Phonon-assisted charge-cycling of nitrogen-vacancy centres in diamond

The nitrogen-vacancy (NV) centre in diamond is a leading platform for room-temperature quantum sensing. Improvements in sensitivity require precise control of the NV charge state. Transitions from the neutral NV${}^0$ charge state to the negative NV${}^{-}$ charge state can occur during excitation with photon energies below the ZPL transition of NV${}^0$. These sub-resonant charge transitions limit modern initialisation protocols and have not been studied in full detail. In this paper we show that sub-resonant charge cycling arises from phonon-assisted anti-Stokes excitation. We further uncover the phonon states which contribute most strongly to the anti-Stokes transition via the development of novel quantitative models. The models indicate that low energy acoustic phonons strongly contribute to the transition close to the ZPL. At longer wavelengths a 43,meV mode additionally impacts the charge cycling dynamics.