Enhanced Optical 13C Hyperpolarization in Diamond Treated by High‐Temperature Rapid Thermal Annealing

Author(s): Gierth, Max; Krespach, Valentin; Shames, Alexander I; Raghavan, Priyanka; Druga, Emanuel; Nunn, Nicholas; Torelli, Marco; Nirodi, Ruhee; Le, Susan; Zhao, Richard; Aguilar, Alessandra; Lv, Xudong; Shen, Mengze; Meriles, Carlos A; Reimer, Jeffrey A; Zaitsev, Alexander; Pines, Alexander; Shenderova, Olga; Ajoy, Ashok | Abstract: Methods of optical dynamic nuclear polarization (DNP) open the door to the replenishable hyperpolarization of nuclear spins, boosting their NMR/MRI signature by orders of magnitude. Nanodiamond powder rich in negatively charged Nitrogen Vacancy (NV) defect centers has recently emerged as one such promising platform, wherein 13C nuclei can be hyperpolarized through the optically pumped defects completely at room temperature and at low magnetic fields. Given the compelling possibility of relaying this 13C polarization to nuclei in external liquids, there is an urgent need for the engineered production of highly "hyperpolarizable" diamond particles. In this paper, we report on a systematic study of various material dimensions affecting optical 13C hyperpolarization in diamond particles -- especially electron irradiation and annealing conditions that drive NV center formation. We discover surprisingly that diamond annealing at elevated temperatures close to 1720C have remarkable effects on the hyperpolarization levels, enhancing them by upto 36-fold over materials annealed through conventional means. We unravel the intriguing material origins of these gains, and demonstrate they arise from a simultaneous improvement in NV electron relaxation time and coherence time, as well as the reduction of paramagnetic content, and an increase in 13C relaxation lifetimes. Overall this points to significant recovery of the diamond lattice from radiation damage as a result of the high-temperature annealing. Our work suggests methods for the guided materials production of fluorescent, 13C hyperpolarized, nanodiamonds and pathways for their use as multi-modal (optical and MRI) imaging and hyperpolarization agents.