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mate 1 sun light intensity. FTIR measurements were performed on a 6030 Mattson Galaxy Series FTIR spectrometer. Spectroscopic characterization was performed using a pressure cell equipped with CaF2 windows. Received: December 22, 2003 Final version: April 1, 2004
[1] B. O'Regan, M. Grtzel, Nature 1991, 353, 737. [2] a) B. O'Regan, D. T. Schwartz, Chem. Mater. 1998, 10, 1501. b) K. Hara, H. Horiuchi, R. Katoh, L. P. Singh, H. Sugihara, K. Sayama, S. Murata, M. Tachiya, H. Arakawa, J. Phys. Chem. B 2002, 106, 374. [3] a) N. Lewis, Annu. Rev. Phys. Chem. 1991, 42, 543. b) K. Hara, H. Sugihara, Y. Tachibana, A. Islam, M. Yanagida, K. Sayama, H. Arakawa, G. Fujihashi, T. Horiguchi, T. Kinoshita, Langmuir 2001, 17, 5992. [4] W. J. Albery, J. Am. Chem. Soc. 1985, 107, 1854. [5] G. Hodes, I. D. J. Howell, L. M. Peter, J. Electrochem. Soc. 1992, 139, 3136. [6] A. Hagfeldt, U. Bjrkstn, S. E. Lindquist, Sol. Energy Mater. Sol. Cells 1992, 27, 293. [7] a) M. K. Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E. Mller, P. Liska, N. Vlachopoulos, M. Grtzel, J. Am. Chem. Soc. 1993, 115, 6382. b) P. Wang, S. M. Zakeeruddin, J. E. Moser, M. K. Nazeeruddin, T. Sekiguchi, M. Grtzel, Nat. Mater. 2003, 2, 402. [8] W. C. Sinke, M. M. Wienk, Nature 1998, 421, 586. [9] W. Kubo, K. Murakoshi, T. Kitamura, S. Yoshida, M. Haruki, K. Hanabusa, H. Shirai, Y. Wada, S. Yanagida, J. Phys. Chem. B 2001, 105, 12 809. [10] a) A. F. Nogueira, J. R. Durrant, M. A. De Paoli, Adv. Mater. 2001, 13, 826. b) T. Stergiopoulos, I. M. Arabatzis, H. Cachet, P. Falaras, J. Photochem. Photobiol. A 2003, 155, 163. [11] a) T. Stergiopoulos, I. M. Arabatzis, G. Katsaros, P. Falaras, Nano Lett. 2002, 2, 1259. b) C. Longo, A. F. Nogueira, M. De Paoli, H. Cachet, J. Phys. Chem. B 2002, 106, 5925. [12] a) J. H. Kim, M.-S. Kang, Y. J. Kim, J. Won, N.-G. Park, Y. S. Kang, Chem. Comm. 2004, 14, 1662. b) M.-S. Kang, J. H. Kim, Y. J. Kim, J. Won, N.-G. Park, Y. S. Kang, unpublished. [13] B. J. B. Folmer, R. P. Sijbesma, R. M. Versteegen, J. A. J. van der Rijt, E. W. Meijer, Adv. Mater. 2000, 12, 12. [14] K. Yamauchi, J. R. Lizotte, D. M. Hercules, M. J. Vergne, T. E. Long, J. Am. Chem. Soc. 2002, 124, 8599. [15] F. H. Beijer, R. P. Sijbesma, H. Kooijman, A. L. Spek, E. W. Meijer, J. Am. Chem. Soc. 1998, 120, 6761. [16] R. P. Sijbesma, F. H. Beijer, L. Brunsveld, B. J. B. Folmer, J. H. K. K. Hirschberg, R. F. M. Lange, J. K. L. Lowe, E. W. Meijer, Science 1997, 278, 1601. [17] S. Kuo, C. Lin, F. Chang, Polymer 2002, 43, 3943. [18] I. Montanari, J. Nelson, J. R. Durrant, J. Phys. Chem. B 2002, 106, 12 203. [19] N. Papageorgiou, W. F. Maier, M. Grtzel, J. Electrochem. Soc. 1997, 144, 876. [20] C. Vandermiers, P. Damman, M. Dosire, Polymer 1998, 39, 5627. [21] W. Kubo, S. Kambe, S. Nakade, T. Kitamura, K. Hanabusa, Y. Wada, S. Yanagida, J. Phys. Chem. B 2003, 107, 4374. [22] P. Wang, S. M. Zakeeruddin, P. Comte, I. Exnar, M. Grtzel J. Am. Chem. Soc. 2003, 125, 1166.

