Neutral silicon vacancy (SiV0) centers in diamond are promising candidates for quantum networks because of their excellent optical properties and long spin coherence times. In this work, we present the observation of previously unreported optical transitions in SiV0 that are capable of efficiently polarizing the ground state spin. We assign groups of transitions from 825 to 890 nm to higher-lying excited states of SiV0 through a combination of optical and spin measurements. We interpret these spectroscopic lines as transitions to bound exciton states of the defect. Optical spin polarization via these bound exciton states enables the observation of optically detected magnetic resonance of SiV0.
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