Thin-film tandem solar cells are drawing interest toward higher power conversion efficiencies and the future of photovoltaics. Within the two-junction tandem architecture, the highest potential can be reached with top-cell bandgaps of about 1.7 eV paired with a bottom cell bandgap of 1.0 eV. [1] High-efficiency and stable-performing CuInSe 2 (CISe) solar cells are attractive for tandem applications due to is ideal bandgap of 1.0 eV. [1] Furthermore, as a direct-bandgap semiconductor, it has a high absorption coefficient, allowing for thin absorber layers and the fabrication of flexible and lightweight solar cells using low-cost roll-to-roll processes. [2] When comparing CISe to other state-of-the-art solar cell materials (Figure 1), the device performance is mainly limited due to a low fill factor (FF) and a high open-circuit voltage (V OC ) deficit. Identical limitations also account for the current (Ag,Cu)(In,Ga)(Se,S) 2 chalcopyrite record device with an efficiency of 23.35%. [3] Aside from adding sulfur to the compound or using high process temperatures, which are incompatible with flexible substrates, Ag alloying provides another strategy for overcoming chalcopyrite limitations.(Ag,Cu)(In,Ga)(S,Se) 2 has shown improved properties such as an enlargement of grain sizes [4] and less intragrain stress, [5] less structural disorder, [6] lower melting temperatures, and enhanced elemental interdiffusion. [5,7] Ag alloying of Cu(In,Ga)Se 2 reached great interest and is widely employed to large bandgap chalcopyrites, [8][9][10] while the implementation of Ag into the low-bandgap CISe has received only limited research attention.In the presented work, Ag is supplied by a precursor layer method, [11] which is easy to implement into the three-stage growth process. [12] We investigate simultaneously different) (I/III) ratios of absorbers which underwent a Rb-In-Se capping layer and a NaF post-deposition treatment (PDT). The AAC ratio is varied between 0, 0.02, and 0.1 for low (%0.89) and high (%0.95) I/III ratios.The I/III ratio affects the presence of Cu-depleted (group-I depleted) phases of CISe, which are also associated with order-vacancy compounds (OVCs) and usually segregate at interfaces or at grain boundaries (GBs). Cu-depleted phases of CISe are well known and have been studied for many decades. [13,14] The Cu-poor compounds are commonly identified as n-type CuIn 3 Se 5 and CuIn 5 Se 8 [15] with enhanced V Cu and In Cu defects [16] and enlarged bandgap energy. [17] The thin n-type OVC layer on top of the p-type CISe layer has been reported as substantial to reach highly efficient CISe solar cells [18] The improvement stems from an enhanced valence band offset which forms a hole barrier at the buried homojunction; thus, interface recombination is reduced, and the V OC is improved. [19][20][21] Nowadays, the role of heavy alkali elements (K, Rb, and Cs) is extensively studied in correlation with OVC phases, the formation of an alkali-In-Se compound at