Photoexcitation-Induced Nonthermal Ultrafast Loss of Long-Range Order in GeTe

Nonadiabatic quantum molecular dynamics is used to investigate the evolution of GeTe photoexcited states. Results reveal a photoexcitation-induced picosecond nonthermal path for the loss of long-range order. A valence electron excitation threshold of 4% is found to trigger local disorder by switching Ge atoms from octahedral to tetrahedral sites and promoting Ge–Ge bonding. The resulting loss of long-range order for a higher valence electron excitation fraction is achieved without fulfilling the Lindemann criterion for melting, therefore utilizing a nonthermal path. The photoexcitation-induced structural disorder is accompanied by charge transfer from Te to Ge, Ge–Te bonding-to-antibonding, and Ge–Ge antibonding-to-bonding change, triggering Ge–Te bond breaking and promoting the formation of Ge–Ge wrong bonds. These results provide an electronic-structure basis to understand the photoexcitation-induced ultrafast changes in the structure and properties of GeTe and other phase-change materials.