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Polymer Transfer Printing: Application to Layer Coating,

Pattern Definition, and Diode Dark Current Blocking**


By Lichun Chen, Patrick Degenaar, and Donal D. C. Bradley*

The solution processability of polymer semiconductors


offers attractive routes to high throughput, low temperature
device fabrication using printing methods (e.g., ink-jet, gravure
and screen). This opens new opportunities in many application
sectors including displays, lighting, large area electronics,
photodetection, imaging, solar energy conversion, and communication.[1,2] Vacuum deposited small molecule devices
utilize multilayer structures to fine tune device performance,
e.g., exciton blocking layers in phosphorescent light emitting
diodes (LEDs).[3] It is not, however, straightforward to do the
same from solution: So-called solvent orthogonality (incompatibility) needs to be engineered for the materials that have to be
sequentially coated so that deposition of one layer doesnt
adversely affect the layers already in place.[4] This has also to
be done in a way that ensures that the deposition of subsequent
layers produces uniform coverage of the underlying material
and an intimate physical contact thereto.
One approach is to solution cast polymer films on water and
to scoop them up as free-standing layers or, equivalently, to
spin-coat on top of a water soluble substrate (e.g., KBr) and
dissolve the substrate to leave a floating layer that can again be
recovered onto a substrate. A related approach uses
LangmuirBlodgett (LB) monolayer deposition. Both float
transfer and LB processes involve immersion of the substrate
in water and require the structure to be carefully dried
afterwards.[5] In addition, it is not straightforward to prepare
flat, unwrinkled, 100 nm thickness films. Other approaches
include precursor-route[6] or cross-linking[7] methods to
generate insoluble layers on top of which others can then be
coated. Drawbacks in the former case can include the
requirement for conversion temperatures and/or environments
(e.g., acidic) that are not conducive to the use of plastic
substrates or a variety of electrodes (e.g., indium tin oxide). In

[*]

Prof. D. D. C. Bradley, Dr. L. Chen


Experimental Solid State Physics Group, Blackett Laboratory
Imperial College London
Prince Consort Road, London
SW7 2AZ (UK)
E-mail: d.bradley@imperial.ac.uk
Dr. P. Degenaar
Institute for Biomedical Engineering, Imperial College London
Exhibition Road, London SW7 2AZ (UK)

[**]

Based in part on a presentation at SID 2007, Long Beach, USA (May


24th 2007). We thank the Research Councils UK Basic Technology
programme (GR/R87642 & EP/E045472) and the Royal Society
Brian Mercer Bequest for Funding.

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DOI: 10.1002/adma.200702304

the latter case there is a need for specific chemical


functionalization and there may be issues over completion
of the reaction (to mop up reactive moities) and/or removal of
initiators. Shrinkage can also be a problem in both cases,
though not always so: The Meerholz et al. oxetane route avoids
this problem.[7]
Here we report a new polymer transfer printing process that
avoids the solvent orthogonality problem in fabricating
polymer multilayers, that can be used to define patterns and
that doesnt require any chemical modification of the materials
to be deposited.[8] The process uses a soft stamp to transfer a
solid polymer layer of the appropriate thickness (10100s nm)
to a substrate and/or (as required) to pattern that layer during
or after transfer. Poly(dimethylsiloxane) (PDMS) stamps are
the bedrock of standard micro contact printing (mCP)
techniques[9] and have also been used here. They readily
make conformal contact with surfaces and (at least in
principle) any type of layer deposited onto a PDMS stamp
should be transferable to a substrate using mCP. In practice,
however, successful transfer requires careful control over the
relative adhesion between layer and substrate and layer and
stamp and over the rigidity of the layer. The challenge has been
to come up with a control process suitable for general use with
the polymers found in typical devices. The benefits of this new
process are illustrated for polymer/fullerene photodiodes
through engineering a significant reduction in reverse bias
dark current via adoption of a multilayer structure. The ability
to sequentially deposit well defined functional layers enables
the shunt resistance to be increased and thereby offers greater
detection sensitivity.
Our polymer transfer printing process generally comprises
four steps (see Fig. 1ad):
Step 1: (N.B. if the substrate to be coated is soft, e.g., a typical
polyester then this step can usually be omitted). For hard substrates
such as glass or metal a thin glycerol film is deposited as an
adhesion/rigidity control agent to aid conformal contact between
the polymer layer to be transferred and the hard substrate.
Step 2: The polymer layer to be transferred needs to be prepared on
the PDMS stamp (see next section for discussion of pattern definition). The polymer-coated stamp is then aligned and brought into
contact with the substrate.
Step 3: After the stamp and substrate are brought into contact they
are briefly heated (typically 3050 s) close to the glass transition
temperature of the polymer to be transferred (i.e., in the range
120140 8C for the polymers we have studied). This step facilitates
adhesive contact between the polymer layer on the PDMS stamp

