the prototypical donor tetrathiafulvalene (TTF). The work
function modification in both systems is found to be determined by a subtle interplay between
adsorption induced geometric distortions and electron donation from the respective molecular
HOMO to the metal. Unlike carbon monoxide or strong electron acceptors, such as F4TCNQ, on
noble metal surfaces, no significant back donation from the metal into the molecule is observed.
Furthermore, we show that work function modification can also be tuned using spacer elements,
e.g. in the form of voluminous groups enforcing a larger distance between molecule and metal.
With increasing distance the transferred charge decreases. Interestingly, we find that the net
interface dipole increases with increasing distance as will be shown here on the example of
viologen. This work has been supported by the EC through the ICONTROL project.


B10.18
Controllable Shifts in Threshold Voltage of Top-Gate Polymer Field-Effect Transistors and
its Application to Organic Transistor Memory Kang-Jun Baeg
1,3
, Yong-Young Noh
3
,
Henning Sirringhaus
2
and Dong-Yu Kim
1
;
1
Dept. of Materials Science and Engineering,
Gwangju Institute of Science and Technology, Gwangju, Korea, South;
2
Department of Physics,
University of Cambridge, Cambridge, United Kingdom;
3
Convergence Components and
Materials Research Laboratory, Electronics and Telecommunications Research Institute,
Daejeon, Korea, South.

Organic materials are attractive for many components of electronic devices such as active
semiconductor layers, insulator layers, and electrodes, due to a lot of unique advantages over
their inorganic counterparts. Although the organic materials are not currently suitable for
applications requiring high-end performances, their low-cost and low-temperature fabrication
using solution-based processing make them ideal for large-area, flexible, transparent, and
disposable applications. Moreover, organic non-volatile memories are another emerging class of
research fields based on the advantages of organic materials. A variety of approaches have been
progressed including cross-point type organic bistable devices and organic transistor-based
memories. Here we report a solution-processed polymer FET memory device with top-gate and
bottom-contact device configuration. With incorporation of gold nanoparticles (NPs) inside
double-layered polymer gate dielectrics, the threshold voltage (VTh) of polymer FET devices
could be reversibly and systemically controlled by application of external gate fields. This
reversible shifts in VTh was originated from charge trapping in Au NPs, and might be used as
organic transistor based non-volatile memory devices.


B10.19
Ion Irradiation Effects on The Transport Properties and Degradation Mechanisms of
Organic Field-Effect Transistors. Beatrice Fraboni
1
, Anna Cavallini
1
, Piero Cosseddu
2
,
Annalisa Bonfiglio
2
, Yongquiang Wang
3
and Michael Nastasi
3
;
1
Physics, University of Bologna,
Bologna, Italy;
2
Electronic Engineering, University of Cagliari, Cagliari, Italy;
3
Los Alamos
National Laboratory, Los Alamos, New Mexico.

The remarkable advances recently made in the development of organic semiconductor field
effect devices (OFET) prospect challenging applications in the field of low-cost flexible,
lightweight, and conformal electronics One of the interesting features of organic active layers is
their capability to respond to the environment chemical composition, but this unfortunately
opens up the issue of long-term stability of devices based on organic materials, as oxidation is
believed to be a major reason for early device failure. The focus of our research is to investigate
the potentiality of low energy ion irradiation in the reduction and control of the degradation of
the organic material due to the exposure to atmosphere (i.e. oxygen and water). We have studied
the effects of N irradiation on pentacene and sexithiophene based OFETs. The damage induced
by the ions can induce a rearrangement of the molecular alignment by breaking covalent bonds,
crosslinking the neighboring polymer chains and forming a hydrogen-depleted three dimensional
carbon network The strong molecular structure modification affects the carrier mobility and the
threshold voltage of the device, but since the electrical transport in OFETs occurs in a few active
molecular layers at the organic/dielectric interface, we have observed that a controlled damage
depth distribution preserves the functionality of the organic active layer. We have studied the
variation of the transport parameters as a function of the irradiation energy and dose by
characterizing the optical and electrical properties of the material by means of electrical transport
analyses and photocurrent spectroscopy. We have monitored the effectiveness of the low energy
irradiation process in providing an hermetic protection to the organic active layer from the
ambient conditions.


B10.20
PN-junction Diodes made of p-type Pentacene and n-type SnO2 Nanowires. Sung Chan
Park
1
, Daeil Kim
1
, Seongmin Yee
2
, Junghwan Huh
2
, Gyu Tae Kim
2
and Jeong Sook Ha
1
;
1
Chemical and Biological Engineering, Korea University, Seoul, Korea, South;
2
School of
Electrical Engineering, Korea University, Seoul, Korea, South.

PN-junctions are of great importance in modern electronic applications for achieving the
integrated circuits and understanding the device characteristics. In our presentation, we will show
the rectifying current-voltage curves and the temperature dependent diode characteristics. Hybrid
pn-junction devices consisted of p-type organic semiconductor (pentacene) and n-type inorganic
semiconductor (SnO2 nanowires). SnO2 nanowires can be easily synthesized or grown by VLS
mechanism in CVD, showing n-type semiconducting properties with a high mobility. SnO2
nanowire networks were formed by a selective growth on the Au catalyst with various growth
conditions. Onto the SnO2 nanowire networks, pentacene was deposited by thermal evaporation
with various thicknesses under 710^-7 Torr. Ti (20 nm) or Cr (20 nm)/Au (300 nm) electrode
and the 300 nm thickness of Au electrode were deposited on the SnO2 channels and pentacene
channels for Ohmic contacts, respectively, which was confirmed by Ohmic current-voltage
characteristics. Microscopic and chemical analyses were investigated for characterizing each
component of the hybrid pn-junctions. As the temperature decreased, the current levels reduced
following the diode equation of I=I0(exp(kT)-1) with the big ideality factor reaching 420,
which indicate the big surface states at the junction parts. Considering the large ideality factor,
the soft-reverse characteristics were not so significant with a good on/off ratio of 10^3 at 60V.
The possible application of organic/inorganic hybrid pn-diodes will be discussed from the point
of the solar-cell or photo-detectors.


B10.21
Synthesis and Characterization of High Efficiency Copolymers via Effective Energy-
Transfer for Polymer Light-Emitting Diodes (PLEDs) Qinghua Zhao
1
, Shuang Zhang
1
, Jong-
Won Park
1
, Sung Ouk Jung
1
, Yun-Hi Kim
2
and Soon-Ki Kwon
1
;
1
school of materials science and
engineering, engineering research institute (ERI),, gyeongsang national university, Jin ju, Korea,
South;
2
department of chemistry, gyeongsang national university, jin ju, Korea, South.

Polymer light-emitting diodes (PLEDs) have been the subject of intense research interests
recently due to their applications in large-area flat panel displays.1 To achieve highly efficient
PLED devices, charge (holes and electrons) injection and transport from both the anode and the
cathode should be balanced at the junction of the emitting layer to yield the maximum exciton
formation.2 Although some polymer LEDs have shown high-enough efficiencies and long
lifetimes, they are mainly multilayer LEDs, which involve complicated and difficult device
fabrication processes, or single layer LEDs based on polymer blends. So, it is important to
achieve conjugated polymers which have both functions of hole/electron affinity in the single
layer LEDs. The bipolar transport characteristics of polymers are important for high EL
efficiency, because the polymers offer good recombination sites for hole and electron charge
carriers.3 In this communication, we designed and synthesized a series of polymers with hole
transporting and electron transporting ability. Their photophysical and thermal properties would
be investigated and further compared. The PLED devices would be fabricated and discussed
further. These polymers are expected to obtain high efficient from PLEDs due to effective
energy transfer from large bandgap site to narrow bandgap site. [1] J. H. Burroughes, D. D. C.
Bradley, A. R Brown, R. N. Marks, K Mackay, R. H. Friend, P. L Burn, A. B. Holmes, Nature
1990, 347, 539. [2] F. Garten, A Hilberer, F. Cacialli, E. Essenlink, Y. van Dam, B. Schlatmann,
R. H. Friend, T. M. Klapwijk, G.. Hadziioannou, Adv Mater 1997, 9, 127. [3] N. Tamoto, C.
Adachi, K. Nagai, Chem. Mater. 1997, 9, 1077.


B10.22
Abstract Withdrawn


B10.23
Para-sexiphenyl Based OLED Devices Grown on a Pre-patterned Polymeric Substrate.
Gerardo Hernandez-Sosa
1
, Clemens Simbrunner
1
, Thomas Hoefler
2
, Armin Moser
3
, Oliver
Werzer
3
, Birgit Kunert
3
, Gregor Trimmel
2
, Wolfgang Kern
4
, Roland Resel
3
and Helmut Sitter
1
;
1
Institute for Semiconductors and Solid State Physics, Johannes Kepler University Linz, Linz,
Austria;
2
Institute for Chemistry and Technology of Materials, Graz University of Technology,
Graz, Austria;
3
Institute of Solid State Physics, Graz University of Technology, Graz, Austria;
4
Institute of Chemistry of Polymeric Materials, Montanuniversitt Leoben, Leoben, Austria.

During the last years organic devices became of increasing interest in many fields of electronics.
A bright future for organic light emitting devices (OLED) is expected as organics provide a wide
spectrum of molecules emitting at various photon energies [1]. Para-sexiphenyl represents an
organic molecule which has been established as active material for blue emitting OLEDs [2, 3].
As a matter of fact, a defined control of the substrate surface properties is a good way to improve
the quality of organic films. Surface properties like polarity, hydrophilicity or hydrophobicity
can be tuned to change the way the film is growing. These changes can lead to an improvement
on the intrinsic properties of the film and consequently have an impact on the performance of the
final device. Para-sexiphenyl (PSP) has been deposited by Hot Wall Epitaxy (HWE) on
poly(diphenyl bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylate) (PPNB), a photosensitive polymer,
which has been pre-treated by UV illumination leading to a change of the surface polarity [4]. A
detailed analysis of the growth morphology as a function of substrate temperature, growth time
and UV illumination of the substrate has been performed by Atomic Force Microscopy. The
surface morphology and growth kinetics of PSP were found to be different depending on which
surface it was deposited, as prepared or UV exposed. Furthermore, the crystallographic
properties has been analysed by X-ray diffraction and Grazing Incidence X-ray Diffraction
(GIXD). The crystal structure and the degree of order of the deposited PSP thin films were
determined by specular scans and reciprocal space maps. Again a clear change on the structural
properties between the films deposited on the as prepared and pre-treated surfaces was observed.
Besides the film characterization we also report on OLEDs based on Para-sexiphenyl (PSP),
which has been deposited by HWE on a UV pre-treated ITO/PEDOT:PSS/PPNB substrate. A
complete quenching of the PSP electroluminescence is observed on the UV pre- illuminated
regions while on the as-prepared one the characteristic PSP emission is observed. Consequently,
this method has proven to be a very effective pre-patterning tool which could be fully compatible
with the actual OLED production technology. [1] M. Muccini, Nature materials 5 (2006), 605 [2]
G. Kranzelbinder et. al.,Synthetic Metals 102 (1999), 1073-1074 [3] A. Niko et. al., J. Appl.
Phys. 82 (1997), 4177 [4] T. Hfler et al., Polymer 48 (2007), 1930-1939


B10.24
Chemical and Electronic Properties of Self-assembled Organic Monolayers on SiC
Surfaces. I. D. Sharp, M. Hoeb, S. J Schoell, C. Diaz Alvarez, J. Howgate, M. S Brandt and M.
Stutzmann; Walter Schottky Institut, Technische Universitt Mnchen, 85748 Garching,
Germany.

Wide bandgap materials are useful systems for the study of electronic processes at the organic-
inorganic hybrid interface due to the large energetic tunability of the semiconductor Fermi level.
Here, the group IV compound semiconductor silicon carbide (SiC) is used as a model substrate
for organic monolayer self-assembly by reaction with organosilanes and alkenes on both C- and
Si-polar surfaces. Comparison of the properties of both types of films on surfaces of both
polarities reveals the important role of interfacial chemistry and the related binding dipole on the
electronic properties at the organic-inorganic interface. In the well-known case of Si, organic
functionalization is typically achieved via hydrosilylation of H-terminated surfaces or
silanization of an intermediate OH-terminated thin oxide. In contrast, SiC surfaces are OH-
terminated following HF etching and are thus ideally suited for silanization reactions. We
demonstrate that reaction of these surfaces with octadecyltrimethoxysilane (ODTMS) yields
stable, high-quality organic monolayers directly bound to the semiconductor surface without an
oxide interlayer. Furthermore, we show by x-ray photoelectron spectroscopy (XPS) and Fourier
transform infrared (FTIR) spectroscopy that reaction of OH-terminated SiC with 1-octadecene
also yields high quality monolayers but occurs over a bridging oxygen atom that is not present in
the case of hydrosilylated Si. Spectrally resolved photocurrent measurements on functionalized
surfaces reveal significant conductivity enhancements relative to oxidized surfaces, indicating a
reduction of interfacial defect concentrations. These enhancements are particularly pronounced
on C-polar SiC and are greater on alkene-reacted surfaces than on silanized surfaces. Transport
and impedance measurements with a mercury-drop-contact across monolayer-SiC structures
yield thermionic emission barriers and flat band potentials that are consistent with large dipolar
contributions to interfacial band alignment and that depend on the specific chemical binding of
the organic monolayers. Patterned arrays of covalently grafted, fluorescence-labeled proteins
onto SiC were fabricated using both functionalization routes, thus further demonstrating the
potential of the stable, biocompatible SiC surface in future biosensor and protein-integrated
electronics applications.


B10.25
Stability Issues of Organic Thin-Film Transistors. Andreas Klug
1
, Raphael Pfattner
2
, Matthias
Baumann
2
, Gerhild Wurzinger
1
, Arno Meingast
1
, Benjamin Souharce
3
, Michael Forster
3
, Ullrich
Scherf
3
and Emil J.W. List
1,2
;
1
NanoTecCenter Weiz Forschungsgesellschaft mbH, Weiz,
Austria;
2
Christian Doppler Laboratory Advanced Functional Materials, Institute of Solid State
Physics, Graz University of Technology and Institute of Nanostructured Materials and Photonics,
Joanneum Research, Graz/Weiz, Austria;
3
Macromolecular Chemistry, University of Wuppertal,
Wuppertal, Germany.

For more than two decades organic thin-film transistors (OTFTs) have been investigated, being
key devices for large-area, low-cost electronics fabricated with cheap and easy processing
techniques such as spin-coating, inkjet-printing or soft lithography. Essential properties of the
applied organic semiconductors include solution-processability, high field-effect mobility,
compatibility with adjacent layers and - not to forget - stability with respect to ambient
conditions. Here we report on the ambient, operational and shelf-life stability of OTFTs with a
polytriphenylamine-(PTPA)-based polymer active material. The results are benchmarked against
the well-established transistor polymer poly(3-hexylthiophene) (P3HT), yielding comparable
mobility values around 10
-4
cm
2
/Vs. However, upon air exposure P3HT-based devices exhibit
switch-on voltage shifts of more than 30 V and a distinct off-current increase due to
oxygen/moisture-induced doping. Stable air operation therefore involves expensive device
encapsulation or a top-gate architecture, where P3HT is shielded by an appropriate dielectric
material. The corresponding device parameters of PTPA-based OTFTs, on the contrary, remain
rather stable and make device encapsulation obsolete. Moreover, we show that PTPA-based
devices with polyvinylalcohol as dielectric yield improved operational stability and we present
flexible OTFTs based on the two active semiconductor materials.


B10.26
Para-sexiphenyl-CdSe Nanocrystals Hybrid Light Emitting Diodes with Optimized Layer
Thickness and Interfaces. Clemens Simbrunner
1
, Gerardo Hernandez-Sosa
1
, Eugen
Baumgartner
1
, Juergen Roither
1
, Guenter Hesser
2
, Wolfgang Heiss
1
and Helmut Sitter
1
;
1
Institute
of Semiconductors and Solid State Physics, Johannes Kepler University Linz, Linz, Austria;
2
ZONA (Zentrum f. Oberflchen- und Nanoanalytik), Johannes Kepler University Linz, Linz,
Austria.

In the variety of molecules used for Organic Light Emitting Diode (OLED) fabrication Para-
sexiphenyl (PSP) represents a well known candidate for the fabrication of high photon energy
emitting devices [1,2]. The high energy gap (3.1 eV) of PSP and consequently its blue
electroluminescence (EL) emission recommends PSP as a component for multi-color OLED
displays and white LEDs. Recent publications promote solution-based semiconducting
nanocrystals or quantum-dots (QD) integrated within the OLED structure leading to a high
efficient electroluminescence emission of organic-inorganic hybrid devices [3-7]. This approach
requires a very good control of the layer thickness and very well defined interface properties of
the multilayer to obtain a good carrier injection and an efficient electroluminescence (EL). In this
contribution we report on the optimization of the interface and thickness between PSP and CdSe
nanocrystals as well as on the role of PSP as electron transport layer on Hybrid-LEDs. The
devices, emitting at 422nm, 549nm and 610 nm, were fabricated by spin coating the CdSe NC
from solution onto (ITO/PEDOT:PSS) anode substrates and subsequently evaporating PSP under
vacuum conditions. Aluminum contacts provide electron injection in the device structure. The
optimal layer thickness and well defined interface was determined by cross sectional scanning
electron microscopy (SEM), while the carrier injection was studied by monitoring the EL
intensity as a function of emission wavelength and applied device current. The optimized values
were found to be less than 25 nm for the PSP layer and 2 monolayers for the CdSe nanocrystals,
resulting in low onset voltages (3-4 V). Homogeneous layers are achieved across the whole
device which is verified by the resulting homogeneous light emission. The obtained spectra of
the optimized devices indicate high color purity, mainly determined by well defined emission
lines, their low FWHM and the absence of parasitic emissions. Consequently the excellent
device properties achieved by the optimization promote the demonstrated material system for a
future candidate in the fabrication of QD-PSP based LED for displays and lighting applications
[8]. [1] S. Tasch, C. Brandsttter, F. Meghdadi, G. Leising, G. Froyer, L. Althoel, Adv.Mat. 9
(1), 33 (1997) [2] G. Kranzelbinder, F. Meghdadi, S. Tasch, G. Leising, L. Fasoli, M. Sampietro,
Syn. Metals 102, 1073 (1999) [3] S. Coe, W. Woo, M. Bawendi, V. Bulovic, Nature 420, 800
(2002) [4] J. Zhao, J. Bardecker, A. Munro, M. Liu, Y. Niu, I. Ding, J. Luo, B. Chen, A. Jen, D.
Ginger, Nano Lett. 6 (3), 463 (2006) [5] Q. Sun, Y. Wang, L. Li, D. Wang, T. Zhu, J. Xu, C.
Yang, Y. Li, Nature Photonics 1, 717 (2007)


B10.27
Patterning of Organic Monolayers on GaN via UV-induced Charge Transfer. S. J Schoell, J.
Howgate, I. D. Sharp, W. Steins, M. S Brandt, M. Eickhoff and M. Stutzmann; Walter Schottky
Institut, Technische Universitt Mnchen, Garching, Germany.

Understanding charge transfer processes and their mechanisms at organic-inorganic interfaces is
of fundamental importance in the emerging field of organic electronics. Wide bandgap
semiconductors are particularly useful for studying interfacial electronic processes since the bulk
Fermi level can be systematically varied over a wide energy window. Here, the affinity of GaN
to form OH-terminated surfaces by wet chemical treatments is exploited to generate functional
organosilane monolayers. In particular, wet-chemically processed layers of
octadecyltrimethoxysilane (ODTMS) and aminopropyl-triethoxysilane (APTES) on n-type as
well as on p-type Ga-face GaN were formed. For comparative purposes, identical layers were
also formed on n- and p-type 6H-SiC surfaces. The structural and chemical properties of these
layers were studied by static water contact angle measurements, thermal desorption spectroscopy
(TDS), X-ray photoelectron spectroscopy (XPS), Fourier transform IR spectroscopy (FTIR), and
X-ray reflectivity measurements. The organic layers are smooth and change their wetting
properties depending on the molecules used. Thermal desorption temperatures in the range of
500C indicate covalent bonding of the organic molecules to the GaN surfaces. UV-induced
charge transfer between the semiconductor substrate and organic monolayers was studied after
irradiation with a low pressure Hg lamp at a wavelength of 253.7 nm. On n-type GaN this results
in a decreased water contact angle and reduced thickness of the organic layer, saturating at an
illumination time of 30 min. Furthermore, analysis via capacitance-voltage and current-voltage
measurements revealed that this effect is accompanied by the accumulation of trapped charge
within the organic layer. XPS data prove a decreased hydrocarbon signal on UV-irradiated n-
type GaN and FTIR shows a complete loss of terminating endgroups. In contrast, the wetting
behavior, as well as the XPS and FTIR results, of silanized p-type GaN, as well as n- and p-type
6H-SiC, are largely unaffected by UV irradiation, suggesting a photoinduced charge transfer
through the organic/semiconductor interface which leads to the observed degradation for n-type
GaN. This effect was exploited to achieve laterally patterned organic monolayers on n-type GaN
by selective UV illumination through a shadow mask, followed by site-sensitive covalent
grafting of proteins. We thus show that GaN is a useful platform for fundamental studies of
charge transfer processes at the organic-inorganic interface as well as a promising material for
future biosensor applications.


B10.28
Field Effect Transistor as a Platform to Study Photoinduced Processes in a Donor-acceptor
System. K. S Narayan and Manohar Rao; JNCASR, Bangalore, India.

The existence of donor-type polymer FETs exhibiting p-type characteristics and acceptor-type
molecular FETs with n-type characteristics provide an interesting possibility of a combined
active bilayer system, especially under photoexcitation. We present studies of single layer p-
channel P3HT, single layer n-channel PCBM, and bilayer PCBM/P3HT based FETs in dark and
illuminated conditions. The single layer p type mobility was estimated to be 10
-2
cm
2
/V-s and n
type mobility in PCBM was 10
-5
cm
2
/V-s. The bilayer structure was fabricated by introducing
the P3HT film on a PCBM device using different methods. The underlying n-type characteristic
of the PCBM device alters significantly upon illuminating the bilayer structure. Variety of
photophysical processes arising from charge generation and interfacial processes can be followed
and studied by transistor characteristics. These results are compared to the switching and
relaxation effects in single layer P3HT device under photoexcitation.
1,2
References 1)Light
Responsive Polymer Field Effect transistor. Applied Physics Letter, 79, 1891 (2001).
2)Nonexponential relaxation of photoinduced conductance in organic filed effect transistors.
Physical Review B, 68, 125208 (2003).


B10.29
Effect of Donor, Acceptor, and Hole/Exciton Blocking Layer Thickness on Power
Conversion Efficiency for Small-molecular Organic Solar Cells Su-Hwan Lee, Dal-Ho Kim,
Ji-Heon Kim, Tae-Hun Shim and Jea-Gun Park; Nano SOI Process Lab., Hanyang university,
Seoul, Korea, South.

We investigated the dependency of the power conversion efficiency on the thickness of donor
(copper phthalocyanine; CuPc), acceptor (fullerene; C60), and hole/exciton blocking (2,9-
Dimethyl-4,7-diphenyl-1,10-phenanthroline; BCP) layers for the organic photovoltaic (OPV)
devices fabricated with double small-molecular layers. The power conversion efficiency peaked
at a specific layer thickness, ~12.7 nm for the donor layer, ~17.5 nm for the acceptor layer, and
~8.0 nm for the hole/exciton blocking layer. This trend is associated with the light absorption
and carrier transport resistance of the small-molecular donor layer, both of which strongly
depend on the layer thickness. Experimental and calculated results showed that the short-circuit
current (Jsc) due to light absorption increased with the donor layer thickness, while that due to
current through the donor layer decreased with 1/R3. Since the total short-circuit current is the
product of the light absorption current and current through the donor layer, there is a trade-off,
and the maximum power conversion efficiency occurs at a specific small-molecular donor layer
thickness (e.g., ~12.7 nm in this experiment). In addition, power conversion efficiency was
determined by short-circuit-current rather than open-circuit-voltage after light absorption.
Furthermore, the donor layer thickness was more sensitive than the thickness of the acceptor or
hole/exciton blocking layers in improving power conversion efficiency; i.e., ~130% for the
donor layer, ~118% for the acceptor layer, and ~112% for the hole/exciton blocking layers.
Acknowledgement * This research was supported by "The National Research Program for
Terabit Nonvolatile Memory Development sponsored by the Korean Ministry of Knowledge
Economy.


B10.30
Multi-Functional Optical Thin Film Elements by an Imprinting Technique Yong-Woon
Lim, Wonsuk Choi and Sin-Doo Lee; Electrical Engineering and Computer Science, Seoul
National University, Seoul, Korea, South.

In recent years, organic electro-optical materials have great interest for applications in optical
components and liquid crystal displays (LCDs). However, a reliable micro-patterning technology
of organic materials is not well-established so far. The imprinting lithography (IL) is a very
useful method of fabricating such organic-based microstructure devices for use in electronics,
optics, microfluidics, biology, and related areas. In this work, we demonstrate two optical
elements of a liquid crystalline polymer (LCP) and dichroic dyes-doped LCP using an IL
technique combined with the exposure of ultraviolet light. The imprinted optical elements (IOEs)
can be used as both a functional optical film and an alignment layer of the liquid crystal (LC) for
the LC-based optical devices. The multi-functional optical films can be used as an in-cell
retarder or a viewing angle enhancement film and in-cell dye-polarizer. In addition, the
microgrooves produced on the LCP through an IL process are well-defined in shape and so that
they provide the uniform alignment of the LC molecules onto the IOEs without extra-coated
alignment layer by taking the Berremans effect. One IOE with function of in-cell retarder (A-
plate) was fabricated using a LCP with positive dielectric anisotropy such as RMS 03-001C (E.
Merck) by an IL process. The phase retardation of the A-plate measured as a function of
azimuthal angle by a photo-elastic modulation technique is about 1.6. The value was about /2
corresponds approximately to /4 of the wavelength, =632.8 nm, used. On the other hand,
another IOE was fabricated by a same IL process of fabricating the above mentioned A-plate
using another LCP with negative dielectric anisotropy such as RMS 03-015 (E. Merck) instead
of LCP with positive dielectric anisotropy. The hydrophobic surface wettability of used mold
was induced the homeotropic aligned (HA) LCP molecules and the microstructure was
transferred on the LCP layer from the mold. The HA IOE shows the dark state in any direction of
optic axis. And thus, the IOE achieved wider viewing characteristics preserved microstructure on
the surface of the LCP film. The other IOE with function of in-cell dye-polarizer with unique axe
or multi-axes was fabricated using dichroic dyes-doped LCP by an IL process. This thin film
polarizer shows excellent optical performances that can be expressed by the polarization
efficiency and the extinction ratio in combination with single-piece transmittance. For using
above mentioned multi-functional IOEs, we proposed two types of high-efficient LC devices.
Consequently, it possesses high contrast and wider viewing characteristics due to employ two
imprinted multi-functional optical films.


B10.31
Comparative Study of Ni or NiO Treated Hole Injection Property for Organic Light
Emitting Diodes.Sung-Ho Woo
1
, Youngkyoo Kim
2
, Gwijeong Cho
2
, Kangpil Kim
1
, Hongkeun
Lyu
1
and Jaehyun Kim
1
;
1
Division of Nano&Bio Technology, DGIST, Daegu, Korea, South;
2
Department of chemical engineering, Kyungpook National University, Daegu, Korea, South.

In this letter, we compared hole injection enhancing effect for Ni and NiO. Deposition of NiO
layer on ITO showed good property for both hole injection and device efficiency, while Ni was
deviated from expectation, though its work function is adequately high to match with that of ITO
electrode, due to dark-spot formation caused by its unstableness with respect to circumstances
and adjacent layer. We obtained about 50% in-crease of device efficiency as well as 3 times
increase of maximum brightness by insertion of NiO. From energy level diagram, we can suggest
a bifunctional property of NiO layer to facilitate hole injection and block the leakage electron to
ITO, which are come from high work function and wide band gap property, respectively. This
results proposed simple method for improving efficiency of OLEDs device by insertion of
thermal evaporated NiO thin layer without any addition of process facility. It is also widely
applicable to other organic electronic devices such as polymer light emitting diodes, and organic
photovoltaics.


