Received: March 6, 2002

Final version: May 15, 2002

[1] S. C. Jain, M. Willander, J. Narayan, R. V. Overstraeten, J. Appl. Phys.

2000, 87, 965.
[2] Z. Hong, C. Liang, R. Li, W. Li, D. Zhao, D. Fan, D. Wang, B. Chu,
F. Zang, H. Long, S. Lee, Adv. Mater. 2001, 13, 1241.
[3] L. Gu, Z. Xiong, G. Chen, Z. Xiao, D. Gong, X. Hou, X. Wang, Adv.
Mater. 2001, 13, 1402.
[4] A. R. Zanatta, L. Nunes, Appl. Phys. Lett. 1998, 72, 3127.
[5] See, for example, various authors in Mater. Res. Soc. Bull. 1999, 24(9).
[6] A. R. Zanatta, C. T. M. Ribeiro, U. Jahn, Appl. Phys. Lett. 2001, 79, 488.
[7] K. Gurumurugan, H. Chen, G. Harp, W. Jadwisienczak, H. Lozykowski,
Appl. Phys. Lett. 1999, 74, 3008.
[8] V. I. Dimitrova, P. G. Patten, H. Richardson, M. E. Kordesch, Appl. Surf.
Sci. 2001, 175176, 480.
[9] S. Strike, H. Morko, J. Vac. Sci. Technol. B 1992, 10, 1237.
[10] J. Siwiec, A. Sokolowska, A. Olszyna, R. Dmilinski, M. Kaminska, J. K.
Hrabowska, Nanostruct. Mater. 1998, 10, 625.
[11] G. H. Dieke, in Spectra and Energy Levels of Rare-Earth Ions in Crystals,
Wiley Interscience, New York 1968.
[12] P. Mikhail, J. Hulliger, M. Schnieper, H. Bill, J. Mater. Chem. 2000, 10,
987.
[13] A. A. Kaminskii, Phys. Status Solidi A 1995, 148, 9.
[14] A. R. Zanatta, M. Bell, L. Nunes, Phys. Rev. B 1999, 59, 10 091.
[15] A. R. Zanatta, F. L. Freire, Jr., Phys. Rev. B 2000, 62, 2016.

Formation of a Surface Relief Grating Using

a Novel Azobenzene-Based Photochromic
Amorphous Molecular Material
By Hideyuki Nakano, Toru Takahashi, Toshiaki Kadota,
and Yasuhiko Shirota*
Organic photochromic compounds have recently attracted
a great deal of attention in view of potential applications for
optical switches and optical memories.[1] In applying photochromic materials for such devices, they may be used in the
form of solid film, and hence extensive studies have been
made of photochromic polymers and composite polymer sys-

tems, where low molecular-weight photochromic compounds

are dispersed in polymer binders.[28] Formation of surface
relief gratings (SRGs) by irradiation of amorphous films of
azobenzene-functionalized acrylate, methacrylate, and epoxybased polymers with two coherent laser beams has been a
topic of current interest.[918] SRGs, which are formed by the
mass transport induced by the photoisomerization of the azobenzene chromophore, may find potential applications for
erasable and rewritable holographic memory, polarization discriminator, and waveguide coupler.
As a part of our studies on amorphous molecular materials,
namely, low molecular weight organic compounds that readily
form stable amorphous glasses above room temperature,[1924]
we have proposed a new concept, photochromic amorphous
molecular materials and studied the creation of such materials based on azobenzene and dithienylethene.[2527] Photochromic amorphous molecular materials constitute a new
class of photochromic materials that form uniform amorphous
films by themselves without polymer binders. They have an
advantage that there is no dilution of photochromic chromophores relative to photochromic polymers and composite
polymer systems, where low molecular weight photochromic
compounds may crystallize at high concentrations.
It is of great interest and significance to create photochromic amorphous molecular materials based on azobenzene and
to investigate SRG formation using such amorphous molecular materials. Compared to polymers, amorphous molecular
materials are expected to provide more simple systems that
are free from polymer chains and hence their entanglement,
and to enable more readily studies of the correlation between
molecular structure and the diffraction efficiency of resulting
SRG. Recently, SRG formation using an amorphous film of a
bisazo compound, N,N-bis(phenyl)-N,N-bis[(4-phenylazo)phenyl]benzidine (AZOPD), has been reported; however, the
diffraction efficiency is only ca. 0.02 % with a small modulation depth of 9 nm.[28] It is of importance to clarify how much
diffraction efficiency and modulation depth of SRG can be attained for azobenzene-based amorphous molecular materials
depending on molecular structures and polarization directions
of writing beams. For the study of SRG formation, monoazo
compounds seem to be more simple and more suitable than
bisazo compounds. We report here SRG formation with a
high diffraction efficiency of 23 % and a large modulation
depth of 280 nm by use of a novel photochromic amorphous
molecular material based on monoazobenzene, 4-[bis(9,9-dimethylfluoren-2-yl)amino]azobenzene (BFlAB).

