Weak Anharmonicity Rationalizes the Temperature-Driven Acceleration of Nonradiative Dynamics in CuZnSnS Photoabsorbers.

We report a time-domain ab initio investigation of the nonradiative electron-hole recombination in quaternary CuZnSnS (CZTS) at different temperatures using a combination of time-dependent density functional theory and nonadiabatic molecular dynamics. Our results demonstrate that higher temperatures increase both inelastic and elastic electron-phonon interactions. Elevated temperatures moderately increase the lattice anharmonicity and cause stronger fluctuations of electronic energy levels, enhancing the electron-phonon coupling. The overall nuclear anharmonic effect is weak in CZTS, which can be ascribed to their stable bonding environment. Phonon-induced loss of electronic coherence accelerates with temperature, due to stronger elastic electron-phonon scattering. The enhanced inelastic electron-phonon scattering decreases charge carrier lifetimes at higher temperatures, deteriorating material performance in optoelectronic devices. The detailed atomistic investigation of the temperature-dependent charge carrier dynamics, with particular focus on anharmonic effects, guides the development of more efficient solar cells based on CZTS and related semiconductor photoabsorbers.