B10.32
Effect of Small-molecular Blocking Layer Thickness on Power Conversion Efficiency in
Small-molecular Blended Polymer Solar Cells Su-Hwan Lee, Dal-Ho Kim, Ji-Heon Kim, Tae-
Hun Shim and Jea-Gun Park; Nano SOI Process Lab., Hanyang university, Seoul, Korea, South.

We investigated the dependency of the power conversion efficiency throughout the blended
donor and acceptor layer thickness variation using poly(3-hexylthiophene (P3HT) and [6,6]-
phenyl-C61 butyric acid methyl ester (PCBM), and small-molecular hole/exciton blocking (2,9-
Dimethyl-4,7-diphenyl-1,10-phenanthroline; BCP) layers for organic solar cells. The power
conversion efficiency peaked at a specific layer thickness, determined by ~1000 rpm for the
blending layer (P3HT and PCBM). This trend is associated with the light absorption and carrier
transport resistance of the blending layer, both of which strongly depends on the blending layer
thickness and shows a trade-off for power conversion efficiency. Also, the blocking efficiency
for the hole/exciton of the BCP layer peaked at a specific thickness (~0.5 nm) of the BCP layer.
This trend is associated with the blocking efficiency and carrier transport resistance, both of
which strongly depends on the blocking layer thickness and shows a trade-off for power
conversion efficiency. In our work, we achieved the maximum power conversion efficiency of
~6.74% for our development small-molecular blended polymer solar cell. Acknowledgement *
This research was supported by "The National Research Program for Terabit Nonvolatile
Memory Development sponsored by the Korean Ministry of Knowledge Economy.


B10.33
Synthesis and Application of New Semiconducting Copolymer for Organic Devices using
N-9-heptadecanyl-dithienopyrrole. Hyung-Gu Jeong, Bogyu Lim, Seok-In Na, Kang-Jun
Beag, Jin-Mun Yun, Juhwan Kim and Dong-Yu Kim; Dept. of Materials Science and
Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju, Korea, South.

The optical and electronic properties of conjugated organic polymers have led to their use in a
variety of applications including organic light-emitting diodes (OLEDs), organic field-effect
transistors (OFETs) and organic photovoltaic cells (OPVs). N-functionalized dithienopyrroles
(DTPs) introduce rigidity to the backbone, resulting in increased planarity and longer
conjugation length. However, some DTPs have low solubilties and low molecular weight, which
greatly limits their use in devices. To make soluble polymers, we incorporated a secondary alkyl
side chains. So we have synthesized N-9-heptadecanyl-dithienopyrrole based copolymers via
stille coupling reaction. The polymer can be easily dissolved in common organic solvents, such
as chloroform, tetrahyrofuran(THF) and chlorobenzene. The good solubility can be attributed to
the bulky side chain. No obvious DSC peak was detected in the trace, suggesting the amorphous
nature of polymer. In this presentation, we will discuss on the performance of OTFTs, OPVs
fabricated using a new semiconducting polymer.


B10.34
Hybrid Organic-Inorganic Heterojunctions made of Doped Crystalline Silicon and a Hole
Conducting Polymer. Roland Dietmueller, Sabrina Niesar, Helmut Nesswetter and Martin
Stutzmann; Walter Schottky Institut, Technische Universitt Mnchen, Garching, Germany.

There is an increasing research activity in hybrid heterojunctions made of organic
semiconductors and inorganic semiconductors, due to their possible applications in new types of
photovoltaic and optoelectronic devices. The use of conjugated polymers for the organic side of
the hybrid heterojunction is especially interesting due to the low-cost fabrication of organic
layers from solution. The inorganic semiconductor, on the other hand, can be easily doped as an
n-type or p-type material at different concentrations, which opens additional possibilities for the
application of hybrid heterostructures. We have studied hybrid heterojunctions as a model
system made of crystalline Silicon (Si) and the organic hole conductor poly(3-hexylthiophene-
2,5-diyl) (P3HT). The heterojunctions were fabricated by spin coating a P3HT layer from
solution on Si wafers with an ohmic metal back contact. Afterwards, a semitransparent
Aluminum front contact was applied on top of the P3HT layer. These devices were characterized
via current-voltage measurements and spectrally resolved photocurrent measurements. To
investigate the influence of doping on the hybrid heterojunction, we performed experiments as
well with n-type Si with a Phosphorus concentration of 1.5 * 10
16
- 1 * 10
17
cm
-3
as with p-type
Si with a Boron concentration of 3 * 10
15
- 2 * 10
16
cm
-3
. Depending on the use of n-type or p-
type Si, we have observed strongly different current-voltage characteristics for the P3HT/Si
heterojunctions. The diode behavior of the p-type Si/P3HT heterojunction can be explained by
the interplay of the p-type Si/P3HT contact and a Schottky contact at the P3HT/Al interface,
which dominates the electrical characteristics of the whole structure. This finding is supported by
the current-voltage characteristics under illumination with white light, when the p-type Si/P3HT
heterostructure works as a solar cell with similar characteristics as a P3HT/Al Schottky solar
cell. However, for the n-type Si/P3HT heterojunction a more complex current-voltage
characteristic is observed, where under illumination of the heterostructure the forward direction
of the diode is inverted. To explain this behavior, we take into account two rectifying interfaces
with different forward directions, namely the Si/P3HT heterojunction and the P3HT/Al Schottky
contact, and also the strong influence of photo-generated charge carriers on the Si/P3HT
heterojunction. These investigations are important for the understanding of the fundamentals of
the organic-inorganic interface in semiconductors.


B10.35
Novel Water-Soluble Polyfluorenes as an Interfacial Layer in Polymer Solar Cells with
High Work-Function Metal Cathodes. Seung-Hwan Oh
1
, Seok-In Na
1
, Jang Jo
1
, Yung-Eun
Sung
2
and Dong-Yu Kim
1
;
1
Department of Materials Science and Engineering, Gwangju
Institute of Science and Technology (GIST), Gwangju, Korea, South;
2
School of Chemical &
Biological Engineering, Seoul National University, Seoul, Korea, South.

Water solubility of conjugated polymers may offer many applications. Potential applications of
water-soluble conjugated polymers include the polymer light-emitting diode and new materials
for nano and micro hollow-capsules, and bio- or chemo-sensors. We synthesized neutral
polyfluorenes containing bromo-alkyl groups by the palladium catalyzed Suzuki coupling
reaction. Bromo-alkyl side groups in neutral polyfluorenes were quaternized by tri-methyl amine
solution. The electrochemical and optical properties of water-soluble conjugated polymers are
discussed. This novel synthesized water-soluble conjugated polymers were used as a dipole layer
between active layer and metal cathode in polymer solar cell for enhancement of open-circuit
voltage (Voc), which is one of the most critical factors in determining device characteristics. We
also investigated the device performance of polymer solar cell with different metal cathode such
as Al, Ag, Au and Cu. In polymer solar cell, novel cationic water-soluble conjugated polymers
were inserted between active layer and high-work function cathode (Al, Ag, Au and Cu).


B10.36
Crystallization of Organic Molecules on the Monolayers of Binaphthyl Derivatives for
Thin-Film TransistorsSang-Mi Jeong
1,2
and Ji-Woong Park
1,2
;
1
Materials Science &
Engineering, Gwangju Institute of Science and Technology, Gwangju, Korea, South;
2
Program
for integrated Molecular Systems, Gwangju, Korea, South.

Monolayers of 1,1-bi-2-naphthol (BN) derivatives, of which the two naphthalene rings are
twisted along the carbon(1)-carbon(1) single bond, were studied for their conformational effect
on the growth of the organic molecules on their monolayer surface. We demonstrate that when
pentacene was thermally evaporated on the BN monolayer, the crystallization of the pentacene
molecules occurred at a low nucleation density and a high growth rate because the amorphous
nature of the BN monolayer hindered the intermolecular packing between neighboring
absorbates in the diffusion regime of the crystallization. We also found that the BN monolayer
caused the similar effect in the solution phase crystallization of anthracenes. We fabricated
organic thin film transistors (OTFTs) with the BN monolayers coated between the insulator and
semiconductor layers. The electrical properties of these devices were compared with those
constructed on the bare silica surface. The field-effect mobility () of the device with the BN
monolayer appeared 50% higher than those of silica. The morphology of the semiconductor layer
was investigated using atomic force microscopy (AFM) and X-ray diffraction (XRD) method.
AFM image showed that the pentacene layer on the BN monolayer consisted of larger and more
interconnected grains than those on the silica surface. XRD spectra of the 50 nm thick pentacene
film exhibited that the pentacene crystals on the BN monolayer consisted of mostly thin film
phase (d
001
= ~15.5 ) while those on the silica surface contained both the thin film phase (d
001
=
~15.5 ) and bulk phase (d
001
= ~14.5 ).


B10.37
Synthesis of Polymeric Self-Assembled Monolayer Using a Surface-Reactive Rod-Coil
Diblock Copolymer. Mingu Han and Ji-Woong Park; Gwangju Institute of Science and
Technology, Gwangju, Korea, South.

Rodlike polymers which are composed of a rigid backbone with alkyl side groups can be
consider as one-dimensional self-assembled monolayers (SAMs). If the rods with alkyl side
groups are aligned on the surface with thickness of a single chain diameter, this SAMs become
two-dimensional. Attaching a short surface-reactive coil to the end of rod, the rigid rodlike
polymer can be anchored onto the surface via covalent bonding. The resulting surface tethered
rodlike chains form a polymeric self-assembled monolayer (PSAM). Because the rodlike blocks
of the PSAM are aligned to rotate in their azimuthal and polar anchoring angle, the PSAM may
be stimuli-responsive. In our previous study, we showed that an amphiphilic rod-coil block
copolymer was strongly adsorbed by the hydrogen bonding of coil blocks onto mica surface and
that the rodlike PHIC blocks oriented planar to the surface to form liquid crystalline SAM[1,2].
Here we synthesize, poly(n-hexylisocyanate)-b-poly[(3-trimethoxysilyl)propyl methacrylate]
(PHIC-b-PTMSPMA), a new rod-coil block copolymer which can form PSAM via covalent
bonding of the alkoxysilyl containing PTMSPMA coil block to the silica substrate. The PSAM
was simply produced by the immersion coating method. It exhibited uniform thickness of about
1.6 nm with low RMS roughness of below 0.4 nm. The water contact angle of the PSAM was
about 100. The PSAM showed an anisotropic morphology resulting from local ordering of
grafted rods on annealing with tetrahydrofuran (THF) vapor. P3HT-based Field-Effect
Transistors (FETs), which were fabricated using a PSAM-coated SiO2/Si substrate, exhibited
about one order of magnitude higher charge carrier mobility than those using untreated silica
dielectric layer. We also demonstrate that PSAM is micro-patternable using UV-induced
photochemical cleavage of the methacrylate moieties of the anchoring blocks (PTMSPMA).
Acknowlegdment : This work was supported by the Korea Science and Engineering Foundation
(KOSEF) grant [R01-2008-000-12246-0] funded by the Korean goverment (MEST) and the
Program for Integrated Molecular System at GIST, Korea Reference : [1] J. H. Kim, M. S.
Rahman, J. S. Lee, J. -W. Park, J. Am. Chem. Soc. 2007, 129, 7756-7757 [2] J. H. Kim, M. S.
Rahman, J. S. Lee, J. -W. Park, Macromolecules 2008, 41, 3181-3189


B10.38
Degradation of Ir(ppy)
2
(dtb-bpy)PF
6
iTMC OLEDs Velda Goldberg
1
, Michael D Kaplan
1,2
,
Leonard Soltzberg
2
, Dolly Armira
2
, Megan Bigelow
1
, Rachel Brady
2
, Shannon Browne
1
, Bianca
Dichiaro
1
, Heather Foley
1
, Lauren Hutchinson
2
, Alison Inglis
2
, Nicole Kawamoto
2
, Amanda
McLaughlin
2
, Caitlin Millett
2
, Hanah Nasri
1
, Sarah Newsky
2
, Tram Pham
2
, Cassandra Saikin
2
,
Mary Scharpf
2
, Melissa Trieu
2
, George G Malliaras
3
and Stefan Bernhard
4
;
1
Physics, Simmons
College, Boston, Massachusetts;
2
Chemistry, Simmons College, Boston, Massachusetts;
3
Materials Science & Engineering, Cornell University, Ithaca, New York;
4
Chemistry, Princeton
University, Princeton, New Jersey.

Simplicity of construction and operation are advantages of iTMC (ionic transition metal
complex) OLEDs compared with multi-layer OLED devices. Unfortunately, lifetimes do not
compare favorably with the best multi-layer devices. We have previously shown for
Ru(bpy)
3
(PF
6
)
2
based iTMC OLEDs that electrical drive produces emission-quenching dimers of
the active species. We report evidence here that a chemical process may also be implicated in
degradation of devices based on Ir(ppy)
2
(dtb-bpy)PF
6
albeit by a very different mechanism. It
appears that degradation of operating devices made with this Ir-based complex is related to
current-induced heating of the organic layer, resulting in loss of the dtb-bpy ligand. (The neutral
dtb-bpy ligand is labile compared with the cyclometallated ppy ligands.) Morphological changes
observed in electrically driven Ir(ppy)
2
(dtb-bpy)PF
6
OLEDs provide evidence of substantial
heating during device operation. Evidence from UV-vis spectra in the presence of an electric
field as well as MALDI-TOF mass spectra of the OLED materials before and after electrical
drive add support for this model of the degradation process.


B10.39
Industrial Applicability of Molecular Acceptors in Organic Electronic Devices using Wet-
chemical Deposition. Sibe Mennema
1
, Stephan Harkema
2
, Ralph Rieger
3
, Walter Stals
1
, Jorgen
Sweelssen
1
, Hans Joachim Raeder
3
, Klaus Muellen
3
and Herman Schoo
2
;
1
TNO Science and
Industry, Eindhoven, Netherlands;
2
Holst Centre, Eindhoven, Netherlands;
3
Max Planck Institute
for Polymer Research, Mainz, Germany.

The relative position of the energy levels of the various materials used in organic electronic
devices is of critical importance for their efficient operation. Molecular acceptors, e.g.
tetracyanoquinodimethane (F4TCNQ), are molecules that have the capacity to raise the work
function of a metal surface upon chemisorption. The chemisorption of such acceptors is
accompanied by an electron transfer from the metal to the molecule, thus introducing local
dipoles with their negative ends oriented away from the surface, and increasing the work
function. The area-averaged work function of a metal surface can be adjusted by controlling the
area density of such dipoles. This principle has previously been demonstrated through UHV
deposition and XPS / UPS analysis [1]. Here the transfer of this concept to a solution-based
process, which was carried out in ambient conditions, is presented. Apart from results on
F4TCNQ, also results are discussed of the purposely synthesised hexacyanohexaazatriphenylene
(HATCN). HATCN is also a very strong acceptor, but is expected to persist better at the
interface due its planar configuration, larger size and six instead of four binding sites. Spin-
coating and dip-coating were used to deposit the electron acceptors onto the metal(oxide)
surface. The area density of acceptors was controlled through the concentration of molecules in
solution. Following deposition, Kelvin Probe Force Microscopy (KPFM) was used to investigate
the induced work function changes. An increase of up to 0.9 eV was observed for various
molecular acceptors on ITO, Ag and Au surfaces, and lower concentrations lead to smaller work
function changes. Furthermore, results of devices in which molecular acceptors were
incorporated are presented. Using wet-chemical processing in ambient conditions, Organic
Light-Emitting Diodes (OLEDs) and Organic Photo-Voltaic Cells (OPVCs) were fabricated on
lab-size 33 cm
2
wafers as well as industrial size 1515 cm
2
wafers. The concentration of
molecular acceptors had a substantial effect on the electronic and optical properties of the
devices, clearly indicating that the work function changes observed by KPFM can be related to
device characteristics. In the case of OLEDs, the onset voltage has been varied by a factor 2, and
the luminance at a fixed voltage by an even larger factor. In the case of OPVCs, the open-circuit
voltage can be controlled in a similar way. Routes towards exploiting these results in practical
applications will be discussed. [1] N. Koch et al., Phys. Rev. Lett. 95 (2005) 237601


B10.40
Comparison of Molecular Monolayer Interface Treatments in Organic-inorganic
Photovoltaic Devices. Jamie Albin
1
, Darick J Baker
1
, Cary G Allen
1
, Tom E Furtak
1
, Reuben T
Collins
1
and David S Ginley
2
;
1
Physics, Colorado School of Mines, Golden, Colorado;
2
National
Renewable Energy Laboratory, Golden, Colorado.

Excitonic hybrid organic-inorganic solar cells are gaining viability as alternatives to p-n junction
photovoltaics. Although hybrid cells typically have lower efficiencies than their inorganic
counterparts, they are more compatible with inexpensive manufacturing techniques such as spray
deposition and roll-to-roll processing, which can reduce the fabrication cost per photovoltaic
watt. Polymer devices with nanostructured ZnO as the electron-accepting layer have the potential
to improve carrier collection and power conversion efficiency in the bulk heterojunction
approach to organic solar cells. The ZnO/polymer interface, however, is not optimal and
properties such as polymer ordering and wetting at the interface need improvement.
Functionalization of the ZnO surface with molecular monolayers has the potential to resolve
these issues. In this study, we compare the performance of inverted planar ZnO/P3HT
photovoltaic cells made from sol gel-derived ZnO that was functionalized using thiol and silane
based attachment chemistries. Differences in the attachment scheme were explored using
molecules with the same end group. For example, octadecyltriethoxysilane (OTES) and
octadecylthiol (ODT) both yield surfaces with an 18 carbon alkyl chain termination. Both
showed improved polymer ordering relative to control samples. The ODT-modified devices had
higher efficiencies than OTES-treated devices, however, both treatments led to decreased short
circuit current compared to optimized control devices. Similarly, the effect of the end group was
explored using molecules that attach with the same chemistry but leave different, exposed,
terminal groups. Phenyltriethoxysilane (PTES) treated ZnO, for example, shows significantly
improved polymer wetting relative to OTES treatment and untreated surfaces. We discuss these
observations in terms of the nature of the terminal group, differences in the attachment scheme
(silicon vs. sulfur), and differences in surface coverage of the molecular layers. This work was
supported by the National Science Foundation under Grants DMR-0606054 and DMR- 0820518.


B10.41
Prediction of Dynamical Properties of Organic Field-Effect Transistors from DC
Transistor Parameters. Benedikt Gburek and Veit Wagner; School of Engineering and Science,
Jacobs University Bremen, Bremen, Germany.

Dynamical properties of Organic Field-Effect Transistors (OFETs) are of crucial importance for
almost any application. However, not direct AC data but DC measurements are usually used to
optimize transistor performance. Here we present a systematic study to which extent DC
parameters can actually be used to predict AC performance and AC limits of transistors. The
standard FET theory for long channel devices predicts a maximum device bandwidth of B =
V / L2. However, this holds only for ideal situations, e.g. without parasitic capacitances, and not
too high frequencies. Furthermore, as was recently shown [1], contact resistances can pose
severe additional high-frequency limits to the AC performance. To check the AC limit of a given
transistor directly we perform a frequency scan up to the frequency where the gate current equals
the drain current, which denes the true bandwidth of the device. The frequency-scanned AC
voltage is applied at the gate while the drain contact is kept at a constant voltage. The
dependence of the bandwidth on the drain-source voltage as well as on the DC offset of the gate-
source voltage is analyzed in detail. Among others, this analysis allows for a more accurate
determination of the threshold voltage, often difficult to be determined from standard DC
transistor characteristics. In addition, it offers better insight into carrier mobility dependencies
and distribution of energy states. A model which denes a correction factor to the ideal B =
V / L2 behavior is proposed in order to predict the measured bandwidth from DC transistor
parameters correctly. The model takes into account parasitic capacitances which occur from the
source and drain contacts. Furthermore, limitations of the bandwidth due to contact resistance are
presented and included in the model. [1] V. Wagner, P. Wbkenberg, A. Hoppe, J. Seekamp,
Appl. Phys. Lett. 89 (2006) 243515


B10.42
Ambipolarity and Light Emission from Acene Based Transistors. Martin Schidleja, Christian
Melzer and Heinz von Seggern; Institute of Material Science, Technische Universitt Darmstadt,
Darmstadt, Germany.

Polycrystalline ambipolar light-emitting organic field-effect transistors (LEOFETs) offer new
possibilities for the characterization of ambipolar devices. The main obstacles for the further
development of LEOFETs is the lack of efficiency, brightness and the limited choice of materials
allowing for high injection efficiency, charge carrier mobility and fluorescence yield. In our
contribution the realization of low injection barrier LEOFETs will be investigated using different
acenes as active layer and its relevance for organic light-emitting diodes (OLEDs) will be
discussed. Devices based on F8BT (poly(9,9-di-n-octylfluorene-alt-benzothiadiazole)) as
semiconductor and gold as source/drain metal show rather efficient light emission. Recent results
disclose a contact dominated device behavior due to high injection barriers for both charge
carrier types. In order to reduce the injection barriers Ca and Au as source and drain contacts in
combination with organic materials such as pentacene, tetracene and ditetracene with electron
affinities (EA) and ionization potentials (IP) matching the metal workfunctions are used. It will
be demonstrated that all these device structures exhibit light emission, meaning ambipolar
conduction, and how that can be utilized to investigate the injection efficiency of the individual
material combinations. Although light emission verifies the presence of electrons and holes in all
devices, the electron conduction in the channel deteriorates for decreasing EA of the organic
semiconductor. Polycrystalline pentacene allows for rather balanced electron and hole
conduction whereas the electron mobility worsens for ditetracene and tetracene. In all acene
based devices the highest intensity of the emitted light is observed in the hole dominated regime,
next to the Ca source electrode, indicating highly efficient electron injection from Ca into the
respective acene. This behavior cannot be observed in F8BT based devices due to the high
injection barriers for both charge carriers from the utilized gold electrodes. In the presented
contribution the relative impact of injection compared to transport will be highlighted and its
applicability to OLEDs will be discussed.


B10.43
Interface Engineering in Organic Thin Film Transistors. Philipp Stadler
1
, Anna Track
3
,
Mujeeb Ullah
2
, Thockchom B Singh
1
, Gebhard J Matt
1,2
, Helmut Sitter
2
, Michael G Ramsey
3

and N. Serdar Sariciftci
1
;
1
Institute for Organic Solarcells, Johannes Kepler University, Linz,
Austria;
2
Institute for Solid State Physics, Johannes Kepler University, Linz, Austria;
3
Institute
for Physics, Karl Franzens University, Graz, Austria.

Interface engineering in organic thin film transistors (oTFT) has become the key issue for
optimizing the device operation. Recent effort has been made by using passivation layers on top
of silicon dioxide (SiOx) and alumina (Al2O3) [1]. In this work we present a oTFT with C60 as
semiconductor in bottom gate and top contact structure. We compared silicon dioxide,
electrochemically grown alumina and divinyltetramethyldisiloxane-bis(benzocyclobutene)
(BCB) on alumina as gate insulator [2,3,4]. The nature of the interfaces between C60 and the
BCB and between C60 and the oxide insulators is studied in detail by X-ray and ultraviolet
photoemission spectroscopy (XPS and UPS). The interface system fullerene and oxide is
displaying large positive threshold voltages and lower drain/source currents in
accumulation/depletion regime as compared to oTFT's using organic gate insulators [5]. Here we
experimentally show that by introducing a thin polymeric buffer layer (BCB) between the oxide
and the fullerene the threshold voltage of the transistor characteristics can be shifted from
positive values in the oxide case to negative values in the polymer case [6]. The transistor is
operating within one volt and we observe an enhanced on/off ratio (4 decades) and an electron
mobility of approx. 1 cm2 V-1 s-1. We correlate this different transport performance to the
change in the work function of the semiconductor seen in the UPS specta and the shift in binding
energy of the C1s peak of the C60 in the XPS spectra respectively. [1] M. Halik, H. Klauk, U.
Zschieschang, G. Schmied, C. Dehm, M. Schtz; S. Maisch, F. Effenberger, M. Brunnbauer, F.
Stellacci, Nature 431, 963-966 (2004) [2] T. D. Anthopoulos, T. B. Singh, N. Marjanovic, N.S.
Sariciftci, A. Ramil, H. Sitter, M. Clle, D. de Leeuw, Appl. Phys. Lett. 89 213504-1 (2006) [3]
T. B. Singh, N. S. Sariciftci, H. Yang, L. Yang, B. Plochberger, H.Sitter, Appl. Phys. Lett., 90
(2007) [4] R. Schroeder, L. A. Majewski, M. Grell, Adv. Mater. 16, 633 (2004) [5] G. Horowitz,
R. Hajlaoui, R. Bourguiga, M. Hajlaoui, Syn. Met. 101, 401-404 (1999) [6] X. H. Zhang and
Kippelen, Appl. Phys. Lett. 93, 133305 (2008)


B10.44
New Air-Stable Organic Semiconductor for p-Channel Transistors with Large Mobility
and Low-Voltage Integrated Circuits on Flexible Substrates. Ute Zschieschang
1
, Tatsuya
Yamamoto
2
, Kazuo Takimiya
2
, Tsuyoshi Sekitani
3
, Takao Someya
3
and Hagen Klauk
1
;
1
Max
Planck Institute for Solid State Research, Stuttgart, Germany;
2
Hiroshima University, Higashi-
Hiroshima, Japan;
3
University of Tokyo, Tokyo, Japan.

The performance of organic thin-film transistors (TFTs) often degrades upon exposure to air.
This is due to the generation of charge traps as a result of the oxidation of the conjugated
molecules. One strategy to improve the air stability of organic TFTs is thus the synthesis of
organic semiconductors with reduced susceptibility to oxidation. For p-channel TFTs this implies
a large ionization potential. However, most organic TFTs using semiconductors with large
ionization potential show rather small hole mobilities, usually below 0.5 cm2/Vs [1-3]. This has
been attributed to poor molecular ordering and hence poor overlap of the molecular orbitals.
Recently, a six-ring fused heteroarene, dinaphtho-[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT),
was synthesized that has a large ionization potential (5.4 eV) and forms well-ordered films, with
hole mobilities as large as 2 cm2/Vs for TFTs made on doped silicon wafers (serving as a global
gate electrode) with a thermally grown SiO2 gate dielectric [4]. Here we report on the
performance and stability of DNTT transistors, inverters and ring oscillators on glass and flexible
polyethylene naphthalate (PEN) substrates. The TFTs and circuits use an inverted staggered
(bottom-gate, top-contact) device structure with patterned aluminum gates, a thin gate dielectric
based on an oxygen-plasma-grown aluminum oxide layer (3.6 nm thick) in combination with a
self-assembled monolayer (SAM) of an aliphatic phosphonic acid (1.7 nm thick), a thermally
evaporated DNTT layer and gold source/drain contacts. Gates, semiconductor, and source/drain
contacts were patterned using shadow masks. Owing to the large capacitance of the AlOx/SAM
gate dielectric (700 nF/cm2), the TFTs and circuits can be operated with low voltages of about 3
V. DNTT TFTs on glass have a mobility of 1.5 cm2/Vs, an on/off ratio of 1e7 and a subthreshold
swing of 80 mV/decade. On flexible PEN, the TFTs have a mobility of 0.6 cm2/Vs, an on/off
ratio of 1e7 and a subthreshold swing of 110 mV/decade. These mobilities are a factor of 2 larger
than those of pentacene TFTs manufactured with the same technology [5]. Because the
ionization potential of DNTT (5.4 eV) is much larger than that of pentacene (5 eV), the DNTT
TFTs have significantly better air stability, showing no degradation while stored in ambient air
for 3 months. Five-stage ring oscillators based on unipolar inverters with saturated load show
stable oscillations for supply voltages between 2.2 and 5 V, with a signal delay of 37 sec per
stage (27 kHz) at 3 V and 18 sec per stage (55 kHz) at 5 V. This is the highest frequency
reported for flexible organic circuits at low supply voltage. [1] H. Meng et al., J. Am. Chem.
Soc., vol. 123, p. 9214, 2001. [2] J. A. Merlo et al., J. Am. Chem. Soc., vol. 127, p. 3997, 2005.
[3] J. Locklin et al., Adv. Mater., vol. 18, p. 2989, 2006. [4] T. Yamamoto et al., J. Am. Chem.
Soc., vol. 129, p. 2224, 2007. [5] H. Klauk et al., Nature, vol. 445, p. 745, 2007.