Transparent Solid-State Lithiated Neutron Scintillators Based on SelfAssembly of Polystyrene-blockpoly(ethylene oxide) Copolymer Architectures**
By Hee-Jung Im, Suree Saengkerdsub, Andrew C. Stephan, Michelle D. Pawel, David E. Holcomb, and Sheng Dai*
Neutrons generated via either nuclear reactors or spallation sources are widely used as unique photon sources to characterize structures of nanomaterials and magnetic materials through various spectroscopic techniques and to diagnose solid-state structures through neutron tomography techniques. These measurement methods depend greatly on the sensitivities of neutron detectors and/or neutron fluxes from nuclear reactors or spallation sources. The increase of neutron fluxes is an extremely costly process and therefore the improvement of the measurement sensitivities lies in the development of sensitive neutron detectors. Another recent important application of neutron detectors is in the area of the prevention of international nuclear smuggling. Because fissile materials (plutonium-239 and uranium-235) emit neutrons via spontaneous fissions, the development of improved neutron scintillators for security and safe-guard applications is of obvious value. Currently, neutrons are mainly detected by scintillation or gas ionization.[1] Because of the low density of gas, gas-ionization detectors are either quite large or operate at high pressure in order to obtain good neutron-detection efficiency. In addition, the response times of the gas-ionization detectors are relatively slow. Liquid scintillators can avoid the problems of gas-based detectors but must be handled carefully (e.g., some must be stored and handled in an oxygen and water-free environment) and are difficult to be integrated for field applications. Thus, a major trend in radiation sensor research emphasizes the development of efficient solid-state scintillating

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[*] Dr. S. Dai, Dr. H.-J. Im, Dr. S. Saengkerdsub Dr. A. C. Stephan, M. D. Pawel Chemical Sciences Division, Oak Ridge National Laboratory Oak Ridge, TN 37831 (USA) E-mail: dais@ornl.gov Dr. D. E. Holcomb Nuclear Science and Technology Division Oak Ridge National Laboratory Oak Ridge, TN 37831 (USA) [**] The Oak Ridge National Laboratory is managed for the Department of Energy under contract No. DE-AC05-00OR22725 by UT-Battelle, LLC. Funding for this work is through the support of the Department of Energy NA-22. This research was supported in part by the appointments for H.-J. Im and S. Saengkerdsub to the ORNL Research Associate Program, administered jointly by ORNL and Oak Ridge Institute for Science and Education. The authors thank Carl Willis for assembling a portable pulse-height analysis system.

