Formation and Transformation of Cu_2-xSe_1-yTe_y Nanoparticles Synthesized by Tellurium Anion Exchange of Copper Selenide

Ion exchange reactions of colloidal nanoparticles post-synthetically modify the composition while maintaining the morphology and crystal structure and therefore are important for tuning properties and producing otherwise inaccessible and/or metastable materials. Reactions involving anion exchange of metal chalcogenides are particularly interesting, as they involve the replacement of the sublattice that defines the structure while also requiring high temperatures that can be disruptive. Here, we show that the tellurium anion exchange of weissite Cu_2-xSe nanoparticles using a trioctylphosphine-tellurium complex (TOP═Te) yields weissite Cu_2-xSe_1-yTe_y solid solutions, rather than complete exchange to weissite Cu_2-xTe, with compositions that are tunable based on the amount of TOP═Te used. Upon storage at room temperature in either solvent or air, tellurium-rich Cu_2-xSe_1-yTe_y solid solution nanoparticles transform, over the span of several days, to a selenium-rich Cu_2-xSe_1-yTe_y composition. The tellurium that is expelled from the solid solution during this process migrates to the surface and forms a tellurium oxide shell, which correlates with the onset of particle agglomeration due to the change in surface chemistry. Collectively, this study demonstrates tunable composition during tellurium anion exchange of copper selenide nanoparticles along with unusual post-exchange reactivity that transforms the composition, surface chemistry, and colloidal dispersibility due to the apparent metastable nature of the solid solution product.