2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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Figure 2. a) Schematic multilayer printed polymer structure comprising a


uniform layer of blue emission polymer, and crossed stripes (150 mm
width) of green then red emission polymers deposited in sequence on a
glass substrate. b)d) show fluorescence microscope images of the
high-tech tartan structure under different broadband excitation conditions:
b) UV excitation (330380 nm), c) blue excitation (465495 nm), and d)
green excitation (510560 nm).
Figure 1. The polymer transfer printing process applied to the deposition
of a polymer (e.g., P3HT) pattern onto a glass substrate (The transfer of a
uniform layer follows the same procedure): a) Coat glass substrate with
glycerol solution, dry and heat on a hot plate at 140 8C for a short period of
time. b) Bring a PDMS stamp bearing the patterned P3HT layer (see (e) to
(h) for patterning process) into intimate contact with the glycerol coated
glass substrate. c) Heat at 140 8C for 30 s on a hot plate. d) Remove the
PDMS stamp leaving the printed P3HT pattern on the glass substrate. The
process of patterning a polymer layer (e.g., P3HT) on a PDMS stamp: e)
Pattern an SU-8 template with the negative of the desired pattern. Coat with
glycerol solution, dry and heat as per (a). f) Deposit a uniform layer of
P3HT with the desired thickness onto a flat PDMS stamp and bring into
intimate contact with the glycerol coated patterned SU-8 template. g) Heat
at 140 8C for 30 s on a hot plate. h) Remove the SU-8 template, leaving the
desired P3HT pattern on the PDMS stamp.

and the substrate. The presence of glycerol aids the formation of


conformal contact and assists layer transfer in the case of hard
substrates. The heating time needs to be kept short enough to avoid
dimensional instabilities in the stamp.
Step 4: The PDMS stamp is carefully removed, releasing the
polymer layer.
To date we have demonstrated the successful transfer of
pin-hole free uniform layers with thicknesses in the range 15 to
220 nm for P3HT, P3HT:PCBM blends, F8BT:PCBM blends,
5BTF8 blends, and state-of-the-art red, green and blue light
emitting LumationTM series polyfluorenes (see Experimental
section) suggesting that the process has wide applicability.
In order to fabricate patterned polymer layers on the
substrate we have chosen to transfer a pre-patterned film (i.e.,
to use additive patterning rather than subtractive). This is
especially desirable in constructing patterned multilayers (c.f.
Fig. 2). We considered two alternatives: (i) use a flat PDMS
stamp and define the desired pattern in the polymer layer
coated thereon or (ii) use a structured PDMS stamp and

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uniformly coat with polymer. In general we have found that (i)


works best, avoiding edge effects associated with the protrusions in the structured stamp that can cause shape distortions of
the pattern cross-section. The process of pre-patterning the
polymer layer on a flat PDMS stamp is illustrated in Figure
1eh and comprises the following steps:
Step 1: An SU-8 template is structured with the negative of the
desired pattern and prepared for use by treating with air plasma for
30 s at 30 W and then spin-coating a very thin glycerol film on top
before drying and heating at 140 8C for 30 s on a hot plate. This
template is used to remove the unwanted portions of the polymer
layer to be transferred.
Step 2: The polymer layer to be transferred is spin-coated onto the
flat PDMS stamp (pre-treated by air plasma at 30 W for 30 s) to form
a layer of the desired thickness.
Step 3: The glycerol coated SU-8 template is brought into intimate
contact with the polymer layer coated PDMS stamp and heated at
140 8C for 30 s.
Step 4: The SU-8 template is carefully removed, taking with it the
unwanted parts of the polymer layer to be transferred. The PDMS
stamp is then ready to transfer the desired pattern onto the substrate,
as per Figure 1ad.
Figure 2 shows a three layer patterned high-tech tartan
structure fabricated using the polymer transfer printing
process. This structure illustrates the flexibility of the process
in a colorful way. The images were taken with a standard
inverted fluorescence microscope using broadband excitation.
Progressing from (b) UV (three layers visible) via (c) blue to
(d) green excitation sequentially removes the visibility of the
blue and then green emitting layers, finally leaving visible only
the uppermost red emitting stripes.