B10.45
Optical Stability of Small-molecule Thin-films Determined by Photothermal Deflection
Spectroscopy. Marco Stella
2
, Monica Beatriz Della Pirriera
1
, Joaquim Puigdollers
1
, Cristobal
Voz
1
, Jordi Andreu
2
, Ramon Alcubilla
1
and Joan Bertomeu
2
;
1
Electronic Engineering,
Universidad Politcnica de Catalua, Barcelona, Spain;
2
Fisica Aplicada y Optica, University de
Barcelona, Barcelona, Spain.

Organic semiconductors represent a new interesting class of materials for several electronic
applications. Organic solar cells performance have improved significantly in the last few years
thanks to the optimization of the solar cell structure and, specially, to the ability to process new
organic semiconductors with optimised properties. Among different deposition techniques,
thermal evaporation in high-vacuum is the more suitable process to obtain small-molecule
organic thin-films with well organize molecular structure. In this paper the optical absorption
properties of n-type (C60 and PTCDA) and p-type (CuPc) small-molecule semiconductors are
investigated by optical transmission and Photothermal Deflection Spectroscopy (PDS). Results
show the usual absorption bands related to HOMO-LUMO transitions in the high absorption
region of transmission spectra. PDS measurements also evidences exponential absorption
shoulders with different characteristic energies (47 meV for CuPc, 50 meV for PTCDA and 87
meV for C60). In addition, broad bands in the low absorption level are observed for C60 and
PTCDA thin-films. These bands have been attributed to contamination due to air exposure (1). In
order to get deeper understanding of the degradation mechanisms single, bilayer and co-
evaporated thin-films have been characterized by PDS. Dependence of the optical coefficient on
light illumination and air exposure have been studied and correlated to the structural properties
of the films (as measured by X-Ray Diffraction Spectroscopy). Results show that CuPc:PTCDA
and CuPc:C60 co-evaporated films are stable after light and air exposition. However, single
layers of C60 shows significant increase of the low level optical absorption coefficient.


B10.46
Non-Volatile Organic Memory based on Electrically Doped Organic Heterostructures.
Frank Lindner, Phillip Sebastian, Bjoern Lussem and Karl Leo; Institut fr Angewandte
Photophysik, TU Dresden, Dresden, Germany.

Within the last few years organic memory devices have attracted considerable attention. Several
different approaches for organic memory devices have been reported in literature that show
bistable memory behaviour with high switching speeds and high ON/OFF ratios [1]. The
drawbacks of most of these devices are a rather low stability and reproducibility and a lack of
knowledge about he precise switching mechanism. Here, we report on a novel approach based on
charge trapping in a two-well heterostructure device. Consisting of materials which are well
known from organic light emitting devices, we obtain reproducible bistable electrical switching
and memory phenomena. Depending on the number of charges stored in the wells the resistance
of the device changes, i.e. the measured current-voltage characteristic shows two states of
different conductivity at the same applied voltage. The ratio between the resistance in the OFF
state and in the ON state can be varied by the write and erase voltage. More than 2000 Write-
Read-Erase cycles are obtained without degradation. The memory state is retained for several
days before reading the devices. In conclusion, the memory concept we present shows higher
reproducibility and stability compared to other organic memories. Device performance tests
show that the heterostructure devices are a promising candidate for low-cost, electrically
addressable data storage applications. [1] J.C. Scott, L.D. Bozano, Nonvolatile Memory
Elements Based on Organic Materials, Advanced Materials 2007, 19, 1452-1463.


B10.47
Synthesis of Monofunctionalized Electroactive Molecules and their Application in
Electrode Modification in Organic Devices. Gabriele Kremser
1
, Thomas Rath
1
, Thomas
Griesser
2
and Gregor Trimmel
1
;
1
Institute for Chemistry and Technology of Materials, Graz
Universitiy of Technology, Graz, Austria;
2
Institute of Chemistry of Polymeric Materials,
Montanuniversitt Leoben, Leoben, Austria.

The control of the interface of organic semiconducting materials and inorganic electrodes or
semiconductors is one of the crucial points for high performing organic electronic devices.
Therefore, different surface treatments and/or interfacial layers are often used in the device
assembly. Self assembled monolayers e.g. organosilanes, thiols or phosphonates have been
employed in the modification of indium tin oxide electrodes and gate oxides in organic field
effect transistors. In this contribution we present the syntheses of novel functionalized
electroactive organic compounds which are capable to interact with inorganic oxide materials.
These molecules consists of an electroactive unit of a stilbene, a quarterthiophene or a
biphenylterthiophene moiety which is asymmetrically capped with a polar group e.g. phosphonic
esters, carboxylic acid and hydroxy functionality. The PPV-compounds have been synthesized
by Wittig reaction or Horner-Emmons, whereas the thiophene-based molecules have been
prepared by Suzuki and Stille cross coupling reactions. All materials were identified by nuclear
magnetic resonance (NMR) and infrared (IR) spectroscopy. The optical properties were
investigated with UV-vis and photoluminescence spectroscopy. First result on the use of these
molecules for the modification of indium tin oxide electrodes in organic electronic devices will
be presented.


B10.48
Bipolar Transport in Organic Field-effect Transistors: Organic Semiconductor Blends
versus Contact Modification. Andreas Opitz, Michael Kraus, Markus Bronner, Julia Wagner
and Wolfgang Bruetting; Institute of Physics, University of Augsburg, Augsburg, Germany.

The achievement of bipolar transport is an important feature of organic semiconductors, both for
a fundamental understanding of transport properties and for applications such as complementary
electronic devices. We have investigated two routes towards organic field-effect transistors
exhibiting bipolar transport characteristics. As a first step, mixtures of p-conducting copper-
phthalocyanine (CuPc) and n-conducting buckminsterfullerene (C
60
) were used to realize
ambipolar field-effect transistors. As a second step, bipolar transport in copper-phthalocyanine
was achieved by a modification of the gate dielectric in combination with a controlled variation
of the electrode materials used for carrier injection. Although both routes are in principle
successful, there are some characteristic differences. In molecular blends, the charge carrier
mobilities decrease exponentially by dilution of the respective transport material. This indicates
that percolation is a crucial feature in mixtures of both materials to achieve ambipolar carrier
flow. In this case, balanced mobilities can be achieved by adjusting the mixing ratio. This is a
necessity to design ambipolar inverters with symmetric transfer characteristics. In neat films of
one single material, suitable contact modification allows for bipolar charge-carrier transport
together with the prevention of charge carrier traps at the insulator/semiconductor interface. Here
the obtained electron and hole mobilities differ by less than one order of magnitude.


B10.49
Hysteresis-free Electron Currents in Conjugated Polymers. Irina Craciun, Yuan Zhang and
Paul Blom; Molecular Electronics, University of Groningen, Groningen, Netherlands.

Charge transport is an important issue with regard to the understanding and optimization of
electronic devices made from conjugated polymers. In the last two decades a large effort has
been put on the characterization of the transport of holes, which is the dominant charge carrier. It
has been demonstrated that the hole transport is governed by hopping between localized states,
characterized by a mobility that depends on density, electric field and temperature.[1] The
transport of electrons is far less well characterized, and the strongly reduced electron currents are
attributed to trapping of electrons.[2] A major problem with the investigation of the electron
transport is the construction of so-called electron only devices, where hole blocking electrodes
are required that are usually reactive. The resulting J-V characteristics of these devices often
exhibit, next to low currents, strong hysteresis effects that strongly hinder the interpretation of,
for example, a temperature scan. Major candidates responsible for the strong hysteresis are
electrons trapped either in the bulk of the polymer or at the hole blocking electrode/ polymer
interface. The transport of electrons in electron-only devices based on poly (2-methoxy, 5- (2
ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV) is investigated for various hole-blocking
bottom electrodes as well as purification of the polymer. Using a variety of metallic electrodes as
a bottom contact no improvement in the observed hysteresis is observed. As a next step a n-type
doped PPV-based polymer was used as bottom electrode for the electron-only devices. Due to
the n-type doping the J-V characteristics of the doped electron-only device are hysteresis free.
However, addition of an undoped MEH-PPV layer on top directly resulted in large hysteresis,
showing that it originates from trapping in the bulk of the undoped polymer. As a final step we
demonstrate that by proper purification of the MEH-PPV hysteresis free electron-only currents
can be obtained, enabling a further quantitative characterization of the electron transport
mechanisms in this class of materials. [1] C. Tanase et al., Phys. Rev. B 70, 193202 (2004) [2]
M. M. Mandoc et al., Phys. Rev. B 73, 155205 (2006)


B10.50
Abstract Withdrawn


B10.51
Hole and Electron Polaron Absorptions Measured using Charge Modulation Spectroscopy
on Ambipolar Polyfluorene-based FETs. Matt Bird, Ni Zhao and Henning Sirringhaus;
Optoelectronics Group, Cambridge University, Cambridge, United Kingdom.

When a charge resides on a polymer it couples strongly to a local distortion in the molecular
structure; the combination is known as a polaron. The polaronic state induces new optical
transitions with sub band gap energies. In combination with quantum chemical modeling, the in-
situ measurement of these new transitions using charge modulation spectroscopy on operating
devices can offer a unique insight into the molecular packing, the degree of polaron localization
and the origin of energetic disorder [1, 2] in semiconducting polymers. We present here for the
first time the charge-induced absorption spectra for both the hole and electron polarons in a
range of polyfluorene-based conjugated polymers. We perform these measurements on polymer
transistor structures with ambipolar charge injection and transport [3] in which one can induce a
hole accumulation layer for negative gate voltage and an electron accumulation layer for positive
gate voltage. By comparing the induced absorption spectra for electron and hole polarons we
obtain information about fundamental electron-hole symmetries in conjugated polymers [4]. In
particular, over the range of polymers tested, we can correlate shifts in the spectra with the
different degrees of localization of electrons and holes on particular units of the backbone and
different degrees of interchain interaction. [1] J-F. Chang, M. Giles, M. Heeney, I. McCulloch
and H. Sirringhaus Phy. Rev. B 76, 205204 (2007) [2] D. Beljonne, J. Cornil, H. Sirringhaus, P.
J. Brown, M. Shkunov, R. H. Friend, J.-L. Brdas, Func. Mater. 11, 229-234 (2001) [3] J.
Zaumseil, C. L. Donley, J.-S. Kim, R. H. Friend, H. Sirringhaus, Adv. Mater. 18, 2708-2712
(2006) [4] K. Fesser, A. R. Bishop, and D. K. Campbell Phys. Rev. B 27, 4804 - 4825 (1983)


B10.52
Fully Solution-Processed Organic Solar Cells on Metal Foil Substrates. Whitney Gaynor
1
,
Jung-Yong Lee
2
and Peter Peumans
2
;
1
Materials Science and Engineering, Stanford University,
Stanford, California;
2
Electrical Engineering, Stanford University, Stanford, California.

Polymer bulk heterojunction photovoltaic cells are an area of intense research because they show
promise as a lower-cost alternative to their inorganic counterparts. Much of this cost reduction
relies on the ability to use high-throughput processing techniques such as roll-to-roll coating and
depositing materials from solution. However, the highest performance polymer bulk
heterojunction cells require a vacuum-deposited metal contact. In this talk, we report polymer
bulk heterojunction cells, based on the poly-3-hexylthiophene and phenyl-C61-butyric acid
methyl ester (P3HT:PCBM) system, in which each layer in the cell, including the top transparent
electrode, is processed from solution onto metal foil substrates. Silver-coated metal foil is used
as the cathode, followed by a solution-processed cesium carbonate interface layer to enhance
electron transport. The active layer is the bulk heterojunction P3HT:PCBM, followed by a
poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) layer for hole
collection, and a laminated transparent solution-processed silver nanowire film as the anode.
Power conversion efficiencies of 1.6% were obtained by optimization of the cathode and anode
interfaces. With continued optimization, efficiencies approaching those of conventionally
fabricated organic PV cells may be reached. The metal foil substrate offers advantages such as
low cost and superior barrier properties. Moreover, the metal foil can be replaced by metal fibers
enabling fiber-shaped solar cells. The metal foil also offers an easy and low-cost way to obtain
substrate shaping to enhance light trapping in the cell, further increasing the power conversion
efficiency.


B10.53
Chemical Modification of Self-assembled Monolayers: Tailor-made and Reversible Surface
Functionalization Schemes. Stephanie Hoeppener
1
, Claudia Haensch
1
, Manuela Chiper
1
and
Ulrich S. Schubert
1,2
;
1
Lab. of Macromolecular Chemistry and Nanoscience, Eindhoven
University of Technology, Eindhoven, Netherlands;
2
Lab. of Macromolecular and Organic
Chemistry, Friedrich-Schiller-University, Jena, Germany.

Chemical surface reactions performed on self-assembled monolayers represent a versatile
method to tailor the properties of surfaces. As a suitable precursor molecule 11-
bromoundecyltrichlorosilane can be used, which forms reasonable well ordered monolayers on
glass and silicon substrates. The bromine functionalities of such monolayers can be employed in
a number of derivatization reactions, leading to a variety of functional groups, i.e. thiols, azides,
or amines. Besides of the direct conversion of the bromine functions, reaction schemes, i.e. click
chemistry, can be employed to further increase the variety of available surface functions and/or
to covalently bind functional molecules. Examples include here the covalent binding of dye
molecules or the introduction of supramolecular precursors, which are able to tailor the
photochemical properties of surfaces. Terpyridine motifs represent here an example that allows
to reversibly modify the optical properties of surfaces, by external stimuli. In combination with
electrochemical structuring techniques it is demonstrated that different functional groups can be
locally introduced in a sequential derivatization approach, which leads to the fabrication of
complex structures, that can be, e.g., used to fabricate nanoelectronic device components.


B10.54
Temperature Modulation Spectroscopy for Probing Excitonic Properties of Organic
Semiconductors.Abhishek Yadav
1
, Kwok L Chan
3
, Max Shtein
2
and Kevin P Pipe
1
;
1
Department of Mechanical Engineering, University of Michigan, Ann Arbor, Michigan;
2
Department of Materials Science and Engineering, University of Michigan, Ann Arbor,
Michigan;
3
Department of Mechanical engineering, Hong Kong Polytechnic University, Hong
Kong, China.

The performance of organic optoelectronic devices is dependent on exciton generation and
transport properties that govern optical absorption and emission. Excitons in organic thin films
fall into two categories: 1) Frenkel excitons in which both the hole and electron are bound on the
same molecule, and 2) charge transfer (CT) excitons in which the hole and electron are bound to
each other but exist on neighboring molecules. Due to disorder and self-polarization, Frenkel
excitons are more common, although CT can also play an important role (e.g. in mediating
charge separation in photovoltaic devices). Optical spectroscopy is widely used to study exciton
transitions, spectral broadening, and oscillator strength. Simple absorption spectroscopy is better
suited for Frenkel excitons, because of their larger oscillator strength. Modulation spectroscopy
can be used to study CT excitons; for example, electric field modulation spectroscopy utilizes the
Stark effect to provide the derivative of the absorption spectrum with respect to exciton transition
level, and can be used to identify weak CT transitions. Unfortunately, the application of electric
fields can create parasitic effects, including strong electric fields at interfaces and destruction of
crystal symmetry, reducing the methods utility for thin films and nanostructured samples. Here,
we introduce temperature modulation spectroscopy as an alternative method to probe excitonic
properties of organic semiconductors. The oscillator strength of CT excitons decreases with
temperature, due to a reduced overlap of wavefunctions between neighboring molecules caused
by lattice thermal expansion [1]. For molecular crystals, with a small intermolecular overlap of
electronic wavefunctions, the oscillator strength of CT excitons is balanced by Frenkel exciton
states [2]. Hence, the oscillator strength of Frenkel excitons is expected to increase with a
decrease in oscillator strength of CT excitons [1]. We use this difference in behavior to
distinguish CT and Frenkel excitons in device-relevant organic thin films, including pentacene
and CuPc deposited on glass. The temperature of the film is modulated in a lock-in amplification
technique by passing a sinusoidal current through a thin silver film heater deposited on top of
organic film, while transmittance is measured using a photomultiplier tube. A Lorentz-Lorenz
dielectric model is used to fit the spectroscopic photometry data, yielding information about
excitonic transitions, oscillator strength, and broadening. To obtain the temperature dependencies
of these exciton properties, we fit the derivative of the Lorentz-Lorenz model to the modulated
transmission data. We show that temperature modulation spectroscopy is useful for studying the
excitonic properties of nanostructured thin films, without many of the parasitic effects of other
modulation spectroscopies. [1] Tanaka et al, J Chem. Phys 95: 2371, 1991 [2] Hernandez et al, J
Chem Phys 50: 1524, 1966


B10.55
3-dimensional Organic Field Effect Transistors: Charge Accumulation in the Vertical
Semiconductor Channels.M. Uno
1,2
, I. Doi
3
, K. Takimiya
3
and Jun Takeya
1
;
1
Osaka University,
Toyonaka, Japan;
2
TRI-Osaka, Izumi, Japan;
3
Hiroshima University, Higashi-hiroshima, Japan.

Organic electronics have attracted much attention as post-silicone electronics due to the
mechanical flexibility, as well as low-cost and energy-saving fabrication processes of their
devices. Among them, organic field-effect transistors (OFETs) are the key devices in which
further development is necessary for such applications as full-flexible displays, incorporated in
their matrix-controlling elements. So far, though much effort have been devoted to material
development, even the best value of the carrier mobility of organic semiconductors remain in
the order of 1 cm
2
/Vs except for single-crystal devices, resulting in unsatisfactory current
amplification per pixcel. Though decreasing the channel length L and increasing the width W can
be another approach, this effect is limited in the condition that the channels and the electrodes
are confined in the same plane as the conventional OFETs. In this presentation, we propose a
three-dimensional organic field-effect transistor (3D-OFET) to accumulate charge in its vertical
semiconductor channel, so that space availability for the field-induced carriers is essentially
enlarged [1]. A multi-columnar structure is built to multiply the channel area, partially dry-
etching Si substrates and thermally oxidizing their surfaces to form gate dielectric SiO
2
layer. On
the sidewall of the column, we deposit a vertical semiconductor layer of dinaphtho[2,3-b:2',3'-f]
thieno[3,2-b]thiophene (DNTT), which was reported to have high (~ 1 cm
2
/Vs) and excellent
air stability. Since W corresponds to the total length of all the column edges and L equals to the
height of the columns, one can design the devices without constraints of the lateral space, which
results in much higher ratio of W/L. Indeed, pronounced field-effect amplification is realized
with 500-nm thick SiO
2
gate insulator with the on-off ration of 10
6
, in which current
amplification up to 100 A in an area of 500 m square pixel is achieved with V
G
of 5 V and
drain voltage V
D
of 5 V. Carrier mobility of the DNTT film in the vertical channel is estimated to
be around 0.7 cm
2
/Vs. On the way for the organic flexible displays, the next challenge is to build
the 3D-OFETs on plastic substrates; however it is not welcomed to complicate the fabrication
process with additional deposition of dielectrics. Therefore, we propose to use an electric double-
layer (EDL) capacitance C
EDL
of ionic liquid, of which we reported outstanding gating
performance recently. Similar current-amplification capability is maintained for the ionic-liquid
gated 3D-OFETs as compared to that of the above SiO
2
-gated devices; 0.5 V is enough for both
V
G
and V
D
to obtain I
D
of 15 A, resulted from much larger C
EDL
but smaller . The results
already demonstrate usefulness of the 3D structure in achieving sufficient current per pixel for
matrix-controlling elements, which can drive industrial development of organic flexible displays.
[1] M. Uno et al., Appl. Phys. Lett. 93, 173301 (2008).


B10.56
Negligible Contact Resistances in Organic Single-crystal Transistors with Secondary Gates
on Source and Drain Electrodes. K. Nakayama
1
, T. Uemura
1
, M. Uno
1,2
and Jun Takeya
1
;
1
Osaka University, Toyonaka, Japan;
2
TRI-Osaka, Izumi, Japan.

To realize the maximum device performance of organic field-effect transistors (OFETs), a
significant challenge is to achieve efficient carrier injection at the electrodes. Such contact
performance is the most seriously concerned for short-channel devices with the channel length
typically less than sub-micrometers, though they are highly attractive because of their high-
frequency response and capability of high-density integration. As compared to common silicon
metal-oxide-semiconductor field-effect transistors where heavily doped carrier-rich region is
incorporated next to the channel, all the reported organic field-effect transistors suffer from the
carrier injection from different materials such as metals. In this presentation, we report that the
influence of injection barriers can be negligible with a construction of a contact between a
carrier-rich region and the channel region to be gated using the same semiconductor material,
even for devices with low channel resistances such as rubrene single crystal transistors with
micron-scale channel lengths. Previously, we reported a device structure with split gates on the
source and drain electrodes buried in the gate-insulating layers, so that the carrier density in the
organic semiconductors in the vicinity of the source and drain electrodes can be varied
independently of the primary gate electric fields applied to the central channel in the
semiconductors. Thereby, the carrier reservoirs are formed in the semiconductor locally near the
electrodes by the secondary gate voltage. To fabricate the bottom contact OFETs, we first
deposit the split-gate electrodes of gold on 500-nm thick SiO
2
/ doped silicon substrates by
evaporation. An amorphous fluoropolymer (CYTOP, Asahi Glass Co.) dielectric is prepared to
the thickness of 1 m for the second gate dielectric layer, and source and drain electrodes are
formed to the size slightly smaller than the split-gate electrodes, so that the split gate extends to
the semiconductor channel in the vicinity of the edges of the source and drain electrodes. Finally,
a thin platelet of rubrene crystal, which was independently grown by physical vapor transport
technique, is laminated by natural electrostatic force. Transfer characteristics of devices with five
different channel lengths are measured sweeping the primary gate voltage with the application of
the maximum secondary split-gate voltages to prepare the hole-rich region in the rubrene
crystals. As the result of the gradual channel plot, the normalized contact resistance R
C
W was
immeasurably small, where R
C
and W represent contact resistance estimated from the intercept of
the plot and the channel width, respectively. The result means that the value is smaller than 100
cm in our present setup. At least being comparable to the smallest contact resistance reported
so far, it is required to be measured with improved measurement systems. [1] K. Nakayama et
al., Appl. Phys. Lett. 93, 153302 (2008).


B10.57
Effect of Monochromatic Wavelength and Intensity on P3HT/PCBM Device
Characteristics. Harold T Evensen
1
, Garth A Berriman
2
, Warwick J Belcher
2
, John L
Holdsworth
2
and Paul C Dastoor
2
;
1
Chemistry & Engineering Physics, University of Wisconsin-
Platteville, Platteville, Wisconsin;
2
Centre for Organic Electronics, University of Newcastle,
Callaghan, New South Wales, Australia.

In order to probe photon energy-dependent mechanisms in bulk heterojunction solar cells, high
intensity LEDs were used to excite poly(3-hexylthiophene) (P3HT)/ [6,6]-phenyl C
61
-butyric
acid methyl ester (PCBM) devices. The light sources, ranging from 450 nm to 640 nm, delivered
a variable, monochromatic intensity from less than 0.5 mW/cm
2
to over 50 mW/cm
2
, or up to
eight to twenty times the equivalent solar irradiance within their bandwidths. The open circuit
voltage and short circuit current varied with intensity, and the open circuit voltage exhibited
distinctly different behavior under red light as compared to the other wavelengths. The results
are compared with the predictions of several device models.


B10.58
Permanent and Pattern-resolved Adjustment of the Surface Potential of Graphene-like
Carbon Through Chemical Functionalization. Fabian M. Koehler
1
, Norman A Luechinger
1
,
Dominik Ziegler
2
, Evagelos K Athanassiou
1
, Robert N Grass
1
, Antonella Rossi
3,4
, Christofer
Hierold
2
, Andreas Stemmer
2
and Wendelin J Stark
1
;
1
Chemistry and Applied Biosciences, ETH
Zurich, Zurich, Switzerland;
2
Mechanical and Process Engineering, ETH Zurich, Zurich,
Switzerland;
3
Materials, ETH Zurich, Zurich, Switzerland;
4
Chimica Inorganica ed Analitica,
Universita degli Studi di Cagliari, Cagliari, Italy.

The potential use of graphene in electronics requires reliable and pattern-controlled methods to
inject or remove electron density from the two-dimensional carbon honeycomb lattices.
Combining well established radical chemistry at ambient conditions and classical lithography,
we find that the structure of graphene layers can be permanently altered through covalent
chemical functionalization. We further demonstrate how the classic Hammett concept and the
Linear Free Enthalpy Relationship from organic chemistry can be used to predict the surface
potential shifts in graphene-like carbon surfaces. Our study (1) reveals an astonishingly simple
yet accurate method to adjust the surface potential in graphene layers. Next to the direct
application of such patterning in device fabrication, the here shown covalent attachment
introduces a third dimension in the two-dimensional graphene base. Such functionalization can
ultimately lead to covalent attachment of molecular electronics, circuitry incorporated chemical
sensors or actuators and offers an alternative approach to address the contacting problem in the
nm range. The possibility to print a potential pattern onto a graphene sheet was only conceptually
shown at present, but this approach offers a permanent polarization of the graphene sheets as in
the case of gate-induced changes in conductivity. Latter will be of crucial importance when using
a larger graphene sheet as a starting material in device fabrication (3D analogy: native Si wafer),
which is then doped and partially oxidized (3D analogy: insulating silicon oxide). One might
envision that for graphene, doping or oxidation to an insulating state could therefore be achieved
through simple chemical processing and classical or dip-pen lithography. [1] F.M. Koehler, N.A.
Luechinger, D. Ziegler, E.K. Athanassiou, R.N. Grass, A. Rossi, C. Hierold, A. Stemmer, W.J.
Stark, Angew. Chem. Int. Ed., 2008, in print


B10.59
Low Temperature Thermal Conductivity of Rubrene Single Crystals. Y. Okada
1
, M. Uno
1,2
,
M. Yamagishi
1
and Jun Takeya
1
;
1
Osaka University, Toyonaka, Japan;
2
TRI-Osaka, Izumi,
Japan.

Recently, organic crystals are gaining considerable interest linked to such practical applications
as electronic semiconductor devices and nonlinear optical components; rubrene single crystal
field-effect transistors exhibit one-order higher performance as compared to popular
polycrystalline thin-film organic transistors and such materials as DAST shows excellent
nonlinearity in response to light irradiation because of vibronic coupling to molecular
polarization. However, it is concerned that density of dilutely distributed defects in these crystals
is generally difficult to define, though it is recognized as crucial factor for transport or optical
performances of the above devices. In this work, we measured low-temperature thermal
conductivity of phonons to estimate their mean-free paths and density of crystalline defects
responsible for scattering the phonons. It is known that temperature dependence of thermal
conductivity in high-quality single crystals shows a pronounced peak in the temperature range
below typically 30 K, below which phonons are predominantly scattered by defects. At higher
temperatures, phonon-phonon Umklapp process dominates their scattering events. Thermal
conductivity is measured from 0.5 K to room temperature using a steady-state one heater two
thermometer technique. A set of mm-size chip resistors are mechanically attached for stand-
alone crystals in case they have the length of subcentimeter. In addition, we have developed a
measurement device incorporating resistive thin films of ZrN with the dimension of 100 m,
which work both for the heater and the thermometers. Employing MEMS (Micro Electro-
Mechanical Systems) technique, these resistive thin films are sustained only by 1-m thick
membrane, so that the heat current is essentially restricted to the crystal. Using the latter
technique, we can measure crystals of submillimeter sizes. Temperature profiles of the thermal
conductivity of rubrene single crystals grown by physical vapor transport showed a well-defined
peak, indicating that the crystal is indeed of exceptional quality as compared to literature for
typical organic charge-transfer complex. The crystals grown from solution have smaller peaks in
general, which suggests more inclusion of defects in the crystals. It turned out that it grows in
proportion to T
2
at low temperatures, meaning that the dominant scattering source is strain
dislocations distributed in the crystals. Moreover, as the result of further quantitative estimation,
typical density of the crystal dislocations is estimated to be in the order of 10
16
cm
-3
, which is
consistent with the performance of double-sided rubrene single crystal transistors interacting
with each other over 1-m distance, if we assume the dislocations themselves induce deep hole-
trap levels in the bulk of the rubrene crystals.


