Ion transport induced room-temperature insulator-metal transition in single-crystalline Cu2Se

Abstract

Cu<inf>2</inf>Se is a superionic conductor above 414 K, with ionic conductivities reaching that of molten salts. The superionic behavior results from hopping Cu ions between different crystallographic sites within the Se scaffold. However, the properties of Cu<inf>2</inf>Se below 414 K are far less known due to experimental limitations imposed by the bulk or polycrystalline samples that have been available so far. Here, we report the synthesis of ultra-thin, large-area single crystalline Cu<inf>2</inf>Se samples using a chemical vapor deposition method. The as-synthesized Cu<inf>2</inf>Se crystals exhibit optically and electrically detectable and controllable robust phases at room temperature and above. We demonstrate that Cu ion vacancies can be manipulated to induce an insulator-metal transition, which exhibits 6 orders of magnitude change in the electrical resistance of two terminal devices, accompanied by an optical change in the phase configuration. Our experiments show that the high mobility of the liquid-like Cu ion vacancies in Cu<inf>2</inf>Se causes macroscopic ordering in the Cu vacancies. Consequently, phase distribution over the crystals is not dictated by the diffusive motion of the ions but by the local energy minima formed due to the phase transition. As a result, long-range vacancy ordering of the crystal below 414 K becomes optically observable at a micrometer scale. This work demonstrates that Cu<inf>2</inf>Se could be a prototypical system where long-range ordering properties can be studied via electrical and optical methods. © 2024 The Royal Society of Chemistry.