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mate 1 sun light intensity. FTIR measurements were performed on a


6030 Mattson Galaxy Series FTIR spectrometer. Spectroscopic char-
Transparent Solid-State Lithiated
acterization was performed using a pressure cell equipped with CaF2 Neutron Scintillators Based on Self-
windows.
Assembly of Polystyrene-block-
Received: December 22, 2003
Final version: April 1, 2004 poly(ethylene oxide) Copolymer
± Architectures**
[1] B. O'Regan, M. Grätzel, Nature 1991, 353, 737.
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[5] G. Hodes, I. D. J. Howell, L. M. Peter, J. Electrochem. Soc. 1992,
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[6] A. Hagfeldt, U. BjörkstØn, S. E. Lindquist, Sol. Energy Mater. Sol.
These measurement methods depend greatly on the sensitiv-
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[7] a) M. K. Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, reactors or spallation sources. The increase of neutron fluxes
E. Müller, P. Liska, N. Vlachopoulos, M. Grätzel, J. Am. Chem. Soc. is an extremely costly process and therefore the improvement
1993, 115, 6382. b) P. Wang, S. M. Zakeeruddin, J. E. Moser, M. K. of the measurement sensitivities lies in the development of
Nazeeruddin, T. Sekiguchi, M. Grätzel, Nat. Mater. 2003, 2, 402.
sensitive neutron detectors. Another recent important appli-
[8] W. C. Sinke, M. M. Wienk, Nature 1998, 421, 586.
[9] W. Kubo, K. Murakoshi, T. Kitamura, S. Yoshida, M. Haruki, K. Ha- cation of neutron detectors is in the area of the prevention of
nabusa, H. Shirai, Y. Wada, S. Yanagida, J. Phys. Chem. B 2001, 105, international nuclear smuggling. Because fissile materials
12 809. (plutonium-239 and uranium-235) emit neutrons via sponta-
[10] a) A. F. Nogueira, J. R. Durrant, M. A. De Paoli, Adv. Mater. 2001, neous fissions, the development of improved neutron scintilla-
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J. Photochem. Photobiol. A 2003, 155, 163.
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ue.
Lett. 2002, 2, 1259. b) C. Longo, A. F. Nogueira, M. De Paoli, H. Ca- Currently, neutrons are mainly detected by scintillation or
chet, J. Phys. Chem. B 2002, 106, 5925. gas ionization.[1] Because of the low density of gas, gas-ioniza-
[12] a) J. H. Kim, M.-S. Kang, Y. J. Kim, J. Won, N.-G. Park, Y. S. Kang, tion detectors are either quite large or operate at high pres-
Chem. Comm. 2004, 14, 1662. b) M.-S. Kang, J. H. Kim, Y. J. Kim, sure in order to obtain good neutron-detection efficiency. In
J. Won, N.-G. Park, Y. S. Kang, unpublished.
addition, the response times of the gas-ionization detectors
[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.
are relatively slow. Liquid scintillators can avoid the problems
[14] K. Yamauchi, J. R. Lizotte, D. M. Hercules, M. J. Vergne, T. E. of gas-based detectors but must be handled carefully (e.g.,
Long, J. Am. Chem. Soc. 2002, 124, 8599. some must be stored and handled in an oxygen and water-free
[15] F. H. Beijer, R. P. Sijbesma, H. Kooijman, A. L. Spek, E. W. Meijer, environment) and are difficult to be integrated for field appli-
J. Am. Chem. Soc. 1998, 120, 6761. cations. Thus, a major trend in radiation sensor research em-
[16] R. P. Sijbesma, F. H. Beijer, L. Brunsveld, B. J. B. Folmer,
phasizes the development of efficient solid-state scintillating
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. [*] Dr. S. Dai, Dr. H.-J. Im, Dr. S. Saengkerdsub
[19] N. Papageorgiou, W. F. Maier, M. Grätzel, J. Electrochem. Soc. 1997, Dr. A. C. Stephan, M. D. Pawel
144, 876. Chemical Sciences Division, Oak Ridge National Laboratory
[20] C. Vandermiers, P. Damman, M. Dosi›re, Polymer 1998, 39, 5627. Oak Ridge, TN 37831 (USA)
E-mail: dais@ornl.gov
[21] W. Kubo, S. Kambe, S. Nakade, T. Kitamura, K. Hanabusa, Y. Wada,
S. Yanagida, J. Phys. Chem. B 2003, 107, 4374. Dr. D. E. Holcomb
[22] P. Wang, S. M. Zakeeruddin, P. Comte, I. Exnar, M. Grätzel J. Am.
Nuclear Science and Technology Division
Oak Ridge National Laboratory
Chem. Soc. 2003, 125, 1166.
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 appoint-
______________________ ments 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.

