We provide direct evidence that the broad Z1/2 peak, commonly observed by conventional deep level transient spectroscopy in as-grown and at high concentrations in radiation damaged 4H-SiC, has two components, namely, Z1 and Z2, with activation energies for electron emissions of 0.59 and 0.67 eV, respectively. We assign these components to Z1/2=Z1/2+eZ1/20+2e transition sequences from negative-U ordered acceptor levels of carbon vacancy (VC) defects at hexagonal/pseudo-cubic sites, respectively. By employing short filling pulses at lower temperatures, we were able to characterize the first acceptor level of VC on both sub-lattice sites. Activation energies for electron emission of 0.48 and 0.41 eV were determined for Z1(/0) and Z2(/0) transitions, respectively. Based on trap filling kinetics and capture barrier calculations, we investigated the two-step transitions from neutral to doubly negatively charged Z1 and Z2. Positions of the first and second acceptor levels of VC at both lattice sites, as well as (=/0) occupancy levels, were derived from the analysis of the emission and capture data.

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