A method for forming a periodic dielectric structure exhibiting photonic band gap effects includes forming a slurry of a nano-crystalline ceramic dielectric or semiconductor material and monodisperse polymer microsphere, depositing a film of the slurry on a substrate, drying the film, and calcining the film to remove the polymer microsphere there from. The film may be cold-pressed after drying and prior to calcining. The ceramic dielectric or semiconductor material may be titania, and the polymer microsphere may be polystyrenemicrosphere.