Polycrystalline, partially epitaxial Sc2O3 films were grown on AlGaN/GaN substrates by atomic layer deposition (ALD). With this ALD Sc2O3 film as the insulator layer, the Sc2O3/AlGaN/GaN metal-insulator-semiconductor high electron mobility transistors showed excellent electrical performance with a high Ion/Ioff ratio of over 108 and a low subthreshold slope of 75 mV/dec. The UV/NH4OH surface treatment on AlGaN/GaN prior to ALD was found to be critical for achieving these excellent figures. In addition, the Sc2O3 dielectric is found to be negatively charged, which facilitates the enhancement-mode operation. While bare Sc2O3 suffers from moisture degradation, depositing a moisture blocking layer of ALD Al2O3 can effectively eliminate this effect.