[*]

Prof. Y. Shirota, Dr. H. Nakano, T. Takahashi, T. Kadota

Department of Applied Chemistry, Faculty of Engineering
Osaka University
Yamadaoka, Suita, Osaka 565-0871 (Japan)
E-mail: shirota@ap.chem.eng.osaka-u.ac.jp

Adv. Mater. 2002, 14, No. 16, August 16

WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2002

0935-9648/02/1608-1157 $ 17.50+.50/0

1157

COMMUNICATIONS

Sm-doped films, the Al target was partially covered with suitable pieces of metallic Sm (99.9 % purity). Before each deposition, the Al (+ Sm) target was
cleaned in an argon plasma for ~30 min. Polished p-type Si<100> and hexagonal Al2O3 (sapphire) substrates were maintained at ~200 C in all deposition
runs. Typically, each deposition was 4 h long, rendering films ~0.5 lm thick, as
determined from a tail-step profilometer. The atomic composition of the AlN
films was determined from X-ray photoelectron spectroscopy (XPS) measurements and indicates that they are near stoichiometric. The XPS data also point
out a Sm concentration of ~3.0 at.-%. The optical bandgap (Eg) of the AlN
films deposited on sapphire substrates was estimated according to Tauc's method and stays around 5.0 eV. In order to investigate the role played by temperature on the AlN films, they were submitted to cumulative thermal annealing
(TA) in the 1501050 C temperature range. Each TA was 15 min long and performed in a flow of argon gas. The atomic structure of all AlN samples was
monitored after each TA by Raman scattering spectroscopy, confirming that
the films remained amorphous even after annealing at 1050 C. The photoluminescence (PL) measurements were performed in a micro-Raman setup by using
488.0 nm photons and a power density of ~7 mW lm2. Most of the measurements were done at room-temperature and on films deposited over c-Si substrates. PL measurements of films deposited on sapphire substrates and in the
40080 K temperature range were also performed.

COMMUNICATIONS

BFlAB was synthesized by the Ullmann reaction of 4-aminoazobenzene and 9,9-dimethyl-2-iodofluorene as described
in the Experimental section. BFlAB was found to readily
form an amorphous glass with a well-defined glass-transition
temperature (Tg) of 97 C when the melt sample was cooled
on standing in air. It also forms amorphous films by spin coating and exhibits photochromism in the amorphous film as well
as in solution.
As Figure 1 shows, irradiation of a BFlAB amorphous film
with 450 nm light at room temperature caused the decrease in
the absorbance around 450 nm due to the photoisomerization

(Eq. 1) with parameters of f1 = 0.05 and k1 = 0.20 min1, and

f2 = 0.95 and k2 = 3.7 103 min1, respectively;
cist
f1 exp k1 t f2 exp k2 t
cis0

(1)

where fi and ki are the fractions and the rate constants for the
faster (i = 1) and the slower (i = 2) components, respectively. It
is suggested that there exist cis-isomers trapped in constrained
conformations as well as structurally relaxed cis-isomers in
the amorphous film, and that the constrained cis-isomers
transform faster into the trans-isomers than the structurally
relaxed cis-isomers.
The experiment of SRG formation using the BFlAB amorphous film was carried out using a 10 mW Ar+ laser (488 nm,
ca. 80 mW cm2) as two writing beams and a HeNe laser
(633 nm) as a probe beam. Figure 2a illustrates the schematic
experimental set-up for SRG formation. After the sample was

Fig. 1. Electronic absorption spectral change of BFlAB amorphous film (sample thickness: 0.38 lm): a) before photoirradiation, b) photostationary state
upon irradiation with 450 nm light.