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as matrices in order to dope scintillating dyes for alpha and materials,[2] which will significantly enhance general capabilibeta radiation sensors.[6] For example, BC-400 (Bicron Direct, ties for in-situ monitoring and imaging of radioactive contaminants in the environment. Saint-Gobain, MA), a polyvinyltoluene-based scintillator Because neutrons have no charge, neutron absorbers such doped with 2,5-diphenyloxazole (PPO) and 1,4-bis-2-(5-pheas 6Li or 10B are required to convert neutrons to detectable nyloxazolyl)-benzene (POPOP), is the best existing plastic scintillator for alpha particle detection.[7] Because 6Li emits charged particles. The 6Li(n, a)H-3 conversion reaction has a large Q value (4.79 MeV), significantly larger than that which an alpha and a triton (H-3) particle upon absorption of a neuresulted from 10B(n, a)7Li (2.79 MeV). Accordingly, 6Li is a tron, a logical approach to synthesizing a neutron scintillator is to place 6Li in a matrix material similar to that of BC-400 or desirable neutron absorber for scintillation applications due to its highly energetic nuclear reaction products. All air-stable other existing organic scintillators without affecting the translithium compounds are extremely polar and hydrophilic. Thus, parency of the resulting materials. Our approach involves this the current solid-state neutron scintillators using the 6Li neuamphiphilic design strategy toward new neutron scintillators with the introduction of a poly(ethylene oxide) functional tron absorber are based on inorganic materials such as 6Ligroup into an aromatic ring-containing backbone for lithium doped silica glasses and solid mixtures of 6LiF and ZnS/Ag. complexation. These scintillators are prepared by high-temperature proThe block copolymer used in our investigation is polystycesses and are therefore difficult to directly integrate into rene-b-poly(ethylene oxide) with the molecular weights of the electronic detection devices as thin films. We have recently polystyrene and poly(ethylene oxide) blocks at 2300 and 3200, developed efficient room-temperature solid-state di-ureasil respectively. The volume fraction of PEO is 0.56, leading to neutron detectors using a silica solgel process.[3] These sol the formation of lamellar microdomains upon the self-assemgel neutron detectors have non-hygroscopic, elastic, transparbly of block copolymer.[8] Homogeneous, transparent, and ent, crack-free, and thick monolithic properties, and can be directly fabricated onto electrical and optical devices. Howcrack-free monolithic films with the thickness of 0.67 (0.17) ever, the photon-conversion yields of the solgel scintillators mm were fabricated upon drying of the block copolymer soluhave not been as high as expected. The quenching effects tions on quartz discs at room temperature. The orientation of induced by hydroxy and other polar groups associated with lamellae close to the surface of the quartz disc is expected to silica solgel and self-absorption of scintillating light caused be parallel to the surface due to the preferential segregation by the very pale yellowish color are considered to be the main of one component (PEO) to the interface.[9] reasons for the limited light yield. These deficiencies with the The PEO hydrophilic domain is expected to complex with current neutron scintillators using 6Li neutron absorbers lithium cations and its crystallinity is expected to be suppressed.[10] The PS hydrophobic domain provides the ideal enprompted us to develop lithiated-organic-polymer neutron scintillators. vironment for dissolution of the organic scintillators (PPO The key challenge in synthesizing lithiated-organic-polymer and POPOP), as well as increases the scintillating efficiency scintillators is how to incorporate hydrophilic lithium salts via the energy transfer mediated by phenyl rings. Scheme 1 into hydrophobic organic media at a sufficient concentration without deN stroying the scintillator's light yield and CH2-CH CH2-CH2-O O + O + + 6LiCl O optical transparency. Recent breakn m N throughs in polymer synthesis have reN sulted in the development of a number POPOP Polystyrene-block-poly(ethylene oxide) PPO of novel methodologies for the preparation of block copolymers with welldefined amphiphilic properties and N ordered mesostructures.[4] Polystyreneblock-poly(ethylene oxide) is an examO ple of an amphiphilic copolymer, conO sisting of hydrophilic poly(ethylene O N oxide) and hydrophobic polystyrene N O domains through self-assembly.[5] The CH2-CH O O hydrophilic domain is ideal for doping n 6 + Li Cllithium salts while the hydrophobic O polystyrene domain can be loaded with O m/5 hydrophobic organic scintillators. In fact, poly(ethylene oxide)s are extenSamples 1-6, 1A, and 1B sively used as electrolytes to solubilize lithium salts in lithium batteries. SimiScheme 1. Preparation of the lithiated scintillator based on the self-assembly of the block copolymer. larly, polystyrenes are widely employed

