Current Opinion in Solid State and Materials Science 5 (2001) 553564

Colloidal crystal templating of three-dimensionally ordered

macroporous solids: materials for photonics and beyond
Andreas Stein*, Rick C. Schroden
Department of Chemistry, University of Minnesota, 207 Pleasant St. SE, Minneapolis, MN 55455, USA

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).

plate to obtain a porous inverse replica. Fig. 1 shows

electron micrographs of typical 3DOM structures. Pore
sizes of a few hundred nanometers, together with the order
of the pore structure, endow 3DOM materials with optical
and photonic crystal properties, which may be utilized in
waveguides, low-threshold lasers, and sensors. With highly
accessible surfaces and large pore sizes these materials
may be useful for chromatography, catalysis, and as
bioactive materials. Multiple pore sizes may permit selective uptake, stabilization, separation, or release of small
and large guest molecules. Furthermore, the skeletal
dimensions can be small enough to produce size-dependent
properties (i.e., nanosize effects). Combinations of these
properties within a given structure may lead to new
multifunctional materials.
The colloidal crystal templating approach is very general
and can be applied to solgel, salt solution, CVD, electrochemical, nanocrystalline, and other precursors to produce
3DOM insulators, semiconductors, and metals of many
different compositions. The range of 3DOM materials
prepared so far includes simple oxides [111], ternary
oxides [5,1214], chalcogenides [1517], non-metallic and
metallic elements [1826], alloys [27,28], hybrid organosilicates [5], and polymers [2938]. Despite the overall
simplicity and generality of colloidal crystal templating,
optimization of chemical processes and precursor / template
interactions must be tailored for each class of precursor to
control the structure and substructure of the framework.

1359-0286 / 02 / $ see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S1359-0286( 01 )00022-5

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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

2.1. The colloidal crystal template

The colloidal crystal templates used for the generation
of 3DOM materials are prepared from monodisperse silica
or polymer spheres, including polystyrene (PS) and poly(methyl methacrylate) (PMMA). The spheres can be
arranged into close-packed structures by many methods
(for recent reviews, see Refs. [44,45]) including gravity
sedimentation, centrifugation, vertical deposition, templated deposition, electrophoresis, patterning, and controlled drying, which provide 26 vol% void space for
penetration by fluid precursors. Multilayers or gradient
layers of spheres with different radii have also been grown
[46,47]. Colloidal crystals can either be used directly as
templates, or annealed or sintered to increase their stability
and ensure interconnection.
The surface chemistry of the sphere templates influences
framework formation. Strong wetting interactions aid
penetration and formation of a continuous network. Strong
interactions with dilute precursors typically lead to films
around the spheres, whose thickness can be increased by
multiple exposures [11]. Framework solidification can be
affected by catalytic groups, such as adventitious carboxylic acid groups on PS spheres which catalyze hydrolysis and condensation of solgel precursors [5], and
thiol-groups on silica spheres which serve as anchors for
nanocrystalline metals that catalyze further metal deposition [19].
Porous structures are produced by removal of the
templates. With polymers, this is often carried out by
calcination simultaneously with conversion of the precursor to a solid in the desired phase. If solidification is
feasible at low temperatures spheres can also be extracted
with appropriate solvents, such as toluene or tetrahydrofuran / acetone mixtures. Photo-degradation of polymer
templates has also been noted [38]. Silica sphere templates
are removed by dissolution in aqueous HF solutions.
Fig. 1. (A) Scanning electron micrograph (SEM) of a polystyrene (PS)
colloidal crystal. (B) Low magnification SEM of a single particle of
3DOM titania. (C) High magnification SEM of 3DOM silica showing
close-packed macropores, which are interconnected through smaller
windows. The white regions are walls of the first layer, the gray regions
are walls of the second layer, and the black regions are voids. (D)
Transmission electron micrograph (TEM) of 3DOM silica, which has
amorphous walls. The dark regions are the silica walls. (E) TEM of
3DOM nickel, which has nanocrystalline walls. Small grains (appearing
as dark spots) fuse together to form the 3DOM skeleton.

