The optimization of growth parameters, epitaxial structure, and device design for full-vertical gallium nitride (GaN) p-i-n rectifiers grown on n-type 6H-SiC substrates employing AlGaN:Si conducting buffer layers have been studied. The Al x Ga1−x N:Si (x = ~0.1) nucleation layer is calibrated to be capable of acting as a good buffer layer for subsequent GaN growth as well as to provide excellent electrical properties. Two types of full-vertical devices were fabricated and compared: one without any current guiding and the other with the current guiding in the p-layer. The reverse breakdown voltage for rectifiers with a relatively thin 2.5-μm-thick i-region without p-current guiding was found to be over −330 V, while one with p-current guiding was measured to be over −400 V. Devices with p-current guiding structures exhibit reduced reverse leakage current by an order of magnitude >4 at −100 V.