Towards Identifying the PL6 Center in SiC: From First-Principles Screening to Hyperfine Validation of Competing Defect Candidates

The PL6 color center in 4H-SiC, known for its excellent ambient-temperature spin and optical properties, has an unresolved microscopic origin. In this first-principles study, we systematically investigate potential structures to clarify its nature. We first rigorously examine the DV-antisite hypothesis (a divacancy paired with a carbon antisite, $\mathrm{C_{Si}}$), analyzing the energetic, electronic, and spin properties of various $V_\mathrm{Si}V_\mathrm{C}+\mathrm{C_{Si}}$ configurations. Two $\mathrm{C_{3v}}$-symmetric $\mathrm{kk+C_{Si}}$ complexes emerge as strong candidates within this framework. Subsequently, a critical comparison of hyperfine interaction signatures is performed between these candidates, the alternative OV model [specifically OV(hh) and OV(kk), an oxygen replacing C together with a Si vacancy], and experimental data. This analysis demonstrates that the OV(hh) structure more accurately reproduces PL6's hyperfine features. Furthermore, re-evaluation of the proposed OV(hk) model for the related PL5 center reveals zero-field splitting parameter $E$ inconsistencies with experimental results, suggesting that PL5 and PL6 may have distinct origins. These findings provide crucial theoretical insights and motivate targeted experimental validation for these quantum defects.