Exciton‐Dominated Ultrafast Optical Response in Atomically Thin PtSe2

Abstract Strongly bound excitons are a characteristic hallmark of 2D semiconductors, enabling unique light–matter interactions and novel optical applications. Platinum diselenide (PtSe 2 ) is an emerging 2D material with outstanding optical and electrical properties and excellent air stability. Bulk PtSe 2 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 PtSe 2 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 PtSe 2 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.