Exciton lifetime and optical linewidth profile via exciton-phonon interactions: Theory and first-principles calculations for monolayer MoS$_2$

TL;DR

This paper develops a first-principles theoretical framework to analyze exciton dynamics in monolayer MoS2, revealing the impact of exciton-phonon interactions on exciton lifetime and optical linewidths, with results aligning well with experimental data.

Contribution

It introduces a rigorous second-order perturbation approach for optical absorption that accounts for exciton-phonon coupling, including off-diagonal elements often neglected in prior studies.

Findings

Long exciton lifetime due to spin-selective exciton-phonon coupling

Accurate exciton linewidths matching experimental measurements

Critical role of off-diagonal exciton-phonon matrix elements in dephasing

Abstract

Exciton dynamics dictate the evolution of photoexcited carriers in photovoltaic and optoelectronic devices. However, interpreting their experimental signatures is a challenging theoretical problem due to the presence of both electron-phonon and many-electron interactions. We develop and apply here a first-principles approach to exciton dynamics resulting from exciton-phonon coupling in monolayer MoS2 and reveal the highly selective nature of exciton-phonon coupling due to the internal spin structure of excitons, which leads to a surprisingly long lifetime of the lowest energy bright A exciton. Moreover, we show that optical absorption processes rigorously require a second-order perturbation theory approach, with photon and phonon treated on an equal footing, as proposed by Toyozawa and Hopfield. Such a treatment, thus far neglected in first-principles studies, gives rise to off-diagonal exciton-phonon coupling matrix elements, which are critical for the description of dephasing mechanisms, and yields exciton linewidths in excellent agreement with experiment.