Anomalous Photoinduced Reconstructing and Dark Self-Healing Processes on Bi₂O₂S Nanoplates

We report an anomalous photoinduced reconstructing and dark self-healing process on Bi₂O₂S nanoplates by monitoring the time profile of open-circuit potential (OCP). When the light was switched on and off on the nanoplates, we observed pronounced and repeatable decrement-recovery cycles of the OCP signal, which are inexplicable by a rapid electron-hole separation-recombination process only as in a conventional semiconductor. It is proposed that upon irradiation, accumulation of photogenerated holes at the electrode surface caused oxidation of the S layers of Bi₂O₂S nanoplates into certain intermediates, which, when the light was turned off, were then reduced back to the original state by the electron back flow. Raman scattering spectroscopy provided te S-S vibrational signature of the intermediate, evidencing the hole oxidative dimerization of the S^2- species and the inverse reductive S-S dissociation process. The photophysics and photochemistry of semiconductor nanoplates reported here may inspire the development of energy devices, switches, and memristors.