Inorganic hole-transport materials (HTMs) have been frequently applied in perovskite solar cells (PSCs) and are a promising solution to improve the poor stability of PSCs. In this study, we investigate solution-processed copper indium gallium disulfide (CIGS) nanocrystals (NCs) as a dopant-free inorganic HTM in n−i−p type PSCs. Moreover, Cs0.05(MA0.17-FA0.83)0.95Pb(I0.83Br0.17)3 mixed-halide perovskite with proper crystalline quality and long-time stability was utilized as the light-absorbing layer under ambient conditions. To optimize the cell performance and better charge extraction from the perovskite layer, the Ga concentration in the Cu(In1−XGaX)S2 composition was changed, and the X value was altered between 0.0 and 0.75. It was shown that the CIGS band gap enhances with increasing Ga content; thus, with tunable band gaps and engineering of the energy level alignment, a better collection of photogenerated holes and a reduced electron−hole recombination rate could be achieved. The maximum power conversion efficiency of 15.6% was obtained for the PSC with Cu(In0.5Ga0.5)S2 hole-transport layer composition, which is the highest efficiency reported so far for CIGS-based dopant-free PSCs. This value is very close to the efficiency of devices fabricated with doped spiro-OMeTAD as an organic HTM. Additionally, the stability of nonencapsulated PSCs was studied, and CIGS-based devices demonstrated 70% retention after 90 days of aging in the dark and in 50% relative humidity conditions. This result is quite better than the similar measurements for the doped spiro-OMeTAD-based devices.