2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Adv. Mater. 2008, 20, 16791683

(1) Glass/ITO/PEDOT:PSS/spin-coated P3HT:PCBM/LiF/Al


(2) Glass/ITO/PEDOT:PSS/P3HT/P3HT:PCBM/LiF/Al
(3) Glass/ITO/PEDOT:PSS/P3HT/P3HT:PCBM/F8BT:PCBM/
LiF/Al
Type 1 is a reference structure for which the P3HT:PCBM
active layer is spin-coated (as in our previous standard devices
reported in the literature[1c,12]). Type 2 introduces an electron
blocking P3HT layer at the PEDOT:PSS interface with this
layer spin-coated and the overlaying P3HT:PCBM layer
transfer printed. Type 3 has an additional F8BT:PCBM (2:1
ratio by weight) hole blocking layer on top of the stack with
both of the polymer-semiconductor-based blend layers transfer
printed. The multiple deposition doesnt appear to adversely
affect the overall layer uniformity (and hence doesnt lead to
inhomogeneous electrical fields): For example, Type 2 devices
showed a root mean square surface roughness (measured with
an atomic force microscope) of 2.9 nm. In addition, no
pin-holes were evident.

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These images demonstrate the capability of our polymer


transfer process to deposit patterned multi-layers, with sharp
lateral interfaces. This is encouraging for potential application
in the fabrication of color displays, complementary logic
circuits, sensing arrays and the like but important questions
remain to be answered concerning resolution limits and the
electrical performance of the transferred layers.
Further insight into the lateral resolution limits can be
obtained from other experiments we have undertaken. For
instance, we have transferred a P3HT:PCBM blend grid
pattern comprising 50 mm wide lines. The highest resolution
features deposited to date have been 60 nm high  300 nm wide
lines in a distributed feedback laser grating structure.[10]
Higher resolution may be possible but has not yet been
attempted. Similarly the largest area we have so far attempted
(successfully) to print is 1.2  1.2 cm2. For large areas it may
well prove necessary to increase the thickness of the PDMS
stamp and/or use a different backing plate in order to maintain
uniformity.
Having described the polymer transfer process in some
detail we now present a practical example of its use to fabricate
devices with improved optoelectronic performance. In particular, we report a study of polymer/fullerene photodiodes for
which we are able to engineer a significant reduction in reverse
bias dark current. The ability to sequentially deposit welldefined functional layers enables the shunt resistance to be
increased and thus offers greater detection sensitivity. This
comes about by ensuring that there are preferred directions for
transport/collection of photogenerated electrons and holes,
something that doesnt necessarily occur when using a
dispersed heterojunction donor/acceptor blend as the active
layer unless suitable post-deposition treatments (e.g., thermal
annealing or solvent vapor exposure) are applied in order to
drive vertical phase separation to favor donor accumulation at
the anode and acceptor at the cathode.[1b,11] We have
fabricated three types of photodiode:

Figure 3. Device characteristics for the three photodiode types studied


(see text). a) Short-circuit photocurrent quantum efficiency spectra. b)
Dark- and photo-current (550 nm illumination) characteristics. Type 1: (I);
Type 2: (II); Type 3: (III).

