Reversible Manipulation of Photoconductivity Caused by Surface Oxygen Vacancies in Perovskite Stannates with Ultraviolet Light

Adv Mater. 2022 Feb;34(5):e2107650. doi: 10.1002/adma.202107650. Epub 2021 Dec 17.

Abstract

Programmable optoelectronic devices call for the reversible control of the photocarrier recombination process by in-gap states in oxide semiconductors. However, previous approaches to produce oxygen vacancies as a source of in-gap states in oxide semiconductors have hampered the reversible formation of oxygen vacancies and their related phenomena. Here, a new strategy to manipulate the 2D photoconductivity from perovskite stannates is demonstrated by exploiting spatially selective photochemical reaction under ultraviolet illumination at room temperature. Remarkably, the ideal trap-free photocurrent of air-illuminated BaSnO3 (≈200 pA) is reversibly switched into three orders of magnitude higher photocurrent of vacuum-illuminated BaSnO3 (≈335 nA) with persistent photoconductivity depending on ambient oxygen pressure under illumination. Multiple characterizations elucidate that ultraviolet illumination of BaSnO3 under low oxygen pressure induces surface oxygen vacancies as a result of surface photolysis combined with the low oxygen-diffusion coefficient of BaSnO3 ; the concentrated oxygen vacancies are likely to induce a two-step transition of photocurrent response by changing the characteristics of in-gap states from the shallow level to the deep level. These results suggest a novel strategy that uses light-matter interaction in a reversible and spatially confined way to manipulate functionalities related to surface defect states, for the emerging applications using newly discovered oxide semiconductors.

Keywords: oxide semiconductors; oxygen vacancies; perovskites; photoconductivity; photolysis.