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A predicted type-II staggered band alignment with an approximately $1.4 eV$ valence band offset at the $ZnGeN_2/GaN$ heterointerface has inspired novel band-engineered $III-N/ZnGeN_2$ heterostructure-based device designs for applications in high performance optoelectronics. We report on the determination of the valence band offset between metalorganic chemical vapor deposition grown $(ZnGe)_{1-x}Ga_{2x}N_2$, for $x = 0$ and $0.06$, and $GaN$ using X-ray photoemission spectroscopy. The valence band of $ZnGeN_2$ was found to lie $1.45-1.65 eV$ above that of $GaN$. This result agrees well with the value predicted by first-principles density functional theory calculations using the local density approximation for the potential profile and quasiparticle self-consistent GW calculations of the band edge states relative to the potential. For $(ZnGe)_{0.94}Ga_{0.12}N_2$ the value was determined to be $1.29 eV$, $~10-20%$ lower than that of $ZnGeN_2$. The experimental determination of the large band offset between $ZnGeN_2$ and $GaN$ provides promising alternative solutions to address challenges faced with pure III-nitride-based structures and devices.
The valence band offsets (VBO) for the b{eta}-type A3B6 layered compounds depending on the thickness of the crystals have been investigated from the first principles, based on the density functional theory. To simulate the structure of a given thickn
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