Photoinduced electronic band dynamics and defect-mediated surface potential evolution in PdSe2

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 PdSe2. 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 ~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 PdSe2 as a prototypical layered quantum material exhibiting exotic photoresponses on ultrafast timescales.