We reveal a new approach for forming a Ag-graded absorber to overcome the large open-circuit voltage deficit in (Cu,Ag)2ZnSn(S,Se)4 solar cells.

The partial substitution of Cu with Ag into the host lattice of CuZnSn(S,Se) thin films can reduce the open-circuit voltage deficit (V) of CuZnSn(S,Se) (CZTSSe) solar cells. In this paper, elemental Cu, Ag, Zn, Sn, S, and Se powders were dissolved in solvent mixture of 1,2-ethanedithiol (edtH) and 1,2-ethylenediamine (en) and used for the formation of (CuAg)ZnSn(S,Se) (CAZTSSe) thin films with different Ag/(Ag + Cu) ratios. The key feature of this approach is that the impurity atoms can be absolutely excluded. Further results indicate that the variations of grain size, band gap, and depletion width of the CAZTSSe layer are generally determined by Ag substitution content. Benefiting from the V enhancement (∼50 mV), the power conversion efficiency is successfully increased from 7.39% (x = 0) to 10.36% (x = 3%), which is the highest efficiency of Ag substituted devices so far.

Cu­(In,Ga)­Se2 (CIGS) is considered a promising photovoltaics material due to its excellent properties and high efficiency. However, the complicated deep defects (such as InCu or GaCu) in the CIGS layer hamper the development of polycrystalline CIGS solar cells. Numerous efforts have been employed to passivate these defects which distributed in the grain boundary and the CIGS/CdS interface. In this work, we implemented an effective Ag substituting approach to passivate bulk defects in CIGS absorber. The composition and phase characterizations revealed that Ag was successfully incorporated in the CIGS lattice. The substituting of Ag could boost the crystallization without obviously changing the band gap. The C–V and EIS results demonstrated that the device showed enlarged Wd and beneficial carrier transport dynamics after Ag incorporation. The DLTS result revealed that the deep InCu defect density was dramatically decreased after Ag substituting for Cu. A champion Ag-substituted CIGS device exhibited a remarkable efficiency of 15.82%, with improved V OC of 630 mV, J SC of 34.44 mA/cm2, and FF of 72.90%. Comparing with the efficiency of an unsubstituted CIGS device (12.18%), a Ag-substituted CIGS device exhibited 30% enhancement.

Additional elements in the Cu 2 ZnSn(S,Se) 4 (CZTSSe) absorber layers can play a crucial role in improving the performance of thin film solar cells. In this paper, a significant performance enhancement of CZTSSe thin film solar cells was achieved by the partial substitution of the Zn 2+ cation with Cd 2+ . A small amount of Cd 2+ can be successfully incorporated into the host lattice of CZTSSe to form a homogeneous Cu 2 Zn 1−x Cd x Sn(S,Se) 4 (CZCTSSe) alloy material. We demonstrated that the crystal growth and the band gap of CZCTSSe thin films are affected by the Cd doping level. Additionally, the impact of Cd content on the space-charge density (N c-v ) and the depletion width (W d ) of CZCTSSe solar cells was systematically investigated. By this cation substitution approach, the power conversion efficiency of the solar cells based on the CZCTSSe absorber was successfully increased from 5.41 to 8.11% for the optimal composition (x = 5%).

Solution processing of Cu(In,Ga)Se2 (CIGS) absorber makes it cost‐competitive in the photovoltaic market. It is reported that copper‐poor ordered vacancy compound (OVC) is crucial for high performance CIGS solar cells. However, in solution process method, controllable formation of OVC is unavailable and limited research has been carried out. In this work, the controllable formation of the OVC phase on the CIGS surface is successful by controlling the selenization temperature and intentional variation of Cu/(In+Ga) stoichiometry in precursors for top layers and bulk layers deposition. The effects of OVC contents on the device performance are investigated. The CIGS thin film with OVC phase exhibits a lower valence band position. Meanwhile, the CIGS devices with optimized OVC content show decreased interface defects density and better carrier collection ability. The above advantages translate into a champion PCE of 16.39% for CIGS device with OVC phase, which is the champion performance among non‐hydrazine solution‐processed CIGS solar cells. The results demonstrate that the controllable formation of OVC phase approach should make a significant contribution to the efficiency promoting of solution processed CIGS solar cells.