CBVB-nH complexes as prevalent defects in metal-organic vapor-phase epitaxy-grown hexagonal boron nitride

Optically active defects in hexagonal boron nitride (hBN) are promising candidates for active components in emerging quantum technologies, such as single-photon emitters and spin centers. However, further progress in hBN-based quantum technologies requires a deeper understanding of the physics and chemistry of hBN defects. In this work, we employ ab initio calculations to investigate the thermodynamic stability and optical properties of defect complexes involving carbon, boron vacancies, and hydrogen. We demonstrate that the formation of C B V B - n H complexes (0 ≤ n ≤ 3) is energetically favorable under nitrogen-rich conditions in the presence of carbon and hydrogen. The low formation energies and high binding energies of these complexes arise from the strong electrostatic attraction between the positively charged carbon substitutional defect (C B ) and the negatively charged hydrogen-passivated boron vacancies (V B - n H). These complexes are particularly likely to form in metal-organic vapor-phase epitaxy (MOVPE)-grown samples, where growth occurs in the presence of carbon and hydrogen and is accompanied by a high density of boron vacancies. The optical properties of C B V B - n H complexes are analyzed and compared to recent photoluminescence measurements on MOVPE-grown hBN samples. In particular, we investigate the origin of the emission peaks at 1.90 eV and 2.24 eV and demonstrate that both the energies and lineshapes are consistent with radiative hole capture by negatively charged C B V B and C B V B -H complexes.