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

Methods of optical dynamic nuclear polarization open the door to the replenishable hyperpolarization of nuclear spins, boosting their nuclear magnetic resonance/imaging signatures by orders of magnitude. Nanodiamond powder rich in negatively charged nitrogen vacancy 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. 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. Here, a systematic study of various material dimensions affecting optical 13C hyperpolarization in diamond particles is reported on. It is discovered surprisingly that diamond annealing at elevated temperatures ∼1720 °C has remarkable effects on the hyperpolarization levels enhancing them by above an order of magnitude over materials annealed through conventional means. It is demonstrated these gains arise from a simultaneous improvement in NV− electron relaxation/coherence times, as well as the reduction of paramagnetic content, and an increase in 13C relaxation lifetimes. This work suggests methods for the guided materials production of fluorescent, 13C hyperpolarized, nanodiamonds and pathways for their use as multimodal (optical and magnetic resonance) imaging and hyperpolarization agents

High contrast dual-mode optical and 13C magnetic resonance imaging in diamond particles

Multichannel imaging -- the ability to acquire images of an object through more than one imaging mode simultaneously -- has opened interesting new perspectives in areas ranging from astronomy to medicine. Visible optics and magnetic resonance imaging (MRI) offer complementary advantages of resolution, speed and depth of penetration, and as such would be attractive in combination. In this paper, we take first steps towards marrying together optical and MR imaging in a class of biocompatible particulate materials constructed out of diamond. The particles are endowed with a high density of quantum defects (Nitrogen Vacancy centers) that under optical excitation fluoresce brightly in the visible, but also concurrently electron spin polarize. This allows the hyperpolarization of lattice 13C nuclei to make the particles over three-orders of magnitude brighter than in conventional MRI. Dual-mode optical and MR imaging permits immediate access to improvements in resolution and signal-to-noise especially in scattering environments. We highlight additional benefits in background-free imaging, demonstrating lock-in suppression by factors of 2 and 5 in optical and MR domains respectively. Ultimate limits could approach as much as two orders of magnitude in each domain. Finally, leveraging the ability of optical and MR imaging to simultaneously probe Fourier-reciprocal domains (real and k-space), we elucidate the ability to employ hybrid sub-sampling in both conjugate spaces to vastly accelerate dual-image acquisition, by as much as two orders of magnitude in practically relevant sparse-imaging scenarios. This is accompanied by a reduction in optical power by the same factor. Our work suggests interesting possibilities for the simultaneous optical and low-field MR imaging of targeted diamond nanoparticles

High Temperature Treatment of Diamond Particles Toward Enhancement of Their Quantum Properties

Fluorescence of the negatively charged nitrogen-vacancy (NV-) center of diamond is sensitive to external electromagnetic fields, lattice strain, and temperature due to the unique triplet configuration of its spin states. Their use in particulate diamond allows for the possibility of localized sensing and magnetic-contrast-based differential imaging in complex environments with high fluorescent background. However, current methods of NV(-)production in diamond particles are accompanied by the formation of a large number of parasitic defects and lattice distortions resulting in deterioration of the NV(-)performance. Therefore, there are significant efforts to improve the quantum properties of diamond particles to advance the field. Recently it was shown that rapid thermal annealing (RTA) at temperatures much exceeding the standard temperatures used for NV(-)production can efficiently eliminate parasitic paramagnetic impurities and, as a result, by an order of magnitude improve the degree of hyperpolarization of(13)C via polarization transfer from optically polarized NV(-)centers in micron-sized particles. Here, we demonstrate that RTA also improves the maximum achievable magnetic modulation of NV(-)fluorescence in micron-sized diamond by about 4x over conventionally produced diamond particles endowed with NV-. This advancement can continue to bridge the pathway toward developing nano-sized diamond with improved qualities for quantum sensing and imaging

Nitrogen control in nanodiamond produced by detonation shock-wave-assisted synthesis

Development of efficient production methods of nanodiamond (ND) particles containing substitutional nitrogen and nitrogen-vacancy (NV) complexes remains an important goal in the nanodiamond community. ND synthesized from explosives is generally not among the preferred candidates for imaging applications owing to lack of optically active particles containing NV centers. In this paper, we have systematically studied representative classes of NDs produced by detonation shock wave conversion of different carbon precursor materials, namely, graphite and a graphite/hexogen mixture into ND, as well as ND produced from different combinations of explosives using different cooling methods (wet or dry cooling). We demonstrate that (i) the N content in nanodiamond particles can be controlled through a correct selection of the carbon precursor material (addition of graphite, explosives composition); (ii) particles larger than approximately 20 nm may contain in situ produced optically active NV centers, and (iii) in ND produced from explosives, NV centers are detected only in ND produced by wet synthesis. ND synthesized from a mixture of graphite/explosive contains the largest amount of NV centers formed during synthesis and thus deserves special attention. © 2011 American Chemical Society

Identification of substitutional nitrogen and surface paramagnetic centers in nanodiamond of dynamic synthesis by electron paramagnetic resonance

Production of nanodiamond particles containing substitutional nitrogen is important for a wide variety of advanced applications. In the current work nanodiamond particles synthesized from a mixture of graphite and hexogen were analyzed to determine the presence of substitutional nitrogen using pulsed electron paramagnetic resonance (EPR) spectroscopy. Nitrogen paramagnetic centers in the amount of 1.2 ppm have been identified. The spin relaxation characteristics for both nitrogen and surface defects are also reported. A new approach for efficient depletion of the strong non-nitrogen EPR signal in nanodiamond material by immersing nanodiamond particles into ice matrix is suggested. This approach allows an essential decrease of the spin relaxation time of the dominant non-nitrogen defects, while preserving the substitutional nitrogen spin relaxation time.Copyright © 2011 American Scientific Publishers. All rights reserved

Atomistic Simulations of Nanotube Fracture

The fracture of carbon nanotubes is studied by atomistic simulations. The fracture behavior is found to be almost independent of the separation energy and to depend primarily on the inflection point in the interatomic potential. The rangle of fracture strians compares well with experimental results, but predicted range of fracture stresses is marketly higher than observed. Various plausible small-scale defects do not suffice to bring the failure stresses into agreement with available experimental results. As in the experiments, the fracture of carbon nanotubes is predicted to be brittle. The results show moderate dependence of fracture strength on chirality.Comment: 12 pages, PDF, submitted to Phy. Rev.

Prediction and measurement of the size-dependent stability of fluorescence in diamond over the entire nanoscale

Fluorescent defects in non-cytotoxic diamond nanoparticles are candidates for qubits in quantum computing, optical labels in biomedical imaging and sensors in magnetometry. For each application these defects need to be optically and thermodynamically stable, and included in individual particles at suitable concentrations (singly or in large numbers). In this letter, we combine simulations, theory and experiment to provide the first comprehensive and generic prediction of the size, temperature and nitrogen-concentration dependent stability of optically active NV defects in nanodiamonds.Comment: Published in Nano Letters August 2009 24 pages, 6 figure