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Abstract: The effects of varying the conditions for the chemical bath deposition (CBD) of cadmium sulfide (CdS) layers on CdS/Cu(In,Ga)Se2 (CIGS) hetero-junctions were investigated using photoluminescence (PL), electroluminescence (EL), deep level transient spectroscopy (DLTS), and red-light-illuminated current-voltage (I–V) measurements. We demonstrated that varying CBD-CdS conditions such as the temperature and time influenced the recombination pathways around the CdS/CIGS junction via the formation of different electronic defects, which eventually changed the photovoltaic conversion efficiency. As the CBD-CdS time and temperature were increased, the cell efficiency decreased. PL measurements revealed that this degradation of the cell efficiency was accompanied by increases in the defect-related recombination, which were attributed to the existence of donor defects around CdS/CIGS having an energy level of 0.65eV below conduction band, as revealed by DLTS. Increasing distortions in the red-light-illuminated I–V characteristics suggested that the related defects might also have played a critical role in metastable changes around the CdS/CIGS junction. Because the CBD-CdS time and temperature were considered to influence the diffusion of impurities into the CIGS surface, the evolution of the efficiency, PL spectra, defect populations, and red-light-illuminated I–V characteristics observed in this work could be attributed to the diffusion of impurities during the CBD-CdS process. [Copyright &y& Elsevier]