Detection of Paramagnetic Spins with an Ultrathin van der Waals Quantum Sensor.

Detecting magnetic noise from small quantities of paramagnetic spins is a powerful capability for chemical, biochemical, and medical analysis. Quantum sensors based on optically addressable spin defects in bulk semiconductors are typically employed for such purposes, but the 3D crystal structure of the sensor inhibits sensitivity by limiting the proximity of the defects to the target spins. Here we demonstrate the detection of paramagnetic spins using spin defects hosted in hexagonal boron nitride (hBN), a van der Waals material that can be exfoliated into the 2D regime. We first create negatively charged boron vacancy (VB-) defects in a powder of ultrathin hBN nanoflakes (<10 atomic monolayers thick on average) and measure the longitudinal spin relaxation time (T1) of this system. We then decorate the dry hBN nanopowder with paramagnetic Gd3+ ions and observe a clear T1 quenching under ambient conditions, consistent with the added magnetic noise. Finally, we demonstrate the possibility of performing spin measurements, including T1 relaxometry using solution-suspended hBN nanopowder. Our results highlight the potential and versatility of the hBN quantum sensor for a range of sensing applications and make steps toward the realization of a truly 2D, ultrasensitive quantum sensor.

Quantum Emitters in Hexagonal Boron Nitride.

Hexagonal boron nitride (hBN) has emerged as a fascinating platform to explore quantum emitters and their applications. Beyond being a wide-bandgap material, it is also a van der Waals crystal, enabling direct exfoliation of atomically thin layers─a combination which offers unique advantages over bulk, 3D crystals. In this Mini Review we discuss the unique properties of hBN quantum emitters and highlight progress toward their future implementation in practical devices. We focus on engineering and integration of the emitters with scalable photonic resonators. We also highlight recently discovered spin defects in hBN and discuss their potential utility for quantum sensing. All in all, hBN has become a front runner in explorations of solid-state quantum science with promising future prospects.

Varied Magnetic Phases in a van der Waals Easy-Plane Antiferromagnet Revealed by Nitrogen-Vacancy Center Microscopy.

Interest in van der Waals materials often stems from a desire to miniaturize existing technologies by exploiting their intrinsic layered structures to create near-atomically thin components that do not suffer from surface defects. One appealing property is an easily switchable yet robust magnetic order, which is only sparsely demonstrated in the case of in-plane anisotropy. In this work, we use widefield nitrogen-vacancy (NV) center magnetic imaging to measure the properties of individual flakes of CuCrP2S6, a multiferroic van der Waals magnet known to exhibit weak easy-plane anisotropy in the bulk. We chart the crossover between the in-plane ferromagnetism in thin flakes down to the trilayer and the bulk behavior dominated by a low-field spin-flop transition. Further, by exploiting the directional dependence of NV center magnetometry, we are able to observe an instance of a predominantly out-of-plane ferromagetic phase near zero field, in contrast with our expectation and previous experiments on the bulk material. We attribute this to the presence of surface anisotropies caused by the sample preparation process or exposure to the ambient environment, which is expected to have more general implications for a broader class of weakly anisotropic van der Waals magnets.

Quantum magnetic imaging of iron organelles within the pigeon cochlea.

The ability of pigeons to sense geomagnetic fields has been conclusively established despite a notable lack of determination of the underlying biophysical mechanisms. Quasi-spherical iron organelles previously termed "cuticulosomes" in the cochlea of pigeons have potential relevance to magnetoreception due to their location and iron composition; however, data regarding the magnetic susceptibility of these structures are currently limited. Here quantum magnetic imaging techniques are applied to characterize the magnetic properties of individual iron cuticulosomes in situ. The stray magnetic fields emanating from cuticulosomes are mapped and compared to a detailed analytical model to provide an estimate of the magnetic susceptibility of the individual particles. The images reveal the presence of superparamagnetic and ferrimagnetic domains within individual cuticulosomes and magnetic susceptibilities within the range 0.029 to 0.22. These results provide insights into the elusive physiological roles of cuticulosomes. The susceptibilities measured are not consistent with a torque-based model of magnetoreception, placing iron storage and stereocilia stabilization as the two leading putative cuticulosome functions. This work establishes quantum magnetic imaging as an important tool to complement the existing array of techniques used to screen for potential magnetic particle-based magnetoreceptor candidates.

Imaging Domain Reversal in an Ultrathin Van der Waals Ferromagnet.

