| Summary: | Optically addressable high-spin states (S ≥ 1) of defects in semiconductors are the basis for the development of solid-state quantum technologies. Recently, one such defect has been found in hexagonal boron nitride (hBN) and identified as a negatively charged boron vacancy (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mi mathvariant="normal">V</mi><mi mathvariant="normal">B</mi><mo>−</mo></msubsup></mrow></semantics></math></inline-formula>). To explore and utilize the properties of this defect, one needs to design a robust way for its creation in an hBN crystal. We investigate the possibility of creating <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mi mathvariant="normal">V</mi><mi mathvariant="normal">B</mi><mo>−</mo></msubsup></mrow></semantics></math></inline-formula> centers in an hBN single crystal by means of irradiation with a high-energy (E = 2 MeV) electron flux. Optical excitation of the irradiated sample induces fluorescence in the near-infrared range together with the electron spin resonance (ESR) spectrum of the triplet centers with a zero-field splitting value of <i>D</i> = 3.6 GHz, manifesting an optically induced population inversion of the ground state spin sublevels. These observations are the signatures of the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mi mathvariant="normal">V</mi><mi mathvariant="normal">B</mi><mo>−</mo></msubsup></mrow></semantics></math></inline-formula> centers and demonstrate that electron irradiation can be reliably used to create these centers in hBN. Exploration of the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mi mathvariant="normal">V</mi><mi mathvariant="normal">B</mi><mo>−</mo></msubsup></mrow></semantics></math></inline-formula> spin resonance line shape allowed us to establish the source of the line broadening, which occurs due to the slight deviation in orientation of the two-dimensional B-N atomic plains being exactly parallel relative to each other. The results of the analysis of the broadening mechanism can be used for the crystalline quality control of the 2D materials, using the <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mi mathvariant="normal">V</mi><mi mathvariant="normal">B</mi><mo>−</mo></msubsup></mrow></semantics></math></inline-formula> spin embedded in the hBN as a probe.
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