AbstractCu‐deficient layer (CDL) on Cu(In,Ga)Se2 (CIGS) promotes Cd diffusion from CdS buffer layer and forms a valence band offset (ΔEV) between CDL and CIGS. We quantitively demonstrate the effects of CDL formation on the performance of CIGS solar cells through experiments and theoretical simulation. To investigate the effects of Cd diffusion and ΔEV by CDL, theoretical analysis was carried out for a CIGS solar cell with a surface layer which simulated the CDL at CdS/CIGS interface. It was revealed that when electron concentration in n‐type surface layer is higher than the absolute carrier concentration in CIGS absorber (ND > |NA, CIGS|), open‐circuit voltage and fill factor are improved. Additionally, ΔEV ≥ 0.15 eV leads to the highest open‐circuit voltage by suppression of interfacial recombination. Transmission electron microscope energy dispersive X‐ray spectrometry and scanning spreading resistance microscopy were employed for the same cross section of a CIGS solar cell fabricated by three‐stage process. Despite CDL with Cu/(Ga + In) of 0.31 formed on the surface had high Cd contents of 3.4 at%, its carrier concentration of 4.8 × 1010 cm−3 was lower than that of 1014 –1016 cm−3 in grain interior owing to insufficient activation of Cd atoms. These results indicate the effectiveness of ΔEV formation by introducing CDL with low Cu/(Ga + In) of 0.31 to boost CIGS solar cell performance and difficulty in realizing ND > |NA, CIGS| by surface Cd doping.
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