Adv. Mater. 2004, 16, No. 19, October 4 DOI: 10.1002/adma.200400337  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1757
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materials,[2] which will significantly enhance general capabili- as matrices in order to dope scintillating dyes for alpha and
ties for in-situ monitoring and imaging of radioactive contami- beta radiation sensors.[6] For example, BC-400 (Bicron Direct,
nants 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-phe-
as 6Li or 10B are required to convert neutrons to detectable nyloxazolyl)-benzene (POPOP), is the best existing plastic
charged particles. The 6Li(n, a)H-3 conversion reaction has a scintillator for alpha particle detection.[7] Because 6Li emits
large Q value (4.79 MeV), significantly larger than that which an alpha and a triton (H-3) particle upon absorption of a neu-
resulted from 10B(n, a)7Li (2.79 MeV). Accordingly, 6Li is a tron, a logical approach to synthesizing a neutron scintillator
desirable neutron absorber for scintillation applications due is to place 6Li in a matrix material similar to that of BC-400 or
to its highly energetic nuclear reaction products. All air-stable other existing organic scintillators without affecting the trans-
lithium 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 neu- amphiphilic design strategy toward new neutron scintillators
tron absorber are based on inorganic materials such as 6Li- with the introduction of a poly(ethylene oxide) functional
doped silica glasses and solid mixtures of 6LiF and ZnS/Ag. group into an aromatic ring-containing backbone for lithium
These scintillators are prepared by high-temperature pro- complexation.
cesses and are therefore difficult to directly integrate into The block copolymer used in our investigation is polysty-
electronic detection devices as thin films. We have recently rene-b-poly(ethylene oxide) with the molecular weights of the
developed efficient room-temperature solid-state di-ureasil polystyrene and poly(ethylene oxide) blocks at 2300 and 3200,
neutron detectors using a silica sol±gel process.[3] These sol± respectively. The volume fraction of PEO is 0.56, leading to
gel neutron detectors have non-hygroscopic, elastic, transpar- the formation of lamellar microdomains upon the self-assem-
ent, crack-free, and thick monolithic properties, and can be bly of block copolymer.[8] Homogeneous, transparent, and
directly fabricated onto electrical and optical devices. How- crack-free monolithic films with the thickness of 0.67 (±0.17)
ever, the photon-conversion yields of the sol±gel scintillators mm were fabricated upon drying of the block copolymer solu-
have 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 sol±gel 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 sup-
prompted us to develop lithiated-organic-polymer neutron pressed.[10] The PS hydrophobic domain provides the ideal en-
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 de-
N
stroying the scintillator's light yield and
CH2-CH CH2-CH2-O + O O
optical transparency. Recent break- n m
+ O + 6LiCl
throughs in polymer synthesis have re- N N
sulted in the development of a number
of novel methodologies for the prepa- Polystyrene-block-poly(ethylene oxide) POPOP PPO
ration of block copolymers with well-
defined amphiphilic properties and
ordered mesostructures.[4] Polystyrene- N
block-poly(ethylene oxide) is an exam- O
ple of an amphiphilic copolymer, con-
sisting of hydrophilic poly(ethylene O O
oxide) and hydrophobic polystyrene N N
domains through self-assembly.[5] The O
CH2-CH O
hydrophilic domain is ideal for doping n 6 +
O
Li Cl-
lithium salts while the hydrophobic
polystyrene domain can be loaded with O
O
hydrophobic organic scintillators. In m/5

fact, poly(ethylene oxide)s are exten-


Samples 1-6, 1A, and 1B
sively used as electrolytes to solubilize
lithium salts in lithium batteries. Simi- Scheme 1. Preparation of the lithiated scintillator based on the self-assembly of the block copoly-
larly, polystyrenes are widely employed mer.

