For three-dimensional photonic crystals, made either by top-down microfabrication or by bottom-up self-assembly approaches, to comply with the stringent requirements of optical telecommunication applications, their degree of structural perfection and optical quality must meet an exceptionally high standard. Only with such superior quality photonic crystals can their unique optical properties be harnessed in optical devices and circuits constructed from micrometer-sized optical components. In this paper, we present a new strategy for making silica colloidal crystal films with a sufficiently high level of structural perfection and optical quality to make it competitive as a practical route to photonic crystal optical components. The attainment of this goal takes due cognizance of three key synergistic factors in the film formation process. The first recognizes the necessity to prepare high-quality silica spheres, which are highly monodisperse, with a polydispersity index significantly better than 2%, and the second recognizes that the population of spheres must be devoid of even the smallest fraction of substantially smaller or larger spheres or sphere doublets. The latter turns out to have a minimal effect on the polydispersity index, and yet a major detrimental effect on the overall structural order of the film. The third concerns the film-forming method itself, which necessitated the development of a novel process founded upon isothermal heating evaporation-induced self-assembly (IHEISA) of spheres on a planar substrate. This new method has several advantages over previously reported ones. It is able to deposit very high-quality silica colloidal crystal film rapidly over large areas, with a controlled thickness and without any restrictions on sphere sizes.

In this tutorial review we highlight fundamental aspects of the physics underpinning the science of photonic crystals, provide insight into building-block assembly routes to the fabrication of different photonic crystal structures and compositions, discuss their properties and describe how these relate to function, and finally take a glimpse into future applications.

Slow photon, or light with reduced group velocity, is a unique phenomenon found in photonic crystals that theoreticians have long suggested to be invaluable for increasing the efficiency of light-driven processes. This thesis demonstrates experimentally the feasibility of using slow photons to optically amplify photochemistry of both organic and inorganic systems. The effect of photonic properties on organic photochemistry was investigated by tracing out the wavelength-dependent rate of photoisomerization of azobenzene anchored on silica opals. The application of slow photons to inorganic photochemical processes was realized by molding nanocrystalline titania into an inverse opal structure and investigating its photodegradation efficiency in relation to the photonic properties. Changes in the photodegradation efficiency were directly linked to modifications of the electronic band gap absorption as a result of the photonic properties.The highest enhancement of twofold was achieved when the energy of the slow photons overlaps with the electronic band gap absorption, such that the loss of light due to photonic stop-band reflection was significantly reduced. In addition, the strength of slowphoton amplification with respect to the macroscopic structural order was studied by ii introducing controlled disorder via the incorporation of guest spheres into the opal templates. For the first time, a correlation between structural order, photonic properties and a photochemical process was established. The ability to combine slow-photon optical amplification with chemical enhancement was further achieved by incorporating platinum nanoparticles in inverse titania opals where the platinum nanoparticles increased the lifetimes of the higher population of electron-hole pairs arising from slow photon.Overall, various important factors governing the slow photon enhancement were investigated in detail, including the energy of the photonic stop band, angle dependence, thickness of the film, degree of structural order, filling fraction of the dielectric material and diffusion of a second medium if present. Theoretical calculations based on scalarwave approximation in support of the experimental findings were provided wherever possible. The findings provide a blueprint for achieving optical amplification using slow photons in the broad range of photochemical or photophysical processes.iii

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Highly monodisperse spherical silica nanoparticles with diameters ranging from ca. 15 to 200 nm were prepared using an environmentally friendly water-based synthesis. The size of the spheres can be precisely controlled by using a facile regrowth procedure in the same reaction media. Furthermore, these monodisperse silica spheres can be successfully used as seeds in the well-established Stöber silica preparation. The regrowth approach allows for easy incorporation of functional additives. High monodispersity and charge stabilization renders these nanoparticles highly suitable for close-packed array formation and colloidal templating.

Monodisperse decahedral silver nanoparticles have been synthesized with excellent shape selectivity (>99%) by novel photochemical transformation of aqueous silver nanoparticle precursors. The procedure employs intense white light and is very robust and reproducible. The precursor solution transforms from a mixture of shapes dominated by small silver platelets into the decahedra, driven by superior stability of decahedral seeds. The decahedra size can be varied by adjusting intensity and spectral properties of the irradiating light. Furthermore, the decahedra can be controllably photochemically regrown to larger sizes, while fully preserving the monodispersity. Silver decahedra exhibit remarkable optical properties featuring a bicolored appearance due to the interplay between plasmonic adsorption and scattering. The sharp plasmon resonances of silver decahedra were tunable from 455 to 570 nm through size variation. Finally, silver decahedra exhibited greatly superior enhancement of Raman scattering compared to other silver nanoparticles. Overall, our findings highlight the importance of pentagonal symmetry in metal nanoparticles and offer a powerful general approach to monodisperse shapes via selective regrowth of appropriately identified and stabilized intermediates.

Monodisperse size-controlled faceted pentagonal silver nanorods were synthesized by thermal regrowth of decahedral silver nanoparticle (AgNPs) in aqueous solution at 95 degrees C, using citrate as a reducing agent. The width of the silver nanorods was determined by the size of the starting decahedral particle, while the length was varied from 50 nm to 2 mum by the amount of new silver added to the growth solution. Controlled regrowth allowed us to produce monodisperse AgNPs with a shape of elongated pentagonal dipyramid (regular Johnson solid, J(16)). Faceted pentagonal particles exhibited remarkable optical properties with sharp plasmon resonances precisely tunable across visible and NIR. Due to the narrow size distribution, faceted pentagonal silver nanorods readily self-assembled into the 3-D arrays similar to smectic mesophases. Hexagonal arrangement in the array completely overrode five-fold symmetry of the nanorods. Overall, our findings highlight the importance of pentagonal symmetry in metal nanoparticles and offer a facile method of the preparation of monodisperse AgNPs with controlled dimensions and plasmonic properties that are promising for optical applications and functional self-assembly.

Experimental and theoretical studies of the self-propelled motional dynamics of a new genre of catalytic sphere dimer, which comprises a non-catalytic silica sphere connected to a catalytic platinum sphere, are reported for the first time. Using aqueous hydrogen peroxide as the fuel to effect catalytic propulsion of the sphere dimers, both quasi-linear and quasi-circular trajectories are observed in the solution phase and analyzed for different dimensions of the platinum component. In addition, well-defined rotational motion of these sphere dimers is observed at the solution-substrate interface. The nature of the interaction between the sphere dimer and the substrate in the aqueous hydrogen peroxide phase is discussed. In computer simulations of the sphere dimer in solution and the solution-substrate interface, sphere-dimer dynamics are simulated using molecular-dynamics methods and solvent dynamics are modeled by mesoscopic multiparticle collision methods taking hydrodynamic interactions into account. The rotational and translational dynamics of the sphere dimer are found to be in good accord with the predictions of computer simulations.