Extraordinary Polarization and Thickness Dependences of Photocarrier Dynamics in PdSe₂ Ribbons

Pentagonal palladium diselenide (PdSe₂) stands out for its exceptional optoelectronic properties, including high carrier mobility, tunable bandgap, and anisotropic electronic and optical responses. Herein, we systematically investigate photocarrier dynamics in PdSe₂ ribbons using polarization-resolved optical pump-probe spectroscopy. In thin PdSe₂ ribbons with a semiconductor phase, the photocarrier dynamics are found to be dominated by intraband hot-carrier cooling, interband recombination, and the exciton effect, showing weak crystalline orientation dependences. Conversely, in thick semimetal-phase PdSe₂ ribbons, the photocarrier relaxations governed by the electron-optical/acoustic phonon scattering strongly depend on the sample orientation, albeit with a degradation in in-plane anisotropy following hot-carrier cooling. Furthermore, we analyze the correlations between photocarrier dynamics and anisotropic energy dispersions of electronic structures across a wide range in k space, as well as the contributions from the anisotropic electron-phonon couplings. Our study provides crucial insights for developing polarization-sensitive photoelectronic devices based on PdSe₂.