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Abstract
This review discusses strategies for the synthesis of three-dimensionally ordered macroporous (3DOM) solids (inverse opals) by
colloidal crystal templating. Compositions of 3DOM structures include simple and ternary oxides, chalcogenides, non-metallic and
metallic elements, hybrid organo-silicates, and polymers. A wide range of 3DOM synthesis techniques, including solgel chemistry,
polymerization, salt-precipitation and chemical conversion, chemical vapor deposition, spray pyrolysis, ion spraying, laser spraying,
nanocrystal deposition and sintering, oxide and salt reduction, electrodeposition, electroless deposition, fabrication from core-shell
spheres, and patterning methods, as well as templating using inverse opal molds to produce new opal compositions are reviewed. Potential
uses of 3DOM solids, including photonic crystal, optical, catalytic, and bioglass applications are briefly discussed. 2002 Elsevier
Science Ltd. All rights reserved.
Keywords: Colloidal crystal templating; Three-dimensionally ordered macroporous solids; Photonics; Inverse opals
1. Introduction
Methods for shaping and structuring solids into functional objects have been developed and improved to create
increasingly more complex features since the fabrication of
early tools. Macroscopic features have traditionally been
attained by physical or mechanical methods, but as features on nanoscopic length scales have become more
important, chemical approaches have made significant
contributions. To achieve further structural complexity,
physical, chemical, and engineering approaches toward
materials fabrication must converge. Novel multidisciplinary approaches toward the synthesis of hierarchically
structured, functional materials are now being developed.
One such class of materials is three-dimensionally ordered
macroporous (3DOM) solids. These materials have been
developed in parallel in different research communities,
including chemists, physicists, and engineers. Syntheses
and potential applications of 3DOM solids will be the
focus of this review.
The general concept of colloidal crystal templating is
simple: form a colloidal crystal of close-packed, uniformly
sized spheres, fill the interstitial spaces with a fluid
precursor capable of solidification, and remove the tem*Corresponding author. Tel.: 11-612-624-1802; fax: 11-612-6267541.
E-mail address: stein@chem.umn.edu (A. Stein).
1359-0286 / 02 / $ see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S1359-0286( 01 )00022-5
554
A. Stein, R.C. Schroden / Current Opinion in Solid State and Materials Science 5 (2001) 553564
The Synthesis section of this review is, therefore, organized by class of reaction used for synthesis. A brief
discussion of potential applications for 3DOM materials
follows. The reader is also referred to a number of related
reviews
that
have
recently
been
published
[10,16,22,29,3943].
2. Synthesis
A. Stein, R.C. Schroden / Current Opinion in Solid State and Materials Science 5 (2001) 553564
555
2.3. Polymerization
Polymerization of organic precursors within silica or
polymer colloidal crystal templates affords mesoporous
and macroporous polymers. In typical syntheses the sphere
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arrays are filled with a liquid monomer, which is polymerized and / or crosslinked by thermal treatment, exposure to
UV light, or catalysis. In this manner, 3DOM compositions
including
poly(divinylbenzene)
(PDVB),
poly(ethyleneglycol dimethacrylate) (PEDMA), polyurethane,
poly(acrylate-methacrylate), PMMA, poly(methyl acrylate)
(PMA), PS, poly( p-phenylenevinylene) (PPV), epoxy, and
epoxy resin have been prepared [3034,36,38]. The mechanical and physical properties of the porous products
depend on the material composition and processing conditions. For example, mesoporous PDVB replicas were
rigid, while the PEDMA replicas were flexible [31]. In
mixtures of PDVB and PEDMA the final pore size
depends on the ratio of the monomers. The window size in
3DOM polyurethane was controlled by adjusting the
polymerization temperature [33].
Instead of in situ polymerization, it is possible to
prepare 3DOM polymers by filling colloidal crystals with
solutions of preformed polymers. For example, a ferroelectric 3DOM polymer structure was obtained by infiltrating
poly(vinylidene fluoride-trifluoroethylene) copolymer solutions (in cyclohexanone) into silica opals at 1551608C
(slightly above the boiling point of the solvent and above
the melting point of the copolymer) followed by solvent
evaporation [37]. A similar method was applied to the
synthesis of a macroporous conducting polymer [35]. A
macroporous conductive glassy carbon was synthesized by
filling the voids of an artificial opal with a phenolic resin,
curing, and removing the silica spheres with HF [18].
Pyrolysis at temperatures up to 10008C converted the
framework to glassy carbon.
