Tuning the Excitonic and Plasmonic Properties of Copper Chalcogenide Nanocrystals

The optical properties of stoichiometric copper chalcogenide nanocrystals (NCs) are characterized by strong interband transitions in the blue part of the spectral range and a weaker absorption onset up to ∼1000 nm, with negligible absorption in the near-infrared (NIR). Oxygen exposure leads to a gradual transformation of stoichiometric copper chalcogenide NCs (namely, Cu_2–<i>x</i>S and Cu_2–<i>x</i>Se, <i>x</i> = 0) into their nonstoichiometric counterparts (Cu_2–<i>x</i>S and Cu_2–<i>x</i>Se, <i>x</i> > 0), entailing the appearance and evolution of an intense localized surface plasmon (LSP) band in the NIR. We also show that well-defined copper telluride NCs (Cu_2–<i>x</i>Te, <i>x</i> > 0) display a NIR LSP, in analogy to nonstoichiometric copper sulfide and selenide NCs. The LSP band in copper chalcogenide NCs can be tuned by actively controlling their degree of copper deficiency via oxidation and reduction experiments. We show that this controlled LSP tuning affects the excitonic transitions in the NCs, resulting in photoluminescence (PL) quenching upon oxidation and PL recovery upon subsequent reduction. Time-resolved PL spectroscopy reveals a decrease in exciton lifetime correlated to the PL quenching upon LSP evolution. Finally, we report on the dynamics of LSPs in nonstoichiometric copper chalcogenide NCs. Through pump–probe experiments, we determined the time constants for carrier-phonon scattering involved in LSP cooling. Our results demonstrate that copper chalcogenide NCs offer the unique property of holding excitons and highly tunable LSPs on demand, and hence they are envisaged as a unique platform for the evaluation of exciton/LSP interactions