2.2. Solgel chemistry

Alkoxide precursors and alkoxide / metal acetate mixtures have been employed to create 3DOM metal oxides by
solgel chemistry (Fig. 2). Precursors are used directly [2]
or diluted in alcohol, in which case repeated filling may be
necessary to form an interconnected network [4]. As layers
build up on the sphere surfaces, they can cause pore

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Fig. 2. Schematic of the preparation of ordered macroporous metal

oxides by solgel chemistry. Latex colloidal crystal templates are
infiltrated with solgel precursors, dried, then calcined to remove the
template and cure the walls of the macroporous solid. Adapted from Ref.
[2].

blockage, resulting in small openings at the intersections of

the solid [4,9,11]. Precursors may be prehydrolyzed before
infiltration [1,3], or hydrolysis can be induced by moisture
within the template or atmosphere [2,5]. Hydrolysis and
condensation can be catalyzed by acidic surface groups on
the spheres [2,5], by added acid or base, or by cationic
surfactants on the polymer sphere surfaces [1,3]. The final
void dimensions are often smaller than the original sphere
diameters (typically 1530%) due to a large volume loss
during the solgel process as alcohol is lost.
Examples of oxides prepared by solgel methods include those of Si [1,3,5], Ti [2,4,5,9,11,48], Zr [5], Al
[2,5,6,49], W, Fe, and Sb [5,6]. Additional elements can be
incorporated either by subsequent doping (e.g., incorporation of the spinel Co 2 TiO 4 into 3DOM titania [7]), or by
employing mixed metal precursors, such as mixed alkoxides (e.g., to prepare yttria-stabilized zirconia [5]) or
alkoxide / acetate mixtures (e.g., titanium butoxide mixed
with barium acetate or lead acetate to produce macroporous BaTiO 3 [14] or PbTiO 3 [13]).
For a given composition, the processing temperature
during template removal influences the crystallographic
phase of the 3DOM walls. In nanocrystalline materials, if
grains grow to dimensions comparable to the macropore
size, the periodicity is reduced and eventually lost. Thus, to
maintain an ordered 3DOM structure, grain growth must
be carefully controlled by choice of reaction temperature
and use of chemical additives [10]. For example, amorphous titania formed from the alkoxide upon solvent
extraction of the template, whereas anatase formed after
calcination at 4508C [5]. Similarly, amorphous alumina
walls were obtained by calcination at 4508C [2,5,6],

555

whereas cubic alumina formed at 10008C (Blanford CF,

Carter CB, Stein A, unpublished results). An a-alumina
phase was prepared from an aluminum nitrate / ammonium
hydroxide solution after calcination at 11008C [49].
In addition to the polymer sphere colloidal crystals used
above, silica templates have been investigated. 3DOM
titania films were formed by filling silica sphere opals on a
quartz substrate with an alcoholic / aqueous solution of
titanium ethoxide [48]. The material was calcined at
temperatures up to 10508C to effect densification of the
anatase walls, causing significant shrinkage, similar to
observations with polymer-based templates.
Multiple levels of porosity can be attained for macroporous silicates by employing dual templating methods.
3DOM silica prepared from alkoxide precursors contains
amorphous walls with a wide distribution of mesopores
from 2 to 40 nm [5]. Addition of cetyltrimethylammonium
hydroxide surfactant to the synthesis gel for 3DOM silica,
followed by calcination, produced a structure with macropores (a few hundred nm) and uniform mesopores (,4
nm), and increased the surface area from 200 to over 1300
m 2 / g [5]. Other surfactants, including amphiphilic triblock-copolymers, have also been employed as secondary
templates [5052]. Dual templating methods have also
yielded macroporous zeolites [53]. In this case, tetrapropylammonium hydroxide [54] and PS were used to
produce 3DOM materials with thin (20220 nm) silicalite
walls and 0.5 nm micropores around larger spheroidal
voids. This material combines the advantages of facile
transport through the macropores, selectivity of the zeolitic
micropores, and short diffusion paths for potential guest
species.
The solgel process is also amenable to the synthesis of
hybrid organicinorganic macroporous silicates. 3DOM
silicates with organic surface functional groups or organic
linkers within a silicate framework can be prepared from
organosiloxanes RSi(OR9) 3 or bis(organosiloxanes)
(R9O) 3 SiRSi(OR9) 3 , in a manner similar to mesoporous
sieves [55], but using colloidal crystals rather than surfactants as templates [5]. Examples include macroporous
silicates with vinyl- or cyanoethyl-surface groups [5], and
macroporous organosilicates, in which Si framework atoms
are linked by CH 2 CH 2 groups (Melde BJ, Skugrud K,
Stein A, unpublished results). Solvent extraction methods
are usually required for template removal to prevent loss of
organic functional groups (exception: phenyl groups [56]).
Organic functionalities have also been directly incorporated in hierarchical meso / macroporous structures by
using dual templating (surfactant and PS) with the addition
of a dye-functionalized precursor to the synthesis gel [57].

