Spectroscopy of photoionization from the $^1E$ singlet state in nitrogen$-$vacancy centers in diamond

The $^1E-^1A_1$ singlet manifold of the negatively charged nitrogen vacancy $(NV^-)$ center in diamond plays a central role in the quantum information and quantum sensing applications of the $NV^-$ center. However, the energy of this manifold within the diamond bandgap and with respect to the $^3A_2-^3E$ triplet manifold has not been measured directly. Using field-quenching effects on photoluminescence (PL) spectra, we report on the energy gap between the $^1E-^1A_1$ singlet manifold and the $^3A_2$ and $^3E$ ground and excited triplet states of the $NV^-$ as a function of excitation wavelength and power, temperature, and applied magnetic field in a heavily nitrogen-doped sample. Increased PL and decreased zero-phonon line width from the $NV^0$ were observed in the presence of an applied magnetic field, indicating ionization from the long-lived $^1E$ singlet state. A temperature-dependent ionization threshold between 532 nm and 550 nm was found, locating the singlet states within the diamond band gap.