Delocalized Impurity Phonon Induced Electron–Hole Recombination in Doped Semiconductors

Abstract

Semiconductor doping is often proposed as an effective route to improving the solar energy conversion efficiency by engineering the band gap; however, it may also introduce electron-hole (e-h) recombination centers, where the determining element for e-h recombination is still unclear. Taking doped TiO₂ as a prototype system and by using time domain ab initio nonadiabatic molecular dynamics, we find that the localization of impurity-phonon modes (IPMs) is the key parameter to determine the e-h recombination time scale. Noncompensated charge doping introduces delocalized impurity-phonon modes that induce ultrafast e-h recombination within several picoseconds. However, the recombination can be largely suppressed using charge-compensated light-mass dopants due to the localization of their IPMs. For different doping systems, the e-h recombination time is shown to depend exponentially on the IPM localization. We propose that the observation that delocalized IPMs can induce fast e-h recombination is broadly applicable and can be used in the design and synthesis of functional semiconductors with optimal dopant control.