Light-Stabilized Metastable Electronic State in NiO with Enhanced Orbital Hybridization

Abstract

Light-driven control of electronic structure in correlated metal oxides offers new opportunities for optimizing materials used in photovoltaic and photoelectrochemical technologies. We show that photoexcitation of NiO, a prototypical transparent semiconductor and hole-transport material, across its charge-transfer gap produces a long-lived metastable state with enhanced Ni 3d-O 2p orbital hybridization. We characterize this state using Ni K-edge X-ray absorption spectroscopy, which probes how structural and electronic changes affect the unoccupied p density of states during continuous and pulsed ultraviolet excitation. Under pulsed excitation, high carrier densities of approximately 10^20 per cubic centimeter generate a state with a lifetime of approximately 600 picoseconds, in which enhanced hybridization coexists with lattice heating. By contrast, continuous ultraviolet irradiation at much lower carrier densities of approximately 10^13 per cubic centimeter stabilizes a similar electronic state with negligible lattice heating, demonstrating that its formation is not solely thermally driven. First-principles DFT+U+V calculations attribute the spectral changes to stronger Ni 3d-O 2p hybridization, which alters the unoccupied Ni 4p states probed by dipole-allowed K-edge transitions. We attribute this change to the dynamic screening of on-site electronic correlations following photoexcitation, which redistributes the charge density. Because orbital hybridization governs carrier transport and charge-transfer energetics, our results identify photoinduced screening as a mechanism for dynamically tuning correlated oxides and suggest new design principles for optoelectronic materials.

81 pages, 5 figures