B10.60
Low and Intermediate Coverage Self-assembled Structures of Alkanethiolates and
Phenylthiolate on Au(111) Incorporating Au-adatoms Peter Maksymovych
1,2
and John T
Yates, Jr.
3,2
;
1
Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak
Ridge, Tennessee;
2
Department of Chemistry, University of Pittsburgh, Pittsburgh,
Pennsylvania;
3
Department of Chemistry, University of Virginia, Charlottesville, Virginia.

Molecular self-assembly is a quickly developing field of nanoscience that aims to tailor self-
recognizing and self-organizing properties of molecules for the bottom-up construction of
complex molecular systems and implementation of designer molecular functionality. Self-
assembled monolayers of alkanethiols on Au(111) are intensely studied both as a model system
yielding three-dimensional, crystalline monolayers and in practical applications involving
surface functionalization. Despite numerous previous attempts to understand the atomistic
picture of self-assembly, most of its aspects have remained controversial. Until only recently, the
gold surface has been considered a passive, unreconstructed template which provides a series of
high-symmetry adsorption sites for the alkylthiolate molecules. Several recent experiments have,
however, challenged this conservative view [1-4]. In this talk we will present self-assembled
structures of the methylthiolate (CH
3
S) from the lowest up to its saturation coverage of 1/3 ML,
developed based on high resolution STM images and DFT modeling. All these structures are
constructed using essentially the same building block of two CH
3
S-species joined by a Au-
adatom. Contrary to a common view that methylthiolate does not form a two-dimensional stripe-
phase monolayer, we show compelling STM evidence that methylthiolate-adatom complexes do
arrange into a stripe-like structure, albeit with preferentially 1D ordering. We compare the
stripe-phases of methylthiolate, propylthiolate and phenylthiolate [4], each of which is distinct
despite being constructured from constitutionally identical building blocks. The case of
phenylthiolate is intriguing as the steric hindrance of the phenyl groups prevents the
phenylthiolate-adatom complexes from forming well-ordered stripes as in methylthiolate.
However, weak C-HS hydrogen bonding does arrange these complexes in a locally-ordered
fashion. Phenylthiolate self-assembly on the Au(111) surface is therefore strikingly similar to its
collective behavior on nanoparticles comprising as few as 100 atoms. Thorough understanding of
the low-coverage phases will enable resolving the self-assembled structures at higher coverages,
with the symmetry of (3x4) and the 3x3R30
o
for methylthiolate and c(4x2) for long-chain
alkanethiolates. [1] P. Maksymovych, D. C. Sorescu, and J. T. Yates, Jr., Phys. Rev. Lett. 97
(2006) 146103. [2] M. Yu, N. Bovet, C. J. Satterley, et. al., Phys. Rev. Lett. 97 (2006) 166102.
[3] A. Cossaro, R. Mazaarello, R. Rousseau, et. al., Science 321 (2008) 943. [4] P.
Maksymovych, J. T. Yates, Jr., J. Am. Chem. Soc. 130 (2008) 7518. P. M. and J.T.Y: Supported
by the W. M. Keck Foundation and by the Army Research Office. P.M.: Research performed in
part as a Eugene P. Wigner Fellow and staff member at the Oak Ridge National Laboratory,
managed by UT-Battelle, LLC, for the U.S. Department of Energy under Contract DE-AC05-
00OR22725.


B10.61
The Self-assembly of Thiol-modified Diamondoids on Silver and Gold Trevor M Willey
1
,
Jonathan R I Lee
1
, Jason D Fabbri
2
, Peter R Schreiner
3
, Andrey A Fokin
3
, Boryslav A
Tkachenko
3
, Natalie A Fokina
3
, Jeremy E P Dahl
4
, Robert M K Carlson
4
, Louis J Terminello
4
,
Nick A Melosh
2
and Tony van Buuren
1
;
1
Lawrence Livermore National Laboratory, Livermore,
California;
2
Stanford University, Stanford, California;
3
Justus-Liebig University, Giessen,
Germany;
4
MolecularDiamond Technologies, Chevron, Richmond, California.

Higher diamondoids, hydrocarbon cages with a diamond-like structure, have largely evaded
laboratory synthesis but can be purified from petroleum sources. This new class of nanometer-
sized rigid hydrocarbon molecules shows promise in various areas of nanotechnology.
Particularly, computation indicates individual diamondoids possess negative electron affinity,
and diamondoid monolayers exhibit incredibly intense, monochromatic photoemission. Such
surface-attached diamondoids have technological possibilities as high-efficiency field emitters in
molecular electronics, as well as other nanotechnological applications, and fundamental studies
of the properties of these monolayers are a necessary precursor. Methods to site-selectively
functionalize diamondoids enable formation of controllable diamondoid self-assembled
monolayers on surfaces. We have investigated a number of thiol-modified diamantanes,
triamantanes, tetramantanes, and pentamantanes adsorbed on silver and gold, using near-edge x-
ray absorption fine structure spectroscopy (NEXAFS) and x-ray photoelectron spectroscopy
(XPS). The results illustrate how thiol position, diamondoid size, and diamondoid shape affect
the diamondoid self-assembled monolayer structure.


B10.62
Abstract Withdrawn


B10.63
Oligothiophene Derivatives Functionalized with a Diketopyrrolopyrrolo Core for Solution-
Processed Field-Effect Transistors: Effect of Alkyl Substituents and Thermal Annealing.
Mananya Tantiwiwat
1,2,3
, Arnold Tamayo
2,3
, Ngoc Luu
2,3
, Xuan-Dung Dang
2,3
and Thuc-Quyen
Nguyen
2,3
;
1
Physics, University of California, Santa Barbara, Goleta, California;
2
Chemistry and
Biochemistry, University of California, Santa Barbara, Goleta, California;
3
Center of Polymers
and Organic Solids, University of California, Santa Barbara, Goleta, California.

Two new oligothiophene derivatives bearing a diketopyrrolopyrrole core, 2,5-di-n-hexyl-3,6-bis-
(5''-n-hexyl-[2,2';5',2'']terthiophen-5-yl)-pyrrolo[3,4-c]pyrrole-1,4-dione (DHT6DPPC6) and 2,5-
di-n-dodecyl-3,6-bis-(5''-n-hexyl-[2,2';5',2'']terthiophen-5-yl)pyrrolo[3,4-c]pyrrole-1,4-dione
(DHT6DPPC12), and their use in solution processed organic field effect transistors are reported.
Depending on the type of alkyl substituent and film annealing temperature, the crystal grain sizes
and interlayer spacing vary as observed using atomic force microscopy and X-Ray
diffractometry, respectively. These changes in film morphology and interlayer spacing lead to
one order of magnitude difference in the field effect mobilities. The field effect mobilities for
annealed DHT6DPPC6 and DHT6DPPC12 films are 0.02 cm2/Vs and 0.01 cm2/Vs,
respectively.


B10.64
Potential Mapping in the Channel of Organic Field Effect Transistors by Additional Sense
Contacts. Risha Sharma, Benedikt Gburek, Torsten Balster and Veit Wagner; Jacobs University
Bremen, Bremen, Germany.

In the past few years organic semiconductors have attracted considerable interest in research as
well as in industrial applications. In particular, they are used in thin film transistors offering the
option for cheap and large area production of electronic circuits. However, organic
semiconductors exhibit a wide range of transport properties with often rather complex behaviors,
which are not well understood compared to their inorganic counterparts. The analysis and
understanding of these properties is often difficult if only the integral IV measurements are
available. A very helpful additional information in this context is the potential distribution in the
channel of the organic field-effect transistor (OFET). One very valuable option for this purpose
is the Scanning Kelvin Probe method, which, however, is often restricted to vacuum environment
and cannot access directly buried interfaces. To overcome these restrictions in our approach we
pattern sense fingers into the channel by lithographic means in addition to the source and drain
electrodes of the transistor. These sense electrodes are in direct contact with the conducting
channel and their potentials can be directly accessed by high impedance electrometers. This
approach works in atmospheric conditions and even for buried channels, i.e. in top gate
geometry. As organic semiconductor thiophenes in form of small molecules, thiophene
oligomers, and as polymers, regio-regular poly-(3-hexylthiophene) (rr-P3HT), are investigated.
These materials are known to show rather differing electronic transport properties. For these
systems the additional sense fingers allow to analyse contact properties to the gold contacts as
well as the charge carrier density dependent mobility in detail. For the consistent interpretation
of the measured current and potential data a combined model of contact resistance, parallel bulk
resistance, and charge carrier density dependent mobility on the basis of the Vissenberg-Matters
model is required. This theoretical model was found to be suitable to describe the various
semiconducting materials investigated as well as different device designs, as there are top and
bottom gate structures or the use of silicon or plastic substrates. The presented method has
proved to provide valuable additional information of the internal properties of the conducting
channel and the contacts and is compatible to standard production techniques and operation
environments of organic field-effect transistors.


B10.65
Semiconducting Polythiophenes at High Carrier Densities: Nonlinear Transport in
Agreement with Luttinger Liquid Theory. Jonathan Dsu-Bei Yuen
1
, Reghu Menon
2
, Nelson E
Coates
1
, Ebinazar B Namdas
1
, Shinuk Cho
1
, Scott T Hannahs
3
, Daniel Moses
1
and Alan J
Heeger
1
;
1
Center for Polymers and Organic Solids (CPOS), University of California, Santa
Barbara, Santa Barbara, California;
2
Department of Physics, Indian Institute of Science,
Bangalore, India;
3
National High Magnetic Field Laboratory, Tallahassee, Florida.

We present strong evidence that the nonlinear temperature-dependent transport data in field
effect transistors (FETs), with poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene)
(PBTTT) as the electronically active semiconductor, and doped PBTTT films agrees with the
predictions of the Luttinger Liquid (LL) theory. Regiosymmetric PBTTT is a planar, rigid rod
conjugated polymer which exhibits a liquid crystalline phase occurring below the melting point.
Thus, thin films can be fabricated with large crystalline domains ranging from hundreds of
nanometers up to a few microns, exhibiting a high degree of crystallinity (90% and above).
Within the domains, the PBTTT chains are straight and aligned parallel to each other, and while
there is possibility for finite overlap of the -orbitals between chains due to - stacking, the
intrachain -electron overlap is similar to that of cis-polyacetylene, exceeding the interchain
overlap. Therefore the bandwidth that determines delocalization and, thus, the transport along the
chain (W) is several eV, whereas the corresponding bandwidth for interchain transport (W) is
comparable to that of molecular crystals and therefore at least an order of magnitude smaller.
Thus, based upon the structure and assuming W/W >> 1, PBTTT would be properly classified
as a quasi-one dimensional (1D) system.


B10.66
Electron Transfer/transport in 2D Nanoparticle Array/polymer Composite Thin Layers.
Shisheng Xiong
1
, Yongqian Gao
2
, John K Grey
2
and Jeffrey C Brinker
1,3
;
1
Department of
Chemical Engineering, University of New Mexico, Albuquerque, New Mexico;
2
Department of
Chemistry, University of New Mexico, Albuquerque, New Mexico;
3
Advanced Material
Laboratory, Sandia National Laboratories, Albuquerque, New Mexico.

The mechanisms of charge carrier transfer across the metal/organic interfaces and the charge
transport at the nanoscale are crucial for molecular electronics and are under extensive
investigation for photovoltaics, light-emitting diodes and sensors. A universal, fast and facile
method to prepare robust, freestanding and patternable NP/polymer composites by evaporation-
induced self-assembly on a fluid interface has been developed (JACS 2008). The thiol-capped
nanoparticles (about 5.5nm in diameter) embedded within the polymer matrix are 2D monolayer
arrays, ordered in a hexagonal close-packed (hcp) arrangement, enabling us to study the charge
transfer/transport characteristics in a 2D configuration. Using a "shadow deposition" technique,
the gold nanoparticle (GNP)/conjugated polymer films are then transferred onto CINT*
Electrical Transport and Optical Spectroscopy Discovery Platforms with prefabricated
interdigitated fingers (grid spacing around 200 microns). The absorption spectra of composite
films are almost identical to the pure P3HT films. AFM scanning has verified that the composite
films are conformal with the electrodes. Sheet resistance of the composite films are measured at
both the ground state and excited state by charge injection through the source-drain setup using a
van der Pauw four probe station. Combining both the intensity and frequency resolved spatial
Raman spectra, acquired by Raman scanning spectroscopy, in terms of the C=C stretching mode
of P3HT with a potential bias applied across the interdigitated electrodes, charge carrier
migration and photophysical processes are interrogated. Experimental results show that the
Raman intensity of the composite films transferred to the Discovery Platform is greater than
films transferred to bare silicon because of possible electrochemical interactions between the
film and gold fingers. Increasing the potential leads to a decrease of the intensity difference due
to charge injection. Both thermal annealing and potential increase result in a downshift of the
Raman frequency of the C=C stretching mode, suggesting that charge transport has been
facilitated. *(Center for Integrated Nanotechnology, Sandia National Laboratories and Los
Alamos National Laboratories)


B10.67
Abstract Withdrawn


B10.68
Investigating the Role of Interfaces in Nanotube Polymer Composite Films by Resonant
Photoconductive Decay. Katherine E. Hurst
1
, Richard K Ahrenkiel
2
and John H Lehman
1
;
1
National Institute of Standards and Technology, Boulder, Colorado;
2
Colorado School of Mines,
Golden, Colorado.

Incorporating single-walled carbon nanotubes into conjugated polymers composite thin films
facilitates the transport of electrons and increases the overall efficiency of organic
photoconductive films. The role of the interface between the nanotube and polymer is
fundamental to the dissociation of photoexcited excitons, and understanding this mechanism is
needed to increase the overall efficiency of devices. In this work, we apply a resonant-coupled
photoconductive decay (RCPCD) method to determine the recombination lifetime of nanotube
polymer composite films. The carrier recombination lifetime of carbon nanotubes is typically
determined by contact-based techniques or spectroscopic methods. RCPCD is a non-contact
measurement that is based on a pump-probe technique in which an optical pump and a low-
frequency microwave probe are employed. This method is well suited for characterization of
bulk and extrinsic material properties. Our results demonstrate the role of interfaces in regards to
nanotube purity, concentration and extent of dispersion on the recombination lifetime. The
mechanisms describing the interaction of photoexcited carriers and the composite material will
be discussed. Raman spectroscopy, UV-VIS absorption and four-point probe measurements
provide further identification and characterization of composite thin films. Finally, we report the
wavelength dependence of photoconductive lifetimes.


B10.69
Molecular Gating of Silicon-on-Insulator Surfaces. Girjesh Dubey
1,2
, Gregory P Lopinski
1

and Federico Rosei
2
;
1
Steacie Institute for Molecular Sciences, National Research Council,
Ottawa, Ontario, Canada;
2
INRS-EMT (Energie, Materiaux, et Telecommunications), Universite
du Quebec, Varennes, Quebec, Canada.

The electronic properties of semiconductors respond strongly to transverse electric fields, which
penetrate susbstantially over macroscopic lengths. Nanometer-scale crystalline films are
therefore attractive systems for detecting charge state occupation at molecular interfaces,
inducing surface band-bending. Silicon-on-insulator (SOI) platforms are especially sensitive to
this, since the thickness of the top silicon layer is comparable to the Debye length of the material.
Therefore conductivity is ideally suited as a dynamic probe of events such as molecular
physisorption
1
,chemisorption
2
, surface dipoles, and occupation of electrically active gap states.
In this work, sheet resistance (R
s
) and Hall effect measurements (V
H
) in high vacuum
environments have been used to monitor adsorption (desorption) events on hydrogen terminated
silicon-on-insulator films (H-SOI). Complementary measurements of pseudo-MOS transistor
characteristics have been used to monitor shifts in threshold voltage (V
T
). Effects from gases in
the torr range are discussed for n and p doping at room temperature. Hole-trapping species,
such as (C
5
H
5
N:) and ammonia (:NH
3
) are found to mimic gate action analagous to a field effect
transistor, biasing p-type surfaces into inversion. Their adsorption on n-type SOI produces a high
concentration electron accumulation layer. These effects are reversible by desorption.
Surprisingly, minority channels have also been formed from water vapor (H
2
O) isotherms. High
electron affinity electron-trapping species, such as tetracyanoethylene (C
2
(CN)
4
), have been
found to severely deplete n-type SOI even at 10 ppb exposure levels. These results demonstrate
the efficacy of dc transport on SOI platforms for studies of molecular adsorption and charge
transfer effects at semiconductor surfaces. References:
1
G. Dubey, G. P. Lopinski, and F. Rosei,
Applied Physics Letters 91, 232111 (2007).
2
G. P. Lopinski, B. J. Eves, O. Hul'ko, et al.,
Physical Review B (Condensed Matter and Materials Physics) 71, 125308 (2005).


B10.70
Understanding the Modulation of Semiconductor Band-bending through Transport
Studies of Metal-molecule-semiconductor Device Junctions. Archana Bahuguna, Fernanda
Alanis-Camacho, Riya Shergill, Avik Ghosh and Nathan Swami; Electrical Engineering,
University of Virginia, Charlottesville, Virginia.

An understanding of the effects of molecular adsorption on the modulation of semiconductor
band-bending is of great significance for the characterization of electronic coupling in a variety
of device paradigms such as contacts for molecular electronics, [1], probing the passivation of
semiconductor surface states,[2], and probing signal transduction for sensor schemes based on
the controlled introduction of surface charge using molecular dipoles on self-assembled
monolayers (SAMs) on semiconductor substrates. [3]. The fitting of experimental transport data
at metal-molecule-semiconductor junctions to models on electronic coupling,[4], can enable the
extraction of significant device parameters that can eventually guide the development of novel
chemistries and device structures that are based on modulated semiconductor band bending.
Much of the prior models do not account for tunnel barrier shape and asymmetry of the Schottky
device junctions. In this study, the Non-equilibrium Greens Function (NEGF) formalism was
used to examine electronic transport and band bending at metal - molecule - semiconductor
device junctions, and correlate transport characteristics to experimental I-V data. COOH-
terminated SAMs of varying length (SH-CnCOOH, n=7, 10, 15) were deposited on patterned
areas (7 m) on GaAs (001) substrates; and copper complexation and electroless deposition
methods were used to ensure the deposition top metal contacts, without any penetration into the
underlying SAM layer [5]. In this manner, the molecular device length was varied from 0.7 nm
to 2 nm, and substrate doping was varied from n+ doping (1018/cm3) to p+ doping (1019/cm3).
Based on this, the effects of varying SAM length, substrate doping, and top-contact work
function on electronic transport mechanisms were interpreted by fitting the model to the
experimental I-V characteristics to enunciate the role of the tunnel barrier shape, semiconductor
band bending, depletion width and surface charge on transport. [1] Lodha S, Carpenter P, Janes
DB, J. Appl. Phys. 2006, 99. [2] Y. Liu, H. Yu, J. Phys. Chem. B 2003, 107, 7803-7811. [3]
Ashkenasy, G.; Cahen, D.; Cohen, R.; Shanzer, A.; Vilan, A. Acc. Chem. Res. 2002, 35, 121. [4]
Nesher G., Vilan A., Hwang J., Cohen H., Cahen D., Amy. F., Chan C., Hwan H., Kahn A., J.
Phys. Chem. B 2006, 110, 14363-14371. [5] Camacho-Alanis F., Wu L., Zangari G., Swami N.
Journal of Mat. Chem. DOI/10.1039/b800001a. In press.


B10.71
Effects of Molecular Packing and Film Thickness on the Performance of N-Channel
Organic Thin Film Transistors. Joon Hak Oh
1
, Ya-Sen Sun
1
, Ruediger Schmidt
2
, Frank
Wuerthner
2
and Zhenan Bao
1
;
1
Department of Chemical Engineering, Stanford University,
Stanford, California;
2
Institut fr Organische Chemie, Universitt Wrzburg, Wrzburg,
Germany.

The availability of high performance n-channel organic semiconductors is indispensable to
practical applications such as p-n junctions, bipolar transistors and complementary circuits. Two
main issues in n-channel organic thin film transistors (OTFTs) are i) high performance and ii)
air-stability. To illuminate the interplays between molecular structures, electronic properties,
solid-state packings, and field-effect mobilities, we have prepared OTFT devices based on a
series of core-halogenated PBIs with varying fluorinated imide substituents. We present a
detailed evaluation on the influence of bay and imide substituents of perylene diimide (PDI)
derivatives on the crystal packing and their electrical performance in n-channel OTFTs.
Furthermore, the air-stability mechanisms have been investigated in depth with PDI thin films as
functions of the lowest unoccupied molecular orbital (LUMO) energy levels and the thin film
thickness. Our findings provide a new insight on the performance and air-stability of n-channel
OTFTs.


B10.72
Abstract Withdrawn


B10.73
Increase in Open-circuit Voltage and Improved Stability of Organic Solar Cells by
Inserting a Molybdenum Trioxide Buffer Layer. Hideyuki Murata, Yoshiki Kinoshita,
Yoshihiro Kanai and Toshinori Matsushima; School of Materials Science, Japan Advanced
Institute of Science and Technology (JAIST), Nomi, Ishikawa, Japan.

Power conversion efficiency (P) of organic solar cells has steadily improved through the use of
new materials and device structures. In particular, great efforts have been made for the
enhancement of short-circuit current density (Jsc). The use of bulk heterojunctions (e.g., the
composite of p-type and n-type materials) as an active layer is very effective to increase in Jsc in
both polymer and small molecule-based solar cells. However, in the bulk heterojunction solar
cells, it is quite challenging to precisely control the formation of interpenetrating network by
fabrication process such as annealing condition. Furthermore, there is no enhancement effect of
open-circuit voltage (Voc) due to the formation of interpenetrating network. For the further
improvement of P, it is essential to enhance Voc, with maintaining the corresponding Jsc. In
this study, we found that a modification of ITO surface by a high work function metal oxide
(molybdenum trioxide MoO3) is very effective to increase in Voc. We demonstrate the
systematic control of Voc as a function of the film thickness of MoO3 buffer layer in the organic
solar cells. The open-circuit voltage increased from 0.57 to 0.97 V as the thickness of MoO3 film
is increased from 0 to 50 nm in the device structure of indium-tin-oxide ITO/ MoO3 (x nm) /
5,10,15,20-tetraphenylporphine (H2TPP, 10 nm) /C60 (40 nm)/bathocuproine (10 nm) /Ag (100
nm). The values between Voc and the ionization potential of MoO3 (x nm) on ITO exhibit linear
relationship, where the Ip values change from 4.92 to 5.92 eV as they increase from 0 to 50 nm.
Interestingly, the enhancement of Voc was achieved without affecting the Jsc and the fill factor.
Consequently, the power conversion efficiency of the device increases from 1.24% to 1.88%
primarily due to the increase in Voc. We also found that a MoO3 buffer layer enhances the
stability of organic solar cells (OSCs) under photo-irradiation. We have investigated the OSCs,
where the structure is ITO/ MoO3 (0 or 20 nm)/ p-type layer/ C60 (40 nm)/ Bathocuproine
(BCP) (10 nm)/ Ag (100). As a p-type layer, we use H2TPP and N,N-di(1-naphthyl)-N,N-
diphenylbenzidine (-NPD). Without MoO3 layer, the devices showed a dramatic decrease in p
as increasing light exposure time (18 % for H2TPP and 45 % for -NPD in initial p after 30
min). On contrary, the both devices with MoO3 layer showed good stability maintaining 72 %
for H2TPP and 95 % for -NPD in initial p at the same measurement conditions. These results
clearly suggest that the ITO/p-type layer interface affects the device stability. We investigated
the enhancement mechanism of the stability and found that the reaction at ITO/p-type layer was
prevented by inserting MoO3 buffer layer.


B10.74
Structural and Electronic Properties of Thin Films of Organic Charge-transfer
Compounds.Michael Kroeger and Antoine Kahn; Department of Electrical Engineering,
Princeton University, Princeton, New Jersey.

So-called organic charge transfer complexes usually consist of a mixture of one species of
molecules with very strong electron-accepting properties and one species which acts as an
electron donor. In single-crystal form, these materials have been extensively studied in the 1970s
and 1980s. It was shown, that in CT-compounds, donor and acceptor molecules form segregated
stacks and very often exhibit one- or two dimensional charge transport along donor and acceptor
planes. Further, the band gap energy of organic CT-compounds and therefore their electric
properties strongly depend on the degree of charge transfer between donor and acceptor
molecules. Despite offering the possibility to tailor-design electric properties by substitution or
chemical modification of the constituting species, organic CT-compounds have not played a
significant role as materials for organic electronic devices. This is due to the technical difficulties
which arise when handling organic single crystals, and which possibly exclude manufacturing of
devices based on organic single crystals. In contrast, most applications for organic
semiconductors, e.g. organic light emitting diodes, organic field-effect transistors and organic
photovoltaic cells, rely on thin-film deposition techniques. Therefore, we studied the thin-film
growth of organic CT-compounds deposited by thermal evaporation and their electronic
structure. Materials which have been used for this study are combinations of the donor molecules
dibenzo-tetrathiafulvalene (DB-TTF) and bis-pentamethylene-tetrathiafulvalene (BPM-TTF) and
acceptor molecules tetracyanoquinodimethane (TCNQ) and tetrafluorotetracyano-
quinodimethane (F4-TCNQ). The film morphology was studied with atomic force microscopy
(AFM) and x-ray diffraction (XRD). For resolving the electronic structure, ultra-violet
photoelectron spectroscopy (UPS) and inverse photoelectron spectroscopy (IPES) were used.
Electrical characterization of two-terminal thin-film devices was carried out in-vacuo at
temperatures between 60 K and 340 K. On glass substrates (quartz), DB-TTF/TCNQ exhibits a
pronounced 3-D growth and continuous thin films could not be achieved. Replacing TCNQ by
F4-TCNQ yields polycrystalline but continuous thin films with grain sizes in the micron-range.
A very similar thin film growth is observed for BPM-TTF/TCNQ deposits on quartz. When
applying ternary CT-compounds the electrical conductivity increases by nearly two orders of
magnitude, for example, comparing DB-TTF/F4-TCNQ(0.9)/TCNQ(0.1) to DB-TTF/F4-TCNQ.
Whether this effect is related to a change in the electronic band structure and/or to a change in
morphology will be discussed.


B10.75
Structure Function Relationships of Conjugated Polyelectrolyte Electron
Injection/Transport Layers in Polymer Light Emitting Diodes. Andres Garcia
1,2
, Jacek Z
Brzezinski
1,2
, Youngeup Jin
3
and Thuc-Quyen Nguyen
1,2
;
1
Department of Chemistry and
Biochemistry, University of California, Santa Barbara, California;
2
Center for Polymers and
Organic Solids, University of California, Santa Barbara, California;
3
Chemistry, Pusan National
University, Busan, Korea, South.

Charge injection and transport play an important role in organic light emitting diodes (OLEDs),
in which holes are injected from the anode into the highest occupied molecular orbital (HOMO)
and electrons are injected from the cathode into the lowest unoccupied molecular orbital
(LUMO) of the organic semiconductor. In the absence of interfacial effects, one needs to match
the energies of the HOMO and the LUMO with the work function of the anode and cathode,
respectively, so to minimize charge injection barriers. Stable metals with high work functions
thus typically give rise to larger electron injection barriers when used as cathodes and hence low
device performance. Recently, excellent device performance have been observed in OLEDs with
high work function cathodes such as Al, Ag, Cu and Au by deposition of a conjugated
polyelectrolyte (CPE) electron injection/transport layer (EIL/ETL). Some CPEs in OLEDs with
high work functions cathodes have been shown to lead to similar or higher performances than
identical OLEDs with no or low electron injection barrier low work function cathodes, allowing
the fabrication of air stable devices. While others CPEs have exhibited much lower
performances. How the molecular features of these materials modify the function of the
multilayer OLED performances remains to be fully understood. Here we present structure
function relationship studies of CPE EILs/ETLs in polymer light emitting diodes (PLEDs) in
which the influence of the conjugated backbone, appended ionic functionality and counter-ion
electronic properties on electron transport and PLED device performance are investigated. In
CPEs with identical appended cationic units and counter-ions but different conjugated backbone
a difference of ~ 10 in electron mobility and PLED luminous efficiency is observed, with the
higher electron mobility CPE exhibiting the higher device efficiency. While CPEs with identical
conjugated backbones but bearing anionic units rather than cationic units, exhibit higher device
efficiencies. The electronic properties of halide counter-anions in cationic CPE are also found to
influence the device efficiency of PLEDs, with a correlation between the oxidative properties of
the counter-ion and device efficiencies. The attractive properties of CPEs with respect to device
improvement together with the uncertainties in mechanistic function argue in favor of systematic
studies with the long term goal of making concrete structure-function predictions.


