Photoinduced Electronic Band Dynamics and Defect-mediated Surface Potential Evolution in PdSe$_2$

TL;DR

This study uses advanced spectroscopy and theoretical calculations to explore ultrafast electronic dynamics and defect-related surface potential changes in PdSe₂, revealing complex photoinduced processes and long-lived surface photovoltage effects.

Contribution

It provides the first detailed investigation of ultrafast carrier dynamics and defect-mediated surface potential evolution in PdSe₂ using TR-ARPES and DFT.

Findings

Valence band shift and broadening occur within less than a picosecond.

A persistent surface photovoltage of ~67 meV lasts over 50 ps.

Native vacancies likely cause mid-gap states responsible for long-lived SPV.

Abstract

We use time- and angle-resolved photoemission spectroscopy (TR-ARPES) combined with density functional theory to investigate ultrafast carrier dynamics in low-symmetry layered semiconducting PdSe$_2$. The indirect bandgap is determined to be 0.55~eV. Following photoexcitation above this gap, we resolve a valence band shift and broadening, both lasting less than a picosecond, consistent with bandgap renormalization and carrier scattering, indicative of strong many-body interactions. Subsequently, hot carriers populate the conduction band minimum and are captured by defect states. A surface photovoltage (SPV) of $\sim$ 67~meV emerges, persisting for over 50~ps, driven by defect-assisted charge separation. The formation of native vacancies, promoted by the low-symmetry lattice, likely gives rise to the mid-gap states responsible for this long-lived SPV response. Detailed analysis of TR-ARPES spectra disentangles the contributions of bandgap renormalization, carrier scattering, defect states, and SPV. These findings establish PdSe$_2$ as a prototypical layered quantum material exhibiting exotic photoresponses on ultrafast timescales.