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.

2.4. Salt-precipitation and chemical conversion

Precipitation and crystallization reactions within a colloidal crystal template provide an alternative to condensation or polymerization processes. This procedure is less
sensitive to atmospheric humidity and permits formation of
ordered structures for compositions difficult to prepare by
solgel methods. 3DOM NaCl can be prepared from a

saturated salt solution [4]. Templated precipitation of metal

salts (acetates, oxalates, oxides) within a polymer colloidal
crystal and subsequent chemical conversion provides a
route to macroporous metal oxides, metals, and metal
carbonates [8,10,20]. For metal oxides, an annealed PS or
PMMA colloidal crystal is immersed in a metal salt
solution. If the metal salt has a low melting point (e.g.,
certain metal acetate hydrates) it is converted to a metal
oxalate by treatment with oxalic acid solution. Upon
calcination, ordered metal oxides or carbonates (Co 3 O 4 ,
Cr 2 O 3 , Fe 2 O 3 , MgO, Mn 2 O 3 , NiO, ZnO, CaCO 3 ) are
obtained in an oxidizing atmosphere, and metals (Ni and
Co) are obtained in an inert atmosphere [60]. Macroporous
Ni prepared in this manner has a surface area exceeding
200 m 2 / g, and ignites if exposed to air rapidly [60].
3DOM alloys have been prepared by the same method
using mixed precursors [27].
Grain sizes of 3DOM materials, which affect the order,
surface area, mechanical, and optical properties, can be
controlled by thermal and chemical methods. For Fe 2 O 3 ,
the oxalate-based synthesis produced materials with smaller grains and more ordered products than the solgel
synthesis [6,8]. In situ transmission electron microscopy
(TEM) demonstrated the effect of temperature on the
structure of 3DOM Fe 2 O 3 prepared from iron oxalate
precursors [10]. When heated to 6508C grains grew 50%
within 15 min, and more than doubled in size by 7508C,
while maintaining an ordered structure. Chemical control
of grain size has been demonstrated with 3DOM zirconia
samples. Average grain sizes of 1030 nm were obtained
with zirconium n-propoxide precursors [2], compared to
only a few nm for zirconium oxalate precursors with
sulfuric acid as an additive [10,61].

2.5. Chemical vapor deposition

Various chemical vapor deposition (CVD) techniques
have been employed to create 3DOM structures involving
group 14 elements. Graphitic carbon was obtained using
CVD with propylene around silica spheres, with periodicity, pore size, and degree of carbonization dependent on
temperature [18]. These properties affected electrical conductivity, magnetoconductance, and optical spectra of the
materials [62]. A dielectric diamond film was prepared on
a macroporous carbon skeleton by seeding opals with
nanocrystalline diamond, which acted as nucleation sites
for further diamond formation, and depositing carbon from
a hydrogen / methane plasma [18].
3DOM Si with a refractive index contrast high enough
to obtain a complete photonic bandgap was prepared by
exposing a sintered silica opal to disilane [23]. The filling
factor increased with deposition temperature between 250
and 3508C with complete filling by Si nanoparticles
achieved at higher temperatures. Annealing at 6008C
produced a connected silicon skeleton that maintained its
periodicity after template removal with HF.

