Demystifying the Semiconductor‐to‐Metal Transition in Amorphous Vanadium Pentoxide: The Role of Substrate/Thin Film Interfaces

Abstract

The precise mechanism governing the reversible semiconductor‐to‐metal transition (SMT) in V2O5 remains elusive, yet its investigation is of paramount importance due to the remarkable potential of V2O5 as a versatile “smart” material in advancing optoelectronics, plasmonics, and photonics. In this study, distinctive experimental insights into the SMT occurring in amorphous V2O5 through the application of highly sensitive, temperature‐dependent, in situ analyses on a V2O5 thin film deposited on soda‐lime glass are presented. The ellipsometry measurements reveal that the complete SMT occurs at ≈340 °C. Remarkably, the refractive index and extinction coefficients exhibit reversible characteristics across visible and near‐infrared wavelengths, underscoring the switch‐like behavior inherent to V2O5. The findings obtained from ellipsometry are substantiated by calorimetry and in situ secondary ion mass spectrometry analyses. In situ electron microscopy observations unveil a separation of oxidation states within V2O5 at 320 °C, despite the thin film retaining its amorphous state. The comprehensive experimental investigations effectively demonstrate that alterations in electronic state can trigger the SMT in amorphous V2O5. It is revealed for the first time that the SMT in V2O5 is solely contingent upon electronic state changes, independent of structural transitions, and importantly, it is a reversible transformation within the amorphous state itself.