Switching between Plasmonic and Fluorescent Copper Sulfide Nanocrystals

[Image: see text] Control over the doping density in copper sulfide nanocrystals is of great importance and determines its use in optoelectronic applications such as NIR optical switches and photovoltaic devices. Here, we demonstrate that we can reversibly control the hole carrier density (varying from >10(22) cm(–3) to intrinsic) in copper sulfide nanocrystals by electrochemical methods. We can control the type of charge injection, i.e., capacitive charging or ion intercalation, via the choice of the charge compensating cation (e.g., ammonium salts vs Li(+)). Further, the type of intercalating ion determines whether the charge injection is fully reversible (for Li(+)) or leads to permanent changes in doping density (for Cu(+)). Using fully reversible lithium intercalation allows us to switch between thin films of covellite CuS NCs (E(g) = 2.0 eV, hole density 10(22) cm(–3), strong localized surface plasmon resonance) and low-chalcocite CuLiS NCs (E(g) = 1.2 eV, intrinsic, no localized surface plasmon resonance), and back. Electrochemical Cu(+) ion intercalation leads to a permanent phase transition to intrinsic low-chalcocite Cu(2)S nanocrystals that display air stable fluorescence, centered around 1050 nm (fwhm ∼145 meV, PLQY ca. 1.8%), which is the first observation of narrow near-infrared fluorescence for copper sulfide nanocrystals. The dynamic control over the hole doping density and fluorescence of copper sulfide nanocrystals presented in this work and the ability to switch between plasmonic and fluorescent semiconductor nanocrystals might lead to their successful implementation into photovoltaic devices, NIR optical switches and smart windows.