Mechanism for Local‐Atomic Structure Changes in Chalcogenide‐based Threshold‐Switching Devices

Threshold‐switching devices based on amorphous chalcogenides are considered for use as selector devices in 3D crossbar memories. However, the fundamental understanding of amorphous chalcogenide is hindered owing to the complexity of the local structures and difficulties in the trap analysis of multinary compounds. Furthermore, after threshold switching, the local structures gradually evolve to more stable energy states owing to the unstable homopolar bonds. Herein, based on trap analysis, DFT simulations, and operando XPS analysis, it is determined that the threshold switching mechanism is deeply related to the charged state of Se–Se homopolar defects. A threshold switching device is demonstrated with an excellent performance through the modification of the local structure via the addition of alloying elements and investigating the time‐dependent trap evolution. The results concerning the trap dynamics of local atomic structures in threshold switching phenomena may be used to improve the design of amorphous chalcogenides. This work investigates amorphous chalcogenides, focusing on local structural evolution and proposing a novel threshold switching mechanism based on Se2− defects. By replacing unstable Ge─Ge and Se─Se homopolar bonds with stable S─Ge and In─Se heteropolar bonds, significant improvements in threshold‐switching devices are achieved. These findings offer insights into the design and predictive modeling of amorphous materials.