of the trans-form to the cis-form. When irradiation was

stopped after the reaction system had reached the photostationary state, the electronic absorption spectrum of the film
gradually recovered to the original one due to the backward
thermal isomerization from the cis-form to the trans-form.
The backward isomerization of BFlAB from the cis-form to
the trans-form also took place by irradiation with 550 nm
light. The cis-fraction of BFlAB at the photostationary state
upon irradiation with 450 nm light was 0.80 and 0.54 in solution and in the amorphous film, respectively. The lower cisfraction in the amorphous film at the photostationary state is
attributed to the existence of remaining trans-form molecules
that can not isomerize to the cis-form in the amorphous film.
It is thought that the local free volume around the remaining
trans-form molecules is not large enough to allow the isomerization from the trans-form to the cis-form to the extent as
observed for the solution.
While the thermal backward reaction of BFlAB from the
cis-form to the trans-form in benzene solution followed first
order kinetics with a rate constant of 4.4 103 min1 at 30 C,
the reaction in the amorphous film did not follow the first order kinetics, and that the apparent rate constant in the amorphous film was initially ca. 3 times larger than that in solution,
gradually approaching the same value as that in solution. The
thermal isomerization from the cis-form to the trans-form
fitted neither the KohlrauschWilliamsWatts (KWW) function[29] nor the Gaussian model,[30] but was successfully analyzed in terms of first-order kinetics of two components

1158

WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2002

Fig. 2. a) Schematic experimental setup for the formation of SRG (S: sample,
D: detector, P: polarizer). b) Irradiation time dependence of diffraction efficiency for an amorphous film of BFlAB.

irradiated with two linearly polarized beams, the first-order

diffraction efficiency, which is defined as the intensity ratio of
the first-order diffraction of the probe beam to the incident
one, was measured.
As Figure 2b shows, when an amorphous film of BFlAB
was irradiated with two linearly polarized Ar+ laser beams
with polarization angles of +45 and 45 with respect to the
s-polarization, the diffraction efficiency gradually increased
with irradiation time and reached ca. 23 %. Even when the
two writing beams were turned off, the diffraction efficiency
remained almost constant after an initial slight change took
place. The result suggests that an SRG is formed on the
BFlAB amorphous film by irradiation with two writing beams.
The diffraction efficiency depended on the polarization directions of two writing beams (Table 1). As reported for the

0935-9648/02/1608-1158 $ 17.50+.50/0

Adv. Mater. 2002, 14, No. 16, August 16

Polarization of writing beams

Diffraction efficiency [%]

s/s
s/p
p/p
+45/+45
+45/45

0.6
0.5
20.4
0.5
23.0

polymers containing the azobenzene moiety,[14,16,17] higher diffraction efficiencies were obtained when p-/p- and +45/45
polarized writing beams were used. These results indicate that
the intensity modulation and the total electric-field vector
pattern produced by the two incident polarized beams play an
important role for the formation of the SRG. The SRG was
found to be quite stable, retaining a diffraction efficiency of
21 % even after three months in the dark at room temperature. When the sample was heated above the Tg, the SRG
disappeared and was again formed by irradiation with the two
writing beams at room temperature.
The formation of the SRG was also confirmed by atomic
force microscopy (AFM). As shown in Figure 3, the AFM
image of the surface of the BFlAB amorphous film after irradiation with the two writing beams clearly demonstrates the

Fig. 3. AFM image of the surface of the amorphous film of BFlAB after irradiation with two coherent writing laser beams.

formation of an SRG. The modulation depth of the surface

relief formed on the BFlAB amorphous film by irradiation
with the writing beams with polarization angles of +45 and
45 with respect to the s-polarization was ca. 280 nm.
It has been suggested that the polymer chain migration in
azobenzene-attached polymers plays an important role for the
formation of SRG, since the formation of SRG for composite
polymer systems where azobenzene derivatives are dispersed
in polymer binders is much less effective than for the azobenzene-attached polymers.[15,16,18] The present study demonstrates for the first time that an SRG with a high diffraction
efficiency is formed for photochromic amorphous molecular
materials that are free from the polymer chain. To the best of
our knowledge, the present study provides the first example
of SRG formation with high diffraction efficiency and large
modulation depth for photochromic amorphous molecular
materials.
In conclusion, a new photochromic amorphous molecular
material based on azobenzene, BFlAB, was designed and
synthesized. It is shown that BFlAB readily forms an amor-

