Effects of Oxygen Vacancies and Cation Valence States on the Triboelectric Property of Substoichiometric Oxide Films

Temperature effects on the contact electrification (CE) is of great interest. Here, different kinds of substoichiometric oxide films, such as TiO2–x, Al2O3–x, Ta2O5–x, and Cr2O3–x, are deposited and annealed at different temperatures, and the CE between the films and a Pt-coated tip is performed by using Kelvin probe force microscopy (KPFM). An intriguing finding is that the polarity on the TiO2–x surface changes from negative to positive with the increase of the sample annealing temperature in air atmosphere. Such a result is attributed to the fact that annealing under an oxidative atmosphere repairs oxygen vacancies and helps upgrade the low valency of Ti3+ to a stable high valency of Ti4+. On the contrary, after annealing occurs in an Ar/H2 atmosphere, the polarity on the TiO2–x surface reverses from positive to negative. This is mainly due to the increase of oxygen vacancies after annealing in reducing atmosphere. Through the KPFM results of Al2O3–x, Ta2O5–x, and Cr2O3–x films, the effect of oxygen vacancies is further confirmed, that is, the decrease of oxygen vacancies eases the films at capturing positive charges. Based on this, TiO2–x-based identical material triboelectric nanogenerators (IM-TENGs) are designed and prepared for the first time to control the current direction. Moreover, a surface state model for explaining the CE mechanism between the metal and annealed dielectric is proposed. This study is conducive to the development of the IM-TENGs which regulate the current direction or voltage output accurately in the future and also provides a further understanding of the dominant mechanism of electron transfer in the CE.