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557

Room temperature CVD, which allows for the use of

PMMA opal templates, was used to prepare thin films
(2040 monolayers) of macroporous SnS 2 [63,64]. The
colloidal crystal was exposed to SnCl 4 vapor and H 2 S gas
at ambient temperature and pressure to produce interconnected SnS 2 nanoparticles that remained stable during
PMMA extraction with THF. Due to the relatively loose
structure of nanoparticles within the walls, the refractive
index was only ca. half that of bulk SnS 2 (n bulk 53.2).

2.6. Spraying techniques

Various spraying techniques, including spray pyrolysis
[65], ion spraying [66], and laser spraying [66], have been
successfully used in the preparation of periodic macroporous structures. These techniques are most suitable for
thin film preparation, since penetration is limited with
spraying. 2D macroporous titania (anatase) was synthesized by using spray pyrolysis to deposit titanyl acetylacetonate in ethanol solution on an array of silica spheres on a
flat glass support, annealing, and removing silica by HF
[65]. Ion spraying was employed for the preparation of 2D
macroporous Au [66]. Pulsed laser deposition was used to
create macroporous silicon films with a thin layer of
surface oxide [66].

2.7. Nanocrystal deposition and sintering

To minimize shrinking and cracking of 3DOM structures during template removal, methods using preformed
nanoparticle precursors have been developed (Fig. 3). The
smaller nanoparticles are codeposited with colloidal
spheres, filling the interstitial spaces. Because the
nanoparticles are already in their desired phase, shrinkage
of the pores is limited to 510%. Products prepared by this
method range from insulators [67] to semiconductors [12]
and metals [21]. Thin films (1020 mm) of macroporous
titania prepared from nanocrystalline titania and PS
spheres, contained ordered domains up to 503100 mm
[6870]. The degree of order depended on the drying rate
and orientation of the flat substrate during deposition, with
best quality for vertical deposition and worst for horizontal
[67].
Hierarchical pore structures can be created by assembling pre-synthesized zeolitic nanocrystallites in polymer
templates [71,72]. For example, silicalite has been prepared in colloidal particles (3080 nm) and infiltrated in
PS colloidal crystal templates. After calcination a sample
containing zeolite micropores, templated macropores, and
mesopores between intercrystalline voids was obtained.
In the preparation of 3DOM CdSe from nanocrystals, a
size dependent melting point was observed [12]. CdSe
nanocrystals were slowly infiltrated into silica opals over
12 months. Sintering at 6008508C and HF etching
produced CdSe inverted opals. Melting of the nanoparticles occurred at 6508C, much below the melting point of

Fig. 3. Schematic of the formation of ordered macroporous solids from

nanocrystalline precursors. Latex or silica spheres and preformed
nanoparticles settle into a colloidal crystal of spheres filled with
nanoparticles. The nanoparticles are fused together by heating and the
template is removed to produce the macroporous solid.

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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A. Stein, R.C. Schroden / Current Opinion in Solid State and Materials Science 5 (2001) 553564

2.8. Oxide and salt reduction

A range of syntheses exist for preparing 3DOM metals
and other elemental compositions in their reduced states.
One approach involves the reduction of 3DOM metal
oxides in a hydrogen atmosphere, e.g., reduction of NiO to
Ni [20]. During reduction the wall grains tend to grow,
resulting in a lower surface area than the starting oxide.
Nonetheless, the periodic structure is maintained. The
surface areas of samples prepared by this method are lower
than those of 3DOM metals synthesized directly from
oxalate precursors (see above).
3DOM Ge was prepared from the oxide by hydrogen
reduction using a silica opal template that was not removed
until the final reduced product formed [28]. First, a
tetramethoxygermane precursor was infiltrated into the
opal to form GeO 2 . During subsequent reduction in
hydrogen at 5508C, grain growth resulted in poor connectivity between the grains. The GeO 2 and Ge formation
processes were therefore repeated several times to maximize filling and connectivity. After template removal by
HF etching the 3DOM Ge product exhibited a high
dielectric contrast, an important property for photonic
crystal applications (see later).
A related method involved reduction of salts within a
colloidal crystal template [73]. Silica colloidal crystals
were filled with aqueous solutions of H 2 PtCl 6 ?6H 2 O or
AuCl 3 , dried, and reduced in hydrogen at 1508C. The
filling and reduction steps were repeated to maximize
filling. Template removal produced mesoporous or macroporous Au and Pt. The Au sample was not as ordered as
the porous Pt, presumably due to less wetting of the silica
surface.

