Band Alignment of the CdS/Cu<sub>2</sub>Zn(Sn<sub>1–<i>x</i></sub>Ge<i><sub>x</sub></i>)Se<sub>4</sub> Heterointerface and Electronic Properties at the Cu<sub>2</sub>Zn(Sn<sub>1–<i>x</i></sub>Ge<i><sub>x</sub></i>)Se<sub>4</sub> Surface: <i>x</i> = 0, 0.2, and 0.4

The surface electronic properties of the light absorber and band alignment at the p/n heterointerface are key issues for high-performance heterojunction solar cells. We investigated the band alignment of the heterointerface between cadmium sulfide (CdS) and Ge-incorporated Cu<sub>2</sub>ZnSnSe<sub>4</sub> (CZTGSe), with Ge/(Ge + Sn) ratios (<i>x</i>) between 0 and 0.4, by X-ray photoelectron, ultraviolet, and inversed photoemission spectroscopies (XPS, UPS, and IPES, respectively). In particular, we used interface-induced band bending in order to determine the conduction band offset (CBO) and valence-band offset (VBO), which were calculated from the core-level shifts of each element in both the CdS overlayer and the CZTGSe bottom layer. Moreover, the surface electronic properties of CZTGSe were also investigated by laser-irradiated XPS. The CBO at the CdS/CZTGSe heterointerface decreased linearly, from +0.36 to +0.20 eV, as <i>x</i> was increased from 0 to 0.4; in contrast, the VBO at the CdS/CZTGSe heterointerface was independent of Ge content. Both UPS and IPES revealed that the Fermi level at the CZTGSe surface is located near the center of the band gap. The hole concentration at the CZTGSe surface was on the order of 10<sup>11</sup> cm<sup>–3</sup>, which is much smaller than that of the bulk (∼10<sup>16</sup> cm<sup>–3</sup>). We discuss the differences in hole deficiencies near the surface and in the bulk on the basis of laser-irradiated XPS and conclude that hole deficiencies are due to defects distributed near the surface with densities that are lower than in the bulk, and the Fermi level is not pinned at the CZTGSe surface.