Photoemission Study of GaN Passivation Layers and Band Alignment at GaInP(100) Heterointerfaces

To date, III-V semiconductor-based tandem devices with GaInP top photoabsorbers show the highest solar-to-electricity or solar-to-fuel conversion efficiencies. In photoelectrochemical (PEC) cells, however, III-V semiconductors are sensitive, in terms of photochemical stability and, therefore, require suitable functional layers for electronic and chemical passivation. GaN films are discussed as promising options for this purpose. The band alignment between such a protection layer and the III-V semiconductor should be aligned to minimize corrosion and nonradiative interfacial recombination and to promote selective charge carrier transport. Here, we investigate the band alignment between GaN passivation layers and n-type doped GaInP(100) photoabsorbers and grew n-type GaInP(100) epitaxially by metalorganic vapor phase epitaxy on oxidized GaAs(100) substrates to mimic a realistic preparation sequence. We prepared 1-20 nm GaN films on top employing atomic layer deposition and studied the band alignment at the GaN/GaInP(100) heterointerface by X-ray and ultraviolet photoelectron spectroscopy. Due to the limited emission depth of photoelectrons, we determined the band alignment by a series of measurements, in which we increased the thickness of the GaN films successively. The n-GaInP(100) surfaces, prepared with a well-known phosphorus-terminated p(2 × 2)/c(4 × 2) reconstruction, show an upward surface band bending (BB) of 0.38 eV and a Fermi level pinning due to the present surface states. Upon oxidation, the surface states are partially passivated, resulting in a reduction of the BB to 0.16 eV and a valence band offset (VBO) between the GaInP(100) and the thin oxide layer of 2.01 eV. Applying Kraut's approach, we identified a VBO of 1.90 eV and a conduction band offset of 0.44 eV between GaInP(100) with a thin oxide layer and the GaN passivation layer. We conclude that the GaN is a well-suited passivation layer for PEC cells and facilitates selective transport of photogenerated electrons.