A completely different approach to synthesize macroporous polymers involves polystyrene / poly(2-hydroxyethyl methacrylate) (PS / polyHEMA) sphere colloidal crystals containing PS-rich cores and polyHEMA-rich shells
[58]. The colloidal crystal arrays were exposed to styrene
or toluene vapor (good solvents for PS but poor solvents
for polyHEMA) to extract PS from the structure, producing
ordered porous polymer nets.
An interesting synthesis of ordered macroporous polymers uses thermocapillary convection for templating,
instead of preformed templates [59]. Hexagonally ordered
porous structures are formed when dilute PS solutions in a
volatile solvent are cast on a flat support and exposed to
moist air flowing across the surface. The velocity of
airflow controlled pore dimensions in the range from 0.2 to
20 mm.
A. Stein, R.C. Schroden / Current Opinion in Solid State and Materials Science 5 (2001) 553564
557
bulk CdSe (12398C). Even before sintering, the semiconductor framework remained self-supporting upon template removal due to van der Waals interactions between
the nanoparticles.
Macroporous gold has been prepared from colloidal gold
particles (1525 nm) by various methods [21,24,26]. In
one approach, macroporous gold flakes were obtained by
depositing colloidal gold particles within a latex sphere
colloidal crystal by filtration. By calcination, smooth gold
surfaces were obtained, whereas extraction produced walls
with interconnected grains. In another method, highly
ordered products were obtained by dispensing a liquid
mixture of latex and gold nanoparticles between two glass
slides and dragging one slide across the other. In another
technique, a colloidal crystal containing gold particles
nucleated outward from the center of a concave meniscus
in an enclosed cell, eventually filling the entire cell to form
thin films of macroporous gold.
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2.9. Electrodeposition
Fig. 4. Schematic of the general procedure for the synthesis of macroporous solids by electrodeposition. Colloidal crystals are assembled onto
an electrode and immersed in an electrobath, along with a counter
electrode. The interstitial space of the colloidal crystal fills upon
application of a potential. Template removal produces the macroporous
solid.
Electrochemical methods have been employed to synthesize macroporous metals, alloys, semiconductors, and
conducting polymers (Fig. 4). In electrodeposition reactions, the colloidal crystal templates are deposited on a
conducting substrate (e.g., ITO-coated or gold-coated
glass), and a counterelectrode (e.g., Pt) is placed above the
sample. Alternately, a conducting film (e.g., Cu) is deposited on one side of millimeter-sized opal pieces [74].
Growth can occur either galvanostatically or potentiostatically [15,17]. Electrodeposition affords good control over
the degree of filling, wall thickness, and window size.
Macroporous metal chalcogenide preparations include
the galvanostatic deposition of CdS (from DMF or DMSO
solutions of sulfur and CdCl 2 ) in silica opals, and potentiostatic growth of CdS (from CdCl 2 and Na 2 S 2 O 3 ) and
CdSe (from CdSO 4 , H 2 SO 4 , and SeO 2 ) in PS colloidal
crystals [15,17]. Nearly complete filling was achieved, and
shrinkage was below 2% for silica and 8% for PS
templates after removal. The macroporous semiconductor
ZnO can also be prepared by electrodeposition [75].
A. Stein, R.C. Schroden / Current Opinion in Solid State and Materials Science 5 (2001) 553564
559
poly(aniline) samples during drying, but less so for poly(bithiophene) which formed collections of hollow polymer
spheres rather than a bicontinuous 3DOM structure [77].
The preparation of 3DOM conductors has been motivated
by the desire to increase their performance in redox
reactions by improving mass transfer kinetics between
liquid and solid phases.
2.12. Patterning
Designed features beyond macropores can be produced
by combining sphere templating with micromolding using
polydimethylsiloxane (PDMS) stamps (Fig. 6) [82,83]. In
this approach, PDMS stamps with micrometer-scale patterns are placed on a Si substrate, creating accessible
channels which can be filled with latex spheres. These
arrays are infiltrated with suitable solgel precursors, and
after sufficient drying and condensation time, the mold is
removed, and organic components are eliminated by
calcination. One particularly interesting example involved
solgels containing block-copolymers for the creation of
patterned structures with mesoporous walls around macropores.
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Fig. 6. Schematic of a patterning method to form hierarchically structured macroporous solids. Colloidal crystal growth on a substrate is
directed by a patterned PDMS stamp. Addition of a solgel precursor,
followed by stamp removal and calcination yields the patterned macroporous solid. Adapted from Ref. [82].
A. Stein, R.C. Schroden / Current Opinion in Solid State and Materials Science 5 (2001) 553564
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Acknowledgements
Portions of the work described here were funded by 3M,
Dupont, the David & Lucile Packard Foundation, the
McKnight Foundation, the NSF (DMR-9701507) and the
MRSEC Program of the NSF under Award Number DMR9809364.
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