Cd-free Cu(In,Ga)(S,Se)2 (CIGSSe) solar cells with a structure of glass/Mo/CIGSSe/Zn1- xMg xO (buffer)/Zn1- xMg xO:Al (TCO), fabricated by an all dry process, are characterized using ultraviolet light excited time-resolved photoluminescence (UV-TRPL). The impact of bandgap energy ( Eg) values of buffer and transparent conductive oxide (TCO) layers, denoted by Eg of buffer and TCO, is examined. The Eg values of buffer and TCO layers are kept almost similar and varied from 3.30 to 3.94 eV. In this work, UV-TRPL measurement is performed to examine the UV-TRPL carrier lifetimes near the Zn1- xMg xO buffer/CIGSSe interface in the solar cell structure. It is revealed that the UV-TRPL carrier lifetimes near the Zn1- xMg xO buffer/CIGSSe interface in Cd-free solar cells are increased upon enhancing the Eg of buffer and TCO from 3.30 to 3.94 eV, thus increasing the open-circuit voltage and fill factor. Additionally, short-circuit current density is enhanced up to about 38 mA/cm2 owing to the highly transparent Zn1- xMg xO/Zn1- xMg xO:Al layers. Ultimately, an 18.5%-efficient Cd-free solar cell with the Eg of buffer and TCO of 3.94 eV, prepared by an all dry process, is fabricated, which has the same level of 18.3% for the reference solar cell (glass/Mo/CIGSSe/CdS/ZnO/ZnO:Al).