Carlos A. Meriles

Nuclear magnetic resonance spectroscopy on a (5-nanometer)3 sample volume.

Nanoscale NMR with Diamond Defects Although nuclear magnetic resonance (NMR) methods can be used for spatial imaging, the low sensitivity of detectors limits the minimum sample size. Two reports now describe the use of near-surface nitrogen-vacancy (NV) defects in diamond for detecting nanotesla magnetic fields from very small volumes of material (see the Perspective by Hemmer). The spin of the defect can be detected by changes in its fluorescence, which allows proton NMR of organic samples only a few nanometers thick on the diamond surface. Mamin et al. (p. 557) used a combination of electron spin echoes and pulsed NMR manipulation of the proton spins to detect the very weak fields. Staudacher et al. (p. 561) measured statistical polarization of a population of about 104 spins near the NV center with a dynamical decoupling method. The optical response of the spin of a near-surface atomic defect in diamond can be used to sense proton magnetic fields. [Also see Perspective by Hemmer] Application of nuclear magnetic resonance (NMR) spectroscopy to nanoscale samples has remained an elusive goal, achieved only with great experimental effort at subkelvin temperatures. We demonstrated detection of NMR signals from a (5-nanometer)3 voxel of various fluid and solid organic samples under ambient conditions. We used an atomic-size magnetic field sensor, a single nitrogen-vacancy defect center, embedded ~7 nanometers under the surface of a bulk diamond to record NMR spectra of various samples placed on the diamond surface. Its detection volume consisted of only 104 nuclear spins with a net magnetization of only 102 statistically polarized spins.

High-resolution correlation spectroscopy of 13C spins near a nitrogen-vacancy centre in diamond

Spin complexes comprising the nitrogen-vacancy centre and neighbouring spins are being considered as a building block for a new generation of spintronic and quantum information processing devices. As assembling identical spin clusters is difficult, new strategies are being developed to determine individual node structures with the highest precision. Here we use a pulse protocol to monitor the time evolution of the (13)C ensemble in the vicinity of a nitrogen-vacancy centre. We observe long-lived time correlations in the nuclear spin dynamics, limited by nitrogen-vacancy spin-lattice relaxation. We use the host (14)N spin as a quantum register and demonstrate that hyperfine-shifted resonances can be separated upon proper nitrogen-vacancy initialization. Intriguingly, we find that the amplitude of the correlation signal exhibits a sharp dependence on the applied magnetic field. We discuss this observation in the context of the quantum-to-classical transition proposed recently to explain the field dependence of the spin cluster dynamics.

Nitrogen-vacancy-assisted magnetometry of paramagnetic centers in an individual diamond nanocrystal.

Semiconductor nanoparticles host a number of paramagnetic point defects and impurities, many of them adjacent to the surface, whose response to external stimuli could help probe the complex dynamics of the particle and its local, nanoscale environment. Here, we use optically detected magnetic resonance in a nitrogen-vacancy (NV) center within an individual diamond nanocrystal to investigate the composition and spin dynamics of the particle-hosted spin bath. For the present sample, a ∼45 nm diamond crystal, NV-assisted dark-spin spectroscopy reveals the presence of nitrogen donors and a second, yet-unidentified class of paramagnetic centers. Both groups share a common spin lifetime considerably shorter than that observed for the NV spin, suggesting some form of spatial clustering, possibly on the nanoparticle surface. Using double spin resonance and dynamical decoupling, we also demonstrate control of the combined NV center-spin bath dynamics and attain NV coherence lifetimes comparable to those reported for bulk, Type Ib samples. Extensions based on the experiments presented herein hold promise for applications in nanoscale magnetic sensing, biomedical labeling, and imaging.

Probing molecular dynamics at the nanoscale via an individual paramagnetic centre

We demonstrate a protocol using individual nitrogen-vacancy centres in diamond to observe the time evolution of proton spins from organic molecules located a few nanometres from the diamond surface. The protocol records temporal correlations among the interacting protons, and thus is sensitive to the local dynamics via its impact on the nuclear spin relaxation and interaction with the nitrogen vacancy. We gather information on the nanoscale rotational and translational diffusion dynamics by analysing the time dependence of the nuclear magnetic resonance signal. Applying this technique to liquid and solid samples, we find evidence that liquid samples form a semi-solid layer of 1.5-nm thickness on the surface of diamond, where translational diffusion is suppressed while rotational diffusion remains present. Extensions of the present technique could be exploited to highlight the chemical composition of molecules tethered to the diamond surface or to investigate thermally or chemically activated dynamical processes such as molecular folding.

Scalable Fabrication of High Purity Diamond Nanocrystals with Long-Spin-Coherence Nitrogen Vacancy Centers

The combination of long spin coherence time and nanoscale size has made nitrogen vacancy (NV) centers in nanodiamonds the subject of much interest for quantum information and sensing applications. However, currently available high-pressure high-temperature (HPHT) nanodiamonds have a high concentration of paramagnetic impurities that limit their spin coherence time to the order of microseconds, less than 1% of that observed in bulk diamond. In this work, we use a porous metal mask and a reactive ion etching process to fabricate nanocrystals from high-purity chemical vapor deposition (CVD) diamond. We show that NV centers in these CVD nanodiamonds exhibit record-long spin coherence times in excess of 200 μs, enabling magnetic field sensitivities of 290 nT Hz(-1/2) with the spatial resolution characteristic of a 50 nm diameter probe.

