Manganese-substituted kesterite thin-films for earth-abundant photovoltaic applications

Thin film photovoltaic devices based on CdTe and Cu(In,Ga)Se2 find in Cu2ZnSn(S,Se)4-based technology a more eco-friendly alternative. To further reduce production costs and improve sustainability, other abundant metals, such as manganese, can be tested as a potential alternative to zinc. Mn is a safe and Earth-abundant element, and it can be used in light absorber materials when it is part of quaternary chalcogenides with copper and tin. This work reports on the growth and characterization of Cu2MnSnS4 thin films produced by a two-step deposition process. The metallic precursors have been deposited by sputtering and the stack annealed at high temperatures in sulphur atmosphere. The layers, obtained in Cu-poor Mn-poor compositional regime, have been tested in solar devices with a record efficiency of 1.13% and a high open-circuit voltage of about 445 mV delivered by the champion device after over one year from the first PV measurement. X-ray diffraction and X-ray photoelectron, Raman, photoluminescence, and admittance spectroscopies have been used to investigate the Cu2MnSnS4 defectivity, and a scenario of high defects has emerged. Therefore, to promote the development of Mn-based photovoltaics the synthesis methodology should be optimized and the device architecture should be specifically designed for the compound.