Figure 3 shows the short-circuit photocurrent quantum


efficiency spectrum and the dark- and photo-current versus
voltage characteristics for each photodiode type. The multilayer structures (Types 2 and 3) show enhanced performance in
respect of both quantum efficiency and reverse bias dark
current over the single layer spin-coated structure (Type 1).
The polymer transfer printing process is thus shown to be
capable of depositing layers with good electrical characteristics. The peak quantum efficiency increases from 50% for
Type 1 devices to 60% for Type 2 and 75% for Type 3. The
reverse bias dark currents at 0.5 V correspondingly reduce
from 2.8  107 A cm2 for Type 1 to 3.0  108 A cm2 for
Type 2 and 1.3  109 A cm2 for Type 3 devices. Both of these
outcomes are advantageous to photodetector function and
hence the results successfully demonstrate the use of the
polymer transfer printing method to achieve enhanced device
performance. Its ability to fabricate structures that are not
readily accessible by solution deposition methods opens
opportunities for novel high-performance device architectures.
Further optimization of layer thicknesses and compositions is
expected to be possible in order to achieve even better
performance and this is the subject of on-going work.

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Many other multilayer devices can be envisaged for


fabrication via the polymer transfer process, including light
emitting diodes for which additional layers can be inserted to
control carrier injection, carrier confinement, coulomb capture
and subsequent radiative decay.[13] Photonic structures are also
of interest. These and other devices will be the subject of future
publications.
In summary, we have presented a new PDMS-stamp-based
polymer transfer printing process that enables multilayer
structure fabrication free from the constraints of normal
solution deposition methods. Smooth pin-hole free polymer
layers of thickness 15220 nm have been successfully printed.
The process can simultaneously be used to define lateral
patterns (as illustrated by the high-tech tartan structures) and
has a resolution expected to be more than adequate for a
variety of device array structures (e.g., the pixels in a portable
color display). It is, moreover, widely applicable in respect of
the materials to be deposited: Standard polymers can be used
without chemical modification. The benefits of this new process
for device fabrication are illustrated for polymer/fullerene
photodiodes by engineering a significant reduction in reverse
bias dark current and an enhancement in short-circuit
photocurrent quantum efficiency. Many other device types
are expected to be amenable to fabrication using this process
and we consider that it has the potential to be widely adopted,
including for example to high-throughput (e.g., reel-to-reel)
manufacturing.

Experimental
The polymers that we have used in the work reported in this paper
are poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) from H.C. Starck; regioregular poly(3-hexylthiophene)
(P3HT) from American Dye Source; poly[(9,9-dioctylfluorene)-cobenzothiadiazole] (F8BT), a blend of 95 wt% poly(9,9-dioctylfluorene)
(PFO) and 5 wt% F8BT (5BTF8), and proprietary red, green and blue
emission LumationTM series polyfluorenes from the Sumitomo
Chemical Co., Ltd. In addition we have used the soluble fullerene
[6,6]-phenyl C61-butyric acid methyl ester (PCBM) and glycerol from
SigmaAldrich. Solutions (10 mg ml1) of 5BTF8 and red, green and
blue LumationTM polymers were prepared in chlorobenzene. P3HT
was dissolved (20 mg ml1) in chlorobenzene. Chlorobenzene blend
solutions comprising P3HT (20 mg ml1) with PCBM (20 mg ml1),
and F8BT (20 mg ml1) with PCBM (20 mg ml1) were also prepared.
Glycerol solutions (500 mg ml1) were prepared in water or
isopropanol. Layers of polymer and polymer/polymer or polymer/
PCBM blends were deposited by spin-coating on flat PDMS blocks.
Thicknesses were typically of order 100 nm for PCBM:P3HT blends,
45 nm for F8BT:PCBM blends, 15 nm for P3HT, and 20 nm for the red,
blue and green LumationTM polymers and the 5BTF8 blend. The