B10.76
Fabrication of Long-Chain Organic Thin films by Physical Vapor Deposition Process for
Gas Sensor Applications Nilima V Hullavarad and Shiva S Hullavarad; Office of Electronic
Miniaturization, University of Alaska Fairbanks, Fairbanks, Alaska.

There is ever growing need for gas detectors characterized by 4 Ss - viz., Sensitivity,
Selectivity, Speed and Stability. Organic based thin films are being investigated for detector
fabrication due to potential of scale up processing for commercial interest . The organic based
thin films have the advantages of higher selectivity because of ease of tailoring the chemical
composition of organic thin films that in turn affect the electronic properties. There have been
various techniques evolved in last two decades to grow organic thin films, predominantly by
solution based chemical techniques allowing to form detectors from bottom-up approach. The
technique described in this paper is CMOS compatible used in standard semiconductor
fabrication. In this paper, we demonstrate the simple physical deposition technique to form
organic thin films. This technique is shown to be useful to deposit long chain molecules with
amphiphilic nature. The long chain molecules such as stearic acid and calcium stearate are
deposited on Si, quartz and alumina substrates. The morphology of thin films is found to depend
on the crystalline nature of the substrates. The FTIR spectroscopy and XRD characterization
reveal that the bonding and the crystalline properties change with deposition temperatures within
20C (+/- 2 C). In conclusion, the feasibility of physical vapor deposition is demonstrated for
fabricating long chain organic molecules for organic electronic applications.


B10.77
Precise Structure of Pentacene Monolayers on Amorphous Silicon Oxide and Relation to
Charge Transport. Stefan C.B. Mannsfeld
1
, Ajay Virkar
1
, Colin Reese
1
, Michael F Toney
2
and
Zhenan Bao
1
;
1
Department of Chemical Engineering, Stanford University, Stanford, California;
2
Stanford synchrotron radiation laboratory (SSRL), Stanford, California.

<p>In the field of organic semiconductors, pentacene has developed into a benchmark material
because it easily and robustly yields high-performance thin film transistor (TFT) devices. The
charge transport in TFT devices occurs predominantly in a few monolayers above the dielectric
interface.[1] Therefore, knowledge of the precise packing in the first monolayer is important to
understand the charge transport properties of pentacene TFTs. Grazing incidence X-ray
diffraction (GIXD) using a synchrotron light source provides structural information on ultra-thin
films down to a single monolayer. Here we present the first direct determination of the molecular
packing in a pentacene monolayer on silicon oxide. Using crystallographic refinement
techniques, it is found that in pentacene monolayers on silicon oxide, the pentacene molecules
pack in a completely tilt-free herringbone motif, unlike in the commonly cited thin-film phase or
in the bulk crystal. The charge transport in the first monolayer is discussed on the basis of
density functional theory calculations. The results explain the high performance of pentacene
TFTs relative to that of pentacene single crystals on the silicon oxide substrates. [1] A.
Dodapalapur, L. Torsi, and H. E. Katz, Organic Transistors: Two-dimensional transport and
improved electrical characteristics, Science 268, 270-917 (1995).


B10.78
Probing the Nanomorphology of Annealed Conjugated Polymer Blends. Sufal Swaraj
1
,
Cheng Wang
2
, Chris R McNeill
3
, Benjamin Watts
4
and Harald Ade
1
;
1
Department of Physics,
North Carolina State University, Raleigh, North Carolina;
2
Advanced Light Source, Lawrence
Berkeley National Laboratory, Berkeley, California;
3
Cavendish Laboratory, Department of
Physics,, University of Cambridge, J J Thomson Ave,, Cambridge, CB3 0HE, United Kingdom;
4
Paul Scherrer Institute, 5232 Villigen PSI, Switzerland.

We investigate the influence of annealing on initially intimately mixed polymer blends of the
conjugated polymers poly(9,9'-dioctylfluorene-co-bis-N,N'(4,butylphenyl)-bis-N,N'-phenyl-1,4-
phenylene-diamine) (PFB) and poly(9,9'-dioctylfluorene-co benzothiadiazole) (F8BT). Scanning
Transmission X-ray Microscopy (STXM) imaging with sub-100 nm resolution was used for
investigating the evolution of the morphology. An increase in domain size is observed with
annealing due to phase separation. Photoluminescence (PL) quantum efficiency studies of these
films indicate a direct correspondence with the domain size for blends annealed at temperatures
above 180 degC. The phase separation first evolves with the evolution of relatively pure phases
at length scales beyond the resolution of STXM. At higher temperatures (>=180degC) the
hierarchy of phase separation is lost and the length scales can be readily imaged by STXM.
Resonant Soft X-ray Scattering (RSoXS) studies show an evolution towards purer domains along
with increase in domains size with annealing. At annealing temperatures below 180oC, the
correlation function analysis of the RSoXS data shows the evolution and distribution of
subdomains that span a range of length scales (4 - 100nm).The correlation function complements
the average domain size obtained from the PL data and a Monte-Carlo model that takes the
excition diffusion into account.


B10.79
Probing the Buried Interface in Annealed Conjugated Polymer Bilayers. Sufal Swaraj
1
,
Cheng Wang
2
, Hongping Yan
1
, Chris R McNeill
3
and Harald Ade
1
;
1
Department of Physics,
North Carolina State University, Raleight, North Carolina;
2
Advanced Light Sounce, Lawrence
Berkeley National Laboratory, Berkeley, California;
3
Cavendish Laboratory, Department of
Physics,, University of Cambridge, J J Thomson Ave,, Cambridge, CB3 0HE, United Kingdom.

The properties of polymer/polymer interfaces in conducting polymeric devises critically
influences device performance, yet relatively few studies of such interfaces have been
performed. We show that Resonant Soft X-ray Reflectivity (RSoXR) as a powerful tool for the
characterization of bilayers of conducting polymers, a material class that had mostly been
investigated with neutron reflectivity. The rapid changes of optical properties near the Carbon
absorption edge provides selectivity to specific chemical moieties and high contrast for
investigated materials. We exemplify the use of this technique for conducting polymers by
characterizing the buried interface in bilayers of poly(9,9'-dioctylfluorene-co-bis-
N,N'(4,butylphenyl)-bis-N,N'-phenyl-1,4-phenylene-diamine) (PFB) and poly(9,9'-
dioctylfluorene-co benzothiadiazole). We investigate the influence of annealing on the
polymer/polymer interface and the surface and quantify the surface and interfacial widths.
RSoXR results point to an interesting strategy that will allow the interdiffusion and physical
roughness at a buried polymer/polymer interface to be determined separately by diffuse
scattering at an angle and photon energy where the top surface exhibits little scattering, yet the
polymer/polymer interfaces will exhibit total internal reflection.


B10.80
Novel Micro and Nano Patterning Techniques for Organic Electronic Systems. Alexander
Zakhidov, Jin-Kyun Lee, John DeFranco, Hon Hang Fong, Priscilla G Taylor, Christopher K
Ober and George G Malliaras; Cornell University, Ithaca, New York.

Organic electronics and optoelectronics are fast developing branches of modern science and
technology that are aiming to replace conventional inorganic materials with light, inexpensive,
flexible organic materials. One of the main issues to be solved on the route to real word
application is patterning and processing of thin layer active organic materials. In this report we
present new reliable photolithography micro and nano patterning techniques for high resolution,
high throughput patterning of solution processable organic materials [1,2]. We also demonstrate
that proposed approach is completely benign [3] to majority of organic electronic materials as
well as environmental friendly and can be easily adopted by industry. In order to demonstrate
potential application of developed patterning technique we fabricate micropatterned top-contact
organic thin film transistors and prototypes of organic light emitting displays. [1] H. S. Hwang,
Al. A. Zakhidov, J.-K. Lee, X. Andre, J. A. DeFranco, H. H. Fong, A. B. Holmes, G. G.
Malliaras, C. K. Ober, Journal of Materials Chemistry, 2008, 18, 3087. [2] J.-K. Lee, M.
Chatzichristidi, Al. A. Zakhidov, P. G. Taylor, J. A. DeFranco, H. S. Hwang, H. H. Fong, A. B.
Holmes, G. G. Malliaras, C. K. Ober, J. Am. Chem. Soc., 2008, 130, 11564. [3] Al. A. Zakhidov,
J.-K. Lee, H. H. Fong, J. A. DeFranco, M. Chatzichristidi, P. G. Taylor, C. K. Ober, G. G.
Malliaras, Advanced Materials, 2008, 20, 3481.


B10.81
Factors Determining the Efficacy of Optical Spacers in Polymer Solar Cells: The Role of
Active Layer Morphology. Anshuman Roy, Sarah Mednick, Sung Heum Park, Ji Sun Moon
and Alan J Heeger; University of California, Santa Barbara, California.

Polymer photovoltaic devices stand at the cusp of rapid commercialization today, with the
maximum power conversion efficiency reported to be over 6% [J. Y. Kim et al., Science, 317
(2007) 222-225]. The photo-active layer in these devices consists of conjugated polymers and
modified fullerenes that form a bulk heterojunction (BHJ) composite film about 100 nm in
thickness. Additionally, a layer of TiOx (Titanium Oxide) approximately 10 nm in thickness is
spin cast on top of the active layer to act as an optical spacer that maximizes the incident light
intensity in the photo-active layer [Kim et al., Adv. Mater., 18 (2006) 572-576]. Using a
combination of numerical modeling and experiments, including ellipsometry, transmission
electron microscopy and cell efficiency, we show that the efficacy of the TiOx layer as an optical
spacer is dependent not only on the thickness of the BHJ layer but also on the nano-scale
structure of the BHJ layer, which in turn depends on a host of processing conditions.


B10.82
Transport Anisotropy in Films of Organic n-type Semiconductor with Controlled In-plane
Grain Boundary Orientation. Jonathan Rivnay
1
, Antonio Facchetti
2,3
and Alberto Salleo
1
;
1
Dept. of Materials Science and Engineering, Stanford University, Stanford, California;
2
Polyera
Corporation, Skokie, Illinois;
3
Dept. of Chemistry, Northwestern University, Evanston, Illinois.

Solution processable small molecule organic semiconductors have gained interest due to their
potential low cost processing and field effect mobilities nearing that of their vapor deposited,
non-soluble counterparts. Unfortunately, pristine films of soluble small molecules suffer from
poor thin-film transistor device-to-device reproducibility (mobility, V
T
and stability) due to the
existence of grain-boundaries that are not uniformly distributed throughout the film. The effect
of grain boundaries in thin films of small molecule semiconductors is relatively large compared
to that of semicrystalline polymer devices for two reasons: the grain size is often on the order of
the channel length preventing averaging effects and boundary regions between grains are more
abrupt. Indeed, in semicrystalline polymer films, a single chain can bridge two or more adjacent
crystallites, facilitating transport through amorphous-like regions/grain boundaries. Research
should thus focus on understanding of the relationship between microstructure and charge
transport in order to design devices that do not necessarily eliminate grain boundaries, but limit
their penalty on electrical performance, while also allowing for lower device-to-device
variability. To this end, in this work we use anisotropic films of the n-type small molecule N,N-
bis(n-octyl)-(1,7&1,6)-dicyanoperylene-3,4:9,10-bis(dicarboximide), (PDI8-CN
2
) to explore the
effect of grain boundaries on field effect mobility, and understand their implication in charge
transport in thin films. To fabricate samples, we use an inclined drop casting method with a
heating stage. In-plane orientation and morphology are characterized with x-ray diffraction,
polarized light microscopy, and AFM. Thin film transistors (TFTs) were made to probe transport
as a function of charge density and temperature across two types of grain-boundaries that are
formed. These PDI8-CN
2
-based TFTs exhibit a mobility anisotropy of two orders of magnitude
depending on the relative orientation of the grains with the current flow. Parallel devices, with
charge transport presumably parallel to the fast growth direction of the crystallites show room
temperature mobilities above ~0.01 cm
2
/Vs (E
A
=120meV), near that of isotropic solution cast
films. Perpendicular devices, on the other hand, show low mobilities of ~10
-4
cm
2
/Vs
(E
A
=340meV). The difference between the two orientations is much larger than a 2-3 fold
difference associated with crystalline anisotropy. The similar mobilities measured in parallel and
isotropic films suggest defects and grain boundaries of this device are similar to those present in
typical devices. Though the morphology and exact nature of grain boundaries in the orthogonal
direction are unknown we postulate that they are host to large energetic barriers, in agreement
with the larger E
A
, and may explain device-to-device non-uniformity in isotropic films, due to
the percolative nature of charge transport.


B10.83
Synthesis and Characterization of Soluble Copolymers Containing Dialkyl
Quarterthiophene. Jun Chen
1
, Sung J Park
1
, Jae W Jang
1
, Yun H Kim
2
and Soon K Kwon
1
;
1
School of Nano and Advanced Material Science & Engineering and ERI, Gyeongsang National
University, Jinju 660-701, Gyeonsangnam-do, Korea, South;
2
Department of Chemistry and
RINS, Gyeongsang National University, Jinju 660-701, Gyeonsangnam-do, Korea, South.

Soluble conjugated 4ThFlu and 4ThNa copolymers were synthesized by the Suzuki coupling
reaction. The weight-average molecular weight of the 4ThFlu and 4ThNa copolymer were
determined to be 16848 and 13505, respectively. And the polydispersity indexes obtained by gel
permeation chromatography (GPC) using polystyrene standards for calibration in the eluent THF
is 1.55 and 1.59, respectively. The thermal, optical and electronic properties of copolymers were
investigated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), UV-
vis absorption, photoluminescence spectroscopies, cyclic voltammetry. The absorption
maximum spectra of copolymers were observed 452, 453 nm in solution state and 563, 563 nm
in film state. The PL maximum spectra of copolymers were observed at 467, 503 nm in solution
state and 585, 624 nm in film state, respectively. The copolymers were showed highly thermal
stability of decomposition temperature over 300 oC. Especially, the copolymers were easy to be
soluble in common solvents (THF, CHCl3, Toluene etc) due to the introduction of long alky
chains.


B10.84
Blue Organic Light Emitting Diodes from Solution Processed Small Molecules. Bright
Walker, Arnold B Tamayo, Wesley Walker, Jihua Yang, Fred Wudl and Thuc-Quyen Nguyen;
Chemistry and Biochemistry, University of California at Santa Barbara, Santa Barbara,
California.

Solution-processed organic light-emitting devices provide the potential for cheap, ultrathin, light-
weight, and large-area illumination sources. In comparison with red or green light-emitting
devices, efficient blue emitting diodes are typically more difficult to obtain because the emitting
material requires a wider band gap for radiative recombination. Organic blue light-emitting
diodes were studied using the solution processed small molecules 2,7-dipyrenyl-9 ,9[|#1#|]-
dioctyl-fluorene as well as 1,3,5-tris(7,10-diphenylfluoranthene-8-yl)benzene as emissive layers
(EMLs). Devices were fabricated using the conjugated polyelectrolyte poly(9,9'-bis[6"-(N,N,N-
trimethylammonium) hexyl]fluorene-alt-co-phenylene) with tetrakis(imidazolyl)borate
counterions (PFN-BIm4) as an electron injecting layer and poly(9-vinylcarbazole) (PVK) as an
electron blocking layer. Efficient blue light emission was observed for devices with the
architecture ITO/PEDOT:PSS/PVK/EML/PFNBIm4/Al in which all organic layers were
deposited by solution processing. Using PVK and PFN-BIm4 layers results in a significant
improvement in device performance compared to devices without the layers or with common
electron injecting layers such as lithium fluoride or barium.


B10.85
Meta-stable Interfaces between Soft-contact and Closed-shell Semiconductor Surfaces.
Yang Li, Wei Long and Raymond T. Tung; Physics Department, Brooklyn College, the City
University of New York, Brooklyn, New York.

The use of a self-assembled monolayer (SAM) of molecules to modify and tailor interface
electronic properties is an attractive approach for sensors and semiconductor electronic
applications, because of the molecules functional variety and flexibility. In studies involving
SAM attached semiconductor surfaces, the deposition/application of metallic contacts is geared
toward minimizing disturbance to the molecular layer, i.e. for a preservation of meta-stable non-
interacting molecule-metal interfaces. However, interactions between the metal and the
molecular layer are often found to influence and even dominate the dipolar effect of the
molecular layer. Significant barrier height inhomogeneity has also been reported. In this work,
we attempt to establish a baseline for studies involving meta-stable metal-molecule interfaces. A
dual-station UHV chamber was constructed for this study. Silicon surfaces terminated with
different types of stable closed-shell configurations (Cl-, S- and H-) are used to simulate the
stable molecular termination on SAM/Si surfaces. Meta-stable metal-Si structures are fabricated
using soft-landing deposition of metal contacts (Au, Ag, and Al) with indirect deposition in an
inert gas ambient or direct deposition in vacuum, and at variable temperatures. In situ
characterization by surface spectroscopies and Kelvin probe techniques showed the varied levels
of intermixing under different deposition conditions. Electrical measurements, by variable
temperature I-V and C-V method, of Au/Si and Ag/Si diodes fabricated on n- and p-type <100>
and <111> substrates also showed a significant dependence on fabrication conditions of the
Schottky barrier. Lower deposition temperature led to more uniform contact between metal and
semiconductor, which then led to higher SBH on n-type Si, with the expected, opposite
dependence observed on p-type Si. Also, the orientation of the semiconductor surface was shown
to have a significant influence on the formation of the SBH. Electrical results and results
obtained from surface chemical analysis and microscopic techniques are presented with special
attention paid to the possible electrical inhomogeneity in the systems. These results are compared
with results involving molecular layers obtained previously in our and other groups.


B10.86
Abstract Withdrawn

B10.87
Picosecond Photoexcitation Dynamics in the Poly(2,7-Carbazole) Copolymer, PCDTBT,and
in Bulk Heterojunction Composites with PC
70
BM. Minghong Tong
1
, Nelson E. Coates
1
,
Daniel Moses
1
, Alan J Heeger
1
, Serge Beaupre
2
, Mario Leclerc
2
and Russell Gaudiana
3
;
1
Center
for Polymers and Organic Solids, University of California, Santa Barbara, Santa Barbara,
California;
2
Departement de Chimie, Universit Laval, Quebec City, Quebec, Canada;
3
Konarka
Technologies, Inc, Lowell, Massachusetts.

We have studied the nature of ultrafast photoexcitations and their recombination dynamics in an
alternating donor-acceptor low-bandgap Poly(2,7-Carbazole) copolymer (PCDTBT; see Blouin,
N.; Michaud, A.; Leclerc, M. Adv. Mater. 2007, 19, 2295 - 2300) and in composites of that
polymer with the fullerene derivative [6,6]-phenyl C70-butyric acid methyl ester (PC
70
BM); This
class of alternating donor-acceptor copolymers (with different acceptor units) holds promise for
photovoltaic applications because of the ability to tune the electronic energy levels by changing
acceptor units. The implied flexibility in the synthesis can lead to both a lower bandgap that
better uses the solar radiation spectrum, and a lower HOMO level that increases the open circuit
voltage of photovoltaic devices. We have used transient photinduced absorption spectroscopy,
over a wide spectral range in order to study the nature of the photoexcitations, and in particular
the carrier generation and recombination dynamics at short time scales. A very long carrier
lifetime (>>1ns) is observed in the PCDTBT-Fullerene composite.


B10.88
Steady-State and Transient Photoconductivity in the Poly(2,7-Carbazole) Copolymer
PCDTBT, and in Bulk Heterojunction Composites with PC
70
BM. Nelson Coates
1
, Minghong
Tong
1
, Daniel Moses
1
, Alan J Heeger
1
, Serge Beaupre
2
, Mario Leclerc
2
and Russell Gaudiana
3
;
1
Physics, University of California, Santa Barbara, Goleta, California;
2
Chimie, Universit Laval,
Quebec City, Quebec, Canada;
3
Konarka Technologies Inc., Lowell, Massachusetts.

We have studied the nature of carrier generation using steady-state and transient
photoconductivity in an alternating donor-acceptor low-bandgap Poly(2,7-Carbazole) copolymer
(PCDTBT; see Blouin, N.; Michaud, A.; Leclerc, M. Adv. Mater. 2007, 19, 2295 - 2300) and in
composites of that polymer with the fullerene derivative [6,6]-phenyl C70-butyric acid methyl
ester (PC
70
BM). This class of alternating donor-acceptor copolymers (with different acceptor
units, X) holds promise for photovoltaic applications because of the ability to tune the electronic
energy levels by changing X. The implied flexibility in the synthesis can lead to both a lower
bandgap that better uses the solar radiation spectrum, and a lower HOMO level that increases the
open circuit voltage of photovoltaic devices. In PCDTBT, the absorption band extends out to ~
700 nm, with two distinct but broad absorption bands that are centered at ~ 400 nm and ~ 600
nm. Higher solar cell power conversion efficiency is achieved in PCDTBT devices than in P3HT
based devices because of the improved light harvesting and larger open circuit voltage. We have
used steady-state and transient photoconductivity to investigate the carrier generation and
collection efficiency of PCDTBT and its composite with the soluble fullerene, PC
70
BM, after
photoexcitation at each of its distinct absorption bands. In pristine PCDTBT, higher carrier
quantum efficiency is observed with excitation at the high energy absorption band, but in the
PCDTBT-fullerene composite, this efficiency is an order of magnitude greater and relatively
wavelength independent.


B10.89
High-Mobility n-Channel Organic Thin-Film Transistors Henry Yan and Antonio Facchetti;
Polyera Corporation, Skokie, Illinois.

We report here our recent progress enabling high-performance top-gate organic thin-film
transistors (OTFT). Electron mobility of ~ 1.0 cm2/Vs was achieved for top-gate bottom-contact
devices tested in ambient using both the semiconductor and dielectric layers fabricated by spin-
coating. To the best of our knowledge, this is first report of solution-processed top-gate n-
channel TFTs with mobility higher than 1 cm2/Vs. Furthermore, we will also present updated
performance of bottom-gate bottom-contact transistors using Polyera materials. Electron
mobility of ~ 0.1 cm2/Vs was achieved in a bottom-gate bottom-contact structure with both the
semiconductor and dielectric layers fabricated by spin-coating process. In this case, the dielectric
material is an UV crosslinkable dielectric polymer having good compatibility with n-type
organic semiconductors.


B10.90
Effects of Metal and Organic Impurities on Pentacene Electronic Structures Jing Xue
1
,
Geunsik Lee
1
and Kyeongjae Cho
1,2
;
1
Physics, University of Texas at Dallas, Richardson, Texas;
2
Materials Science and Engineering, University of Texas at Dallas, Richardson, Texas.

Organic semiconductors have received much attention due to their successful application in
optical and electronic areas. Pentacene is one of the most promising materials in the organic
semiconductors because of its highest hole mobility. In this work, we study the effects of metal
contact and organic impurities on pentacenes electronic structure by using ab initio density
functional theory (DFT) methods. Pentacene in the electronic devices directly contacts with
metal electrode, and metal atoms may diffuse into pentacene and form impurities interacting with
pentacene. Therefore, the interface between metal and pentacene can be modified by the metal
atomic diffusion. We calculate electronic structure of pentacene adsorbed with different metallic
elements (Au, Pd, Ni) and study their effects on the carrier injection barrier. We found that the
calculated energy gap for isolated pentacene molecule is 1.13 eV. The main contribution of
HOMO and LUMO come from pi orbital of C-atoms. For metal adsorption, the energy gap will
be decreased. Compared the binding energy and the bulk cohesive energy, Ni and Pd are easier
to diffuse into the pentacene than Au. Depending on the valence electron structure of the metal
atom to be adsorbed, the electronic structure of pentacene near the Fermi level has changed
differently. For Au and Ni, there will form new mid gap states and the new mid-gap states
decrease the contact barriers to improve the charge injection from the electrode. Organic
semiconductor device characteristics is also sensitive to organic impurities which may be
introduced during synthesis or by air exposure. It is worth to focus that dissociation of H2O into
H and OH may form some organic defect. We consider the defect in pentacene in forms of C-H2,
C=O and OH. All these organic impurities will give rise to gap states. For C-H2 or C=O defect,
the 6-top site is mostly favored energetically by an additional H adsorption (C22H15)or H
replacement by O (C22H13O), respectively. In both systems, the pz orbital on the perturbed C
atom no longer participates in the bonding once the defect is introduced. For H replacement by
an OH, it seems that, there are no much differences between C22H14O and C22H14 because all
C atoms are still participates in their bonding. However, for additional adsorption of OH,
C22H15O, the electronic structure is different from that of pentacene molecule. In addition, it is
shows that the electronic structure of pentacene with the same type of defect is affected by the
defect position. These calculations show the role of metal or organic impurities in generating the
defect states with the HOMO-LUMO gap of the pentacene molecules. These gap states may play
the critical role in limiting the mobility of the organic semiconductor channel and the efficiency
of the optical device applications. Our detailed electronic structure study provides a fundamental
insight on the effects of impurities in the pentacene device performance.


B10.91
Interface Reaction of Aluminum and 8-hydroxyquinolatolithium. Young Mi Lee
1
, Yeonjin
Yi
2
, Jeong Won Kim
2
and Yongsup Park
1
;
1
Dept.of Physics, Kyung Hee University, Seoul,
Korea, South;
2
Korea Research Institute of Standards and Science, Daejeon, Korea, South.

One of organic electron injection layer materials, Liq (8-hydroxyquinolatolithium) shows a few
advantages over other inorganic materials for organic light emitting device (OLEDs). As the Liq
possesses the similar structure to Alq3, the most common light emission layer material, it is
believed to provide a smooth interface and be more compatible to flexible displays. The energy
alignment and device performance including the Liq between Al and Alq3 have recently been
demonstrated. Here the interface chemical reaction at the Liq/Al interfaces was investigated by
using high resolution synchrotron radiation photoelectron spectroscopy. The different deposition
sequence gives different reactions. While strong reactions are observed throughout the Liq film
when Al is deposited on Liq layer, an interface localized reaction occurs just at the interface
upon the Liq deposition onto Al surface. Either sequence of film stacks, Liq/Al and Al/Liq
produce an interface gap state respectively at 2.1 eV and 2.8 eV below the Fermi level. Both of
the highest occupied molecular orbital (HOMO) and N 1s core level peaks are shifted to the high
binding energy side by 0.35 eV on Al/Liq whereas it is not the case on Al/Liq. Based on these
observations, the differences in electron injection barrier and interface dipole between the two
opposite deposition sequences could be drawn.


B10.92
Formation of Ohmic Carrier Injection at Anode/organic Interfaces and Carrier Transport
Mechanisms of Organic Thin Films. Toshinori Matsushima, Guang-He Jin, Yoshihiro Kanai,
Tomoyuki Yokota, Seiki Kitada, Toshiyuki Kishi and Hideyuki Murata; School of Materials
Science, Japan Advanced Institute of Science and Technology, Nomi, Ishikawa, Japan.

