We have developed boiling emulsifier-free emulsion polymerization recipes for the synthesis of monodisperse polystyrene (PS) nanospheres with diameters between ca. 100 and 300 nm. The morphologies of the nanospheres during growth were characterized and the results showed that the PS nanospheres with uniform structures could be synthesized rapidly by modifying the reaction conditions. These nanospheres readily self-assemble into three-dimensionally colloidal photonic crystal film and whose photonic band-stop could be tuned over the entire visible spectral region by altering the sphere diameters.
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