Colloidal crystal approach to the fabrication of photonic band gap materials
Colvin, Vicki L.
Doctor of Philosophy
Planar single-crystalline colloidal crystals are fabricated by exploiting the spontaneous crystallization of monodisperse silica spheres into close-packed arrays using a convective self-assembly method. Film thicknesses ranging from single monolayers to over 200 layers can be precisely controlled through varying solution concentration and colloid diameter. These high quality periodic arrays exhibit partial photonic band gaps, whose positions and band width depends on the sphere diameters and the number of layers. Their optical transmission is well described by the scalar wave approximation to Maxwell's equations. The thickness dependence of the photonic band gap has also been studied for the first time. Superlattice colloidal crystals comprised of alternating layers of different sphere sizes can also be formed by the convective self-assembly method. The resulting photonic crystal structures exhibit optical properties which resemble the superposition of the properties of each individual component, with additional structure that suggests the onset of superlattice-type miniband formation. These superlattice structures thus provide a new way to couple light into and out of photonic crystals. These planar colloidal films are then used as scaffolds to make macroporous materials with crystalline arrays of voids. Macroporous polymers are formed by filling the interstitial area with monomer which is subsequently polymerized. The silica templates can be removed by etching with hydrofluoric acid. The large voids defined by the silica colloids are not isolated, but rather interconnected by a network of monodisperse smaller pores whose sizes can be controlled by varying the polymerization temperature. These membranes exhibit striking optical properties and their photonic band gap behavior agrees well with theory. A seeded electroless deposition technique has also been developed for forming macroporous metal membranes. The gold particles attached to the thiol-coated silica colloidal crystals can catalyze the electroless deposition of metals (Ag, Au, Cu, Ni, Co, Pt) inside the arrays and lead to fully dense macroporous metallic films after silica removal. These samples are mechanically robust, electrically active, and possess unusual diffractive optical properties. The macroporous polymers are again used as hosts to grow a wide variety of complex and unusual colloidal structures. This modern "lost-wax" method effectively capitalizes on the perfection of the starting colloids and the resulting template voids to form monodisperse colloids and their colloidal crystals. A wide variety of highly monodisperse inorganic, polymeric and metallic solid and core-shell colloids, as well as hollow colloids with controllable shell thickness and their colloidal crystals can be made. The polymer template can be uniformly deformed to alter colloidal shape and elliptical particles with precisely controlled aspect ratios are formed for the first time. The hollow sphere titania colloidal crystals exhibit partial photonic band gaps, whose spectral position and width depend on the thickness of the shell and on the overlap between adjacent spheres, in a manner consistent with numerical simulations.