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].

Gold deposited potentiostatically from HAuCl 4 solution

produced ordered structures with silica colloidal crystals;
however, only small gold flakes with a few macropores
were obtained with PS templates [25]. Gold structures
prepared by constant current electrodeposition using commercial gold plating solutions and a silica opal template
collapsed after template etching [74]. Thin films of ordered
macroporous Pt, Pd, and Co have been prepared with PS
templates by electrochemical reduction of [PtCl 6 ] 22 ,
[PdCl 4 ] 22 , or [Co(Ac) 2 ] in aqueous solution [76]. 3DOM
Ni has been prepared by electrodeposition from a plating
bath containing NiSO 4 ?6H 2 O, H 3 BO 3 , and NH 4 Cl [66], or
from a commercial plating solution [74]. A macroporous
SnCo alloy was synthesized from a plating bath containing
SnCl 2 , CoCl 2 , and K 4 P2 O 7 ?3H 2 O [66].
Electrochemical polymerizations have produced electrically conducting macroporous poly(pyrrole), poly(aniline),
and poly(bithiophene) around PS or silica templates
[77,78]. Shrinkage was observed for poly(pyrrole) and

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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.

2.10. Electroless deposition

3DOM metals can be synthesized by electroless deposition, i.e., without an electric circuit, by using templates
modified with catalysts for metal plating. This approach
has been used for the synthesis of 3DOM Ag, Au, Co, Cu,
Ni, and Pt [19]. Thiol-functionalized colloidal silica on
glass slides is immersed into a solution of gold nanocrystals (which act as catalysts), annealed, then immersed into
metal plating baths. Macroporous films are obtained after
HF etching. 3DOM Ni formed free-standing films, whereas
Ag and Au films fragmented.
Another electroless approach, oxidation polymerization,
has been employed for the synthesis of 3DOM poly(aniline) [79]. Aqueous aniline hydrochloride was infiltrated into a wet PS colloidal crystal template where in situ
oxidation by K 2 S 2 O 8 , followed by template removal in
THF, yielded porous poly(aniline). In situ polymerization
is particularly useful for the preparation of macroporous
conducting polymers, since they tend to have low solubility in common solvents making them difficult to introduce directly into a colloidal crystal array.

2.11. Fabrication from coreshell spheres

Using coreshell spheres as templates allows good
control of the 3DOM wall thickness [80]. Macroporous
titania was produced with this method by coating PS
spheres with polyelectrolyte layers, packing by centrifugation, infiltration with titanium isopropoxide and drying
(multiple cycles), and calcination. The wall thickness
increased with the number of polyelectrolyte layers. When
PS spheres coated with layers of polyelectrolyte and silica
nanoparticles were used as a template, macroporous TiO 2 /
SiO 2 was obtained. This approach also lends itself to the
formation of macroporous silicates with zeolitic walls (Fig.
5) [81]. Alternate deposition of negatively charged zeolite
nanoparticles (silicalite) and positively charged polyelectrolyte layers (poly(diallyldimethylammonium chloride)),
produced materials with continuous networks of relatively
ordered macropores, random mesoporosity between the
zeolite grains, and the microporosity of silicalite.

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

Fig. 5. Schematic of the fabrication of macroporous silicates with zeolitic

walls by the coreshell building block approach. Latex spheres are
primed with a polyelectrolyte, then layers of oppositely charged zeolite
nanoparticles (silicalite) and polyelectrolyte are alternately deposited until
a desired wall thickness is achieved. Centrifugation produces a closepacked structure, and calcination removes the organic components,
leaving a macroporous solid. Adapted from Ref. [81].

