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Sputter‐deposited GaOx (i.e., oxygen‐deficient gallium oxide) films are evaluated as a potential replacement for the standard CdS buffer layers in Cu(In,Ga)Se2 (CIGSe) based thin‐film photovoltaics. The energy level alignment at the GaOx/CIGSe and CdS/CIGSe interfaces are compared by means of direct and inverse photoemission. For the GaOx/CIGSe a (0.04 ± 0.07) eV (i.e., a small spike‐like) conduction band offset (CBO) and a (−3.21 ± 0.19) eV (i.e., a large cliff‐like) valence band offset (VBO) are found, which suggests a nearly ideal charge‐selective contact. The derived GaOx band gap of (4.80 ± 0.25) eV confirms its utility as a highly transparent buffer layer. However, the GaOx (with x derived to be 1.1 ± 0.1) exhibits considerable (presumably) defect‐related occupied states above the valence band maximum. It is proposed that these states may increase charge carrier recombination and decrease open circuit voltage in respective devices; also explaining why solar cells with standard CdS buffer outperform devices with GaOx buffer, despite less ideal electronic interface properties (CBO: (−0.18 ± 0.07) eV, VBO: (−0.98 ± 0.15) eV) and the smaller CdS band gap of (2.35 ± 0.22) eV. [ABSTRACT FROM AUTHOR]

The electronic band alignment of the Zn(O,S)/Cu(In,Ga)Se2 interface in high-efficiency thin-film solar cells was derived using X-ray photoelectron spectroscopy, ultra-violet photoelectron spectroscopy, and inverse photoemission spectroscopy. Similar to the CdS/Cu(In,Ga)Se2 system, we find an essentially flat (small-spike) conduction band alignment (here: a conduction band offset of (0.09 ± 0.20) eV), allowing for largely unimpeded electron transfer and forming a likely basis for the success of high-efficiency Zn(O,S)-based chalcopyrite devices. Furthermore, we find evidence for multiple bonding environments of Zn and O in the Zn(O,S) film, including ZnO, ZnS, Zn(OH)2, and possibly ZnSe. Copyright © 2016 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]