Excitonic Mott transition without population inversion

TL;DR

This study shows that the excitonic Mott transition can occur rapidly without population inversion in monolayer transition metal dichalcogenides, challenging traditional understanding and highlighting nonthermal effects.

Contribution

It demonstrates an ultrafast, non-equilibrium pathway to exciton ionization that does not require population inversion, supported by combined experimental and ab initio simulations.

Findings

Excitonic resonance is quenched within ~100 fs under ultrafast excitation.

Optical gain is absent despite the occurrence of the Mott transition.

Nonthermal carrier populations and dynamical screening govern the transition.

Abstract

Exciton dissociation via the excitonic Mott transition (EMT) governs the high-density optical response of semiconductors and sets fundamental limits for optoelectronic devices. The EMT is conventionally linked to the onset of population inversion and the emergence of optical gain. Here, we demonstrate that this paradigm can break down under ultrafast non-equilibrium excitation. Using femtosecond pump-probe optical spectroscopy, we drive a monolayer transition metal dichalcogenide into a dense photoexcited state in which the excitonic resonance is completely quenched within ~100 fs, while the optical gain is entirely absent across the explored fluence range. State-of-the-art real-time ab initio simulations reveal that the EMT is governed by an interplay of strongly nonthermal carrier populations and nonequilibrium dynamical screening of the Coulomb interaction. The quantitative agreement between theory and experiment identifies a distinct, ultrafast pathway to exciton ionization beyond quasi-equilibrium descriptions and demonstrates that population inversion is not a universal prerequisite for the EMT.