Dopant Control of Electron-Hole Recombination in Cesium-Titanium Halide Double Perovskite by Time Domain Ab Initio Simulation: Codoping Supersedes Monodoping.

Using nonadiabatic (NA) molecular dynamics combined with time domain density functional theory, we simulate electron-hole recombination in pristine and doped inorganic Pb-free double perovskite Cs2TiBr6. We show that replacing the titanium and/or bromine with silicon and/or chlorine extends the charge carrier lifetime. Importantly, dopants avoid deep traps despite the fact that they do not change the fundamental band gap of Cs2TiBr6, and they decrease the NA electron-phonon coupling and accelerate decoherence arising from the reduced overlap of electron and hole wave functions as well as fast phonon modes induced by light dopants, respectively, suppressing electron-hole recombination. More importantly, codoping can reduce the formation energy of silicon and achieve higher doping concentration, potentially increasing the lifetime further. Our study suggests a rational strategy to reduce energy losses by codoping in design of high-performance all-inorganic Pb-free perovskite solar cells.