Adv. Mater. 2002, 14, No. 16, August 16

phous glass with a Tg of 97 C and exhibits photochromism in

the amorphous solid film as well as in solution. The BFlAB
amorphous film was found to form an SRG with a high diffraction efficiency of 23 % by irradiation with two coherent
488 nm Ar+ laser beams with polarization angles of +45 and
45 with respect to the s-polarization. The present study
shows that the existence of polymer chain bonded to an azobenzene moiety is not necessarily required for the formation
of SRG with a high diffraction efficiency and that azobenzene-based photochromic amorphous molecular materials are
promising candidates for materials for SRG formation.
Further studies of the correlation between molecular structure and SRG formation are underway.

Experimental
4-Aminoazobenzene was commercially available and purified by recrystallization from ethanol before use. 9,9-Dimethyl-2-iodofluorene was synthesized
according to the procedure described in our previous paper [31]. BFlAB was
synthesized by refluxing the mesitylene solution (150 mL) of 4-aminoazobenzene (2.6 g, 13 mmol) and 9,9-dimethyl-2-iodofluorene (9.7 g, 30 mmol) in the
presence of copper powder (2.1 g, 33 mmol), K2CO3 (5.2 g, 38 mmol), and 18crown-6 (600 mg, 2.2 mmol) for 35 h under nitrogen atmosphere. It was purified by silica-gel column chromatography, followed by recrystallization from
toluene/hexane. Yield: 4.6 g (60 %), m.p. 167 C; Tg = 97 C; 1H NMR (CDCl3,
750 MHz): d 7.88 (d, 2H, J=7.3 Hz), 7.86 (d, 2H, J=9.0 Hz), 7.66 (d, 2H,
J=8.2 Hz), 7.63 (d, 2H, J=8.2 Hz), 7.47 (t, 2H, J=7.3 Hz), 7.40 (t, 1H, J=7.3 Hz),
7.39 (d, 2H, J=7.0 Hz), 7.29 (s, 2H), 7.27 (t, 2H, J=7.3 Hz), 7.26 (d, 2H,
J=9.0 Hz), 7.17 (d, 2H, J=8.0 Hz), 1.42 (s, 12H) ppm; 13C NMR (CDCl3,
188 MHz): d 155.2, 153.6, 153.0, 150.7, 147.3, 146.4, 138.7, 135.3, 130.2, 129.0,
127.0, 126.8, 124.3, 124.2, 122.5, 122.5, 122.0, 120.8, 119.6, 119.6 ppm; MS
(MALDI-TOF) (m/z) 582 (M+); EA: Calcd. for C42H35N3: C, 86.71; H, 6.06; N,
7.22 %. Found: C, 86.45; H, 6.23; N, 7.00 %.
BFlAB amorphous films with a thickness of ca. 510 lm for SRG formation
were prepared as follows. An appropriate amount of the polycrystalline sample
of BFlAB was heated to melt on a glass substrate, and a Kapton film was put on
the melt sample, followed by pressing with another glass substrate. After the
sample was allowed to cool to room temperature, the Kapton film was
removed.
Received: February 25, 2002
Final version: March 21, 2002

