Influence of annealing on the photodeposition of silver on periodically poled lithium niobate

The preferential deposition of metal nanoparticles onto periodically poled lithium niobate surfaces, whereby photogenerated electrons accumulate in accordance with local electric fields and reduce metal ions from solution, is known to depend on the intensity and wavelength of the illumination and the concentration of the solution used. Here, it is shown that for identical deposition conditions (wavelength, intensity, concentration), post-poling annealing for 10 h at 200°C modifies the surface reactivity through the reorientation of internal defect fields. Whereas silver nanoparticles deposit preferentially on the +z domains on unannealed crystals, the deposition occurs preferentially along 180° domain walls for annealed crystals. In neither case is the deposition selective; limited deposition occurs also on the unannealed –z domain surface and on both annealed domain surfaces. The observed behavior is attributed to a relaxation of the poling-induced defect frustration mediated by Li+ ion mobility during annealing, which affects the accumulation of electrons, thereby changing the surface reactivity. The evolution of the defect field with temperature is corroborated using Raman spectroscopy.