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We study spectroscopy of negatively charged nitrogen-vacancy center in diamond at high temperatures under high vacuum conditions. Spin resonances are studied using optical detection of magnetic resonance (ODMR), and optical spectroscopy is employed to study radiative transitions. Upon increasing the temperature the intensity of radiative decay in visible and infra-red decreased. In addition, the ODMR resonance frequencies were decreased, and the phonon line emission shifted to higher wavelengths. Fitting the measured intensity of photo-luminescence with the theoretical predictions of the Mott-Seitz model yields the value of for the energy barrier associated with nonradiative decay.

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