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GaN based heterostructures have recently gained increased interest due to their applications for high electron mobility transistors. In this letter AlInN/AlN/GaN heterojunctions grown by metal-organic chemical-vapor deposition with different AlN thicknesses have been investigated by surface photovoltage spectroscopy. The density of the two-dimensional electron gas (2DEG) forming at the interface has been measured by Hall effect. A band gap shift has been detected and its dependence on the 2DEG electron density at the AlN/GaN interface has been analyzed on the basis of the Moss–Burstein and renormalization effects.