Cu-deficient phases of chalcopyrite Cu(In,Ga)Se2 (CIGS), such as Cu(In,Ga)3Se5 and Cu(In,Ga)5Se8, which are occasionally referred to as ordered vacancy compounds and often unintentionally form on CIGS film surfaces and at grain boundaries, are among the most important subjects in developing chalcopyrite thin-film energy-conversion materials and devices. Here, we revisit the role of the Cu-deficient surface layer (CDL) present at the p-CIGS/n-CdS interface in photovoltaic devices with the effects of alkali-metal doping. The device structure used is alkali-containing soda-lime glass or alkali-free zirconia substrate/Mo/CIGS/CuInSe2-based CDL/CdS/intrinsic and Al-doped ZnO. The photovoltaic device performance deteriorates with increasing CDL thickness when no alkali metal is added. However, the CDL thickness significantly affects the results of alkali-halide RbF postdeposition treatment (PDT) and the use of a thick CDL enhances the beneficial effects of RbF PDT, resulting in photovoltaic performance enhancements manifested by improvements in the open-circuit voltage and fill-factor values. On the other hand, RbF PDT leads to degradation of the device performance when the CDL is thin. High Rb concentration and significant Ga diffusion from the CIGS layer to the surface CDL with RbF PDT are observed when the CDL is thick. The formation of metastable acceptors, namely, an increase in the nominal carrier density in CIGS, is observed with light-soaking (LS) treatments, regardless of the thickness of CDL. Nevertheless, improvements in photovoltaic efficiency with LS treatments are observed only from devices grown with a thick CDL.
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