Organic light-emitting diodes (OLEDs) are being developed due to their high potentials for use
in low-cost, mechanically flexible, and lightweight display, and lighting applications. In typical
multilayer OLEDs, a hole-injection barrier is present at the interface of an indium tin oxide
(ITO) anode and a hole-transport layer (HTL) and causes an increase in driving voltage of
OLEDs. Various organic and inorganic hole-injection layers (HILs) have been inserted between
ITO and HTL to reduce the driving voltages. However, Ohmic contacts have never been
achieved at the ITO/HIL/HTL interfaces to date. If Ohmic contacts can be formed, further
improvements of driving voltages, power conversion efficiencies, and stability of OLEDs are
possible. Besides the improvements in OLED performance, understanding carrier transport
mechanisms in organic films is very crucial to developing fundamental science. However, the
carrier transport mechanisms have not yet been elucidated, and must be further clarified to bring
about maximum device performance. Large charge carrier injection barriers at anode/HTL
interfaces would make clarifying the carrier transport mechanisms difficult because observed
currents are governed by both carrier injection and transport. Therefore, the formation of Ohmic
contacts at the interfaces is indispensable to clarifying the carrier transport mechanisms. In this
study, we found that insertion of an ultrathin molybdenum oxide (MoO3) HIL between ITO and
HTL provides Ohmic hole injection at the interfaces. We fabricated the hole-only devices with a
glass substrate/ITO anode (150 nm)/MoO3 HIL (X nm)/organic HTL (100 nm)/MoO3 electron-
blocking layer (10 nm)/Al cathode (100 nm) structure. As the HTL, we used pentacene, alpha-
sexithiophene (a-6T), copper phthalocyanine (CuPc), 4',4"-tris(N-3-methylphenyl-N-phenyl-
amino)triphenylamine (m-MTDATA), 4,4',4"-tris(N-2-naphthyl-N-phenyl-amino)triphenylamine
(2-TNATA), N,N-di(m-tolyl)-N,N-diphenylbenzidine (TPD), rubrene, or N,N-diphenyl-N,N-
bis(1-naphthyl)-1,1-biphenyl-4,4-diamine (a-NPD). Although the thickness of MoO3 HILs
previously used is in the range between 5 and 50 nm, the results in the present study clearly
indicated that such thick MoO3 HILs do not provide Ohmic hole injection. We found that the
optimized X is smaller than 1 nm. The hole-only devices with the optimized X exhibited
completely transport-limited currents, indicating that an Ohmic contact is formed at the
interfaces. By analyzing the current density-voltage characteristics of the devices with a space-
charge-limited current theory, we clarified the carrier transport mechanisms of the above-
mentioned organic HTLs.


B10.93
High Efficiency Bulk Heterojunction Solar Cells with Internal Quantum Efficiency (IQE)
approaching 100% fabricated with the Poly(2,7-Carbazole) Copolymer, PCDTBT Sung
Heum Park
1,2
, Anshuman Roy
1
, Shinuk Cho
1
, Ji Sun Moon
1
, Nelson E Coates
1
, Daniel Moses
1
,
Kwanghee Lee
1,2
, Alan J Heeger
1,2
, Serge Beaupre
3
, Mario Leclerc
3
and R. Gaudiana
4
;
1
Center
for Polymer and Organic Solids, University of California at Santa Barbara, Santa Barbara,
California;
2
Heeger Center for Advanced materials, Gwangju Institue of Science and
Technology, Gwangju, Korea, South;
3
Departement de Chimie, Universit Laval, Quebec,
Quebec, Canada;
4
Konarka Technologies, Inc, Lowell, Massachusetts.

We report here that we have successfully fabricated a single polymer solar cell with 6% power
conversion efficiency using an alternating donor-acceptor low-bandgap Poly(2,7-Carbazole)
copolymer (PCDTBT; see Blouin, N.; Michaud, A.; Leclerc, M. Adv. Mater. 2007, 19, 2295 -
2300) in composite with the fullerene derivative [6,6]-phenyl C70-butyric acid methyl ester
(PC70BM). This class of alternating donor-acceptor copolymers (with different acceptor units,
X) holds promise for photovoltaic applications because of the ability to tune the electronic
energy levels by changing X. The implied flexibility in the synthesis can lead to both a lower
bandgap that better uses the solar radiation spectrum, and a lower HOMO level that increases the
open circuit voltage of photovoltaic devices. The PCDTBT device performance is as follows: Jsc
= 10.5 mA/cm2, Voc = 0.88 V, FF = 0.66 and e = 6.1% under air mass 1.5 global (AM 1.5G)
illumination from a calibrated solar simulator with irradiation intensity of 100 mW/cm2. The
IQE approaches 100%, implying that essentially every photon absorbed leads to a charge
separated pair and that every photogenerated carrier is collected at the electrodes.


B10.94
Self Sorted Carbon Nanotube Transistors and Conductive Films Soumendra Barman,
Melburne C Lemieux and Zhenan Bao; Department of Chemical Engineering, Stanford
University, Stanford, California.

Single-walled carbon nanotubes (SWNTs) possesses great potential to be the next breakthrough
for sensors, flexible computing networks and next generation electronics. The manufacture of
carbon nanotubes involves the decomposition of carbon into graphitic tubes of different
diameters and chiralities. Depending on the chirality of the nanotube, it behaves as a
semiconductor or a metal. One of the greatest obstacles for creating the next generation of
devices is the separation of nanotubes by chirality. Here, we refine the surface sorting separation
technique we have developed by modifying the solution processing conditions and self
assembled monolayer functionalities in an effort to understand the interactions leading to
chirality selectivity. Using self sorting we have fabricated high performance SWNT thin film
transistors (TFTs) and transparent conductive electrodes. UV-vis-NIR spectroscopy, Raman
spectroscopy, AFM and semiconductor parameter analysis were used to characterize the results.
The knowledge gained from understanding the mechanism for surface self sorting is critical for
the fabrication of devices and could be important for the integration of carbon nanotubes into
large scale electronics.


B10.95
Accurate and Simultaneous Determination of Carrier Density and Mobility in Organic
Semi-conducting Materials. Kai Shum
1
and Jim Shi
2
;
1
Physics, Brooklyn College - CUNY,
Brooklyn, New York;
2
Chemistry, College of Staten Island - CUNY, Staten Island, New York.

Accurate and simultaneous determination of carrier mobility and density in organic
semiconducting materials is very important for their optoelectronic applications including light-
emitting diodes (LEDs), solar cells, and thin film field-effect transistors. In this work, we report
on a unique data analysis procedure for space-charge limited currents to obtain the carrier density
and carrier mobility for our newly synthesized perylene tetracarboxylic diimides with finely
tuned pi-stack structures without altering the electronic characteristic of individual molecules.
How pi-stack structural variations affect charge transport performance will be discussed.


B10.96
High Efficiency, Solution-Processed Bulk Heterojunction Solar Cells Using
Diketopyrrolopyrrole-Containing Thiophene Oligomers Arnold Tamayo, Xuan-Dung Dang,
Bright Walker and Tyler Kent; Center for Polymers and Organic Solids, University of California,
Santa Barbara, California.

Bulk heterojunction (BHJ) solar cells are fabricated from blends of 2,5-di-(2-ethylhexyl)-3,6 bis-
(5''-n-hexyl-[2,2';5',2'']-terthiophen-5-yl)pyrrolo[3,4-c]pyrrole-1,4-dione:[6,6]-phenyl C71
butyric acid methyl ester (SMDPPEH:C71-PCBM). Absorption and photocurrent of the blend
films extend to 800 nm. A power conversion efficiency of 3.0% with a 50:50 donor-acceptor
ratio is obtained under simulated 100 mW/cm2 AM 1.5 illumination with a 9.2 mA/cm<2>
short-circuit current density and an open-circuit voltage of 0.72 V. The hole and electron
mobilities in the 50:50 blend are fairly balanced, 1.0 10<-4> cm<2>/V-s and 4.3 10<-4>
cm2/V-s, respectively. This is the highest PCE reported to date for BHJ solar cells using solution
processable small molecules.


B10.97
Abstract Withdrawn


B10.98
Harvesting Lost Photons: Minimizing Sub-Bandgap Losses in Organic Photovoltaic
Devices by Up-conversion Sebastien Loranger
1
, David Banville
1
, Jennifer McLeod
3
, Rosei
Federico
3
, Dmytro F Perepichka
2
and Clara Santato
1
;
1
Genie Physique, Ecole Polytechnique de
Montreal, Montreal, Quebec, Canada;
2
Chemistry, McGill University, Montreal, Quebec,
Canada;
3
INRS, Varennes, Quebec, Canada.

Organic semiconductors (OSC) for photovoltaic applications offer advantages that include
significantly lowered manufacturing costs (solution processing), flexibility of the device (roll-up
PV panels), and the possibility to easily tailor the optoelectronic properties through chemical
synthesis. Unfortunately, the maximum conversion efficiency obtained so far in Organic PV
(OPV) devices is ~5 %. Among other reasons, this is due to a large mismatch between the
absorption characteristics of organic semiconductors and the solar spectrum. A significant
portion of the solar photons are lost (can not be converted). To increase the power efficiency
of OPV devices the materials properties need to be tuned to increase light absorption. Our
approach is based on the use of the well known phenomenon of up-conversion of rare earth-
doped nanocrystals. We investigate conventional OPV devices where rare earth-doped
nanoparticles, dispersed in the organic active layer, can transfer the up-converted energy of NIR
photons to the polymer semiconductor, improving the overall efficiency. The key physical
process in the proposed hybrid PV system is the energy transfer from the excited up-converting
material to the organic semiconductor of the PV cell. We focus on a hybrid organic/inorganic
system prepared by blending organic and up-converting nanoparticles (UCNPs) components. [1]
Specifically, polythiophenes are considered as the p-type materials and functionalized fullerenes
as the n-type. Systematic investigations of the energy transfer between UCNPs and conjugated
polymers have been performed by means of steady-state NIR spectroscopy (UCNP-induced
emission of the polymers). Interestingly, the photoluminescence of UCNP decreases with the
increase of the polythiophene component in the blend. This suggests the possibility of significant
energy transfer between the UCNP and the organic semiconductors. On the other hand, the
fullerene has no significant effect on the UCNP emission. UCNP of different qualities are being
investigated, with different crystallographic structures (cubic and hexagonal) and stabilized with
different capping agents (oleic acid versus oleilamine). Time resolved spectroscopy is going to
be performed to measure life-times of the UCNP excited states in presence of the organic
semiconductors. To assess the effect of the UCNP on the electrical properties of the active layer
of the OPV device, we performed charge transport measurements in field-effect transistor
configuration, irradiating the layer with a low power NIR laser (phototransistor configuration).
This approach permits to identify the optimum size of the UCNP to be incorporated in the active
layer, together with their optimum concentration in the layer. [1] J.-C. Boyer,F. Vetrone, L. A.
Cuccia, J. A. Capobianco J. Am. Chem. Soc. 2006, 128, 7444.


B10.99
Ordered Titanium Dioxide Films Grown on Self-Assembled Monolayers. Shirin M Usmani,
Diana Mars and Andrew S Ichimura; Chemistry & Biochemistry, San Francisco State University,
San Francisco, California.

Titanium dioxide finds extensive applications as pigments, in medicine, wastewater remediation,
oxidative photocatalysis, and in dye-sensitized solar cells. Applications such as hybrid solar cells
utilize thin films of titanium dioxide as the electron transport material. Typically, the films are
prepared from TiO2 nanoparticle containing sols that are spin-coated onto substrates and
subsequently sintered to induce phase transformation and interparticle contact. We have pursued
a strategy of thin film preparation that involves growth of crystalline TiO2 directly onto a
functionalized surface from homogeneous solutions. In this approach, a densely packed self-
assembled monolayer (SAM) with a terminal Ti-OH functional group is used to chemically bond
the film to the underlying gold substrate. The advantage of this method is that resultant films are
highly ordered polycrystalline arrays in which monolithic crystals span the film from substrate to
external surface. This arrangement may facilitate charge transport across the layer and thus
decrease the probability of electron-hole recombination. In a larger sense, SAM chemistry allows
us to explore avenues for controlling crystal growth through a tailoring of the surface of the
substrate. In this work, anatase and rutile films grown on Ti-OH terminated SAMs from
homogeneous solution will be described. Characterization methods include powder X-ray
diffraction, HR-SEM, IR, UV-vis-NIR spectroscopy, and 4-probe conductivity studies.


B10.100
Self-Assembled Monolayers to Support the Growth of Inorganic Films Diana Mars, Shirin
M Usmani and Andrew S Ichimura; Chemistry & Biochemistry, San Francisco State University,
San Francisco, California.

Self-assembled monolayers (SAMs) provide a direct route to modify the interfacial chemistry
between a metal surface such as gold to organic or inorganic films. SAM chemistry and
formation on gold substrates is well-known and organo-sulfur compounds such as
hexadecanethiol self-assemble to form densely packed quasicrystalline 2D arrays. Depending on
the terminal functional groups, SAMs can be used to passivate a surface, control macroscopic
surface properties such as wetting and friction, and block or permit charge transport across the
film. Despite advances in SAM chemistry in recent years, considerable opportunities to develop
new monolayers remain. For example, increasing the thermal stability of SAMs and tailoring the
terminal group to specific add-layers would extend the range of applications. In this work, we
have prepared SAMs through the reaction of SiCl
4
, TiCl
4
, P(O)Cl
3
, and P(S)Cl
3
with densely
packed -OH terminated monolayers. The result is a trithiolate or tripod SAM that has three
thiolate bonds to the gold surface. The tripod SAM proves to have a higher thermal stability than
single thiolate-Au bonds as measured by temperature programmed desorption (TPD) even for
very short alkyl chains. By terminating the tripod SAM with a SiOH, TiOH, P=O, or P=S
functional group, these films can be used as supports for the growth of inorganic films such as
silica zeolites, TiO
2
, or other chalcogonide based films. The structures and properties of the
monolayers were elucidated by fourier transform infrared (FTIR) spectroscopy, single
wavelength ellipsometry (SWE), TPD, and density functional theory (DFT) and will be reported
in this paper.


B10.101
Solvent Induced Structural Transition in Continuous and Nanopatterned Pentacene Thin
Films. Aram Amassian
1
, Vladimir A Pozdin
1
, Alexander Zakhidov
1
, Detlef M Smilgies
2
and
George G Malliaras
1
;
1
Materials Science and Engineering, Cornell University, Ithaca, New York;
2
Cornell High Energy Synchrotron Source, Cornell University, Ithaca, New York.

Solvent vapor annealing is increasingly used to induce structural and morphological changes in
polymer systems with the goal of increasing intermediate and long range order. In this paper, we
demonstrate that solvent vapor annealing can be used in small-molecule polycrystalline thin
films of pentacene to control its structure and polymorphism. Using acetone solvent vapor we
have transformed pentacene films which form in the thin film polymorph into the bulk phase.
In situ time-resolved grazing incidence X-ray diffraction measurements suggest that the phase
transformation occurs throughout the depth of the film. Closer inspection of diffraction patterns
reveals smearing and dissolution of the lattice followed by formation of the bulk lattice,
indicating a first-order phase transition. This enables fabrication of OTFTs with the bulk phase
films of pentacene and makes it possible to compare charge transport measurement from the thin
film and bulk polymorphs. This was previously impossible due to the fact that as-deposited
pentacene films are dominated by the thin film phase. We have gone a step further and
performed solvent-vapor annealing on nanopatterned pentacene films to investigate size effects
and to produce arrays of well-ordered crystalline microdomains for transistor fabrication.


B10.102
Novel Morphological Relationship between Field-Effect Mobility and Molecular Layer
Population at the Semiconductor-Dielectric Interface. Aram Amassian
1
, Tushar V Desai
2
,
Vladimir A Pozdin
1
, Stefan Kowarik
4
, Sukwon Hong
2
, Arthur R Woll
3
, Detlef M Smilgies
3
,
Frank Schreiber
4
, George G Malliaras
1
and James R Engstrom
2
;
1
Materials Science and
Engineering, Cornell University, Ithaca, New York;
2
School of Chemical and Biomolecular
Engineering, Cornell University, Ithaca, New York;
3
Cornell High Energy Synchrotron Source,
Cornell University, Ithaca, New York;
4
Institute fr Angewandte Physik, Universitt Tbingen,
Tbingen, Germany.

We report a novel relationship between the morphology of the semiconductor-dielectric interface
and the field-effect mobility of top-contact organic thin film transistors (OTFTs). We have
achieved a variation of the field effect mobility by 4 orders of magnitude (from 10
-5
to 10
-1
cm
2
-
V
-1
-s
-1
) in small-molecule thin films of diindenoperylene (DIP) by controlling the morphology
and molecular layer population of the DIP films near the semiconductor-dielectric interface. The
morphological differences appear to be related to the degree to which molecular layers near the
semiconductor-dielectric interface are populated during deposition of the molecular
semiconductor. Control of layer population at the semiconductor-dielectric interface was
achieved by depositing DIP films in a variety of processing conditions, including by vacuum
sublimation, by supersonic molecular beam deposition, on bare SiO
2
and on SiO
2
treated with
hexamethyldisilazane (HMDS). To measure variations in layer population, we have used a
combination of in situ time-resolved X-ray reflectivity and ex situ non-contact atomic force
microscopy. The histogram of surface height obtained independently from these two methods
hold crucial clues about the morphology of the interfacial region and can be directly linked to the
performance of top-contact OTFTs. In particular, the asymmetry or skewness of these
distributions can be related directly to the transport properties of OTFTs. When the histograms
are strongly skewed toward the interface (layer population at the interface is deficient), mobility
is substantially lower than when the histogram is symmetric or skewed toward the surface (layer
population at the interface is adequate). Remarkably, the lateral size of crystalline and
morphological features does not appear to have a strong bearing on the performance of devices.
Our study suggests that layer population near the semiconductor-dielectric interface may be
influencing the degree of interconnectivity between crystallites, i.e., at grain boundaries.


B10.103
Highly Soluble Polymer Containing Thiophene and Alkyl-substituted Fluorene for Organic
Thin Film Transistors (OTFTs) Jae Wan Jang, Jin Uk Ju, Peng Tao Kang, Qinghua Zhao and
Soon-Ki Kwon; Polymer Engineering, Gyeongsang National University, JinJu, Korea, South.

Highly soluble conjugated a new p-type copolymers (PBTADF and PD5TADF) were
synthesized by the Suzuki coupling reaction. The newly designed copolymers are expected to
have high mobility because long-linked thiophene and long alkyl chains can give a high charge
density, -stacking, and orderness. The monomers were prepared with highly overall yields.
Chemical structures and optoelectronic properties of the copolymers were characterized by
elemental analysis, 1H NMR, FT-IR, UV absorption, cyclic voltammetry (CV), and
photoluminescence (PL). In the case of the PBTADF, the absorption maximum was observed at
455 nm for solution and 520 nm for film, respectively. The PL maximum was observed at 561
nm for solution and 610 nm for film, respectively. The thermal properties of copolymers were
characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC).
The copolymers were showed 5% weight losing temperature at 407 oC for PBTADF and 419 oC
for PD5TADF, respectively. The weight-average molecular weight of the copolymers were
determined to be 41,202 for PBTADF and 29,322 for PD5TADF by gel permeation
chromatography (GPC) using polystyrene standards for calibration in the eluent THF with
polydispersity indexes of 1.66 for PBTADF and 1.29 for PD5TADF, respectively. The solubility
of the copolymers were important property for conjugated polymers used in OTFTs. Especially,
the copolymers were easy to be soluble in common solvents, such as chloroform, tetrahydrofuran
(THF), toluene, chlorobenzene, and dichlorobenzene., this is due to the introduction of long alky
chains.


B10.104
Synthesis and Characterization of High-Performance Semiconductors based on
Alkoxylnaphthyl for Organic Thin Film Transistors Dong Hee Lee
1
, Qinghua Zhao
1
, Jong-
Won Park
1
, Sung Ouk Jung
1
, Yun-Hi Kim
2
and Soon-Ki Kwon
1
;
1
GNU, Jinju, Korea, South;
2
department of chemistry, Gyeongsang national university, Jinju, Korea, South.

Organic semiconductors that consist of conjugated oligomers or polymers have attracted much
interest in recent years, due to their potential applications in organic thin-film transistors
(OTFTs). OTFTs can be fabricated at a low cost, over large areas, using flexible substrates. Over
the past decade, many researchers have made great progress in increasing the performances
(charge-carrier mobility, on/off ratio) of organic semiconductors for OTFTs, by designing new
fused aromatic compounds. Suzuki et al. reported oligo(2,6-anthrylene) derivatives with a
mobility of 0.18 cm2V-1s-1. Frisbie et al. demonstrated high mobility thiophene/acene hybrid
semiconductors, showing anthracene end-capped oligomers with stable device performance with
a mobility of up to 0.12 cm2V-1s-1. Moreover, TFT values of up to 0.40 cm2V-1s-1 were
reported for naphthyl end-capped quarterthiophene, 5,5- bis(naphth-2-yl)-2,2:5, 2:5, 2-
quaterthiophene (NaT4), by Tian et al. Recently, we reported thienothiophene end-capped new
oligo acene derivatives, 2,6-bis(5-hexyl-thieno[3,2-b]thiophen-2-yl)anthracene (DH-TAT),
which showed a hole mobility of 0.14 cm2V-1s-1 , and an on/off current ratio of 6.3 x 106. In
this paper, we synthesized a series of new organic semiconductors, one of them showed a field
effect mobility value higher than 0.50 cm2V-1s-1, on/off ratios greater than 7.5 x 105 along with
a low threshold voltage of 4.4 V and subthreshold slope of 0.8 V/dec. Their properties of optical,
thermal stability and device performance would be discussed further.


B10.105
A Nanoengineering Path Towards All-printed DH4T-based Thin Film Transistors by Soft
Lithography.Dana Alina Serban
1
, Alexandru Vlad
1
, Constantin A Dutu
1
, Sorin Melinte
1
,
Pierpaolo Greco
2
, Massimiliano Cavallini
2
, Fabio Biscarini
2
, Stefano Zacchini
3
and Maria C
Iapalucci
3
;
1
Electrical Engineering, Universite catholique de Louvain, Louvain-la-Neuve,
Belgium;
2
Istituto per lo Studio dei Materiali Nanostrutturati, Bologna, Italy;
3
Dipartimento di
Chimica Fisica e Inorganica, Universita di Bologna, Bologna, Italy.

Organic semiconductors have received utmost attention recently due to their increasing role in
emergent electronic devices and optoelectronics. As the deposition method dictates key physical
characteristics of the semiconductor such as molecular packing and charge carrier mobility,
various techniques have flourished in the quest of fulfilling various performance requirements.
Yet, the need of innovative approaches should not be limited to the semiconductor deposition,
but ought to also touch other transistor components. Here we report on a simple and versatile
method of fabricating dihexylquaterthiophene (DH4T)-based coplanar bottom-gate thin film
transistors by means of soft lithography. Namely, microinject molding in capillaries (MIMIC) [1]
has been used by turns to define the electrodes and the active layer. In a first set of experiments,
metallic stripes - 3 mm long spaced by 200 m - acting as source and drain have been deposited
from Pt salts [2] on heavily-doped Si wafers bearing 200-nm-thick silicon dioxyde dielectrics.
Electrical conductivity measurements of the Pt MIMIC stripes have been consistently reproduced
upon several voltage-sweep cycles. Finally, the devices were completed by drop-casting a
solution of DH4T diluted at 0.2% wt. in tetrahydrofuran. On the other hand, we have employed
the MIMIC approach to pattern the DH4T on top of conventional transistors [3]. These devices
have electron-beam evaporated Pd source and drain electrodes, channel width of 1 mm and
length of 10 m. We formed the active layer by depositing the DH4T using a
poly(dimethylsiloxane) stamp accommodating 800-nm-wide channels. Samples have been
analyzed by Polarized Optical Microscopy, Tapping-Mode Atomic Force Microscopy and X-Ray
Reflectometry. They uncovered the formation of multidomains with preferential orientation
along the long axis of the stripes, as well as the organization in (32-high) monomolecular
terraces [3]. Electrical characterisation of the transistors revealed the key role of the
nanostructuration: higher field effect mobilities are achievable when the semiconductor is
deposited by MIMIC with respect to homogeneous films. We explain the improved mobility by a
preferential charge transport taking place inside the stripes, as their increased internal order
provides a better pathway for the hole carriers. Our findings that nanoengineered transistors
exceed in performance those fabricated by standard approaches are very encouraging in the light
of fabricating fully-patterned devices from solution processable materials. [1] E. Kim, Y. Xia, G.
M. Whitesides, Nature 1995, 376, 581; M. Cavallini and F. Biscarini, Nano Lett. 2003, 3, 1269.
[2] P. Greco et al., J. Am. Chem. Soc. 2008, 130, 1177. [3] D. A. Serban et al., Appl. Phys. Lett.
2008, 92, 143503.


B10.106
Ultrathin High Efficiency Solar Cell Based on Vapor Deposited Squaraine Dye. Siyi Wang
1
,
Elizabeth Mayo
2
, Dolores Perez
1
, Laurent Griffe
1
, Guodan Wei
2
, Brian Lassiter
2
, Peter
Djurovich
1
, Stephen Forrest
2
and Mark Thompson
1
;
1
Chemistry, university of southern
california, Los angeles, California;
2
Electrical Engineering and Computer Science, Physics,
Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan.

Squarains are a family of dyes with sharp and intense absorption in solution, which exhibit
panchromatic absorption in the solid state. Squaraines have highest occupied molecular orbital
(HOMO), lowest unoccupied molecular orbital (LUMO) energy levels comparable to the
common OPV donor material copper phthalocyanine (CuPc). 2,4-Bis [4-(N,N-diisobutylamino)-
2,6-dihydroxyphenyl] squaraine (SQ1) is demonstrated to be a successful donor like material in
organic heterojunction photovoltaics. Optimal SQ1 device is fabricated as ITO/SQ1 /C
60
/BCP
/Al, which generates high short circuit current J
sc
of 6.54 mA/cm2, and open circuit voltage V
oc

of 0.80 V , resulting in power conversion efficiency of 3.4 %, at 1 sun incident irradiation
(AM1.5). Compared with the 2% power conversion efficiency of our conventional CuPc device
[ITO/CuPC (400 )/C
60
(400 )/BCP (100 )/Al (1000 )]. It is possible to tune the absorption
spectra of squaraines to near infrared region by varying the substituent groups. The
demonstration of sublimable SQ1 as a donor material opens up a new family of compounds for
small molecular heterojunction photovoltaics.


B10.107
Abstract Withdrawn


B10.108
Towards Greatly Improved Efficiency of Polymer LED. Zhang-Lin Zhou
1
, Lihua Zhao
1,2
,
James Brug
1
, Xia Sheng
1
, Gary Gibson
1
, Sity Lam
1
and K. Nauka
1
;
1
Hewlett Packard Labs, Palo
Alto, California;
2
University of California, Berkeley, California.

Organic/polymer light-emitting diodes (OLEDs) show great promise of revolutionizing display
technologies. Hence, these devices and the materials that render them functional are the focus of
intense scientific and technological interest. The archetypical multilayer OLED heterostructure
introduces numerous chemical and physical challenges to the develoment of efficient and robust
devices. This requires placing a nanoscale feature at desired sites within the thin film stack.
These layered structures are formed from solution based spin-casting or printing with
subsequesnt removal of the solvent. However, solvent from the freshly deposited film can
dissolve or partially dissolve the underlying layer resulting in loss of the desired structure and
corresponding device functionality. Undesirable redistribution of the nanoscale features within
the polymer is another detrimental effect associated with solvent removal. In this paper, we will
describe a new solution to the above problem by embedding hole transporting materials (HTLs)
in a cross-linked polymer matrix. We have successfully demonstrated this technique to deposit
the HTL in our OLED device. In this device, the HTL is deposited together with cross-linkable
monomers on the HIL that is pre-deposited over the patterned ITO anode. The next layer for the
stacking process is EML (PFO) that is followed by the deposition of the ETL. Since solvents that
are used for EML polymer are commonly shared by the under-layer HTL polymer, embedding
the HTL molecules into the inert cross-linked polymer network is a good way to minimize the
undesirable impact from solvents that are used by the EML polymer. There are many options that
could be employed to form the cross-linked inert polymer network: a mixture of cross-linkable
monomer, oligomers, and polymers, in addition to cross-linking agent and an initiator. The cross-
linking agent could be a 2-branch, 3-branch, or 4-branch cross-linker. Cross-linking could be
activated using appropriate energy sources such as UV-exposure or thermal process. Device
fabrication together with the total luminance and external quantum efficiency of such devices
will be presented.


