Towards hyperpolarization of oil molecules via nitrogen-vacancy centers in diamond
P. Fernández-Acebal, O. Rosolio, J. Scheuer, C. Müller, S. Müller, S. Schmitt, L. P. McGuinness, I. Schwarz, Q. Chen, A. Retzker, B. Naydenov, F. Jelezko, M. B. Plenio
Efficient polarization of organic molecules is of extraordinary relevance when performing nuclear magnetic resonance (NMR) and imaging. Commercially available routes to dynamical nuclear polarization (DNP) work at extremely low-temperatures, thus bringing the molecules out of their ambient thermal conditions and relying on the solidification of organic samples. In this work we investigate polarization transfer from optically-pumped nitrogen vacancy centers in diamond to external molecules at room temperature. This polarization transfer is described by both an extensive analytical analysis and numerical simulations based on spin bath bosonization and is supported by experimental data in excellent agreement. These results set the route to hyperpolarization of diffusive molecules in different scenarios and consequently, due to increased signal, to high-resolution NMR.
We report bulk, room-temperature hyperpolarization of 13C nuclear spins observed via high-field nuclear magnetic resonance (NMR). The hyperpolarization is achieved by optical pumping (OP) of nitrogen vacancy defect centers in diamond accompanied by dynamic nuclear polarization (DNP). The technique harnesses the large optically-induced spin polarization of NV- centers at room temperature, which is many orders of magnitude greater than thermal equilibrium polarization and typically achievable only at sub-Kelvin temperatures. Transfer of the spin polarization to the 13C nuclear spins is accomplis…
Nanodiamonds containing nitrogen vacancy (NV-) centers show promise for a number of emerging applications including targeted in vivo imaging and generating nuclear spin hyperpolarization for enhanced NMR spectroscopy and imaging. Here, we develop a detailed understanding of the magnetic resonance behavior of NV- centers in an ensemble of nanodiamonds with random crystal orientations. Two-dimensional optically detected magnetic resonance spectroscopy reveals the distribution of energy levels, spin populations, and transition probabilities that give rise to a complex spectrum. We identify overto…
Here we propose and analyse in detail protocols that can achieve rapid hyperpolarization of 13C nuclear spins in randomly oriented ensembles of nanodiamonds at room temperature. Our protocols exploit a combination of optical polarization of electron spins in nitrogen-vacancy centers and the transfer of this polarization to 13C nuclei by means of microwave control to overcome the severe challenges that are posed by the random orientation of the nanodiamonds and their nitrogen-vacancy centers. Specifically, these random orientations result in exceedingly large energy variations of the electron s…
We investigate nuclear spin hyperpolarization from nitrogen vacancy centers in isotopically enriched diamonds with $^{13}$C concentrations up to 100%. $^{13}$C enrichment leads to hyperfine structure of the nitrogen vacancy electron spin resonance spectrum and as a result the spectrum of dynamic nuclear polarization. We show that strongly-coupled $^{13}$C spins in the first shell surrounding a nitrogen vacancy center generate resolved hyperfine splittings, but do not act as an intermediary in the transfer of hyperpolarization of bulk nuclear spins. High levels of $^{13}$C enrichment are desira…
The nuclear spin singlet order involving coupled pairs of spins-1/2 may be used to store nuclear spin hyperpolarization in a room temperature liquid for a time much longer than the spin-lattice relaxation time $T_1$. There both are observations of long-lived homonuclear and heteronuclear spin-singlet order. Although hyperpolarized singlet order of the same species are accessible, hyperpolarized heteronuclear spin-singlet order has not been presented yet. Here we show hyperpolarized singlet order is achievable in the sample of $^{13}$C-labeled formic acid solution at room temperature by using o…
Polarizing nuclear spins is of fundamental importance in biology, chemistry and physics. Methods for hyperpolarizing 13C nuclei from free electrons in bulk, usually demand operation at cryogenic temperatures. Room-temperature approaches targeting diamonds with nitrogen-vacancy (NV) centers could alleviate this need, but hitherto proposed strategies lack generality as they demand stringent conditions on the strength and/or alignment of the magnetic field. We report here an approach for achieving efficient electron->13C spin alignment transfers, compatible with a broad range of magnetic field st…