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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A. Stein, R.C. Schroden / Current Opinion in Solid State and Materials Science 5 (2001) 553564

were obtained in cases with weak interactions between

precursors and the polymer template (e.g., for TiO 2 /
PMMA), while hollow spheres resulted if the polymer
template was wetted strongly by the precursors (e.g., for
TiO 2 / PS). Multi-composition shells could be generated by
sequential deposition of different precursors. Distortion of
the polymer template permitted fabrication of ellipsoidal
colloids. Non-polymeric 3DOM templates have also been
employed, including 3DOM NiO for electrochemical templating of gold sphere arrays [86], and macroporous
conductive carbon for templating low melting metals (Bi,
Pb, Sb, Te) near their melting points [86].

3. Materials properties and potential applications

3.1. Optical applications

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].

2.13. Inverse opal templating

3DOM materials (or inverse opals), generated by
templating with opal structures, may in turn be used as
templates to form another opal replica. Using this templating procedure a mesoporous polymer mold, that had been
prepared from silica colloidal crystals, was used to produce
small silica replica particles [31]. The order of the silica
replicas was limited, possibly due to the relatively small
pore sizes in the mold. A more ordered replica opal
composed of mesoporous silica was obtained by infiltrating
a 3DOM PS mold with a solgel precursor for mesoporous
sieves, followed by PS removal by solvent extraction or
calcination [84]. This method permits assembly of ordered
mesoporous sieve particles with controlled diameters and
dispersities. A similar approach was used to form spherical
and ellipsoidal colloids of a wide range of compositions
(TiO 2 , ZrO 2 , Al 2 O 3 , polypyrrole, PV, CdS, AgCl, Au, Ni)
with narrow size distributions [85]. Solid colloidal crystals

Dielectric 3DOM structures are promising materials for

photonic crystals materials with foreseeable applications involving the control of photons (waveguides, microcavity lasers, inhibitors of light emission) [39]. In order
to obtain the complete photonic bandgaps desired for these
applications various requirements, including sub-micrometer dimensions, low solid fractions, high refractive index
contrast (ca. 3) [87], optical transparency, and specific 3D
periodicity must be met. Control of dimensions and low
solid fractions are relatively easily met with colloidal
crystal templating. A more difficult aspect involves the
choice of wall material. 3DOM titania has a transparent
window in the visible, but in the form of anatase it exhibits
a broad stop band, not a full bandgap [4,9,11,48,8890].
The optical stop band width and peak attenuation are
controllable by the number of layers and the dielectric
contrast between walls and voids [34]. Complete bandgaps
are possible with 3DOM Si [23] or Ge [28], but absorptions in the visible spectrum limit applications to the
near-IR region. Other materials with sufficiently high
refractive index in bulk form (e.g., SnS 2 ) often exhibit
much lower refractive indices in 3DOM solids [63].
Perhaps the most difficult requirement to achieve synthetically is better control of the periodicity with limited or
controlled defects. Numerical simulations have shown that
2% fluctuations in lattice constant can close a photonic
bandgap even for high refractive index contrasts [91,92].
Most of these challenges can be addressed by process
optimization, and chemical syntheses of photonic crystals
are likely to remain viable competitors to lithographic
techniques.
Several optical properties with less stringent structural
requirements have been investigated. One involves
changes in color (stop band position and intensity) as a
3DOM material is filled with fluids of varying refractive
index [61]. The stop band position varies nearly linearly
with refractive index of the penetrating fluid, and can be
controlled by adjusting the pore spacing, and the thickness,

A. Stein, R.C. Schroden / Current Opinion in Solid State and Materials Science 5 (2001) 553564

density, and composition of the walls. If luminescent dyes

are incorporated in the structure [57,93], or the 3DOM
structure exhibits intrinsic luminescence [94], overlaps
between stop bands and emission bands can be used to
suppress the luminescence in a controlled manner [95].
When optically birefringent nematic liquid crystals are
infiltrated in 3DOM Si, it is possible to tune the photonic
bandgaps by aligning the liquid crystals in an electric field
[96]. A promising new application of thin macroporous
gold films involves surface-enhanced Raman spectroscopy
[24,26]. The periodicity of the structure appeared to play
an important role in enhancing the Raman signal of probe
molecules, as the signal intensity with a macroporous film
was twice that of an unstructured film.

