Evidence for Cu2–xSe platelets at grain boundaries and within grains in Cu(In,Ga)Se2 thin films

Cu(In,Ga)Se₂ (CIGS)-based solar cells reach high power-conversion efficiencies of above 22%. In this work, a three-stage co-evaporation method was used for their fabrication. During the growth stages, the stoichiometry of the absorbers changes from Cu-poor ([Cu]/([In] + [Ga]) < 1) to Cu-rich ([Cu]/([In] + [Ga]) > 1) and finally becomes Cu-poor again when the growth process is completed. It is known that, according to the Cu-In-Ga-Se phase diagram, a Cu-rich growth leads to the presence of Cu₂–ₓSe (x = 0–0.25), which is assumed to assist in recrystallization, grain growth, and defect annihilation in the CIGS layer. So far, Cu₂–ₓSe precipitates with spatial extensions on the order of 10–100 nm have been detected only in Cu-rich CIGS layers. In the present work, we report Cu₂–ₓSe platelets with widths of only a few atomic planes at grain boundaries and as inclusions within grains in a polycrystalline, Cu-poor CIGS layer, as evidenced by high-resolution scanning transmission electron microscopy (STEM). The chemistry of the Cu–Se secondary phase was analyzed by electron energy-loss spectroscopy, and STEM image simulation confirmed the identification of the detected phase. These results represent additional experimental evidence for the proposed topotactical growth model for Cu–Se–assisted CIGS thin-film formation under Cu-rich conditions.