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depicts schematic presentations of the composite neutron scintillators based on the self-assembly of the block copolymer. The doping concentrations for 6Li+ were 0.80, 1.49, 2.70, 3.70, 4.70 and 5.86 wt.-% for samples 1, 2, 3, 4, 5 and 6, respectively. Films 1A and 1B were four and eight times thicker than film 1, respectively. Control monolithic films C1 (without 6Li+, PPO and POPOP) and C2 (without 6Li+) were also prepared. As a primary fluor, PPO absorbs resonance energy from the block copolymer substrate during radiation ionization and emits energy as fluorescent light. The secondary fluor (POPOP, wavelength shifter) shifts the wavelength of the emitted light to a wavelength that is more suitable for photomultiplier tube (PMT) detection. As a result, samples 16, 1A, 1B, and C2 all produced peak light emission in the range of 409 nm under UV excitation, suitable for use with PMTs (Fig. 1). The control samples C1 and blank quartz disc did not show any detectable wavelength emission peak in this range due to the absence of PPO and POPOP. The comparative measurements of intrinsic peak efficiency, light yield, and peak resolution for thermal neutrons from a thermalized AmBe and Cf neutron source were made using the various lithiated-block-copolymer scintillator samples. Figure 2 shows the superimposed pulse-height spectra from experimental monolithic films 1, 1A, and 1B and quartz. Inspection of the pulse-height spectra shows that the three experimental films all exhibit a peak around a relative pulse amplitude of 1.7. This peak is attributed to thermal neutron capture events by 6Li+. This peak is noticeably absent in the quartz data, which supports this conclusion. All of the experi-

mental films also show a significant number of events below the neutron peak. These events are attributed to gamma rays interacting in the scintillators and PMT and fast neutrons scattering off of hydrogen atoms in the scintillators. Although most neutrons from the source are thermalized, some fast neutron leakage can occur. Although quartz is not a scintillator, there is significant low-amplitude noise in the quartz pulse-height spectrum. The noise is attributed to gamma rays producing pulses by interacting inside the PMT. Because our lithiated organic scintillators are colorless, homogeneous, and transparent films, increasing the thickness of the monolithic films (1: 0.5 mm thickness; 1A: 1.21 mm thickness; 1B: 1.95 mm thickness) should increase the neutron count rate without losing light output (relative pulse height). As seen from Figure 2, this assertion is consistent with the experimental observation. Figure 3 shows total peak counts versus pulse height for a set of the scintillating films after removal of the background determined with the quartz disc. All data were based on 0.67 0.17 mm thick film samples. This format uses the integrated peak area (error bar is ca. 10 %) for total counts, avoiding the visually misleading peak heights encountered in the spectra plot. Counts are proportional to the intrinsic peak efficiency, and pulse height is proportional to light yield. Accordingly, the better detectors yield higher neutron counts and relative pulse height. As can be seen from Figure 3, the increase of 6Li+ concentration up to approximately 4.7 %, leads to an increase in the intrinsic peak efficiency (net counts) even though the pulse height is reduced. The reduction of the pulse

Poly(styrene-b-ethylene oxide)

Sample 3

Emission [a.u.]
290

340

390

440

490

540

Wavelength [nm]
Figure 1. Scaled emission spectra of the polystyrene-b-poly(ethylene oxide) substrate and the lithiated organic polymer scintillator 3 at 284 nm excitation.

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3,5

quartz 1(0.8 weight% Li, 0.5 mm thickness)

1A(4 times the amount of 1, 1.21 mm thickness) 1B(8 times the amount of 1, 1.95 mm thickness)

2,5

Log (Counts)

1,5

0,5

0 0 0.5 1 1.5 2 2.5

Relative Pulse Height [(Channel #) / (Amplifier Gain)]

Figure 2. Comparison of neutron pulse-height spectra of experimental samples (quartz, samples 1, 1A, and 1B).

height with the increase of 6Li+ concentration indicates that the polarity of 6Li+ has a negative effect on ionization events in the domain of polystyrene. Further work will be focused on synthesizing and testing scintillators based on different combinations of polystyrene and poly(ethylene oxide) blocks and also exploration of new block copolymer matrix materials consisting of poly(ethylene oxide) and polyvinylxylene. The work on polystyrene-b-poly(ethylene oxide) with a wide range of PEO volume fractions will represent various microdomain morphologies and their correlation (if any) with the efficiency of films as neutron scintillators.

