The effect of KOH pretreatment for Au/Ni Schottky contacts to GaN is investigated using I-V and x-ray photoemission spectroscopy (XPS) analysis. The molten KOH pretreatment reduces the interface trap density from 1.0 X 10(12) to 2 X 10(11) cm(-2) eV(-1), improves the on-state performance, and increases the barrier height by 10%. XPS indicates that KOH improves the GaN Schottky diode performance by eliminating an oxide layer between the metal and the semiconductor, increasing the band bending through charge transfer, and improving the GaN stoichiometry at the surface. First principle simulations indicate that the nitrogen antisite and to a minor extent the gallium antisite are also possible constituents of this interfacial layer along with gallium and nitrogen vacancies. These antisite defects can be passivated by KOH. (C) 2010 American Vacuum Society. [DOI: 10.1116/1.3299253]