[1] For example, see special issue of Chem. Rev. 2000, 100, 16841890.
[2] H. Drr, H. Bouas-Laurant, Photochromism, Molecules and Systems,
Elsevier, Amsterdam 1990.
[3] C. B. McArdle, Applied Photochromic Polymer Systems, Blackie & Son,
New York 1992.
[4] C. S. Paik, H. Morawetz, Macromolecules 1972, 5, 171.
[5] L. Lamarre, C. S. P. Sung, Macromolecules 1983, 16, 1729.
[6] I. Mita, K. Horie, K. Hirao, Macromolecules 1989, 22, 558.
[7] G. S. Kumar, D. C. Neckers, Chem. Rev. 1989, 89, 1915.
[8] K. Ichimura, in Organic Photochromic and Thermochromic Compounds
(Eds: J. C. Crano, R. J. Guglielmetti), Plenum Press, New York 1999, p. 9.
[9] P. Rochon, E. Batalla, A. Natansohn, Appl. Phys. Lett. 1995, 66, 136.
[10] D. Y. Kim, S. K. Tripathy, L. Li, J. Kumar, Appl. Phys. Lett. 1995, 66, 1166.
[11] C. Barret, A. Natansohn, P. Rochon, J. Phys. Chem. 1996, 100, 8836.
[12] P. Lefin, C. Fiorini, J. M. Nunzi, Pure Appl. Opt. 1998, 7, 71.
[13] T. G. Pedersen, P. M. Johansen, N. C. R. Holme, P. S. Ramanujam,
S. Hvilsted, Phys. Rev. Lett. 1998, 80, 89.
[14] J. Kumar, L. Li, X. L. Jiang, D. Y. Kim, T. S. Lee, S. K. Tripathy, Appl.
Phys. Lett. 1998, 72, 2096.
[15] F. Lagugn Labarthet, T. Buffeteau, C. Sourisseau, J. Phys. Chem. B 1998,
102, 2654.
[16] N. K. Viswanathan, D. Y. Kim, S. Bian, J. Williams, W. Liu, L. Li, L. Samuelson, J. Kumar, S. K. Tripathy, J. Mater. Chem. 1999, 9, 1941.
[17] N. K. Viswanathan, S. Balasubramanian, L. Li, L. Samuelson, S. K. Tripathy, J. Kumar, Jpn. J. Appl. Phys. 1999, 38, 5928.

WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2002

0935-9648/02/1608-1159 $ 17.50+.50/0

1159

COMMUNICATIONS

Table 1. Diffraction efficiencies of SRG formed on a BFlAB amorphous film.

COMMUNICATIONS

[18] C. Fiorini, N. Prudhomme, G. de Veyrac, I. Maurin, P. Raimond, J.-M.

Nunzi, Synth. Met. 2000, 115, 121.
[19] Y. Shirota, T. Kobata, N. Noma, Chem. Lett. 1989, 1145.
[20] W. Ishikawa, H. Inada, H. Nakano, Y. Shirota, Chem. Lett. 1991, 1731.
[21] A. Higuchi, H. Inada, T. Kobata, Y. Shirota, Adv. Mater. 1991, 3, 549.
[22] H. Inada, Y. Shirota, J. Mater. Chem. 1993, 3, 319.
[23] Y. Kuwabara, H. Ogawa, H. Inada, N. Noma, Y. Shirota, Adv. Mater. 1994,
6, 677.
[24] Y. Shirota, J. Mater. Chem. 2000, 10, 1.
[25] Y. Shirota, K. Moriwaki, S. Yoshikawa, T. Ujike, H. Nakano, J. Mater.
Chem. 1998, 8, 2579.
[26] T. Ujike, K. Moriwaki, H. Nakano, Y. Shirota, J. Photopolym. Sci. Technol. 1998, 11, 33.
[27] H. Utsumi, D. Nagahama, H. Nakano, Y. Shirota, J. Mater. Chem. 2000,
10, 2436.
[28] T. Fuhrmann, T. Tsutsui, Chem. Mater. 1999, 11, 2226.
[29] G. Williams, D. C. Watts, Trans. Faraday Soc. 1970, 66, 80.
[30] W. J. Albery, P. N. Bartlett, C. P. Wilde, J. R. Darwent, J. Am. Chem. Soc.
1985, 107, 1854.
[31] Y. Shirota, M. Kinoshita, T. Noda, K. Okumoto, T. Ohara, J. Am. Chem.
Soc. 2000, 121, 11 021.

Metallodielectric Opals of Layer-by-Layer

Processed Coated Colloids**
By Zhijian Liang, Andrei S. Susha, and Frank Caruso*
Currently, immense efforts are being focused on creating
photonic crystals derived from self-assembled colloids
because of their relative ease of preparation and the low cost
associated with their manufacture.[1] Monodisperse colloid
spheres of silica or polystyrene are known to spontaneously
self-organize into crystal structures at optical wavelength
scales with long range periodicity, and have been shown to
possess an optical stop band in the visible and near IR-spectral ranges.[1] These findings have stimulated extensive studies
of structural and optical properties of colloidal crystals.[211]
Furthermore, colloidal crystals can be used as templates for
fabricating 3D replicas, known as inverse opals, of metals
through to carbon and silicon and polymers.[12]
To date, the majority of photonic crystals prepared from
colloid particles have employed commercially available colloids, such as silica or polystyrene spheres. Utilization of composite colloids, in particular coreshell or coated particles,
represents an interesting alternative to the formation of novel
photonic crystals.[11,1317] Structures fabricated from coreshell
colloids are expected to exhibit unique optical properties. For
example, theoretical calculations indicate that metallodielectric spheres assembled into photonic crystals can have a full
photonic bandgap.[13] Recent experimental studies have focused on the preparation of, for example, zinc sulfide-coated