3.2. Catalytic applications

Similar to other silicates, 3DOM silica can be used as a
support for catalytically active species. A recent study
compared the influence of pore structure on the activity of
various silica samples modified with transition metal-substituted polyoxometalates (TMSP) [97]. Clusters of the
type
[Co II (H 2 O)PW11 O 39 ] 52
and
II
102
[SiW9 O 37 hCo (H 2 O)j 3 ]
were chemically anchored to
amine-functionalized macroporous (350450 nm),
and non-porous silica surfaces.
mesoporous (3060 A),
Whereas the mesoporous silica support had the highest
surface area, partially restricted access of the clusters to the
mesopore channels limited the cluster loading. The more
open macroporous structure supported more TMSP clusters
per amine anchoring group. Because the clusters were
attached datively to the surface, they were retained in
catalytic reactions involving the epoxidation of cyclohexene to cyclohexene oxide, with comparable conversion and
reaction rates on all three supports.
Redox active g-decatungstosilicate clusters (g-SiW10 O 36 )
were incorporated into the wall structures of 3DOM silica
by a direct synthesis approach [98]. The clusters were
reacted with TEOS, with or without addition of 1,2bis(triethoxysilyl)ethane as a linking group, and the mixture was molded by a polymer colloidal crystal, using the
methods described above. The linking group connected the
clusters covalently to the silica support. When the polymer
spheres were removed by extraction, the intact polyoxometalate clusters remained attached to the hybrid 3DOM
structures and were highly dispersed throughout the walls.
The materials exhibited catalytic activity for the epoxidation of cyclooctene.
3DOM a-alumina was used as a support for metallic
silver and was tested as a catalyst for the conversion of
ethylene to ethylene oxide [49]. The productivity (mass of
ethylene oxide produced per hour per gram of catalyst)
was significantly greater for this macroporous support than
for a commercial silver-modified a-alumina catalyst, while
selectivity and conversion were slightly higher for the
commercial material.

561

3.3. Bioglass applications

Bioactive glasses are materials that can bond to bone
through a hydroxy apatite layer that spontaneously deposits
on their surface in a body environment. They may be
surface reactive or bioresorbable and can be used as bone
graft substitutes. Conventionally, these materials are prepared from the melt of glass components or by solgel
methods [99]. Recently, the colloidal crystal templating
method was adapted to the synthesis of bioactive glass
structures with uniform macropores (3DOM CaO / SiO 2 )
[100]. When immersed in simulated body fluids (resembling the inorganic composition of human blood), apatite
growth occurred more rapidly for 3DOM bioactive glasses
than for the corresponding control samples without macropores. Amorphous calcium phosphate clusters formed on
the 3DOM walls within 3 h and hydroxy apatite aggregates
replaced much of the original structure after 4 days. The
excellent bioactivity was attributed to the highly accessible
surface of the 3DOM materials.

4. Conclusions and outlook

The development of the new field of colloidal crystal
templating has occurred very rapidly over the last few
years. The field is driven not only by the aesthetics of the
resulting 3DOM structures and the versatility of the
method, but also by the exciting properties that 3DOM
materials promise to exhibit for the benefit of several key
technologies. Studies of physical and chemical properties
of 3DOM solids are just emerging, as control over the
quality of the materials is being improved. This review has
described many techniques for the preparation of macroporous solids of numerous compositions. Often a particular
composition can be obtained by more than one route, but
the phase, nanostructure, and properties may vary with the
production method.
In order to tailor better materials, it will be necessary to
gain greater understanding of several issues. Much research is currently aimed at advances in colloidal crystallization techniques, including defect minimization and
control. So far, only a limited number of template compositions (mainly silica, PS, PMMA) have been employed.
New template compositions may be beneficial for easier
template removal, or possibly for providing additional
functionality. Advances will be possible with a better
understanding of interactions between the templates and
precursors. Functional groups on the sphere surfaces
influence wetting, penetration, and solidification to allow
more uniform products. This chemistry influences sample
shrinkage during template removal and grain size, which in
turn affects the smoothness, density, effective refractive
index, reactive surface area of the wall, and mechanical
properties. As these synthetic issues are addressed, 3DOM
materials will move closer to desired applications.

562

A. Stein, R.C. Schroden / Current Opinion in Solid State and Materials Science 5 (2001) 553564

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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