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Three‐dimensional photonic crystals made from an organic semiconductor—poly(p‐phenylenevinylene) (PPV)—are studied here. Their synthesis (via colloidal assembly), physical appearance, and optical properties are investigated. The Figure shows optical micrographs of a polished PPV photonic crystal under ultraviolet (top) and white (bottom) light illumination, indicating fluorescence and optical diffraction, respectively (see also cover).

We show how optical microscopy can be used to study the optical properties of a single crystalline domain in a self-assembled photonic crystal. By measuring spatially resolved reflection and emission spectra from a synthetic opal, inhomogeneities due to averaging over inherent disorder can be avoided. From “defect-free” reflection and emission spectra, the intrinsic photonic band structure can be extracted and inhibition of spontaneous emission can be verified.

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