[*] Dr. F. Caruso, Dr. Z. Liang, Dr. A. S. Susha

Max Planck Institute of Colloids and Interfaces
D-14424 Potsdam (Germany)
E-mail: frank.caruso@mpikg-golm.mpg.de

[**] We thank D. Gittins for assistance with the synthesis of the gold nanoparticles, and N. Gaponik and D. Talapin (Hamburg University) for help with
recording the optical spectra. D. Wang is acknowledged for helpful discussions and H. Mhwald for supporting this work within the MPI-Interface
department. Funding was provided by the DFG and the Volkswagen
Foundation.

1160

WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2002

polystyrene[14] or silica spheres,[15] coreshell latex particles

with semiconductors[11] or dyes incorporated into the shell,[16]
and silica-core gold-shell particles,[17] suggesting that such particles would have potential as photonic crystals. These investigations highlight the increasing interest in the development of
new synthesis routes for producing homogeneously coated
particles with sufficient colloidal stability, which may then be
used in colloidal crystal fabrication.[1417]
The layer-by-layer (LbL) colloid-templating strategy, the
basis of which is primarily the electrostatic attraction between
oppositely charged species deposited from solution onto colloids, lends itself well to the task of producing colloidally
stable, homogeneously coated particles.[18] This flexible and
facile procedure permits the coating of colloids of various
shapes and sizes with uniform layers of diverse composition
and controllable thickness.[19] The advantages associated with
the use of LbL constructed coreshell particles as building
blocks for the formation of engineered photonic crystals are
that the composition of the core and shell can be controlled
the spheres can be designed to contain a core with a low
refractive index surrounded by a shell of material with a high
refractive index (e.g., titania)[20,21]and the shell thickness
and hence final particle diameter can be manipulated.[18,19]
Modulation of these parameters will allow extensive control
of the spectral position and magnitude of the optical stop
band. Control of the position and magnitude of the optical
stop band of colloidal crystals is often desired.[2225] The stop
band can be varied from the visible to the near IR by changing the diameter of spheres used.[5,8] The stop band of 3D crystalline arrays fabricated from silica and polystyrene bare colloid spheres can also be altered by sintering the samples at
elevated temperatures, thus reducing the lattice spacing,[22,23]
or by infiltrating with materials (e.g., solvents) with different
refractive indices.[24] For photonic crystals of 280 nm hollow
titania spheres, the stop band could be adjusted by altering
the shell thickness of the spheres.[25]
In this communication, we report on the fabrication and
optical properties of colloidal crystals derived from coated
colloids prepared by the LbL approach, focusing on the preparation of metallodielectric opals. In the first system, polystyrene (PS) spheres of 640 nm diameter were coated with
poly(allylamine hydrochloride) (PAH)/poly(sodium 4-styrenesulfonate) (PSS) multilayers. A maximum of 8 layers total
[(PAH/PSS)4] were deposited, although colloids with more
layers can be readily prepared.[18c] The colloids were then
further modified by adsorption of an amine-terminated random copolymer of 70 % poly(ethylene oxide) (PEO) with
30 % poly(propylene oxide), forming a brush layer and facilitating assembly of the colloids into ordered assemblies.[26] The
second system of coated particles was obtained by exposing
the PAH/PSS-coated PS spheres (with different coating thicknesses) to a 4-dimethylaminopyridine-stabilized gold nanoparticle (Aunp) dispersion (Aunp diameter = 6 2 nm),[27]
which results in the nanoparticles infiltrating and binding to
the polyelectrolyte (PE) layers, yielding a dense nanoparticulate gold coating. After removal of excess nanoparticles, the

0935-9648/02/1608-1160 $ 17.50+.50/0

Adv. Mater. 2002, 14, No. 16, August 16