B10.109
Hysteresis Mechanism and Reduction in the Bis(triisopropylsilylethynyl)Pentacene Thin
Film Transistors with Polymer Blend, Cross-linked Poly(vinyl phenol). Jin Young Oh
1
,
Young Bum Yoo
1
, Man Hyeop Han
1
, Byeong har Hwang
1
, Hyeon Seok Hwang
1
, Joo Hee Kim
2

and Hong Ku Baik
1
;
1
material science, Yonsei university, seoul, Korea, South;
2
chemistry, Iwha
woman university, seoul, Korea, South.

We have studied the electrical stability of cross-linked Poly(Vinyl Phenol) dielectric and active
layer with polymer blend for the Bis(triisopropylsilylethynyl)Pentacene[tips-pentacene] thin film
transistors. the hysteresis occurs mainly due to the dielectric surface -OH group and the rough
surfaces which are induced by trap sites at the interface in OTFTs. In order to reduce hysteresis,
we used an OH free and smooth dielectric and active layer with Polymer blend(PaMS). As a
result, Increased mobility and decreased hysteresis are observed in Tips-pentacene thin film
transistors with polymer blend(PaMS) and PVP dielectric.


B10.110
-Conjugated Molecules based on Thiophene Derivatives as Organic Semiconductors for
Thin Film Transistor Applications. Ki Hwa Jung, kyung Hwan Kim, Min Ju Cho and Dong
Hoon Choi; Korea university, Seoul, Korea, South.

Organic semiconductor materials based on extended linear-conjugated systems have been very
intriguing and significant development has been achieved in these materials over the one decade.
In the exploration of the application as organic semiconductors in organic field effect transistor
(OFET) is an important component for developing future flexible displays. Accordingly, a
number of researchers have attempted to synthesize -conjugated small molecules, dendrimers,
oligomers, and polymers because of their strong potential applications to electronics and
optoelectronics such as in organic light-emitting diodes (OLEDs), organic field effect transistors
(OFETs), and photovoltaic cells. In organic semiconductors, the intrinsic carrier mobility
depends critically on the degree of molecular orientation and on the extent of the intermolecular
interaction. In this study, new conjugated crystalline cruciform molecules have been synthesized
through the Sonogashira coupling reaction. Introduction of thiophene-based peripheral moiety
into an aromatic core improve the solubility in organic solvent for facilitating the solution device
fabrication. They display a p-type semiconducting behaviors and their electrical properties are
investigated in detail. We investigated the UV-visible spectroscopy, photoluminescence
spectroscopy, cyclic voltammetry, thermogravimetric analysis and differential scanning
calorimetry properties of the new -conjugated molecules. Finally, we fabricated thin film
transistor to investigate the carrier mobility and its photosensitivity under light illumination.


B10.111
Abstract Withdrawn


B10.112
Fused Aromatic Thienopyrazine Copolymers for Photovoltaic and Thin Film Transistor
Applications. Rajib Mondal
1
, Nobuyuki Miyaki
1
, Hector A Becerril
1
, Jack Parmer
2
, Michael D
McGehee
2
and Zhenan Bao
1
;
1
Chemical Engineering, Stanford University, Stanford, California;
2
Materials Science and Engineering, Stanford University, Stanford, California.

Development and tuning the fundamental properties of polymeric semiconducting materials have
become an active area of research in recent years due to their potential uses in light weight and
flexible optoelectronic devices, such as organic photovoltaics (OPVs) and organic thin film
transistors (OTFTs). In this regard, several fused aromatic thienopyrazine (TP) copolymers were
synthesized and investigated. The fused aromatic TP unit provides a planar and rich -face,
which promotes the - stacking between the polymeric chains and enhances the device
efficiencies. The electronic properties of these polymers can also be tuned significantly using
different aromatic group used in TP unit. For example, band gap of TP-fluorene copolymer was
reduced to ~1.4 eV from ~1.7 eV by replacing phenanthrene from acenaphthyl. Various alkyl
chains were used at different positions of the polymers to achieve the morphological control.
Power conversion efficiency more than 1% in OPV devices and hole carrier mobility of ~0.2
cm2/Vs in OTFT devices have already been achieved using some of these polymers. Further
optimization of the newer polymers is currently underway.


B10.113
Abstract Withdrawn


B10.114
Synthesis of Donor-Acceptor Diblock Copolymer Based on Regioregular Poly(3-
hexylthiophene) and Fullerene and Its Use as a Compatibilizer in P3HT/PCBM Bulk
Heterojunction Solar Cells. Jea Uk Lee, Jae Woong Jung and Won Ho Jo; Materials Science
and Engineering, Seoul National University, Seoul, Korea, South.

Among various organic photovoltaics, the conjugated polymer/fullerene bulk heterojunction
system is one of the most promising ones for achieving high performance of polymer
photovoltaics. Recently, it has been reported that thin-film bulk heterojunction solar cells
fabricated by simple blending of regioregular poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-
C61-butyric acid methyl ester (PCBM) show high power conversion efficiency. Despite
remarkable recent progress, the bulk heterojunction system still has some problems to be solved
for commercialization. The most serious problem is that this approach is largely dependent upon
the solid state phase morphology of the two components (donor/acceptor) in the photoactive
layer because the exiton diffusion length is limited within 10 nm. Although nanometer scale
phase separation of donor/acceptor blend can be attained through optimized device conditions in
laboratory (specific blending ratio, very short thermal annealing time), exposure to sun light for
long time will cause macrophase separation in the blend of conjugated polymer and fullerene
derivatives. The macrophase separation may limit charge separation and thus lower the power
conversion efficiency in the photovoltaic device. For the purpose to solve this problem, in this
study a novel diblock copolymer composed of regioregular poly(3-hexylthiophene) and fullerene
derivates (P3HT-b-C60) was synthesized and used as a compatibilizer for P3HT/PCBM bulk
heterojunction system. It has been well known that a proper compatibilizer can reduce the
domain size of phase separation and also retard the rate of phase separation in the blend system.
With varying the fabrication conditions, the change of domain size and the power conversion
efficiencies of P3HT/PCBM/P3HT-b-C60 blends were measured. First, to examine the effect of
compatibilizer on the performance of heterojunction solar cells, P3HT/PCBM bulk
heterojunction devices were fabricated with varying the amount of P3HT-b-C60 compatibilizer.
Second, the effect of the thermal annealing time and temperature on the performance of
P3HT/PCBM/P3HT-b-C60 bulk heterojunction solar cells was investigated. Third, the solvent
annealing (slow drying) method was also applied to the P3HT/PCBM/P3HT-b-C60 blend in
order to obtain the desirable morphology. AFM and TEM images of blend films with
compatibilizer exhibited uniform morphology with finer domain size after annealing as
compared with the blends without compatibilizer, when a small amount of compatibilizer was
added to the blend. The power conversion efficiency of blend with compatibilizer was improved
as compared with the blend without compatibilizer. Particularly, the short circuit current (Jsc) of
the blend with the compatibilizer was higher than the blend without the compatibilizer due to
improvement of phase morphology of P3HT/PCBM/P3HT-b-C60 blend.


B10.115
High Electron Carrier Mobility Electron Transport Materials for OLED Devices Heh-Lung
Huang, Teng-Chih Chao and Mei-Rurng Tseng; Industrial Technology Research Institute,
Chutung, Hsinchu, Taiwan.

We developed a series of new electron transport materials. These materials contain heterocyclic
related core structure and with other electron withdrawing group. The electron mobility of
thermal deposition for these materials are greater than 10-4 cm2/Vs. We are now investigating
the effect of new electron transport materials for the OLED devices and lifetime. Currently, the
current efficiency and brightness of green phosphorescent OLED devices with new electron
transport materials are 46.0 cd/A and 82123 cd/m2 respectively. We are still investigating and
optimize the OLED devices with those new electron transport materials. With the increasing
mobility of the new electron transport materials, we can apply on the flexible plastic substrate to
fabricate the flexible OLED device.


B10.116
Multilayer Formation Using a Lamination Process Toward Efficient Polymer Solar Cells
Keisuke Tajima
1
, Motoshi Nakamura
1
, Erjun Zhou
2
, Chuhe Yang
2
and Kazuhito Hashimoto
1,2
;
1
Department of Applied Chemistry, The University of Tokyo, Tokyo, Japan;
2
HASHIMOTO
Light Energy Conversion Project, Exploratory Research for Advanced Technology (ERATO),
Japan Science and Technology Agency (JST), Tokyo, Japan.

Polymer solar cells (PSCs) are drawing much attention these days because of their potentials for
the production of flexible and large-area solar cells at dramatically low costs. In the fabrication
method commonly used now, however, an metal electrode is deposited on the polymer layer by
vacuum evaporation, which is both costly and time-consuming process. Furthermore, it is
suggested that the device performance and stability is detracted by physical or chemical damage
to the organic active layer form the evaporated metals. In this presentation, first we report the use
of a lamination method to fabricate the PSCs. Two different polymer layers are coated on
conductive substrates (ITO covered with TiO2 and Au with PEDOT:PSS) and the substrates
were simply laminated by applying pressure (2-6 MPa) and heat (100-150 C) to fabricate the
devices. By this simple method, we obtained physically and electronically connected interface
between the polymer layers. The photovoltaic performances of the devices with P3HT:PCBM
bulk heterojunction are compared to those of the conventional devices with the electrode
deposited by vacuum evaporation. As the result, the two devices showed almost identical J-V
curves, and the PCE reached 3.3% in both devices under the AM1.5 irradiation. This result opens
up the possibility of low-cost mass production of the PSC through a roll-to-roll lamination
system. Since we can apply this method to the heterointerface of the semiconducting polymers, it
is possible to enhance the light absorption of the PSCs by combining the two polymer layers with
different absorption ranges. For this purpose, a novel low band gap polymer, PDTPDTBT was
synthesized with an alternating structure of N-substituted dithieno[3,2-b:2,3-d]pyrrole (DTP) as
a new donor, and 4,7-dithien-2-yl-2,1,3-benzothiadiazole as an acceptor group. The new polymer
has a low optical band gap (1.46 eV) and broad absorption with peaks at 451 and 697 nm in the
film, which is complementary to the absorption of P3HT. Preliminary results showed that the
power conversion efficiency of bulk heterojunction type PSC with PDTPDTBT reached 2.18%
in combination with PCBM. The combination of P3HT and PDTPDTBT layers using the
lamination method gave the devices that respond to the broad range of the solar spectrum.
Further optimization of the layer components would give us a possibility to reach higher
conversion efficiency. [1] Nakamura, M.; Tajima, K.; Yang, C.-H.; Hashimoto, K. Control of the
Active Layer/Metal Electrode Interface Using a Lamination Process toward Efficient Polymer
Solar Cells. Submitted. [2] Zhou, E.J.; Nakamura, M.; Nishizawa, T.; Zhang, Y.; Wei, Q.S.;
Tajima, K.; Yang, C.H.; Hashimoto, K. Synthesis and Photovoltaic Properties of A Novel Low
Band Gap Polymer Based on N-substituted dithieno[3,2-b:2,3-d]pyrrole. Macromolecules in
press.


B10.117
Synthesis and Molecular Orientation Control of Oligo(p-phenylenevinylene) Derivatives
for the Application to Organic Photovoltaic Devices. Keisuke Tajima
1
, Takeshi Nishizawa
1
,
Hady Kesuma Lim
1
and Kazuhito Hashimoto
1,2
;
1
Department of Applied Chemistry, The
University of Tokyo, Tokyo, Japan;
2
HASHIMOTO Light Energy Conversion Project,
Exploratory Research for Advanced Technology (ERATO), Japan Science and Technology
Agency (JST), Tokyo, Japan.

Nanoscale morphology of the donor and acceptor is of high significance to achieve a high
efficiency in the organic bulk heterojunction (BHJ) solar cells. Namely, large interface and
interpenetrating network of the donor and acceptor realize the efficient charge separation and
transport in the organic film, respectively. In the solution-processed BHJ solar cells, formation of
such a nanostructure is simply achieved by spin-coating and thermal annealing and it is affected
by many factors such as solvent, donor/acceptor mixing ratio, character of the materials used,
etc. Important characters of the materials are crystallinity and molecular orientation that facilitate
the formation of the network to achieve the efficient charge transport. In this presentation, we
first report the synthesis of novel oligo(p-phenylenevinylene)s (OPV) to demonstrate the effect
of the crystallinity of the donor on the morphology and solar cell efficiency in the OPV and
fullerene derivative (PCBM) BHJ solar cells. The crystallinity of the OPVs is tuned by changing
the alkyl side chain length. AFM images revealed that the film with highly crystalline OPV
showed a significantly different morphology and prevented the large PCBM aggregation that was
observed in the films with the lower crystalline OPVs. The solar cell with the highly crystalline
OPV showed the improvement in the short circuit current and the fill factor. These results
suggest that the highly crystalline OPV formed the donor network and prevented the PCBM
aggregation, resulting in the improved efficiency in the solar cells. Similarly, the crystallinity of
the donor group in the donor-acceptor dyad is also of high importance to achieve a high
efficiency in the solar cells [1, 2]. We also report the synthesis of novel oligo(p-
phenylenevinylene)-fullerene dyads and their solar cell efficiency. The strong pi-pi interaction in
the highly crystalline donor groups enhances the intermolecular charge hopping, resulting in the
improved fill factor and efficiencies over 1%. Finally, highly uniaxial alignment of the OPVs
were demonstrated in the as-cast films spin-coated from the solutions on mechanically rubbed
polymer alignment layers such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid)
(PEDOT:PSS) films. High dichroic ratio (Ap / An) of 41.0 and order parameter ([An - Ap] / [An
+ 2Ap]) of 0.93 were estimated from the polarized absorption spectra of the films. The molecular
orientation was also investigated by in-plane X-ray diffraction measurements, revealing the
highly uniaxial alignment of the molecules with its long axis parallel to the rubbing direction.
This spontaneous alignment could be a new method useful to control the
electronic/optoelectronic properties of the semiconducting materials in the thin films. [1] T.
Nishizawa, K. Tajima, K. Hashimoto, J. Mater. Chem. 2007, 17, 2440-2445. [2] T. Nishizawa,
K. Tajima, K. Hashimoto, Nanotechnology, 2008, 19, 424017.


B10.118
Solution Processed High Mobility Tetrathienoacene Polymer Semiconductors with a Long
Shelf Life in Ambient Environment. H. H. Fong
1
, Vladimir Pozdin
1
, Aram Ammassian
1
,
George Malliaras
1
, Mingqian He
2
, Susan Gasper
2
, Feixia Zhang
2
and Michael Sorensen
2
;
1
Materials Science and Engineering, Cornell University, Ithaca, New York;
2
Corning
Incorporated, Corning, New York.

We demonstrate that high performance, soluble polymeric semiconductors can be achieved by
increasing the rigidity of the thiophene monomer through the use of an alkyl-substituted core that
consists of four fused thiophene rings. We report on a member of the family of di-alkylated
tetrathienoacene copolymers, namely poly(2,5-bis(thiophene-2-yl)-(3,7-
ditridecanyltetrathienoacene) (P2TDC13FT4), that can be deposited from a 1,2-dichlorobenzene
solution into highly ordered films with a field-effect hole mobility exceeding 0.3 cm2/V/s.
Devices prepared on vapor phase deposition of silane based oxide gate oxide show a remarkably
long life-time of one year in ambients, with no significant change on the performance. We show
that di-alkylated tetrathienoacene copolymers represent a new class of organic semiconductors
that can be easily processed from solution into ordered, high mobility thin films. The
straightforward processing and the relatively low temperatures involved make them particularly
attractive for the development of electronics on plastic substrates.


B10.119
Photolithographic Micropatterning of Organic Electronic Materials. H. H. Fong, Jin-Kyun
Lee, Alexander Zakhidov, Priscilla Taylor, John DeFranco, Christopher Ober and George
Malliaras; Materials Science and Engineering, Cornell University, Ithaca, New York.

We developed a class of organic electronic materials that can be processed using fluorinated
solvents. These materials can function as imaging materials for photolithographic applications
and light-emitting applications for full color display. We demonstrate a critical technique of
patterning multi-layer organic devices by different orthogonal development media including
hydrofluoroethers and supercritical carbon dioxide. Small molecules and polymer materials can
be patterned on top of different substrates such as metal, transparent conducting oxide, and even
polymer, with a spatial resolution down to a micron. Using supercritical carbon dioxide, we
fabricated a patterned polymer light-emitting diode. A molecularly-doped polymer light emitting
diode is patterned on top of Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)
(PEDOT:PSS). This green-emitting device exhibits an efficiency of 22 cd/A and 8 lm/W at 100
cd/m2, which is compatible to the typical device performance. Using hydrofluoroethers as
development media, we developed a novel photosensitive material that allows us to pattern
traditional organic electronic materials without any damage. A stack structure of patterned multi-
layers is demonstrated. Furthermore, P3HT and pentacene transistors with patterned Au top
contacts using lift-off method are demonstrated with decent performance. We also fabricate a
class of highly fluorinated red, green, and blue light-emitting materials that can be only
processed using fluorinated solvents. These materials show superior stability in common organic
solvents including xylene, toluene, acetone, isoproponal and chlorinated solvents. Preliminary
results show a current efficiency of >5 cd/A. We can therefore pattern these solution processed
light-emitting materials using traditional photolithography under aqueous based media and
further aim for fabricating RGB pixels.


B10.120
Charge Injection in Polyfluorene Films using High Conductivity Thiophene Copolymers.
H. H. Fong, Arunabh Batra and George Malliaras; Materials Science and Engineering, Cornell
University, Ithaca, New York.

Fluorene-based copolymer is considered to be one of the most promising hole transporting and
blue light-emitting conjugated polymers used in polymeric light-emitting diodes (PLEDs) due to
its high-lying highest occupied molecular orbital (HOMO) of arylamine moiety and high carrier
mobilities. It is therefore desirable to boost up the charge injection. Our work attempts to provide
a comprehensive understanding on charge transport of fluorine-arylamine copolymers and
examine new approaches to improve carrier injection. Time-of-flight (TOF) technique has been
employed to evaluate the charge drift mobility at the thick film regime (1-10 micron) and shows
the polymer possesses superior mobility of > 0.01cm2V-1s-1. We examine the hole injection in
the polyfluorenes using chemically doped thiophene copolymers. Furthermore, the effect using
molecular additives on tuning the conductivity of these thiophene polymers is also investigated.
Results show a significant improvement of charge injection efficiency by tuning the conductivity
of the doped thiophene hole injecting layer. Moreover, the charge injection in this polyfluorene
with high-lying HOMO can be further enhanced by using vapor phase polymerization of
thiophene contained monomers that increases the injection efficiency to ~ 0.1 for a 100nm
polyfluorene film. Results will shed light on the enhancement of device efficiency and stability
in the future polymer electronic devices.


B10.121
Spin-Cast High- Non-Hysteresis Barium Titanate Nanoparticle Thin Film as Gate
Dielectric in Organic Thin Film Transistors. Zhang Jia
1
, Limin Huang
1
, Stephen O'Brien
1
and
Ioannis Kymissis
2
;
1
Applied Physics and Applied Mathematics, Columbia University, New
York, New York;
2
Electrical Engineering, Columbia University, New York, New York.

We demonstrate the usage of spin-cast 8nm-diameter high- BaTiO3 nanocrystals as gate
dielectric with parylene C coating as surface treatment in the fabrication of high-performance
pentacene organic field effect transistors (OFETs). Thanks to the extremely small size of BaTiO3
nanocrystals, the hysteresis seen in bulk material is quenched. This structure enhances the
OFETs performance while retaining all the processing advantages of organic semiconductors:
low temperature processing (<60 Celsius), low cost, applicability for large area casting, spraying
and printing on various substrates, etc. Pentacene mobility in the linear region was enhanced
from ~0.03 cm2/(Vs) at gate bias -20V in Parylene OFETs to ~0.35 cm2/(Vs) at gate bias -20V
in BaTiO3/Parylene OFETs under identical conditions, resulted from increased concentration of
accumulated carriers in the latter.


B10.122
Photocurrent Study of Traps States in Pentacene Thin Film Transistors. Zhang Jia
1
, Laura
Banu
2
and Ioannis Kymissis
2
;
1
Applied Physics and Applied Mathematics, Columbia University,
New York, New York;
2
Electrical Engineering, Columbia University, New York, New York.

We demonstrate the gate-bias dependent and wavelength dependent photocurrent study of both
UV-ozone treated and air-free pentacene transistors with bottom gate top contact structure. Our
unique facility enables us to fabricate the pentacene transistors without the exposure to air in any
phase of the fabrication process. Traps states are intentionally introduced by treating the
dielectric surface with UV ozone before the pentacene deposition. The photocurrent
measurement is carried out utilizing chopped excitation with wavelength between 300~800nm
and a lock-in amplifier with the frequency locked to the chopping frequency. The wavelength
dependent photocurrent spectrum shows extra peaks from the UV-ozone sample in the range of
350nm to 470nm, which correspond to energy transitions larger than the pentacene HOMO-
LUMO gap. This indicates extra trap states are introduced by UV-ozone treatment. The gate
dependent photocurrent spectrum shows the photocurrent intensity is proportional to the square
root of source-drain current at various gate bias in the saturation region. It also shows that the
UV-ozone treated samples have a positively shifted threshold voltage, which is confirmed by
direct electrical measurements. A more detailed transport model is proposed based on the trap
and release model and these photocurrent studies.



SESSION B11: Processing, Sensing & Memory
Chairs: Norbert Koch and George Malliaras
Friday Morning, April 17, 2009
Room 2001 (Moscone West)

8:30 AM B11.1
Organic Device Fabrication by Nanoskiving: Conjugated Polymer Photovoltaic Cells,
Nanowires, and Templates for Electropolymerization. Darren John Lipomi
1
, Ryan C
Chiechi
1
, Michael D Dickey
2
, William F Reus
1
and George M Whitesides
1
;
1
Department of
Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts;
2
Chemical
and Biomolecular Engineering, North Carolina State University, Raleigh, North Carolina.

This paper describes a new technique for the fabrication of conjugated polymer nanostructures
by sectioning thin films with an ultramicrotome. In the first application, a laterally ordered bulk
heterojunction of two conjugated polymers is fabricated by a three-step process: i) spin-coating a
multilayered film of the two polymers, ii) rolling the film into a cylinder (a jelly roll) and iii)
sectioning the film perpendicular to the axis of the roll with an ultramicrotome (nanoskiving).
The conjugated polymers are poly(benzimidazobenzophenanthroline ladder) (BBL, e-acceptor)
and poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV, e-donor). The
procedure produces sections with an interdigitated junction of the two polymers. The spacing
between the phases is determined by spin-coating (~15 nm to 100 nm) and the thickness of each
section is determined by the ultramicrotome (100 to 1000 nm). The minimum width of the MEH-
PPV layers accessible with this technique (~15 nm) is close to reported exciton diffusion lengths
for the polymer. When placed in a junction between two electrodes with asymmetric work
functions (tin-doped indium oxide (ITO) coated with poly(3,4-
ethylenedioxythiophene:poly(styrenesulfonate) (PEDOT:PSS), and eutectic gallium-indium,
EGaIn) the heterostructures exhibit a photovoltaic response under white light, although the
efficiency of conversion of optical to electrical energy is low. Selective excitation of BBL with
red light confirms that the photovoltaic effect is the result of photoinduced charge transfer
between BBL and MEH-PPV. In the second application, a similar process is used to generate
uniaxial collections of nanowires of BBL and MEH-PPV. These nanowires function as high-
surface-area chemical sensors. In the third application, gold nanowire electrodes are prepared
with 30-nm spacing using micromolding in capillaries and nanoskiving and addressed
individually. These nanowires serve as a template for the electrochemical deposition of
polyaniline.


8:45 AM B11.2
Abstract Withdrawn


9:00 AM *B11.3
Photolithographic Patterning of Organic Semiconductors George Malliaras, Materials
Science, Cornell University, Ithaca, New York.

A critical step for the realization of organic electronics is the availability of patterning techniques
that are compatible with these materials. Although great strides have been achieved in our ability
to pattern organics, the techniques used in the mature and entrenched industry of silicon
processing have made little impact in this field. This is primarily due to incompatibilities
between chemicals used in photolithography and the vast majority of organics. Overcoming
these incompatibilities promises a breakthrough in the manufacturing of organic electronics since
it would provide for massively parallel output along with process knowledge and equipment
already available from a very successful industry. We report on a few generic approaches for the
photolithographic patterning of organic materials using sacrificial layers as well as photoresists
that can be processed with solvents that are orthogonal to organics. We demonstrate the
applicability of these approaches to the additive and subtractive patterning of several organic
semiconductors, including polymers and small molecules. The application of photolithography to
pattern various organic devices with micron-scale features is demonstrated.


9:30 AM B11.4
Printable Organic-Metal Electrodes for Controlled Carrier Injections in Organic
Transistors Tatsuo Hasegawa, PRI, AIST, Tsukuba, Japan.

In this talk we report our recent studies on contact engineering of organic thin-film transistors
(TFTs) with use of conductive charge-transfer (CT) complex films as source/drain electrodes.
We successfully produced metallic CT compound films with predefined structures by "double-
shot" inkjet printing (DS-IJP) technique, in which soluble donor and acceptor components are
printed individually and combine on the substrates to form barely-soluble compound films. For
predefining shapes of the electrodes, we used hydrophobic/hydrophilic surface modifications on
top of the substrates. We found that the microscale intermixing of the printed droplets results in
the instantaneous formation of high-quality polycrystalline CT compound films. We consider
that this new type of solution process should allow us to make full use of highly-functional
organic CT compound materials in organic electronics devices. It is fount that fairly good
electrical contacts are obtained in the pentacene TFTs with the printed tetrathiafulvalene-
tetracyanoquinodimethane (TTF-TCNQ) films as bottom-contact source/drain electrodes that
show high mobility and sharp on/off switching at low gate voltages. We will present and discuss
various interesting aspects of the functional organic-metal electrodes. 1) Y. Takahashi et al. APL
86, 63504 (2005), 2) Y. Takahashi et al. APL 88, 073504 (2006), 3) Y. Takahashi et al. Chem.
Mater. 19, 6382 (2007), 4) M. Hiraoka et al. APL 89, 173504 (2006), 5) M. Hiraoka et al. Adv.
Mater. 19, 3248 (2007).


9:45 AM B11.5
Introduction of Innovative Dopant Concentration Profiles to Broaden the Recombination
Zone of Phosphorescent OVPD-Processed Organic Light Emitting Diodes. Manuel Bosing
1
,
Christoph Zimmermann
1
, Florian Lindla
1
, Frank Jessen
1
, Philip van Gemmern
2
, Dietrich
Bertram
2
, Dietmar Keiper
3
, Nico Meyer
3
, Michael Heuken
1,3
, Holger Kalisch
1
and Rolf Jansen
1
;
1
1Chair of Electromagnetic Theory, RWTH Aachen University, Aachen, NRW, Germany;
2
Philips Technologie GmbH, Aachen, Germany;
3
AIXTRON AG, Aachen, Germany.