In conclusion, a new class of organic neutron scintillators containing organic fluors and 6Li+ has been developed based on a room-temperature synthesis method with block copolymers. The detecting efficiency achieved with such thin-film neutron scintillators is very promising for the fabrication of large-scale position-sensitive neutron scintillators. The unique self-assembly nanostructure of block polymers makes it possible to homogenize hydrophilic neutron absorbers and hydrophobic organic scintillators in nanometer scale. The use of nanoscopic materials highlights new opportunities in the development of highly sensitive radiation sensors.

4000

3500

1(0.80% Li)

3000

2(1.49% Li)

Net Counts

2500

3(2.70% Li)
2000

4(3.70% Li)
1500

1000

5(4.70% Li)

500

6(5.86% Li)

0 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8

Relative Pulse Height

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Figure 3. Experimental total peak counts plotted against pulse height (peak centroid) based on 0.67 ( 0.17) mm thick samples. This format is less misleading and easier to read but contains essentially the same information as Figure 2.

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Experimental
Synthesis Protocol: Polystyrene-b-poly(ethylene oxide) [P1503SEO, Mn: PS (2300) -PEO (3100), Mw/Mn: 1.08, PEO volume fraction: 0.56, calculated using known densities of polystyrene and poly(ethylene oxide) at room temperature (rPS = 1.05 g cm3, rPEO = 1.13 g cm3) [11] Polymer Source, Inc.], liquid scintillation mixture containing 1,4bis-2-(5-phenyloxazolyl)-benzene (POPOP) and 2,5-diphenyloxazole (PPO) in toluene (Aldrich, 1 L contains 1.25 g POPOP and 100 g PPO in toluene), 6LiOH.H2O (95 %), HCl (12.2 M, EM Science), toluene (Aldrich, anhydrous, 99.8 %), and methyl alcohol (MeOH, Burdick & Jackson, HPLC grade) were used as received. The liquid scintillation mixture (600 lL) was diluted (to 2500 lL) with toluene beforehand. In a typical synthesis, 40.6 mg of P1503-SEO was dissolved in 500 lL of MeOH with varying amounts (1, 2.4 mg; 2, 4.7 mg; 3, 9.4 mg; 4,14.1 mg; 5,18.8 mg; 6, 28.3 mg) of 6LiCl. Subsequently, 20 lL of the diluted PPO/POPOP solution was added to each solution. The control samples (C1 and C2) were prepared with P1503SEO (40.6 mg) in MeOH (500 lL) for C1 and P1503-SEO (40.6 mg) in MeOH (500 lL) containing diluted PPO/POPOP (20 lL) for C2. Each precursor solution was sonicated for about 10 min. The viscous solutions were then applied to 1 in. (1 in. = 2.54cm) diameter quartz discs to give thick monolithic films. After drying for one week at room-temperature, these monolithic films were tested for neutron detection capabilities. Characterization: The pulse-height analysis system consisted of a one-inch-diameter PMT (Hamamatsu R1924A), amplifiers (Ortec 113 preamplifier and 575A shaping main amplifier), and a computerinterfaced multichannel analyzer (Spectrum Techniques UCS-20). The procedure for neutron measurements involved placing a specific scintillator near a neutron source storage drum containing a 3 Ci AmBe neutron source and a 3 mCi 252Cf spontaneous fission neutron source. The drum uses a thick neutron moderator/absorber shield, so that thermal neutrons predominate in the energy distribution outside the drum. The scintillator and PMT were shielded from fission gamma radiation by 5 cm lead bricks, and an additional 3 cm of high-density polyethylene moderator was interposed between the bricks and the source drum. Pulse-height spectra were accumulated over 1.5 104 s for each neutron detector sample. Fluorescence emission and excitation spectra were recorded on a SPEX Fluorolog spectrofluorometer Model FL3-22, equipped with two double-grating monochromators and a 450 W xenon lamp as an excitation source. Received: March 6, 2004 Final version: May 3, 2004

[8] F. S. Bates, G. H. Fredrickson, Phys. Today 1999, 52, 32. [9] S. H. Anastasiadis, T. P. Russell, S. K. Satija, C. F. Majkrzak, Phys. Rev. Lett. 1989, 62, 1852. [10] T. H. Epps, T. S. Bailey, R. Waletzko, F. S. Bates, Macromolecules 2003, 36, 2873. [11] H. Yu, A. Natansohn, M. A. Singh, I. Torriani, Macromolecules 2001, 34, 1258.