1758  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
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depicts schematic presentations of the composite neutron mental films also show a significant number of events below
scintillators based on the self-assembly of the block copoly- the neutron peak. These events are attributed to gamma rays
mer. The doping concentrations for 6Li+ were 0.80, 1.49, 2.70, interacting in the scintillators and PMT and fast neutrons scat-
3.70, 4.70 and 5.86 wt.-% for samples 1, 2, 3, 4, 5 and 6, respec- tering off of hydrogen atoms in the scintillators. Although
tively. Films 1A and 1B were four and eight times thicker than most neutrons from the source are thermalized, some fast
film 1, respectively. Control monolithic films C1 (without 6Li+, neutron leakage can occur. Although quartz is not a scintilla-
PPO and POPOP) and C2 (without 6Li+) were also prepared. tor, there is significant low-amplitude noise in the quartz
As a primary fluor, PPO absorbs resonance energy from the pulse-height spectrum. The noise is attributed to gamma rays
block copolymer substrate during radiation ionization and producing pulses by interacting inside the PMT. Because our
emits energy as fluorescent light. The secondary fluor (PO- lithiated organic scintillators are colorless, homogeneous, and
POP, wavelength shifter) shifts the wavelength of the emitted transparent films, increasing the thickness of the monolithic
light to a wavelength that is more suitable for photomultiplier films (1: 0.5 mm thickness; 1A: 1.21 mm thickness; 1B:
tube (PMT) detection. As a result, samples 1±6, 1A, 1B, and 1.95 mm thickness) should increase the neutron count rate
C2 all produced peak light emission in the range of 409 nm without losing light output (relative pulse height). As seen
under UV excitation, suitable for use with PMTs (Fig. 1). The from Figure 2, this assertion is consistent with the experimen-
control samples C1 and blank quartz disc did not show any tal observation.
detectable wavelength emission peak in this range due to the Figure 3 shows total peak counts versus pulse height for a
absence of PPO and POPOP. set of the scintillating films after removal of the background
The comparative measurements of intrinsic peak efficiency, determined with the quartz disc. All data were based on
light yield, and peak resolution for thermal neutrons from a 0.67 ± 0.17 mm thick film samples. This format uses the inte-
thermalized AmBe and Cf neutron source were made using grated peak area (error bar is ca. 10 %) for total counts, avoid-
the various lithiated-block-copolymer scintillator samples. ing the visually misleading peak heights encountered in the
Figure 2 shows the superimposed pulse-height spectra from spectra plot. Counts are proportional to the intrinsic peak effi-
experimental monolithic films 1, 1A, and 1B and quartz. In- ciency, and pulse height is proportional to light yield. Accord-
spection of the pulse-height spectra shows that the three ex- ingly, the better detectors yield higher neutron counts and rel-
perimental films all exhibit a peak around a relative pulse am- ative pulse height. As can be seen from Figure 3, the increase
plitude of 1.7. This peak is attributed to thermal neutron of 6Li+ concentration up to approximately 4.7 %, leads to an
capture events by 6Li+. This peak is noticeably absent in the increase in the intrinsic peak efficiency (net counts) even
quartz data, which supports this conclusion. All of the experi- 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 excita-
tion.

Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1759
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3,5 quartz

1(0.8 weight% Li, 0.5 mm thickness)

3 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 In conclusion, a new class of organic neutron scintillators
the polarity of 6Li+ has a negative effect on ionization events containing organic fluors and 6Li+ has been developed based
in the domain of polystyrene. Further work will be focused on on a room-temperature synthesis method with block copoly-
synthesizing and testing scintillators based on different combi- mers. The detecting efficiency achieved with such thin-film
nations of polystyrene and poly(ethylene oxide) blocks and neutron scintillators is very promising for the fabrication of
also exploration of new block copolymer matrix materials large-scale position-sensitive neutron scintillators. The unique
consisting of poly(ethylene oxide) and polyvinylxylene. The self-assembly nanostructure of block polymers makes it possi-
work on polystyrene-b-poly(ethylene oxide) with a wide ble to homogenize hydrophilic neutron absorbers and hydro-
range of PEO volume fractions will represent various micro- phobic organic scintillators in nanometer scale. The use of na-
domain morphologies and their correlation (if any) with the noscopic materials highlights new opportunities in the
efficiency of films as neutron scintillators. 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

5(4.70% Li)
1000

500 6(5.86% Li)


Figure 3. Experimental total peak counts
plotted against pulse height (peak centroid)
0 based on 0.67 (± 0.17) mm thick samples. This
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 format is less misleading and easier to read
but contains essentially the same information
Relative Pulse Height as Figure 2.

