Impressive power densities have been demonstrated for GaN-on-SiC based high-power high-frequency transistors, although further gains can be achieved by further minimizing the device thermal resistance. A significant 10-30% contribution to the total device thermal resistance originates from the high defect density AlN nucleation layer at the GaN/SiC interface. This thermal resistance contribution was successfully reduced by performing systematic growth optimization, investigating growth parameters including: Substrate pretreatment temperature, growth temperature and deposition time. Interfacial thermal resistance, characterized by time resolved Raman thermography measurements AlGaN/GaN HEMT structures, were minimized by using a substrate pretreatment and growth temperature of 1200 °C. Reducing the AlN thickness from 105 nm (3.3×10-8 W/m2K) to 35 nm (3.3×10-8 W/m2K), led to a ~2.5× interfacial thermal resistance reduction and the lowest value reported for a standard AlGaN/GaN HEMT structure.