Dynamics of frequency-swept nuclear spin optical pumping in powdered diamond at low magnetic fields.

A broad effort is underway to improve the sensitivity of NMR through the use of dynamic nuclear polarization. Nitrogen vacancy (NV) centers in diamond offer an appealing platform because these paramagnetic defects can be optically polarized efficiently at room temperature. However, work thus far has been mainly limited to single crystals, because most polarization transfer protocols are sensitive to misalignment between the NV and magnetic field axes. Here we study the spin dynamics of NV-13C pairs in the simultaneous presence of optical excitation and microwave frequency sweeps at low magnetic fields. We show that a subtle interplay between illumination intensity, frequency sweep rate, and hyperfine coupling strength leads to efficient, sweep-direction-dependent 13C spin polarization over a broad range of orientations of the magnetic field. In particular, our results strongly suggest that finely tuned, moderately coupled nuclear spins are key to the hyperpolarization process, which makes this mechanism distinct from other known dynamic polarization channels. These findings pave the route to applications where powders are intrinsically advantageous, including the hyperpolarization of target fluids in contact with the diamond surface or the use of hyperpolarized particles as contrast agents for in vivo imaging.

Charge Dynamics in near-Surface, Variable-Density Ensembles of Nitrogen-Vacancy Centers in Diamond.

Although the spin properties of superficial shallow nitrogen-vacancy (NV) centers have been the subject of extensive scrutiny, considerably less attention has been devoted to studying the dynamics of NV charge conversion near the diamond surface. Using multicolor confocal microscopy, here we show that near-surface point defects arising from high-density ion implantation dramatically increase the ionization and recombination rates of shallow NVs compared to those in bulk diamond. Further, we find that these rates grow linearly, not quadratically, with laser intensity, indicative of single-photon processes enabled by NV state mixing with other defect states. Accompanying these findings, we observe NV ionization and recombination in the dark, likely the result of charge transfer to neighboring traps. Despite the altered charge dynamics, we show that one can imprint rewritable, long-lasting patterns of charged-initialized, near-surface NVs over large areas, an ability that could be exploited for electrochemical biosensing or to optically store digital data sets with subdiffraction resolution.

On-Demand Generation of Neutral and Negatively Charged Silicon-Vacancy Centers in Diamond.

Point defects in wide-band-gap semiconductors are emerging as versatile resources for nanoscale sensing and quantum information science, but our understanding of the photoionization dynamics is presently incomplete. Here, we use two-color confocal microscopy to investigate the dynamics of charge in type 1b diamond hosting nitrogen-vacancy (NV) and silicon-vacancy (SiV) centers. By examining the nonlocal fluorescence patterns emerging from local laser excitation, we show that, in the simultaneous presence of photogenerated electrons and holes, SiV (NV) centers selectively transform into the negative (neutral) charge state. Unlike NVs, 532 nm illumination ionizes SiV^{-} via a single-photon process, thus hinting at a comparatively shallower ground state. In particular, slower ionization rates at longer wavelengths suggest the latter lies approximately ∼1.9 eV below the conduction band minimum. Building on the above observations, we demonstrate on-demand SiV and NV charge initialization over large areas via green laser illumination of variable intensity.

Stability of Near-Surface Nitrogen Vacancy Centers Using Dielectric Surface Passivation.

We study the photophysical stability of ensemble near-surface nitrogen vacancy (NV) centers in diamond under vacuum and air. The optically detected magnetic resonance contrast of the NV centers was measured following exposure to laser illumination, showing opposing trends in air compared to vacuum (increasing by up to 9% and dropping by up to 25%, respectively). Characterization using X-ray photoelectron spectroscopy (XPS) suggests a surface reconstruction: In air, atmospheric oxygen adsorption on a surface leads to an increase in NV- fraction, whereas in vacuum, net oxygen desorption increases the NV0 fraction. NV charge state switching is confirmed by photoluminescence spectroscopy. Deposition of ∼2 nm alumina (Al2O3) over the diamond surface was shown to stabilize the NV charge state under illumination in either environment, attributed to a more stable surface electronegativity. The use of an alumina coating on diamond is therefore a promising approach to improve the resilience of NV sensors.

Orientation-independent room temperature optical 13C hyperpolarization in powdered diamond.

Dynamic nuclear polarization via contact with electronic spins has emerged as an attractive route to enhance the sensitivity of nuclear magnetic resonance beyond the traditional limits imposed by magnetic field strength and temperature. Among the various alternative implementations, the use of nitrogen vacancy (NV) centers in diamond-a paramagnetic point defect whose spin can be optically polarized at room temperature-has attracted widespread attention, but applications have been hampered by the need to align the NV axis with the external magnetic field. We overcome this hurdle through the combined use of continuous optical illumination and a microwave sweep over a broad frequency range. As a proof of principle, we demonstrate our approach using powdered diamond with which we attain bulk 13C spin polarization in excess of 0.25% under ambient conditions. Remarkably, our technique acts efficiently on diamond crystals of all orientations and polarizes nuclear spins with a sign that depends exclusively on the direction of the microwave sweep. Our work paves the way toward the use of hyperpolarized diamond particles as imaging contrast agents for biosensing and, ultimately, for the hyperpolarization of nuclear spins in arbitrary liquids brought in contact with their surface.

Long-term data storage in diamond.

The negatively charged nitrogen vacancy (NV-) center in diamond is the focus of widespread attention for applications ranging from quantum information processing to nanoscale metrology. Although most work so far has focused on the NV- optical and spin properties, control of the charge state promises complementary opportunities. One intriguing possibility is the long-term storage of information, a notion we hereby introduce using NV-rich, type 1b diamond. As a proof of principle, we use multicolor optical microscopy to read, write, and reset arbitrary data sets with two-dimensional (2D) binary bit density comparable to present digital-video-disk (DVD) technology. Leveraging on the singular dynamics of NV- ionization, we encode information on different planes of the diamond crystal with no cross-talk, hence extending the storage capacity to three dimensions. Furthermore, we correlate the center's charge state and the nuclear spin polarization of the nitrogen host and show that the latter is robust to a cycle of NV- ionization and recharge. In combination with super-resolution microscopy techniques, these observations provide a route toward subdiffraction NV charge control, a regime where the storage capacity could exceed present technologies.

Optical patterning of trapped charge in nitrogen-doped diamond.

The nitrogen-vacancy (NV) centre in diamond is emerging as a promising platform for solid-state quantum information processing and nanoscale metrology. Of interest in these applications is the manipulation of the NV charge, which can be attained by optical excitation. Here, we use two-colour optical microscopy to investigate the dynamics of NV photo-ionization, charge diffusion and trapping in type-1b diamond. We combine fixed-point laser excitation and scanning fluorescence imaging to locally alter the concentration of negatively charged NVs, and to subsequently probe the corresponding redistribution of charge. We uncover the formation of spatial patterns of trapped charge, which we qualitatively reproduce via a model of the interplay between photo-excited carriers and atomic defects. Further, by using the NV as a probe, we map the relative fraction of positively charged nitrogen on localized optical excitation. These observations may prove important to transporting quantum information between NVs or to developing three-dimensional, charge-based memories.