Energy-band alignment of II-VI/Zn3P2 heterojunctions from x-ray photoemission spectroscopy

The energy-band alignments for zb-ZnSe(001)/a-Zn 3 P 2 (001), w-CdS(0001)/a-Zn 3 P 2 (001), and w-ZnO(0001)/a-Zn 3 P 2 (001) heterojunctions have been determined using high-resolution x-ray photoelectron spectroscopy via the Kraut method. Ab initio hybrid density functional theory calculations of the valence-band density of states were used to determine the energy differences between the core level and valence-band maximum for each of the bulk materials. The ZnSe/Zn 3 P 2 heterojunction had a small conduction-band offset, DE C , of À0.03 6 0.11 eV, demonstrating a nearly ideal energy-band alignment for use in thin-film photovoltaic devices. The CdS/Zn 3 P 2 heterojunction was also type-II but had a larger conduction-band offset of DE C ¼ À0.76 6 0.10 eV. A type-III alignment was observed for the ZnO/Zn 3 P 2 heterojunction, with DE C ¼ À1.61 6 0.16 eV indicating the formation of a tunnel junction at the oxide–phosphide interface. The data also provide insight into the role of the II-VI/Zn 3 P 2 band alignment in the reported performance of Zn 3 P 2 heterojunction solar cells.