Three-dimensional crystals of air spheres in titania (TiO2) with radii between 120 and 1000 nanometers were made by filling the voids in artificial opals by precipitation from a liquid-phase chemical reaction and subsequently removing the original opal material by calcination. These macroporous materials are a new class of photonic band gap crystals for the optical spectrum. Scanning electron microscopy, Raman spectroscopy, and optical microscopy confirm the quality of the samples, and optical reflectivity demonstrates that the crystals are strongly photonic and near that needed to exhibit band gap behavior.

We made large, highly ordered structures consisting of crystals of macropores in titania (TiO 2 ), by template-assisted growth. The crystals were characterized by synchrotron smallangle X-ray diffraction, X-ray absorption, wide-angle X-ray diffraction, scanning electron microscopy, optical microscopy, optical reflectivity, and Raman spectroscopy. Care was taken to make well-ordered templates, by slowly growing colloidal crystals from lightly charged polystyrene latex particles and carefully drying them to form opals. Solid material was deposited in the opal template by precipitation from an alkoxide hydrolysis. Subsequently, the samples were heated to 450 °C to form anatase TiO 2 and to remove the latex template, which resulted in a macroporous crystal, inverse opal, or air-sphere crystal. The macropores were close-packed and interconnected by windows, and small additional voids were located at interstices between the pores. The macropores were arranged on a face-centered cubic lattice with domains of more than 750 × 350 × 250 unit cells. The size polydispersity of the air spheres and mean-squared displacements from the lattice sites were studied for the first time. Both quantities were small, thus quantifying the excellent long-range order. The lattice parameter was shrunk by about 30% relative to the template, irrespective of the radii of the pores, while the long-range order persisted. The surfaces of the macropores appeared to be rough up to length scales of ∼10 nm, the sizes of the largest TiO 2 crystallites, with a roughness distribution following a power law. The volume fraction of the solid backbone was determined for the first time in situ by X-ray absorption and was found to be between 5 and 12 vol % TiO 2 . The wavelengths of the optical Bragg reflections were proportional to the radii of the air spheres. By the use of the measured TiO 2 fraction, the refractive index of the solid matrix was found to be 2.7 ( 0.4, in good agreement with the refractive index of massive anatase TiO 2 . We briefly explored the assembly of macropores in rutile-TiO 2 and in rock salt. It was concluded that macroporous crystals are highly effective three-dimensional photonic crystals.

A novel application of vibrational sum frequency generation (VSFG) is developed to study the molecular properties of the surface of submicron particles in suspension. The Rayleigh-Gans-Debye scattering theory is extended to extract the local molecular response from the macroscopic nonlinearly scattered spectral intensity. These results demonstrate the use of VSFG to investigate quantitatively the surface molecular properties of submicron particles, dispersed in solution. It provides information on the order and density of alkane chains and allows us to determine the elements of the local second-order surface susceptibility.

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We have measured spectrally resolved fluorescence lifetimes of dye incorporated in high-quality photonic crystals, made of colloidal spheres. The emission spectrum shows a pronounced Bragg notch. In contrast, the fluorescence lifetime does not depend on the interaction between light and the photonic crystal. The results are explained with a simple model of an atom in a cavity. The effects of homogeneous and inhomogeneous broadening of the emission spectrum of dye inside photonic crystals are discussed.

We have measured the optical fluorescence spectra of dye incorporated in high-quality photonic crystals made from colloids. The spectra reveal a stopgap that is due to Bragg reflection with strikingly reduced attenuation compared with plane-wave transmission. The modified attenuation is independent of the position of the sources in the sample and is brought about by diffuse scattering from defects near the surface. In the presence of a photonic bandgap, the diffuse component would disappear. Thus we have found a simple, unambiguous probe for the presence of photonic bandgaps.

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We study the competition between sedimentation, gelation, and liquid crystal formation in suspensions of colloidal gibbsite platelets of five different sizes at three ionic strengths. For large particles (with diameters of 350, 420, and 570 nm) sedimentation is initially the most important factor determining the macroscopic behavior. Only after the main part of the sample has sedimented in an amorphous phase, phase separation takes place. For the smallest particles (diameter 210 and 270 nm), it is the other way around: fast (within one week) phase separation or gelation takes place, after which sedimentation determines the final macroscopic appearance. We distinguish six different scenarios within this two-fold scheme and interpret these on the basis of the previously obtained phase diagram of colloidal gibbsite platelets (van der Beek, D.; Lekkerkerker, H. N. W. Langmuir 2004, 20, 8582).