Microwave-Free $^{13}$C Hyperpolarization of Diamond Particles Enabled by Magic Angle Spinning and NV Centers

Abstract

Nuclear hyperpolarization from optically pumped color centers in solids offers an alternative to conventional microwave-driven dynamic nuclear polarization (DNP). Diamond can host the nitrogen vacancy (NV) center, whose ground spin state can be readily polarized by light at room temperature, making diamond a candidate platform for nuclear hyperpolarization. We report $^{13}{\rm C}$ nuclear hyperpolarization in randomly oriented diamond particles with sizes ranging from 0.2 to 2 $μ$m, both at natural $^{13}{\rm C}$ abundance (1.1 %) and at 20 % isotopic enrichment, at magnetic fields of 7.1 T and 9.4 T. The protocol combines optical illumination with magic angle spinning (MAS) and does not require microwave irradiation. By investigating the nuclear polarization as a function of the MAS frequency between 0 and 6 kHz at the magnetic field of 7.1 T, we find maximum light-induced polarization enhancements of $280$-fold for the isotopically enriched sample and $411$-fold for the natural abundance sample. Under continuous illumination, steady-state absolute $^{13}{\rm C}$ polarization levels above 0.1 % are reached. A model involving optical pumping of NV centers and spin dynamics near level anticrossings (LACs) in three-spin clusters formed by NV, a substitutional nitrogen (P1) and $^{13}{\rm C}$ is used to describe these findings. The protocol strongly mitigates the effect of the anisotropy of the NV spin Hamiltonian, allowing more than $99.9\%$ of NV orientations to participate in the polarization transfer process. These results represent a first step toward transferring nuclear polarization from diamond particles to external nuclei, with potential applications in sensitive and high-resolution NMR at room temperature.