Alkali halide postdeposition treatments (PDTs) have become a key tool to maximize efficiency in Cu(In_xGa_1−x)Se₂ (CIGS) photovoltaics. RbF PDTs have emerged as an alternative to the more common Na‐ and K‐based techniques. This study utilizes temperature‐dependent current–voltage (JVT) measurements to study a unique RbF PDT performed in a S atmosphere. The samples are measured before and after 6 months in a desiccator to study device stability. Both samples contain Na and K which diffuse from the soda–lime glass substrate. A reference sample and a RbF + S PDT sample both show the development of a rear contact barrier after aging. The contact barrier is higher for the RbF + S PDT sample, leading to decreased current in forward bias. Series resistance is also higher in the RbF + S PDT device which leads to lower fill factor. However, after aging the reference sample has a larger decrease in open‐circuit voltage (V_OC). Ideality factor measurements suggest Shockley–Read–Hall recombination dominates both samples. V_OC versus temperature and a temperature‐dependent activation energy model are used to calculate diode activation energies for each sample condition. Both techniques produce similar values that indicate recombination primarily occurs within the bulk absorber.