Optically addressable spins in wide-bandgap semiconductors have become one of the most prominent platforms for exploring fundamental quantum phenomena. While several candidates in 3D crystals including diamond and silicon carbide have been extensively studied, the identification of spindependent processes in atomically-thin 2D materials has remained elusive. Although optically accessible spin states in hBN are theoretically predicted, they have not yet been observed experimentally. Here, employing rigorous electron paramagnetic resonance techniques and photoluminescence spectroscopy, we identify fluorescence lines in hexagonal boron nitride associated with a particular defect-the negatively charged boron vacancy ( )-and determine the parameters of its spin Hamiltonian. We show that the defect has a triplet (S = 1) ground state with a zero-field splitting of ≈3.5 GHz and establish that the centre exhibits optically detected magnetic resonance (ODMR) at room temperature. We also demonstrate the spin polarization of this centre under optical pumping, which leads to optically induced population inversion of the spin ground state-a prerequisite for coherent spin-manipulation schemes. Our results constitute a leap forward in establishing twodimensional hBN as a prime platform for scalable quantum technologies, with extended potential for spin-based quantum information and sensing applications, as our ODMR studies on hBN -NV diamonds hybrid structures show.

Nitrogen-vacancy colour centres in diamond can undergo strong, spin-sensitive optical transitions under ambient conditions, which makes them attractive for applications in quantum optics 1 , nanoscale magnetometry 2,3 and biolabelling 4 . Although nitrogen-vacancy centres have been observed in aggregated detonation nanodiamonds 5 and milled nanodiamonds 6 , they have not been observed in very small isolated nanodiamonds 7 . Here, we report the first direct observation of nitrogen-vacancy centres in discrete 5-nm nanodiamonds at room temperature, including evidence for intermittency in the luminescence (blinking) from the nanodiamonds. We also show that it is possible to control this blinking by modifying the surface of the nanodiamonds.Detonation nanodiamond is routinely produced on an industrial scale, and the raw material can be disintegrated into a stable 5-nm monodisperse colloid 8 . The combination of inert core and chemically reactive surface, which can host a variety of moieties, is appealing for chemists, biologists and material scientists 9,10 . Quantum magnetometry 2,3 is an example of an emerging technology that will directly benefit from the availability of nanocrystals with welldefined sizes in the 5-nm range, because the sensitivity to single spins is inversely proportional to the cube of the distance between the sensor (that is, the nitrogen-vacancy (NV) centre) and the spin being detected.Producing and detecting NV colour centres in isolated 5-nm detonation nanodiamond has been controversial, and there has been some scepticism regarding their stability as a useful emitter in a discrete crystal. For example, theoretical calculations of the crystal energy budget favour the location of nitrogen on the surface rather than in the core, which seems to explain the limited observation of NV centres in chemical vapour deposition and high-pressure high-temperature grains of less than 40 nm in size 11,12 , and favours the prediction that nanodiamonds smaller than 10 nm in size do not contain NV centres 7,13 . Although sub-10-nm nanodiamonds with NV centres have been produced using a top-down approach (milling luminescent high-pressure hightemperature microdiamonds into 7-nm particles 6,14 ), the question of NV stability in isolated detonation nanodiamonds persists.In aggregated detonation nanodiamonds (agglomerates and agglutinates 8 ), high-sensitivity, time-gated luminescence and electronic paramagnetic resonance spectroscopy have been used to extract a weak NV signal from a strong luminescence background 5 . The experiments highlight the eclipsing nature of the graphitic surface layers in nanodiamond aggregates-NV centres were simply not visible through the broadband luminescence from the surface and grain boundary material. To distinguish the NV spectral signature from the large grain boundary luminescence overhead, diamond synthesis yielding discrete sub-10-nm detonation nanodiamonds is vital. Here, we use a robust deaggregation and dispersion method, which diminishes the crystal-crystal interaction to...

Single photon emitters (SPEs) in hexagonal boron nitride (hBN) have garnered significant attention over the last few years due to their superior optical properties. However, despite the vast range of experimental results and theoretical calculations, the defect structure responsible for the observed emission has remained elusive. Here, by controlling the incorporation of impurities into hBN via various bottom-up synthesis methods and directly through ion implantation we provide direct evidence that the visible SPEs are carbon related. Room temperature optically detected magnetic resonance (ODMR) is demonstrated on ensembles of these defects. We perform ion implantation experiments and confirm that only carbon implantation creates SPEs in the visible spectral range. Computational analysis of the simplest 12 carbon-containing defect species suggest the negatively charged V B C N − defect as a viable 53 candidate and predict that out-of-plane deformations make the defect environmentally sensitive. 54Our results resolve a long-standing debate about the origin of single emitters at the visible range 55 grown epitaxially. 28, 29 The energy detuning between the ZPL of the ensemble and phonon sideband (PSB) peak is ~176 meV on average (Extended Data Fig. 1). 30, 31 X-ray photoelectron spectroscopy (XPS) was used to quantify the incorporation of carbon (Extended Data Fig. 2). Figure 1b(c) demonstrate a near linear correlation between C-B (C-N) bonding and increasing TEB flux, with C-B bonding being roughly an order of magnitude more prevalent than C-N bonding. Preferential formation of C-B bonds follows logically from noting the B species are introduced with three pre-existing bonds to C. PL intensity of the resulting ensemble emission likewise displays a linear correlation with carbon concentration (Extended Data Fig. 3). Based on these results, we advance that the SPE emission at ~580 nm in hBN is likely to originate from a carbon-related defect complex. Figure 1-Photoluminescence from MOVPE hBN Samples. a. MOVPE hBN grown with increasing flow rates of triethyl borane (TEB). As TEB flow increases, the fluorescence of SPE ensembles increases. b. Percentage of B-C bonding with increasing TEB flow evaluated by XPS. c. Percentage of N-C bonding with increasing TEB flow evaluated by XPS. d. Room temperature ODMR displayed as relative contrast, spin-dependent variation in photoluminescence (∆PL/PL), observed from the ~585 nm ensemble emission of MOPVE hBN (TEB 60) at applied fields of 19, 24, and 29 mT respectively. e.