Broadband phase modulation by adiabatic pulses

The use of inhomogeneous but spatially correlated static and radiofrequency (RF) magnetic fields offers a potential methodology for performing magnetic resonance spectroscopy of samples placed outside the bore of the magnet. However, its practical implementation still presents challenging problems, among them the control of nuclear spins over broad frequency offset intervals. The present study introduces an efficient method of encoding the phase of the magnetization when the variation of the static field along the sample is much larger than the RF amplitude. The procedure is based on the use of consecutively applied full-passage adiabatic pulses. The induced phase modulation is broadband and selective because it does not depend on the offset relative to the central frequency and the limits can be sharply defined. Finally, the encoded phase depends almost linearly on the local RF amplitude. All these features enable the recovery of an inhomogeneity-free spectrum with amplitudes close to the theoretically attainable maximum.

Dynamic nuclear spin polarization of liquids and gases in contact with nanostructured diamond.

Optical pumping of spin polarization can produce almost complete spin order but its application is restricted to select atomic gases and condensed matter systems. Here, we theoretically investigate a novel route to nuclear spin hyperpolarization in arbitrary fluids in which target molecules are exposed to polarized paramagnetic centers located near the surface of a host material. We find that adsorbed nuclear spins relax to positive or negative polarization depending on the average paramagnetic center depth and nanoscale surface topology. For the particular case of optically pumped nitrogen-vacancy centers in diamond, we calculate strong nuclear spin polarization at moderate magnetic fields provided the crystal surface is engineered with surface roughness in the few-nanometer range. The equilibrium nuclear spin temperature depends only weakly on the correlation time describing the molecular adsorption dynamics and is robust in the presence of other, unpolarized paramagnetic centers. These features could be exploited to polarize flowing liquids or gases, as we illustrate numerically for the model case of a fluid brought in contact with an optically pumped diamond nanostructure.

Imaging thermal conductivity with nanoscale resolution using a scanning spin probe

The ability to probe nanoscale heat flow in a material is often limited by lack of spatial resolution. Here, we use a diamond-nanocrystal-hosted nitrogen-vacancy centre attached to the apex of a silicon thermal tip as a local temperature sensor. We apply an electrical current to heat up the tip and rely on the nitrogen vacancy to monitor the thermal changes the tip experiences as it is brought into contact with surfaces of varying thermal conductivity. By combining atomic force and confocal microscopy, we image phantom microstructures with nanoscale resolution, and attain excellent agreement between the thermal conductivity and topographic maps. The small mass and high thermal conductivity of the diamond host make the time response of our technique short, which we demonstrate by monitoring the tip temperature upon application of a heat pulse. Our approach promises multiple applications, from the investigation of phonon dynamics in nanostructures to the characterization of heterogeneous phase transitions and chemical reactions in various solid-state systems.

Time-resolved, optically detected NMR of fluids at high magnetic field

We report on the use of optical Faraday rotation to monitor the nuclear-spin signal in a set of model (19)F- and (1)H-rich fluids. Our approach integrates optical detection with high-field, pulsed NMR so as to record the time-resolved evolution of nuclear-spins after rf excitation. Comparison of chemical-shift-resolved resonances allows us to set order-of-magnitude constrains on the relative amplitudes of hyperfine coupling constants for different bonding geometries. When evaluated against coil induction, the present detection modality suffers from poorer sensitivity, but improvement could be attained via multipass schemes. Because illumination is off-resonant i.e., the medium is optically transparent, this methodology could find extensions in a broad class of fluids and soft condensed matter systems.

Magneto-optical contrast in liquid-state optically detected NMR spectroscopy

We use optical Faraday rotation (OFR) to probe nuclear spins in real time at high-magnetic field in a range of diamagnetic sample fluids. Comparison of OFR-detected NMR spectra reveals a correlation between the relative signal amplitude and the fluid Verdet constant, which we interpret as a manifestation of the variable detuning between the probe beam and the sample optical transitions. The analysis of chemical-shift-resolved, optically detected spectra allows us to set constraints on the relative amplitudes of hyperfine coupling constants, both for protons at chemically distinct sites and other lower-gyromagnetic-ratio nuclei including carbon, fluorine, and phosphorous. By considering a model binary mixture we observe a complex dependence of the optical response on the relative concentration, suggesting that the present approach is sensitive to the solvent-solute dynamics in ways complementary to those known in inductive NMR. Extension of these experiments may find application in solvent suppression protocols, sensitivity-enhanced NMR of metalloproteins in solution, the investigation of solvent-solute interactions, or the characterization of molecular orbitals in diamagnetic systems.