Defects Slow Down Nonradiative Electron-Hole Recombination in TiS3 Nanoribbons: A Time-Domain Ab Initio Study.

Abstract

Layered TiS3 materials hold appealing potential in photovoltaics and optoelectronics due to their excellent electronic and optical properties. Using time domain density functional theory combined with nonadiabatic (NA) molecular dynamics, we show that the electron-hole recombination in pristine TiS3 nanoribbons (NRs) occurs in tens of picoseconds and is over 10-fold faster than the experimental value. By performing an atomistic ab initio simulation with a sulfur vacancy, we demonstrate that a sulfur vacancy greatly reduces electron-hole recombination, achieving good agreement with experiment. Introduction of a sulfur vacancy increases the band gap slightly because the NR's highest occupied molecular orbital is lowered in energy. More importantly, the sulfur vacancy partially diminishes the electron and hole wave functions' overlap and reduces NA electron-phonon coupling, which competes successfully with the longer decoherence time, slowing down recombination. Our study suggests that a rational choice of defects can control nonradiative electron-hole recombination in TiS3 NRs and provides mechanistic principles for photovoltaic and optoelectronic device design.