typical PEDOT-PSS layer thickness was 50 nm, deposited by


spin-coating.
The PDMS stamps were prepared by casting a mixture of Sylgard
184 silicone elastomer (Dow Corning) and a curing agent (10:1 ratio
Sylgard:curing agent by mass). The two components were stirred
thoroughly in a beaker for thirty minutes and degassed in-vacuo for an
hour before being gently poured onto the surface to be replicated. For a
flat surface stamp the mixture was poured onto a 50 nm thickness
Au-coated Si wafer, and cured at 70 8C in an oven overnight. The
PDMS stamps were peeled away from the Aucoated silicon wafer
after cooling, placed on a glass surface, and then cut into pieces
(1.2 cm  1.2 cm squares). The thickness of the PDMS was typically 2 to
4 mm. The resulting PDMS stamp structures were lifted with tweezers,
attached to glass backing plates, and placed within a plasma asher
(EMITECH K1050X) for plasma treatment. The power was set to 30W
for 30 s and the working gas was air at 0.2 mbar pressure.
An SU-8 template was used to pattern polymer layers on flat PDMS
stamps. The template was fabricated as follows. A 400 silicon wafer was
cleaned at 80 8C using H2O:NH4OH:H2O2 in the ratio 5:1:1, rinsed with
DI water, and dried under N2 gas. On top of the wafer, a 14 mm SU-8 10
film was spin-coated at 3000 rpm for 15 s. Following a soft bake at 65 8C
for 5 min the SU-8 was exposed to UV light for 12 s using a chromium
mask in a Karl Suss mask aligner to define the required pattern. The
wafer was baked at 65 8C for 1 min and 95 8C for 2 min and the template
pattern was then developed for 2 min using SU-8 developer. The
template was finally cured at 200 8C in an oven.
The glass substrates and ITO coated glass substrates used in our
studies were ultrasonic bath cleaned (30 min) using deionized (DI)
water mixed with Decon 90 (20%), and subsequently rinsed three times
with DI water, and ultrasonic bath cleaned again in pure DI water
(30 min). They were finally dried using a high-pressure air-line. The
thickness of the samples was characterized using an Alphastep 200
surface profilometer. Optical images were recorded using a Zeiss
Axioskop microscope equipped with a Kodak DC290 Zoom digital
camera. A Digital Instruments DI 3100 atomic force microscope was
employed in tapping mode to study film surface topography.
Photocurrent and I-V characteristics were measured using a Keithley
238 Source Measure Unit connected to a computer via a GPIB
interface. Illumination was performed with the monochromatic
(Bentham monochromator) output from a Tungsten halogen source
and the polymer photodiode response was calibrated using a Newport
UV-818 photodiode. Fluorescence images were obtained using a Nikon
TE 2000-S inverted microscope with a Xenon source and G-2A (Ex
510560 nm, DM 575 nm, BA 590 nm), a modified FITC (Ex
465495 nm, DM 505 nm), and UV-2A (Ex 330380 nm, DM
400 nm, BA 420 nm) filter sets.
Photodiode structures (c.f. Table 1) were fabricated via a
combination of spin-coating and polymer transfer printing using
pre-patterned indium tin oxide (ITO) coated glass substrates
(1.2  1.2 cm2 glass slides with an ITO (25 V/square) stripe). PEDOT-PSS was first spin-coated (50 nm), followed by heating at 150 8C for
30 min. In Type 1 devices the P3HT:PCBM layer was also spin-coated.
In Type 2 devices the P3HT layer was spin-coated and the
P3HT:PCBM blend layer was transfer printed. In Type 3 devices
the P3HT layer was spin-coated, and the other two layers (comprising
P3HT:PCBM and F8BT:PCBM blends) were transfer printed.
Cathode stripes comprising stacked LiF (1 nm) and Al (100 nm)
were sequentially deposited through a shadow mask using an Edwards

Table 1. Polymer photodiode structures.


Substrate/Anode
Type 1: Glass/ITO/PEDOT:PSS (50 nm)
Type 2: Glass/ITO/PEDOT:PSS (50 nm)
Type 3: Glass/ITO/PEDOT:PSS (50 nm)

EB/HTL[a]

CGL[b]

HB/ETL[c]

Cathode

N/A
P3HT (15 nm)
P3HT (15 nm)

P3HT:PCBM (110 nm)


P3HT:PCBM (110 nm)
P3HT:PCBM (110 nm)

N/A
N/A
F8BT:PCBM (45 nm)

LiF/Al
LiF/Al
LiF/Al

[a]Electron Blocking/Hole Transport Layer. [b]Charge Generation Layer. [c]Hole Blocking/Electron Transport Layer.

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Adv. Mater. 2008, 20, 16791683

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Adv. Mater. 2008, 20, 16791683

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307A evaporator. The active photodiode area (defined by the overlap


between orthogonal ITO and LiF/Al stripes) was 1.5  3 mm2. After
cathode deposition, the samples were transferred into a N2 atmosphere
glove box (O2  0.1 ppm, H2O < 1 ppm) and annealed on a hot plate at
140 8C for 15 min.
Received: September 11, 2007
Revised: November 28, 2007
Published online: April 15, 2008

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