Photothermal patterning of microgel/gold nanoparticle composite colloidal crystals.

We present a new method for laser direct writing in self-assembled hydrogel microparticle colloidal crystals via photothermal excitation of co-assembled colloidal Au particles. Close-packed colloidal crystals are assembled from approximately 224 nm diameter, thermoresponsive, poly-N-isopropylacrylamide hydrogel microparticles (microgels); these crystals display sharp Bragg diffraction peaks in the mid-visible region of the spectrum due to the periodic dielectric function of the assembly. Raising the temperature of the crystal above the characteristic volume phase transition temperature of the microgel particles results in a reversible melting of the crystalline material due to the particle-based deswelling event. This transition can be used either to anneal defects from the crystalline material or to controllably and reversibly convert the assembly from the colored, crystalline state to a nondiffracting glassy material. Crystal-to-glass transitions are similarly accomplished via photothermal excitation when 16 nm diameter colloidal Au particles are co-assembled with the responsive microgels. Excitation of the colloidal Au plasmon absorption with a frequency doubled Nd:YAG laser (lambda = 532 nm) results in optically directed conversion of either glasses to crystals or crystals to glasses, depending on the initial state of the assembly and the illumination time. These results represent a fundamentally new method for the patterning of self-assembled photonic materials.