Characterization of Surface and Heterointerface of Cu2ZnSn1–xGexSe4 for Solar Cell Applications

This study analyzes the electronic structure of Cu2ZnSn1–xGexSe4 (CZTGSe) surface and band alignments of CdS and CZTGSe using the Ge/(Sn + Ge) composition ratios of x = 0–1 based on inversed, ultraviolet, and X‐ray photoemission spectroscopy. The conduction band offsets of the CdS/CZTGSe interface linearly decrease with increasing x, which are so‐called spike conduction band connections, whereas the valence band offsets are observed to be independent of x. Moreover, the hole density near the CZTGSe surface increases with an increase in x; this corresponds to the increase in the measured built‐in‐potential with x. However, the open circuit voltage (VOC) saturates to ≈0.5 V for x over 0.2 in spite of the favorable band alignment and larger built‐in‐potential of x at the interface. External‐quantum‐efficiency spectral analysis shows that the carrier recombination in CZTGSe bulk is suppressed with an increase in x, whereas the recombination near the CZTGSe surface is enhanced. The relationship between these recombination centers, electronic structure, and saturation of VOC is discussed. Solar cell performance is saturated by the formation of recombination centers near the Cu2ZnSn1–xGexSe4 (CZTGSe) surface in spite of having a preferred band alignment of the CdS/CZTGSe interface. Moreover, these surface recombination centers increase with x, whereas the recombination centers in CZTGSe bulk decrease.