1760  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
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Experimental [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.
Synthesis Protocol: Polystyrene-b-poly(ethylene oxide) [P1503-
[10] T. H. Epps, T. S. Bailey, R. Waletzko, F. S. Bates, Macromolecules
SEO, Mn: PS (2300) -PEO (3100), Mw/Mn: 1.08, PEO volume fraction:
2003, 36, 2873.
0.56, calculated using known densities of polystyrene and poly(ethyl-
[11] H. Yu, A. Natansohn, M. A. Singh, I. Torriani, Macromolecules
ene oxide) at room temperature (rPS = 1.05 g cm±3, rPEO = 1.13 g cm±3)
[11] Polymer Source, Inc.], liquid scintillation mixture containing 1,4- 2001, 34, 1258.
bis-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), tol-
uene (Aldrich, anhydrous, 99.8 %), and methyl alcohol (MeOH, Bur-
dick & Jackson, HPLC grade) were used as received. The liquid scin- Molecular-Scale Tracking of the
tillation mixture (600 lL) was diluted (to 2500 lL) with toluene
beforehand. In a typical synthesis, 40.6 mg of P1503-SEO was dis- Self-Healing of Polycrystalline
solved 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. Subse-
Monolayers at the Solid±Liquid
quently, 20 lL of the diluted PPO/POPOP solution was added to each Interface**
solution. The control samples (C1 and C2) were prepared with P1503-
SEO (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. By Paolo Samorí,* Klaus Müllen,* and Jürgen P. Rabe*
Each precursor solution was sonicated for about 10 min. The viscous
solutions were then applied to 1 in. (1 in. = 2.54cm) diameter quartz Dedicated to Professor Roeland J. M. Nolte on the occasion of
discs to give thick monolithic films. After drying for one week at
room-temperature, these monolithic films were tested for neutron de-
his 60th birthday
tection capabilities.
Characterization: The pulse-height analysis system consisted of a Since thin films grown under non-equilibrium conditions
one-inch-diameter PMT (Hamamatsu R1924A), amplifiers (Ortec are always prone to rearrangement,[1,2] understanding the
113 preamplifier and 575A shaping main amplifier), and a computer-
interfaced multichannel analyzer (Spectrum Techniques UCS-20).
mechanisms and kinetics of such a reorganization is necessary
The procedure for neutron measurements involved placing a specific to predict film stability. The temporal evolution towards the
scintillator near a neutron source storage drum containing a 3 Ci equilibrium state involves coarsening, i.e., an increase in the
AmBe neutron source and a 3 mCi 252Cf spontaneous fission neutron characteristic length-scale of the dominant structure. Previous
source. The drum uses a thick neutron moderator/absorber shield, so
studies have been mainly devoted to the dynamics of metallic
that thermal neutrons predominate in the energy distribution outside
the drum. The scintillator and PMT were shielded from fission gamma or semiconducting thin films.[3±6] At organic interfaces, the
radiation by 5 cm lead bricks, and an additional 3 cm of high-density underlying processes still need to be better understood at the
polyethylene moderator was interposed between the bricks and the molecular level.[2] In particular, little is known of the pro-
source drum. Pulse-height spectra were accumulated over 1.5 ” 104 s
cesses occurring at the liquid±solid interface.
for each neutron detector sample.
Fluorescence emission and excitation spectra were recorded on a A scanning tunneling microscopy (STM) study of Ostwald
SPEX Fluorolog spectrofluorometer Model FL3-22, equipped with ripening in two dimensions revealed that the underlying mo-
two double-grating monochromators and a 450 W xenon lamp as an lecular process is a reaction-controlled phenomenon that
excitation source.
Received: March 6, 2004
Final version: May 3, 2004
±
[*] Dr. P. Samorí
Istituto per la Sintesi Organica e la Fotoreattività
± Consiglio Nazionale delle Ricerche
[1] J. B. Birks, in The Theory and Practice of Scintillation Counting, via Gobetti 101, I-40129 Bologna (Italy)
Pergamon Press, New York 1964. E-mail: samori@isof.cnr.it
[2] G. Blasse, Chem. Mater. 1994, 6, 1465. Dr. P. Samorí
[3] H.-J. Im, C. Willis, A. C. Stephan, M. D. Pawel, S. Saengkerdsub, Institut de Science et d'IngØnierie SupramolØculaires
S. Dai, Appl. Phys. Lett. 2004, 84, 2448. UniversitØ Louis Pasteur
[4] H.-A. Klok, S. Lecommandoux, Adv. Mater. 2001, 13, 1217. 8, allØe Gaspard Monge, F-67083 Strasbourg Cedex (France)
[5] a) Z. Lin, D. H. Kim, X. Wu, L. Boosahda, D. Stone, L. LaRose, Prof. K. Müllen
T. P. Russell, Adv. Mater. 2002, 14, 1373. b) I. W. Hamley, Nanotech- Max-Planck-Institute for Polymer Research
nology 2003, 14, R39-R54. c) S. H. Kim, M. J. Misner, T. Xu, M. Ki- Postfach 3148, D-55021 Mainz (Germany)
E-mail: muellen@mpip-mainz.mpg.de
mura, T. P. Russell, Adv. Mater. 2004, 16, 226. d) B. Smarsly, G. Xo-
meritakis, K. Yu, N. Liu, H. Fan, R. A. Assink, C. A. Drewien, Prof. J. P. Rabe
Department of Physics, Humboldt University Berlin
W. Ruland, C. J. Brinker, Langmuir 2003, 19, 7295. e) L. Zhu,
Newtonstrasse 15, D-12489 Berlin (Germany)
P. Huang, W. Y. Chen, X. Weng, S. Z. D. Cheng, Q. Ge, R. P. Quirk,
E-mail: rabe@physik.hu-berlin.de
T. Senador, M. T. Shaw, E. L. Thomas, B. Lotz, B. S. Hsiao, F. Yeh,
[**] We thank Dr. Viola Francke for the synthesis of the molecule and
L. Liu, Macromolecules 2003, 36, 3180. f) B. Reining, H. Keul,
Dr. N. Severin for his assistance with Molecular Modeling. This
H. Hocker, Polymer 2002, 43, 7145. work was supported by TMR project SISITOMAS (project reference
[6] S. W. Moser, W. F. Harder, C. R. Hurlbut, M. R. Kusner, Radiat. FMRX970099) and by the European Science Foundation through
Phys. Chem. 1993, 41, 31. SMARTON and SONS-BIONICS. P. S. wishes to thank the EU for a
[7] H. Leutz, Nucl. Instrum. Methods Phys. Res. Sect. A 1995, 364, 422. Marie Curie fellowship.

Adv. Mater. 2004, 16, No. 19, October 4 DOI: 10.1002/adma.200400132  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1761