Si2Te3 is attracting attention due to its compatibility with Si technology while still showing advantages as a two-dimensional layered material. Although recent experimental studies have observed the resistive switching process in Si2Te3-based memristors, the mechanism has not been clearly identified. In this study, first-principles density functional theory calculations are employed to understand the relationship between the phase transition of Si2Te3 and the reversible resistive switching of the Si2Te3-based memristor. Our calculation results show that although semiconducting Si2Te3 is energetically more stable than two metallic Si2Te3 phases (α and β), two metallic Si2Te3 can be energetically stabilized by excess holes. The enhanced energetic preference of two metallic Si2Te3 by excess holes is explained by the reduced occupation of antibonding states between Si and Te. Our study finds that the energy barrier for the phase transition between semiconducting Si2Te3 and α-metallic Si2Te3 varies significantly by excess charge carriers so the phase transition can be directly connected to the reversible resistive switching of the Si2Te3-based memristor under external bias. Our finding will serve as a cornerstone for optimizing the resistive switching process of the Si2Te3-based memristor.
Keywords: density functional theory; layered crystals; memristor; phase transitions; reversible resistive switching; semiconductor−metal transition.