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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 novelband-engineered $III-N/ZnGeN_2$ heterostructure-based device designs forapplications in high performance optoelectronics. We report on thedetermination of the valence band offset between metalorganic chemical vapordeposition 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 foundto lie $1.45-1.65 eV$ above that of $GaN$. This result agrees well with thevalue predicted by first-principles density functional theory calculationsusing the local density approximation for the potential profile andquasiparticle self-consistent GW calculations of the band edge states relativeto the potential. For $(ZnGe)_{0.94}Ga_{0.12}N_2$ the value was determined tobe $1.29 eV$, $~10-20\%$ lower than that of $ZnGeN_2$. The experimentaldetermination of the large band offset between $ZnGeN_2$ and $GaN$ providespromising alternative solutions to address challenges faced with pureIII-nitride-based structures and devices.

Experimental determination of the valence band offsets of $ZnGeN_2$ and $ZnGe_{0.94}Ga_{0.12}N_2$ with $GaN$