Cu2Se Nanoparticles with Tunable Electronic Properties Due to a Controlled Solid-State Phase Transition Driven by Copper Oxidation and Cationic Conduction

Stoichiometric copper(I) selenide nanoparticles have been synthesized using the hot injection method. The effects of air exposure on the surface composition, crystal structure, and electronic properties were monitored using X-ray photoelectron spectroscopy, X-ray diffraction, and conductivity measurements. The current-voltage response changes from semiconducting to ohmic, and within a week a 3000-fold increase in conductivity is observed under ambient conditions. The enhanced electronic properties can be explained by the oxidation of Cu+ and Se2- on the nanoparticle surface, ultimately leading to a solid-state conversion of the core from monoclinic Cu2Se to cubic Cu1.8Se. This behavior is a result of the facile solid-state ionic conductivity of cationic Cu within the crystal and the high susceptibility of the nanoparticle surface to oxidation. This regulated transformation is appealing as one could envision using layers of Cu2Se nanoparticles as both semiconducting and conducting domains in optoelectronic devices simply by tuning the electronic properties for each layer through controlled oxidation.