Mechanism of Laser-Induced Bulk and Surface Defect Generation in ZnO and TiO₂ Nanoparticles: Effect on Photoelectrochemical Performance

Laser processing of neat and gold-nanoparticle-functionalized ZnO and TiO2 nanoparticles by nanosecond–355 nm or picosecond–532 nm light enabled control of photocurrent generation under simulated sunlight irradiation in neutral aqueous electrolytes. We obtained more than 2-fold enhanced photoelectrochemical performance of TiO2 nanoparticles upon irradiation by picosecond–532 nm pulses that healed defects. Laser processing and gold nanoparticle functionalization of ZnO and TiO2 nanomaterials resulted in color changes that did not originate from optical bandgaps or crystal structures. Two-dimensional photoluminescence data allowed us to differentiate and quantify surface and bulk defects that play a critical yet oft-underappreciated role for photoelectrochemical performance as sites for detrimental carrier recombination. We developed a detailed mechanistic model of how surface and bulk defects were generated as a function of laser processing parameters and obtained key insights on how these defects affected photocurrent production. The controlled healing of defects by pulsed-laser processing may be useful in the design of solar fuels materials.