Molecular-Scale Tracking of the Self-Healing of Polycrystalline Monolayers at the SolidLiquid Interface**

By Paolo Samor,* Klaus Mllen,* and Jrgen P. Rabe*
Dedicated to Professor Roeland J. M. Nolte on the occasion of his 60th birthday Since thin films grown under non-equilibrium conditions are always prone to rearrangement,[1,2] understanding the mechanisms and kinetics of such a reorganization is necessary to predict film stability. The temporal evolution towards the equilibrium state involves coarsening, i.e., an increase in the characteristic length-scale of the dominant structure. Previous studies have been mainly devoted to the dynamics of metallic or semiconducting thin films.[36] At organic interfaces, the underlying processes still need to be better understood at the molecular level.[2] In particular, little is known of the processes occurring at the liquidsolid interface. A scanning tunneling microscopy (STM) study of Ostwald ripening in two dimensions revealed that the underlying molecular process is a reaction-controlled phenomenon that

[1] [2] [3] [4] [5]

[6] [7]

J. B. Birks, in The Theory and Practice of Scintillation Counting, Pergamon Press, New York 1964. G. Blasse, Chem. Mater. 1994, 6, 1465. H.-J. Im, C. Willis, A. C. Stephan, M. D. Pawel, S. Saengkerdsub, S. Dai, Appl. Phys. Lett. 2004, 84, 2448. H.-A. Klok, S. Lecommandoux, Adv. Mater. 2001, 13, 1217. a) Z. Lin, D. H. Kim, X. Wu, L. Boosahda, D. Stone, L. LaRose, T. P. Russell, Adv. Mater. 2002, 14, 1373. b) I. W. Hamley, Nanotechnology 2003, 14, R39-R54. c) S. H. Kim, M. J. Misner, T. Xu, M. Kimura, T. P. Russell, Adv. Mater. 2004, 16, 226. d) B. Smarsly, G. Xomeritakis, K. Yu, N. Liu, H. Fan, R. A. Assink, C. A. Drewien, W. Ruland, C. J. Brinker, Langmuir 2003, 19, 7295. e) L. Zhu, P. Huang, W. Y. Chen, X. Weng, S. Z. D. Cheng, Q. Ge, R. P. Quirk, T. Senador, M. T. Shaw, E. L. Thomas, B. Lotz, B. S. Hsiao, F. Yeh, L. Liu, Macromolecules 2003, 36, 3180. f) B. Reining, H. Keul, H. Hocker, Polymer 2002, 43, 7145. S. W. Moser, W. F. Harder, C. R. Hurlbut, M. R. Kusner, Radiat. Phys. Chem. 1993, 41, 31. H. Leutz, Nucl. Instrum. Methods Phys. Res. Sect. A 1995, 364, 422.

[*] Dr. P. Samor Istituto per la Sintesi Organica e la Fotoreattivit Consiglio Nazionale delle Ricerche via Gobetti 101, I-40129 Bologna (Italy) E-mail: samori@isof.cnr.it Dr. P. Samor Institut de Science et d'Ingnierie Supramolculaires Universit Louis Pasteur 8, alle Gaspard Monge, F-67083 Strasbourg Cedex (France) Prof. K. Mllen Max-Planck-Institute for Polymer Research Postfach 3148, D-55021 Mainz (Germany) E-mail: muellen@mpip-mainz.mpg.de Prof. J. P. Rabe Department of Physics, Humboldt University Berlin Newtonstrasse 15, D-12489 Berlin (Germany) E-mail: rabe@physik.hu-berlin.de [**] We thank Dr. Viola Francke for the synthesis of the molecule and Dr. N. Severin for his assistance with Molecular Modeling. This work was supported by TMR project SISITOMAS (project reference FMRX970099) and by the European Science Foundation through SMARTON and SONS-BIONICS. P. S. wishes to thank the EU for a Marie Curie fellowship.

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