We consider the problem of determining the spectrum of an electronic spin via polarization transfer to coupled nuclear spins and their subsequent readout. This suggests applications for employing dynamic nuclear polarization (DNP) for "ESR-via-NMR". In this paper, we describe the theoretical basis for this process by developing a model for the evolution dynamics of the coupled electron-nuclear system through a cascade of Landau-Zener anti-crossings (LZ-LACs). We develop a method to map these traversals to the operation of an equivalent "Galton board". Here, LZ-LAC points serve as analogues to …
Dense ensembles of nitrogen vacancy (NV) centers in diamond are of interest for various applications including magnetometry, masers, hyperpolarization and quantum memory. All of the applications above may benefit from a non-linear response of the ensemble, and hence multiphoton processes are of importance. We study an enhancement of the NV ensemble multiphoton response due to coupling to a superconducting cavity or to an ensemble of Nitrogen 14 substitutional defects (P1). In the latter case, the increased NV sensitivity allowed us to probe the P1 hyperfine splitting. As an example of an appli…
Nuclear magnetic resonance (NMR) spectroscopy is a widely used tool for chemical analysis and molecular structure identification. Because it typically relies on the weak magnetic fields produced by a small thermal nuclear spin polarization, NMR suffers from poor molecule-number sensitivity compared to other analytical techniques. Recently, a new class of NMR sensors based on optically-probed nitrogen-vacancy (NV) quantum defects in diamond have allowed molecular spectroscopy from sample volumes several orders of magnitude smaller than the most sensitive inductive detectors. To date, however, N…
The integration of NMR and high pressure technique brings unique opportunities to study electronic, structural and dynamical properties under extreme conditions. Despite a great degree of success has been achieved using coil-based schemes, the contradictory requirement on sample volume of these two techniques remains an outstanding challenge. In this letter, we introduce diamond nitrogen-vacancy (NV) centers, as the source and probe of in-situ nuclear spin polarization, to address the sample volume issue. We demonstrate hyperpolarization and coherent control of $^{14}$N nuclear spins under hig…
Dynamic nuclear polarization via contact with electronic spins has emerged as an attractive route to enhance the sensitivity of nuclear magnetic resonance (NMR) 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. Here we overcome this hurdle …
In this paper cross-relaxation between nitrogen-vacancy (NV) centers and substitutional nitrogen in a diamond crystal was studied. It was demonstrated that optically detected magnetic resonance signals (ODMR) can be used to measure these signals successfully. The ODMR were detected at axial magnetic field values around 51.2~mT in a diamond sample with a relatively high (200~ppm) nitrogen concentration. We observed transitions that involve magnetic sublevels that are split by the hyperfine interaction. Microwaves in the frequency ranges from 1.3 GHz to 1.6 GHz ($m_S=0\longrightarrow m_S=-1$ NV …
We demonstrate a robust experimental method for determining the depth of individual shallow Nitrogen-Vacancy (NV) centers in diamond with $\sim1$ nm uncertainty. We use a confocal microscope to observe single NV centers and detect the proton nuclear magnetic resonance (NMR) signal produced by objective immersion oil, which has well understood nuclear spin properties, on the diamond surface. We determine the NV center depth by analyzing the NV NMR data using a model that describes the interaction of a single NV center with the statistically-polarized proton spin bath. We repeat this procedure f…
Understanding the origins of spin lifetimes in hybrid quantum systems is a matter of current importance in several areas of quantum information and sensing. Methods that spectrally map spin relaxation processes provide insight into their origin and can motivate methods to mitigate them. In this paper, using a combination of hyperpolarization and precision field cycling over a wide range (1mT-7T), we map frequency dependent relaxation in a prototypical hybrid system of 13C nuclear spins in diamond coupled to Nitrogen Vacancy centers. Nuclear hyperpolarization through the optically pumped NV ele…
Nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) spectroscopy of bulk quantum materials have provided insight into phenomena such as quantum phase criticality, magnetism, and superconductivity. With the emergence of nanoscale 2-D materials with magnetic phenomena, inductively-detected NMR and NQR spectroscopy are not sensitive enough to detect the smaller number of spins in nanomaterials. The nitrogen-vacancy (NV) center in diamond has shown promise in bringing the analytic power of NMR and NQR spectroscopy to the nanoscale. However, due to depth-dependent formation effi…
Nuclear magnetic resonance (NMR) spectroscopy has approached the limit of single molecule sensitivity, however the spectral resolution is currently insufficient to obtain detailed information on chemical structure and molecular interactions. Here we demonstrate more than two orders of magnitude improvement in spectral resolution by performing correlation spectroscopy with shallow nitrogen-vacancy (NV) magnetic sensors in diamond. In principle, the resolution is sufficient to observe chemical shifts in $\sim$1 T magnetic fields, and is currently limited by molecular diffusion at the surface. We…
Small volume nuclear magnetic resonance spectroscopy (NMR) has recently made considerable progress due to rapid developments in the field of quantum sensing using nitrogen vacancy (NV) centers. These optically active defects in the diamond lattice have been used to probe unprecedented small volumes on the picoliter range with high spectral resolution. However, the NMR signal size depends strongly on both the diamond sensor's and sample's geometry. Using Monte-Carlo integration of sample spin dipole moments, the magnetic field projection along the orientation of the NV center for different geom…
Here we report the fabrication of stable, shallow (< 5 nm) nitrogen-vacancy (NV) centers in diamond by nitrogen delta doping at the last stage of the chemical vapor deposition (CVD) growth process. The NVs are stabilized after treating the diamond in $SF_6$ plasma, otherwise the color centers are not observed, suggesting a strong influence from the surface. X-Ray photoelectron spectroscopy measurements show the presence of only fluorine atoms on the surface, in contrast to previous studies, and suggests very good surface coverage. We managed to detect hydrogen nuclear magnetic resonance signal…
Bulk 13C polarization can be strongly enhanced in diamond at room-temperature based on the optical pumping of nitrogen-vacancy color centers. This effect was confirmed by irradiating suitably aligned single-crystals at a ~50 mT field promoting anti-crossings between electronic excited-state levels, followed by shuttling of the sample into a custom-built NMR setup and by subsequent 13C detection. A nuclear polarization of ~0.5% - equivalent to the 13C polarization achievable by thermal polarization at room temperature at fields of ~2000 T - was measured, and its bulk nature determined based on …
Most of dynamic nuclear polarization (DNP) has been requiring helium cryogenics and strong magnetic fields for a high degree of polarization. In this work, we instead demonstrate an optical hyperpolarization of naturally abundant $^{13}$C nuclei in a diamond crystal at a low magnetic field and an ambient temperature. It exploits continuous irradiations of pump laser for polarizing electron spins of nitrogen vacancy centers and microwave for transferring the induced polarization to $^{13}$C nuclear spins. Triplet structures corresponding to $^{14}$N hyperfine splitting were clearly observed in …
Dynamic Nuclear Polarization (DNP) is a powerful suite of techniques that deliver multifold signal enhancements in NMR and MRI. The generated athermal spin states can also be exploited for quantum sensing and as probes for many-body physics. Typical DNP methods require use of cryogens, large magnetic fields, and high power microwaves, which are expensive and unwieldy. Nanodiamond particles, rich in Nitrogen-Vacancy (NV) centers, have attracted attention as alternative DNP agents because they can potentially be optically hyperpolarized at room temperature. Indeed the realization of a miniature …
Nitrogen vacancy (NV) centers in diamond have been used as ultrasensitive magnetometers to perform nuclear magnetic resonance (NMR) spectroscopy of statistically polarized samples at 1 - 100 nm length scales. However, the spectral linewidth is typically limited to the kHz level, both by the NV sensor coherence time and by rapid molecular diffusion of the nuclei through the detection volume which in turn is critical for achieving long nuclear coherence times. Here we provide a blueprint for a set-up that combines a sensitivity sufficient for detecting NMR signals from nano- to micron-scale samp…
