Exciton-Dominated Ultrafast Optical Response in Atomically Thin PtSe₂

Strongly bound excitons are a characteristic hallmark of 2D semiconductors, enabling unique light–matter interactions and novel optical applications. Platinum diselenide (PtSe₂) is an emerging 2D material with outstanding optical and electrical properties and excellent air stability. Bulk PtSe₂ is a semimetal, but its atomically thin form shows a semiconducting phase with the appearance of a band-gap, making one expect strongly bound 2D excitons. However, the excitons in PtSe₂ have been barely studied, either experimentally or theoretically. Here, the authors directly observe and theoretically confirm excitons and their ultrafast dynamics in mono-, bi-, and tri-layer PtSe₂ single crystals. Steady-state optical microscopy reveals exciton absorption resonances and their thickness dependence, confirmed by first-principles calculations. Ultrafast transient absorption microscopy finds that the exciton dominates the transient broadband response, resulting from strong exciton bleaching and renormalized band-gap-induced exciton shifting. The overall transient spectrum redshifts with increasing thickness as the shrinking band-gap redshifts the exciton resonance. This study provides novel insights into exciton photophysics in platinum dichalcogenides.