Oxygen-vacancy quantum spin defects in silicon carbide

Optically addressable spin defects in wide-bandgap semiconductors are promising building blocks for quantum sensing and quantum networks. Establishing their atomic structure is essential for understanding functionality and enabling controlled engineering. In 4H-SiC, the PL5 and PL6 centers have long been recognized for their exceptional charge stability and room-temperature optically detected magnetic resonance (ODMR) performance, but their structural origin has remained elusive for over a decade. Here, we provide direct evidence for their oxygen-vacancy (${\rm O_C V_{Si}}$) origins through a combined chemical and isotopic control strategy. Under oxygen ion implantation, we observe over tenfold enhancement in the yield of PL5 and PL6 compared to nitrogen ion implantation. Furthermore, implantation with $^{17}{\rm O}$ ions produces PL5 and PL6 defects that exhibit a characteristic six-fold $^{17}{\rm O}$ hyperfine splitting in their ODMR spectra. These results affirm PL6 as the ${\rm O_C V_{Si}}$ defect in the $hh$ configuration. For PL5, the oxygen-related evidence, together with \textit{ab initio} calculations and additional measurements of the zero-field splitting and hyperfine structure, establishes it as the ${\rm O_C V_{Si}}$ defect in the $kh$ configuration. This unambiguous structural identification, achieved through materials-level chemical control, provides the microscopic foundation for deterministic engineering of these defects, paving the way for scalable photonic devices and high-sensitivity ensemble quantum sensors based on oxygen-vacancy centers.