In this study, the PV performance of Au/BSF/CTS/CdS/i-ZnO/ITO thin-film solar cell (TFC) structure was systematically investigated using SCAPS-1D software. The effects of several critical parameters, including interface defect density, recombination mechanisms, absorber defect density, operating temperature, parasitic resistances, and different back surface field (BSF) layers, were comprehensively analyzed. The SCAPS-1D software results reveal that the photovoltaic performance is highly sensitive to the defect density at the absorber layer interface. When the interface defect density increased from 1012 cm−3 to 1016 cm−3, the open-circuit voltage ((Formula presented.)) decreased from approximately 0.68 V to 0.45 V, while the power conversion efficiency (PCE) declined from nearly 19% to about 7%. Similarly, an increase in absorber defect density enhanced the Shockley–Read–Hall recombination rate, thereby reducing carrier lifetime and significantly deteriorating PV parameters. The influence of radiative and Auger recombination ((Formula presented.)) processes was also examined, revealing that higher recombination coefficients lead to substantial reductions in current density and efficiency due to increased carrier losses. Furthermore, the impact of parasitic resistances was evaluated, demonstrating that decrease the series resistance from 9.5 Ω·cm2 to 0.5 Ω·cm2 increased the fill factor ((Formula presented.)) from about 48% to nearly 78%, while the device efficiency improved to approximately 32%. In addition to these parameters, particular emphasis was placed on the investigation of different BSF materials to enhance back contact performance. Various BSF layers, including SnS, PbS, V2O5, and Sb2S3, were examined to improve band alignment and suppress minority carrier recombination at the rear interface. Among these materials, the SnS BSF layer provided the most favorable band alignment with the CTS absorber, leading to a notable improvement in PV parameters and increasing the efficiency to approximately 25%. Overall, the results demonstrate that optimizing defect densities, recombination mechanisms, parasitic resistances, and especially the selection of appropriate BSF materials plays a crucial role in improving the performance of CTS-based TFCs.