Small Atom Doping: A Synergistic Strategy to Reduce Sn_Zn Recombination Center Concentration in Cu₂ZnSnSe₄

Abstract

Kesterite Cu 2 ZnSnS x Se 4− x (CZTSSe) is among the most promising inorganic Earth‐abundant thin‐film photovoltaic technologies, although currently, the larger voltage deficit compared with more mature chalcogenide technologies is hampering solar‐to‐electricity conversion efficiency progress in these materials. Most of the latest reports agree on the CZTSSe defect structure as the main limitation for the open‐circuit voltage. Small atom doping is suggested as an interesting strategy to reduce the concentration of defects without affecting secondary phase formation. Herein, an innovative approach based on the introduction of LiAlH 4 and its further decomposition during the selenization process of CZTSe precursors, as a pathway for hydrogen and lithium/alkali transient doping, is explored. This process shows a strong beneficial influence on the crystal growth and solar cell device performance, especially with a significant improvement in V oc and fill factor. A reduction of nonradiative recombination and a remarkable fourfold increase in the carrier lifetime correlating with the reduction of the open‐circuit voltage ( V oc ) deficit below 330 mV is demonstrated. A mechanism on how small atoms (Li and H) interact to reduce the concentration of Sn Zn recombination centers while keeping doping relatively unchanged is proposed, opening fundamental perspectives for the simple and universal transient doping of thin‐film chalcogenide compounds.