The introduction of phosphorescent emitters for OLED has established a basis for the
development of OLED with impressive luminous efficiencies. However, to exploit the full
potential of phosphorescent light emission, it is crucial to develop device structures which lead to
a relatively broad exciton recombination zone in order to avoid triplet-triplet-annihilation (TTA).
In many OLED, matrix and emitter contribute differently to the mobility of holes and electrons
within the emissive layer, so the concentration of the dopant can be used to locate and/or broaden
the recombination zone. In contrast to VTE (Vacuum Thermal Evaporation), OVPD (Organic
Vaporphase Deposition) offers the opportunity to vary the concentration of the dopant during the
deposition of the emissive layer, so that complex concentration profiles can be realized. In this
work, the concept of non-constant dopant concentration profiles was tested on a green
phosphorescent OLED. All samples have been deposited employing AIXTRON OVPD systems.
The investigated OLED consist of an ITO anode, a hole injection layer (HIL), NPB (N,N'-
diphenyl-N,N'-bis(1-naphthylphenyl)-1,1'-biphenyl-4,4'-diamine) as hole transporting layer, an
emissive layer of Ir(ppy)3 doped in a suitable host material (PH1), Alq3 (tris-(8-
hydroxyquinoline) aluminum) as electron transporting layer and finally a LiF/Al cathode. PH1 is
a good electron conductor, but conducts holes poorly. Therefore, the hole transport in the
emissive layer is sustained mainly by the dopant Ir(ppy)3 and consequently depends strongly on
the Ir(ppy)3 concentration. OLED with various dopant concentration profiles have been
processed and compared with regard to their luminous efficacy and I-V characteristics. When
processed with a constant dopant concentration, the OLED described above reached a luminous
efficacy of up to 18 cd/A and 11 lm/W (at 1000 cd/m2). By means of more complex
concentration profiles, the luminous efficacy could be increased to 24 cd/A and 19 lm/W (at
1000 cd/m2). All OLED with a dopant concentration profile starting with a rather high dopant
concentration on the anode side of the emissive layer, showed steeper I-V-curves and therefore
needed lower driving voltages than their conventional counterparts. So apparently, a higher
initial dopant concentration improves the hole injection into the emissive layer. This approves
that the balancing act of high dopant concentrations (to improve hole mobility) versus low
dopant concentrations (to avoid triplet-triplet-annihilation) can be embraced with this concept.
Parallel to these experiments, the width and location of the recombination zone have been
simulated for all investigated concentration profiles by numerical solution of the semiconductor
device equations using experimentally determined doping-dependent charge carrier mobilities.
The obtained theoretical results are discussed with regard to the accomplished experiments.


10:30 AM B11.6
Organic Thin-Film Transistor based Sensors used for Low-Concentration Ammonia
Detection. Andreas Klug
1,2
, Martin Denk
2
, Martina Sandholzer
3
, Thomas Bauer
3
, Christian
Slugovc
3
, Ullrich Scherf
4
and Emil J.W. List
1,2
;
1
NanoTecCenter Weiz Forschungsgesellschaft
mbH, Weiz, Austria;
2
Institute of Solid State Physics, Graz University of Technology, Graz,
Austria;
3
Institute for Chemistry and Technology of Organic Materials, Graz University of
Technology, Graz, Austria;
4
Macromolecular Chemistry, University of Wuppertal, Wuppertal,
Germany.

Organic materials can be easily tailored to enable, increase or optimize sensitivity and selectivity
with respect to an analyte of interest and therefore organic-based devices such as organic thin-
film transistors (OTFTs) are also believed to find their application as smart disposable sensor
devices in health-, food- and environmental monitoring, diagnostics and control, ranging from
light- and chemical vapor sensors to transducers for ions and biological substances. Compared to
resistor-based sensors, OTFTs generally have the advantage of being more sensitive due to the
inherent amplification of the sensing event. Moreover, they usually exhibit higher response
times, low power consumption, the ability to implement multi-parameter sensing as well as the
possibility to be integrated in complex circuits including signal processing. Here we present an
electrical sensor based on an OTFT, which is used for detecting ammonia as gaseous analyte via
functionalized ring-opening methathesis polymerized materials, strongly changing the electrical
properties when exposed to NH
3
. In detail, a source-to-drain current increase of 500% and more
is observed upon exposure to ammonia gas with a concentration <=1%. Besides current-voltage
OTFT analysis, UV/Vis spectroscopy measurements, Fourier transform infrared spectroscopy, C-
V/C-f measurements and atomic force microscopy are used to investigate the NH
3
-sensitive
materials constituting the sensor device.


10:45 AM B11.7
Organic Transistors for Sensor Applications under Gaseous and Aqueous Conditions
Anatoliy N Sokolov, Mark E Roberts and Zhenan Bao; Stanford University, Stanford, California.

Organic field-effect transistors (OFETs) are ideal for inexpensive, chemical sensors owing to
their compatibility with flexible, large-area substrates, simple processing, and tunable active
layer materials. Specifically, the use of small molecule-based organic semiconductors or single-
walled carbon nanotubes allows specific recognition site incorporation to achieve selectivity.
Previously, the use of OTFTs as sensors has been limited to vapor phase systems. However,
while chemical detection for comprehensive monitoring will require the sensors to operate under
both aqueous and ambient air conditions, the OTFTs reported to-date have not been suitable for
applications in aqueous media owing to high operating voltages, degradation and delamination.
We now introduce novel low-temperature cross-linkable gate dielectric films compatible with
vapor and solution deposited semiconductors for aqueous sensors. The polymer matrix for the
gate dielectric layer in this study is poly(4-vinylphenol), selected for its dielectric characteristics
and compatibility with various organic semiconductors. These materials exhibit stability in
aqueous operation for over 10^4 electrical cycles. The work has led to the observation of a
significant drain current response for solutions with concentrations as low as parts per billion of
trinitrobenzene and methylphosphonic acid. We now describe the initial investigation of
semiconductor materials to achieve air- and water-stable sensors, as well as the introduction of
specific recognition elements to enhance sensitivity. The investigations will focus on the use of
functional groups as binding sites for the semiconductor:analyte interaction both under aqueous
and ambient air conditions, with the goal of developing environmentally stable sensors. The
mechanism for OTFT sensing is investigated by varying device parameters including
semiconductor thickness and operating conditions, such as analyte concentration and gate bias.


11:00 AM B11.8
Organic versus Inorganic Thin-Film Transistor Chemical Vapor Sensors Soumya Dutta and
Ananth Dodabalapur; Microelectronics Research Centre, University of Texas at Austin, Austin,
Texas.

This presentation will highlight the differences between responses of thin-film transistor (TFT)
based chemical vapor sensors with organic semiconductors such as pentacene and inorganic
semiconductors such as Zinc Tin Oxide (ZTO). In organic TFT chemical vapor sensors,
numerous studies have shown that trapping of charges by polar analytes at grain boundaries and
other device interfaces often results in a decrease in drain current (Id) [1-2]. In ZTO TFT
sensors, the drain current increases substantially upon exposure to such polar analytes. For
example, the drain current of a ZTO TFT sensor exhibits a substantial (~ 6-7 fold) increase of Id
upon exposure to IPA. The differences in response between the organic and inorganic TFT
sensors to the same analytes is due to the strong effects that polar molecules/materials have in
trapping charges in organic semiconductors. Increase in Id is also sometimes seen in organic
TFT sensors upon exposure to polar analytes. This happens when the molecular ordering is not
good and the mobilities are very low. Under these conditions, the extra charge density in the
channel induced by the polar analytes overwhelms the drain current reduction due to the trapping
of charges. We point out that this trapping of charges in the presence of polar molecules is also
seen when water is present in the vicinity of the transistor channel. A possible reason for the
trapping and mobility reduction in organic TFTs is the formation of bipolarons which are
stabilized by the polar analyte molecules. Since bipolarons have much lower mobilities, we have
a decrease in current. Activation energy measurements of charge carriers in organic TFT sensors
indicates that polar analyte molecules result in increased activation energies, supporting this
physical model. We further investigate the differences between OTFT sensors and inorganic TFT
sensors with the help of a novel four-terminal device configuration which allows us to extract
important information about trapping and threshold voltage shifts. In this four-terminal sensor
device, there are two coupled channels, one in an organic semiconductor and the second in an
inorganic semiconductor. These channels are electrostatically coupled, permitting both
capacitance-voltage and current voltage measurements. References: [1] L. Torsi and A.
Dodabalapur, Anal. Chem. 77, 380A (2005). [2] B. Crone, A. Dodabalapur, A. Gelperin, L.
Torsi, H. E. Katz, A. J. Lovinger, and Z. Bao, Appl. Phys. Lett. 87, 2229 (2001).


11:15 AM B11.9
The Development of Biosensors Based on Organic Thin Film Transistors Warwick J
Belcher, Xiaojing Zhou, Kathleen Sirois, Daniel Elkington and Paul Christopher Dastoor; Centre
for Organic Electronics, University of Newcastle, Callaghan, New South Wales, Australia.

Field effect transistors (FETs) are commonly used as the basis of sensor devices because of their
attractive combination of transduction and amplification properties. In particular, organic thin
film transistors (OTFTs) have received increased recent interest because they also offer
improved material compatibility with enzymes and biomolecules in general. This overcomes, in
part, the traditional issue of forming an effective recognition element - transducer interface. The
possibility of these also being all plastic devices means that biosensors based on OTFTs have
the potential to be easy and cheap to fabricate. A relatively new class of OTFTs are based on a
hygroscopic insulator layer. These function via a mechanism that involves ionic drift within the
insulator layer, resulting in electrochemical doping of the channel, and the formation of charged
layers at the insulator-gate and insulator-channel interfaces. The result of this dual mechanism is
a device that has remarkably low turn on voltages compared to a traditional OTFT or metal-
based FETs. This makes this class of OTFT particularly attractive for use with biological
molecules which may not be compatible with the high operating voltages required in most FETs.
We have fabricated and characterised all-polymer devices based on a variety of hygroscopic
insulators. Using glucose oxidase as a model system we have investigated interfacing enzymes
with these devices to create working biosensors. The results of this research, along with recent
developments, will be presented.


11:30 AM B11.10
Interfacial Effects Affecting Data Retention in Organic Non-volatile Memory Elements
Based on Ferroelectric Field-effect Transistors. Tse Nga Ng, Sanjiv Sambandan, Robert Street
and Ana Claudia Arias; Electronic Materials Lab, Palo Alto Research Center, Palo Alto,
California.

Non-volatile memory elements for mechanically flexible electronics are being developed using
organic materials to integrate data-sensing and storage. Ferroelectric field effect transistors
(feFETs) offer the advantages of non-destructive read-out and smaller cell size when compared
to capacitor structures. Unlike resistive switches for which the memory mechanism is still
unclear, it is well-established that ferroelectric devices switch states by dipole alignment and
allow faster switching speed than memories based on charge trapping in floating-gate transistors.
However, the retention time of ferroelectric memory is merely on the order of days, and
systematic studies of degradation mechanisms are needed to improve the retention time. In this
paper, factors affecting the current output of feFETs are examined, including changes in
semiconductor mobility, threshold voltage, and dielectric capacitance with time. Degradation in
the dielectric and in the semiconductor is separated for understanding the origins of instability.
Measurement results indicate that the semiconductor-dielectric interface is critical for
polarization retention in feFETs. The current decay of feFET hysteresis was partly caused by
charge trapping due to ferroelectric polarization. Another contribution to hysteresis loss is the
depolarization field at the channel interface; the depolarization field is not completely
compensated because of low carrier density in organic semiconductor. With better understanding
of the interfacial effects, memory cell structures are improved to retain 50% of output current
over 7 days. Due to the gradual decrease in feFET current, calibration method for extracting the
original input voltage is demonstrated, enabling feFETs to be used as analog memory. Finally,
ferroelectric transistor dimensions will be discussed with regards to improving data retention
time.


11:45 AM B11.11
Direct Tunneling into the Gate Dielectric by both Holes and Electrons in an Ambipolar
Organic Memory Transistor. Maarten Debucquoy
1,2
, M. Rockele
1
, Jan Genoe
1
, Gerwin
Gelinck
3
and Paul Heremans
1,2
;
1
SOLO/PME, IMEC vzw, Leuven, Belgium;
2
ESAT/INSYS,
Katholieke Universiteit Leuven, Leuven, Belgium;
3
TNO, Eindhoven, Belgium.

The flash memory transistor is the standard non-volatile memory device in silicon industry, and
responsible for the omnipresence of portable data storage media in our electronic environment.
For organic semiconductor applications to become fully mature, a non-volatile organic memory
device, which can be as easily integrated into existing circuit technology, would be desirable.
Different structures for organic memory transistors have been proposed in literature. The
mechanisms identified to change the threshold voltage of the memory transistor and in this way
to switch between the different memory states, include polarization of the gate dielectric,[1]
charge carrier trapping in the semiconductor[2] and charge carrier trapping in the gate
dielectric.[3-5] This last mechanism, where a floating gate is suggested to charge and discharge
comparable to the operation of the standard flash memory transistor, has shown promising results
in terms of switching speed and retention.[4] In our work we studied a top contact pentacene
memory transistor with a structure similar to the structure used by Baeg et al. We show that the
dependence of the threshold voltage shift on the length of the programming pulse indeed accords
to the direct tunneling of charge carriers from the channel into the gate dielectric, as known from
inorganic flash memory transistors.[6] Even more, we prove that not one type of charge carrier
tunnels, but both holes and electrons do, depending on the sign of the programming voltage. The
result is a nearly perfect symmetrical switching of the transfer characteristics around the initial
threshold voltage of the memory transistor. The limiting factor for this tunneling is the supply of
these charge carriers in the channel of the transistor: exposure to air kills the tunneling of the
electrons, while with a purely n-type semiconductor no tunneling of holes is observed. Based on
these experiments, we pinpoint the important role of the polymer used as the gate dielectric in an
organic memory transistor. It does not only act as the floating gate but as this polymer controls
the interface with the organic semiconductor,[7] it also controls the supply of charge carriers in
the channel and in that way the tunneling of these charge carriers and the behavior of the organic
flash memory transistor. [1] R. C. G. Naber et al. Nat. Mater. 4, 243 (2005) [2] A. R. Vlkel et
al. Phys. Rev. B 66, 195336 (2002) [3] H. E. Katz et al. J. Appl. Phys. 91, 1572 (2002) [4] K.-J.
Baeg et al. Adv. Mater. 18, 3179 (2006) [5] Wu et al. Adv. Func. Mater. 18, 2593 (2008) [6]
Ferris-Prabhu A. V. IEEE Trans. Electron Dev. ED-24, 524 (1977) [7] L.-L. Chua et al. Nature
434 194 (2005)



SESSION B12: Light Emission
Chair: Egbert Zojer
Friday Afternoon, April 17, 2009
Room 2001 (Moscone West)

1:30 PM B12.1
Solution-processible Phosphorescent Polymers for Electroluminescence and Light-
harvesting Andrew B Holmes
1,2
, Robert J Borthwick
1
, Inam Ul Haq Raja
1
, David J Jones
1
, Tae-
Hyuk Kwon
1
, Georgia E McCluskey
1
, Weihua Tang
1
, Doojin Vak
1
, Scott E Watkins
2
and
Wallace W H Wong
1
;
1
Bio21 Institute, University of Melbourne, Parkville, Victoria, Australia;
2
Division of Molecular and Health Technologies, CSIRO, Clayton, Victoria, Australia.

In this paper we report the synthesis of solution-processible conjugated polymers in which a
phosphorescent organometallic iridium complex is either conjugatively or non-conjugatively
linked to the polymer host. Phosphorescent emission is dependent on the appropriate design of
the triplet energy of the polymer host and the energy transfer to the emissive organometallic
ligand. Examples of high triplet energy hosts with the potential to support blue emissive guests
will be reported. In a parallel investigation we report the efficacy of using low band gap solution-
processible phosphorescent polymers as potential light harvesting agents for organic photovoltaic
cells. Performance will be compared with conventional excitonic heterojunction cells.


1:45 PM B12.2
White-Light Emitting Supramolecular Polymers.Philippe Leclere
1,2
, Robert Abbel
2
, Mathieu
Surin
1
, Wojciech Pisula
3
, Roberto Lazzaroni
1
, W. Stouwdam
2
, Christophe Grenier
2
, Bert Meijer
2

and Albertus P.H.J. Schenning
2
;
1
University of Mons-Hainaut, Mons, Belgium;
2
Eindhoven
University of Technology, Eindhoven, Netherlands;
3
Max-Planck Institute for Polymer Research,
Mainz, Germany.

White-light emitting plastic materials are attractive candidates for applications in flexible organic
based lighting applications and in backlights for liquid crystalline displays. Common approaches
to obtain emission over the whole visible spectrum include energy transfer from donor polymers
mixed with luminescent acceptor chromophores, or copolymers containing moieties emitting at
different wavelengths. Multicomponent pi-conjugated systems based on supramolecular
interactions combine the advantages of small molecules with those of polymers and therefore can
facilitate energy transfer processes due to a spatial proximity and controlled orientation between
the different species. In this work, this concept is developed to create white emitting
supramolecular polymers by using two novel different approaches based on (i) the self
complementarity of multiple hydrogen bonding moieties or (ii) polycatenars (rigid molecules
equipped with flexible wedges at the ends). The first approach makes use of 2-ureido-4[H]-
pyrimidinone (UPy), as a strongly self-complementary H-bonding moiety, for the formation of
noncovalent polymers with high molecular weight. Difunctionalized UPy oligomers (fluorene as
blue emitter, para-phenylenevinylene as green emitter, and perylene as red emitter) have been
synthesized and mixed together to create white photoluminescent supramolecular polymers. In
the second approach, fluorene-based co-oligomers have been prepared in order to study
differences in their aggregation behavior upon subtle modifications of their chemical structures.
They consist of two fluorene units linked by a central aromatic moiety (fluorene, naphthalene,
quinoxaline, benzothiadiazole or thienopyrazine) that has been chosen such that the emission
color covers the entire visible range. Amide linkers between the chromophores and the wedges
were chosen in order to introduce hydrogen bonding as a noncovalent ordering interaction. These
chromophores form organogels in which the emission wavelength can be tuned by partial
energry transfer yielded blue, red and white fluorescence systems. For the two approaches, the
degree of polymerization is sufficiently high to fabricate white photoluminescent supramolecular
polymers. The morphology of these organogels has been studied by Scanning Probe Microscopy
and Wide Angle X-ray Scattering. In order to understand the results in terms of supramolecular
organization within the fibrillar morphology, comparisons with molecular modeling simulations
are performed. LEDs based on these noncovalent polymers have been successfully prepared
from all three types of pure materials, yielding blue, green and red devices, respectively. At an
appropriate mixing ratio of the three compounds, white electroluminescence is observed. This
modular approach yields a toolbox of molecules that can be easily used to construct pi-
conjugated electroactive supramolecular polymers with a variety of compositions and tunable
emission colors.


2:00 PM B12.3
Efficient Electron Injection via Organic Interlayers for Inverted Organic Light-emitting
Diodes Free of Dopants and Reactive Metals. Seunghyup Yoo, Chang-Hun Yoon and Hyunsu
Cho; Electrical Engineering, KAIST, Daejeon, Korea, South.

Inverted organic light-emitting diodes (OLEDs) are highly desired from both fabrication and
driving standpoint in active-matrix OLED (AMOLED) displays based on n-type thin-film
transistors (TFTs), which include a-Si TFTs as well as a variety of emerging ZnO-based TFTs.
However, the actual application of the inverted OLED technologies has been rather slow due to
the lack of reliable means for electron injection from the bottom cathodes to typical electron
transport or emission layers. Moreover, from the point of view of practicality in fabrication and
operational stability, it is considered that one should avoid or minimize, if possible, use of low
work function metals like Mg as cathodes or alkali-based doping for electron transport layers[1],
rendering the realization of inverted OLEDs even more challenging. Here we present our study
of using organic electron injection layers (OEIL) to realize efficient inverted organic light-
emitting diodes (IOLEDs) via cascaded electron injection from bottom aluminum cathodes.
These IOLED devices exhibit luminescence of 1,000 cd/m
2
at 5 V with a maximum luminous
efficacy of 5 cd/A in a typical OLED using Alq
3
as a light emitter. Our study of Al/OEIL/Al
devices shows that electrons can be efficiently injected to the OEIL from both top and bottom
electrodes depending on the polarity of the applied bias. Further analysis indicates that the
successful operation of these IOLEDs can be attributed to (i) the relatively high electron mobility
of OEIL films studied and (ii) its ideal LUMO energy level positioned between that of Alq
3
and
the workfunction of Al. Finally, we demonstrate the versatility of the OEIL under study by
presenting ITO-free, transparent inverted OLEDs in which the OEIL plays a critical role for
enhancement in both electrical injection and optical transmission. Reference [1] C.-C. Wu, C.-W.
Chen, C.-L. Lin, and C.-J. Yang, J. of Display Tech. 1 (2), 248 (2005)


2:15 PM B12.4
The Mechanism for Improved Charge Injection in Polymer Light Emitting Diodes with
Conjugated Polyelectrolyte Electron Transporting Layers. Corey V. Hoven
1,3
, Rengiang
Yang
2,3
, Andres Garcia
2,3
, Jeffrey Peet
1,3
, Alan J Heeger
1,2,3
, Thuc-Quyen Nguyen
2,3
and
Guillermo C Bazan
1,2,3
;
1
Department of Materials, University of California, Santa Barbara,
California;
2
Department of Chemistry and Biochemistry, University of California, Santa Barbara,
California;
3
Institute for Polymers and Organic Solids, University of California, Santa Barbara,
California.

Polymer light emitting diodes (PLEDs) with conjugated polyelectrolyte (CPE) electron
transporting layers (ETLs) and high work function cathodes exhibit excellent efficiencies,
despite apparently large electron injection barriers. The improvement is found to be due an
electric field redistribution within the PLED through a combination of hole accumulation at the
emitting layer (EML)/ETL interface and ionic rearrangement within the ETL layer. Efficient
PLEDs typically require low work function metal cathodes to provide balanced charge injection.
However, low work function metals, such as Ba and Ca, are unstable and decrease device
operational lifetimes. Although the improved electron injection from high work function metals
by the insertion of a CPE ETL is quite valuable, the mechanism behind the improved injection
has been poorly understood. The improved electron injection has typically been attributed to a
permanent interfacial dipole at the CPE/cathode interface. However, a correlation of electrical
measurements (current density (J)-voltage (V), luminance (L)-V, time response of J and L under
constant V, electroabsorption, and impedance measurements) with device structure (with or
without the ETL, choice of cathode, choice of counterion and layer thickness) provided evidence
that a combination of hole accumulation and ion redistribution leads to screening of the internal
electric field and an effective lowering of the electron injection barrier. As holes are injected they
accumulate at the EML/ETL interface and screen the electric field in the EML. The electric field
is thereby redistributed so that voltage drops predominantly across the ETL producing a large
internal field in that layer. The electric field across the ETL is redistributed by the mobile ions
equally into two double layers at the EML/ETL interface and the ETL/cathode interface. The end
result is that the electric fields in both layers are screened with the entire applied voltage
localized across the double layers. Efficient electron injection occurs via tunneling through the
ultra-thin double layer at the ETL/cathode interface. The hole and electron currents are diffusion
currents rather than drift currents. The diffusion currents in each layer are space charge limited,
the EML conducts only holes, the ETL conducts only electrons, and recombination takes place at
the interface.


2:30 PM B12.5
Multi-color High Performance Organic Light Emitting Transistors. Ebinazar B Namdas
1
,
Ifor D. W. Samuel
1,2
and Alan J Heeger
1
;
1
Center for Polymers and Organic Solids, University of
California, Santa Barbara, California;
2
School of Physics and Astronomy, University of St
Andrews, St Andrews, United Kingdom.

Recently organic light emitting field effect transistors (LEFET) are of interest as a new
architecture with potential for new applications such as simplified pixels in flat panel displays, as
optoelectronic devices in communications, and potentially as electrically driven organic lasers. A
LEFET combines the emission properties of a diode with the switching properties of a transistor
in a single device structure. The brightness and light emission performance reported for LEFETs
in the literature are low. Here we present and discuss our latest results on the design and
fabrication of high performance LEFETs. In particular we have demonstrated red, green and blue
light-emission, as would be required for display applications of these devices. The
semiconducting polymer layers were deposited from solution by spin-coating. The interface with
the dielectric is an important issue in such devices, and we find that the best performance can be
obtained by using a device structure with two organic layers. The first is a hole transporting
polymer, poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b] thiophene) and the second is a
light-emitting polymer. The devices were fabricated in the bottom gate architecture (Si/SiO2)
with top-contact Ca/Ag as source/ drain electrodes. Our results show the interplay between
charge injection, charge transport and photo-physical properties in the operation of LEFETs,
enabling their efficiency to be improved.


3:15 PM B12.6
Trap-assisted Recombination in Polymer Light-emitting Diodes. Martijn Kuik, Martijn
Lenes, Herman Nicolai and Paul W. M. Blom; Zernike Institute for Advanced Materials,
University of Groningen, Groningen, Groningen, Netherlands.

Polymer light-emitting diodes (PLEDs) are promising candidates for displays and lighting
applications. To further improve the light output efficiency of these devices a fundamental
understanding of the charge recombination mechanisms is required. Until now the recombination
process is assumed to be bimolecular between free electrons and free holes (Langevin
recombination). However, measurements on electron-only devices demonstrate that a large part
of the injected electrons in a PLED are being trapped. The fundamental question arises whether
these trapped electrons recombine with free holes and as a result limit the performance of a
PLED, since such a trap-assisted recombination mechanism is often of non-radiative nature. To
unravel the various recombination processes in PLEDs we investigate the photocurrent that can
be generated in PLED devices. Earlier work on the photoconduction in organic solar cells has
shown that a linear dependence of the open-circuit voltage (Voc) on the light intensity only
occurs when both the electron and hole transport is trap free, leading to a dominance of
bimolecular Langevin recombination [1]. Furthermore, it has been demonstrated that for
polymer/polymer solar cells [2], where the electron transport is limited by traps in the polymer,
or by deliberately adding electron traps in a trap-free bulk heterojunction solar cell [3], the
dependency of Voc on the light intensity becomes superlinear. This can be quantitatively
explained by the recombination of trapped with free charges (Shockley Read Hall
recombination), in addition to Langevin recombination. As a result the light intensity dependence
of the Voc in a PLED is a measure for the occurrence of trap-assisted recombination. We have
investigated the dependence of the open-circuit voltage on the light intensity in pristine MEH-
PPV and MDMO-PPV based LEDs: Our measurements revealed that the Voc dependence on the
light intensity turned out to be even stronger then quadratic, indicating a strong trap-assisted
recombination mechanism in the PLEDs. We present a novel device model for PLEDs based on
these observations, which includes Langevin as well as Shockley Read Hall recombination. In
contrary to common beliefs we show for PPV-based PLEDs the trap assisted recombination rate
is at least equal to the free carrier recombination rate, demonstrating the significant contribution
of the trap assisted recombination in a PLED. [1] L. J. A. Koster, V. D. Mihailetchi, R. Ramaker
and P. W. M. Blom, Appl. Phys. Lett. 86, 123509 (2005). [2] M. M. Mandoc, W. Veurman, L. J.
A. Koster, B. de Boer and P. W. M. Blom, Adv. Func. Mater. 17, 2167-2173 (2007). [3] M. M.
Mandoc, F. B. Kooistra, J. C. Hummelen, B. de Boer and P. W. M. Blom, Appl. Phys. Lett. 91,
263505 (2007).


3:30 PM B12.7
Silicon Based Organic Materials for Light Emitting Diodes. Colin Keyworth
1,3,2
, Andrew B
Holmes
3,1
and Charlotte K Williams
1
;
1
Chemistry, Imperial College London, London, United
Kingdom;
2
Cambridge Display Technology (CDT), Cambridge, United Kingdom;
3
Bio21
Laboratory, The University of Melbourne, Melbourne, Victoria, Australia.

A range of organic conjugated materials have been developed, utilising Suzuki methods and
some novel synthetic methodologies, for the practical application of blue light emitting diodes.
The use of silicon as a heteroatom within the organic framework has been explored and the
effects on the electroluminescence of the prepared materials has been studied in order to gain
insight into the role of silicon within organic fluorescent polymers and small molecule systems.
Back To Top
Science Enthusiasts
Be a Materials Science Enthusiast
Do Something
Learn Something
Watch Something
Strange Matter Green Earth
Sustainability Resources
More about public outreach
Corporate Partners





Member Benefits
Print and online subscription to MRS Bulletin
Discounted Registration to MRS Spring and Fall Meetings
Access almost 100,000 papers in the MRS Online Proceedings Library
Get Involved
Join an MRS Operating Committee
Propose a Meeting Symposium
Join a University Chapter
More opportunities to Get Involved
Stay Connected
Facebook
Twitter
LinkedIn
RSS
MRS OnDemand
Materials360 Online
Member Directory
Job Postings

About MRS
Meetings & Exhibits
Publications & News
Advocacy
MRS Membership
Home
Contact Us
Sitemap
MRS Transaction Policy
Materials Research Society

: 506 Keystone Drive, Warrendale, PA, 15086-7537, USA

Phone: 724.779.3003 Fax: 724.779.8313 Contact Us: info@mrs.org 1995-2014
Web Site Development by The Berndt Group