Plasmon-Induced Ultrafast Hot Hole Transfer in Nonstoichiometric Cu_xIn_yS/CdS Heteronanocrystals

Plasmonic semiconductors are promising candidates for developing energy conversion devices due to their tunable band gap, cost-effectiveness, and nontoxicity. Such materials exhibit remarkable capabilities for harvesting infrared photons, which constitute half of the solar energy spectrum. Herein, we have synthesized near-infrared (NIR) active Cu_xIn_yS nanocrystals and Cu_xIn_yS/CdS heterostructure nanocrystals (HNCs) to investigate plasmon-induced charge transfer dynamics on an ultrafast time scale. Employing femtosecond transient absorption spectroscopy, we demonstrate that upon exciting the HNCs with sub-band gap NIR photons (λ = 840 nm), the hot holes are generated in the valence band of plasmonic Cu_xIn_yS and transferred to the adjacent semiconductor. The decreased signal intensity and accelerated hole phonon relaxation dynamics for HNCs reveal efficient transfer of plasmon-induced hot carriers from Cu_xIn_yS to CdS under both 840 and 350 nm laser excitations, providing a pathway for enhanced carrier utilization. These findings shed light on the potential of ternary chalcogenides in plasmonic applications, highlighting efficient hot carrier extraction to adjacent semiconductors.