Epitaxial growth on Si-face nominally on-axis 4H-SiC substrates has been performed using horizontal Hot-wall chemical vapor deposition system. The formation of 3C inclusions is one of the main problem with growth on on-axis Si-face substrates. In situ surface preparation, starting growth parameters and growth temperature are found to play a vital role in the epilayer polytype stability. High quality epilayers with 100% 4H-SiC were obtained on full 2? substrates. Different optical and structural techniques were used to characterize the material and to understand the growth mechanisms. It was found that the replication of the basal plane dislocation from the substrate into the epilayer can be eliminated through growth on on-axis substrates. Also, no other kind of structural defects were found in the grown epilayers. These layers have also been processed for simple PiN structures to observe any bipolar degradation. More than 70% of the diodes showed no forward voltage drift during 30 min operation at 100 A/cm2.