Trion formation resolves observed peak shifts in the optical spectra of transition metal dichalcogenides

TL;DR

This paper demonstrates that the formation of negative trions explains the peak shifts and broadening observed in the optical spectra of monolayer transition metal dichalcogenides, resolving previous contradictory explanations.

Contribution

It introduces a many-body ab initio based model that accurately describes the optical spectra and their dependence on potential and carrier dynamics in TMDs.

Findings

Trion formation accounts for peak shifts in TMD spectra.

The model fits experimental electrochemical data well.

Trion dynamics explain non-monotonic spectral changes.

Abstract

Monolayer transition metal dichalcogenides (TMDs) have the potential to unlock novel photonic and chemical technologies if their optoelectronic properties can be understood and controlled. Yet, recent work has offered contradictory explanations for how TMD absorption spectra change with carrier concentration, fluence, and time. Here, we test our hypothesis that the large broadening and shifting of the strong band-edge features observed in optical spectra arise from the formation of negative trions. We do this by fitting an ab initio based, many-body model to our experimental electrochemical data. Our approach provides an excellent, global description of the potential-dependent linear absorption data. We further leverage our model to demonstrate that trion formation explains the non-monotonic potential dependence of the transient absorption spectra, including through photoinduced derivative lineshapes for the trion peak. Our results motivate the continued development of theoretical methods to describe cutting-edge experiments in a physically transparent way.