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