AlGaN/GaN/AlN transistor structures were grown onto SiC substrates by molecular-beam epitaxy. Under aluminum-rich growth conditions for the AlN nucleation layer, undesirable n-type conduction is observed near the GaN/AlN interface for even thick (≫1000 Å) AlN layers. Silicon is identified as the unwanted dopant from secondary-ion mass spectroscopy measurements. Atomic force microscopy surface maps reveal free aluminum metal on AlN surfaces grown under modest aluminum-rich conditions. It is proposed that rapid silicon migration is caused by molten aluminum reacting with the SiC substrate resulting in dissolved silicon that rapidly migrates through the growing AlN layer. This behavior is significantly reduced using a growth flux ratio of aluminum to reactive nitrogen close to unity. The resulting buffer leakage current of the GaN high electron mobility transistor structure is reduced by more than four orders of magnitude.