Colloidal crystal templating of three-dimensionally ordered macroporous solids: materials for photonics and beyond

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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 sol–gel 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.

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 template 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 sol–gel, 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 [1], [2], [3], [4], [5], [6], [7], [8], [9], [10], [11], ternary oxides [5], [12], [13], [14], chalcogenides [15], [16], [17], non-metallic and metallic elements [18], [19], [20], [21], [22], [23], [24], [25], [26], alloys [27], [28], hybrid organo-silicates [5], and polymers [29], [30], [31], [32], [33], [34], [35], [36], [37], [38]. 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. 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], [39], [40], [41], [42], [43].

Section snippets

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

Optical applications

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

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

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 DMR-9809364.

References (100)

  • B.T. Holland et al.

    Synthesis of macroporous minerals with highly ordered three-dimensional arrays of spheroidal voids

    Science

    (1998)
  • O.D. Velev et al.

    Microstructured porous silica obtained via colloidal crystal templates

    Chem Mater

    (1998)
  • J.E.G.J. Wijnhoven et al.

    Preparation of photonic crystals made of air spheres in titania

    Science

    (1998)
  • B.T. Holland et al.

    Synthesis of highly ordered, three-dimensional, macroporous structures of amorphous or crystalline inorganic oxides, phosphates, and hybrid composites

    Chem Mater

    (1999)
  • C.F. Blanford et al.

    Mater Res Soc Symp Proc

    (1999)
  • J.S. Yin et al.

    Template-assisted self-assembly and cobalt doping of ordered mesoporous titania nanostructures

    Adv Mater

    (1999)
  • H. Yan et al.

    General synthesis of periodic macroporous solids by templated salt precipitation and chemical conversion

    Chem Mater

    (2000)
  • A. Richel et al.

    Observation of bragg reflection in photonic crystals synthesized from air spheres in a titania matrix

    Appl Phys Lett

    (2000)
  • C.F. Blanford et al.

    Gems of chemistry and physics: macroporous metal oxides with 3D order

    Adv Mater

    (2001)
  • D.W. McComb et al.

    Synthesis and characterization of photonic crystals

    J Mater Chem

    (2001)
  • Y.A. Vlasov et al.

    Synthesis of photonic crystals for optical wavelengths from semiconductor quantum dots

    Adv Mater

    (1999)
  • Z.B. Lei et al.

    Fabrication and characterization of highly-ordered periodic macroporous barium titanate by the sol–gel method

    J Mater Chem

    (2000)
  • P.V. Braun et al.

    Electrochemically grown photonic crystals

    Nature

    (1999)
  • D.J. Norris et al.

    Chemical approaches to three-dimensional semiconductor photonic crystals

    Adv Mater

    (2001)
  • P.V. Braun et al.

    Electrochemical fabrication of 3D microperiodic porous materials

    Adv Mater

    (2001)
  • A.A. Zakhidov et al.

    Carbon structures with three-dimensional periodicity at optical wavelengths

    Science

    (1998)
  • P. Jiang et al.

    Preparation of macroporous metal films from colloidal crystals

    J Am Chem Soc

    (1999)
  • H. Yan et al.

    A chemical synthesis of periodic macroporous NiO and metallic Ni

    Adv Mater

    (1999)
  • O.D. Velev et al.

    A class of porous metallic nanostructures

    Nature

    (1999)
  • K.M. Kulinowski et al.

    Porous metals from colloidal templates

    Adv Mater

    (2000)
  • A. Blanco et al.

    Large-scale synthesis of a silicon photonic crystal with a complete three-dimensional bandgap near 1.5 micrometres

    Nature

    (2000)
  • P.M. Tessier et al.

    Assembly of gold nanostructured films templated by colloidal crystals and use in surface-enhanced raman spectroscopy

    J Am Chem Soc

    (2000)
  • J.E.G.J. Wijnhoven et al.

    Electrochemical assembly of ordered macropores in gold

    Adv Mater

    (2000)
  • P.M. Tessier et al.

    Structured metallic films for optical and spectroscopic applications via colloidal crystal templating

    Adv Mater

    (2001)
  • Yan H, Blanford CF, Smyrl WH, Stein A. Preparation and structure of 3D ordered macroporous alloys by PMMA colloidal...
  • H. Mı́guez et al.

    Germanium fcc structure from a colloidal crystal template

    Langmuir

    (2000)
  • S.H. Park et al.

    Macroporous membranes with highly ordered and three-dimensionally interconnected spherical pores

    Adv Mater

    (1998)
  • S.H. Park et al.

    Fabrication of three-dimensional macroporous membranes with assemblies of microspheres as templates

    Chem Mater

    (1998)
  • S.A. Johnson et al.

    Ordered mesoporous polymers of tunable pore size from colloidal silica templates

    Science

    (1999)
  • B. Gates et al.

    Fabrication and characterization of porous membranes with highly ordered three-dimensional periodic structures

    Chem Mater

    (1999)
  • P. Jiang et al.

    Template-directed preparation of macroporous polymers with oriented and crystalline arrays of voids

    J Am Chem Soc

    (1999)
  • J.F. Bertone et al.

    Thickness dependence of the optical properties of ordered silica-air and air-polymer photonic crystals

    Phys Rev Lett

    (1999)
  • M. Deutsch et al.

    Conjugated-polymer photonic crystals

    Adv Mater

    (2000)
  • T.B. Xu et al.

    Fabrication and characterization of three-dimensional periodic ferroelectric polymer-silica opal composites and inverse opals

    J Appl Phys

    (2000)
  • H. Mı́guez et al.

    Synthesis and photonic bandgap characterization of polymer inverse opals

    Adv Mater

    (2001)
  • Special issue on photonic crystals. Adv Mater...
  • Y. Xia et al.

    Self-assembly approaches to three-dimensional photonic crystals

    Adv Mater

    (2001)
  • O.D. Velev et al.

    Structured porous materials via colloidal crystal templating: from inorganic oxides to metals

    Adv Mater

    (2000)
  • Y. Xia et al.

    Monodispersed colloidal spheres: old materials with new applications

    Adv Mater

    (2000)
  • B. Gates et al.

    Fabrication and characterization of chirped 3D photonic crystals

    Adv Mater

    (2000)
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