The recent isolation of 2D van der Waals magnetic materials has uncovered rich physics that often differs from the magnetic behavior of their bulk counterparts. However, the microscopic details of fundamental processes such as the initial magnetization or domain reversal, which govern the magnetic hysteresis, remain largely unknown in the ultrathin limit. Here a widefield nitrogen-vacancy (NV) microscope is employed to directly image these processes in few-layer flakes of the magnetic semiconductor vanadium triiodide (VI3 ). Complete and abrupt switching of most flakes is observed at fields Hc  ≈ 0.5-1 T (at 5 K) independent of thickness. The coercive field decreases as the temperature approaches the Curie temperature (Tc  ≈ 50 K); however, the switching remains abrupt. The initial magnetization process is then imaged, which reveals thickness-dependent domain wall depinning fields well below Hc . These results point to ultrathin VI3 being a nucleation-type hard ferromagnet, where the coercive field is set by the anisotropy-limited domain wall nucleation field. This work illustrates the power of widefield NV microscopy to investigate magnetization processes in van der Waals ferromagnets, which can be used to elucidate the origin of the hard ferromagnetic properties of other materials and explore field- and current-driven domain wall dynamics.

Real-time detection and identification of nematode eggs genus and species through optical imaging.

Nematode eggs are pervasive pathogens that infect billions of people and livestock every year. Adult parasitic nematode worms can be distinguished based on their size and morphology. However, their eggs, particularly their species Ascaris lumbricoides and Ascaris suum cannot be identified from each other. Identifying eggs of helminths from wastewater and sludge is important from a public health perspective to minimize the spread of Ascaris infections. Numerous methods exist for nematode identification, from a morphological-based approach to high throughput sequencing technology. However, these techniques are not consistent and often laborious and time-consuming. In this study, we demonstrate that non-invasive real-time identification of eggs is possible based on their intrinsic fluorescence. Using confocal microscopy, we investigate the autofluorescence properties of five species of nematode eggs and observe clear differences between genus and for the first time their species in sludge samples. This non-invasive imaging technique could lead to better understanding of these species and may assist in early control of diseases.

Enhanced Widefield Quantum Sensing with Nitrogen-Vacancy Ensembles Using Diamond Nanopillar Arrays.

Surface micro- and nano-patterning techniques are often employed to enhance the optical interface to single photoluminescent emitters in diamond, but the utility of such surface structuring in applications requiring ensembles of emitters is still open to investigation. Here, we demonstrate scalable and fault-tolerant fabrication of closely packed arrays of fluorescent diamond nanopillars, each hosting its own dense, uniformly bright ensemble of near-surface nitrogen-vacancy centers. We explore the optimal sizes for these structures and realize enhanced spin and photoluminescence properties resulting in a 4.5 times increase in optically detected magnetic resonance sensitivity when compared to unpatterned surfaces. Utilizing the increased measurement sensitivity, we image the mechanical stress tensor in each diamond pillar across the arrays and show that the fabrication process has a negligible impact on in-built stress compared to the unpatterned surface. Our results represent a valuable pathway toward future multimodal and vector-resolved imaging studies, for instance in biological contexts.

Laser Modulation of Superconductivity in a Cryogenic Wide-field Nitrogen-Vacancy Microscope.

We realize a cryogenic wide-field nitrogen-vacancy microscope and use it to image Abrikosov vortices and transport currents in a superconducting Nb film. We observe the disappearance of vortices upon increase of laser power and their clustering about hot spots upon decrease, indicating local quenching of superconductivity by the laser. Resistance measurements confirm the presence of large temperature gradients across the film. We then investigate the effect of such gradients on transport currents where the current path is seen to correlate with the temperature profile even in the fully superconducting phase. In addition to highlighting the role of temperature inhomogeneities in superconductivity phenomena, this work establishes that under sufficiently low laser power conditions wide-field nitrogen-vacancy microscopy enables imaging over mesoscopic scales down to 4 K with submicrometer spatial resolution, providing a new platform for spatially resolved investigations of a range of systems from topological insulators to van der Waals ferromagnets.

Biocompatible and Biodegradable Magnesium Oxide Nanoparticles with In Vitro Photostable Near-Infrared Emission: Short-Term Fluorescent Markers.

Imaging of biological matter by using fluorescent nanoparticles (NPs) is becoming a widespread method for in vitro imaging. However, currently there is no fluorescent NP that satisfies all necessary criteria for short-term in vivo imaging: biocompatibility, biodegradability, photostability, suitable wavelengths of absorbance and fluorescence that differ from tissue auto-fluorescence, and near infrared (NIR) emission. In this paper, we report on the photoluminescent properties of magnesium oxide (MgO) NPs that meet all these criteria. The optical defects, attributed to vanadium and chromium ion substitutional defects, emitting in the NIR, are observed at room temperature in NPs of commercial and in-house ball-milled MgO nanoparticles, respectively. As such, the NPs have been successfully integrated into cultured cells and photostable bright in vitro emission from NPs was recorded and analyzed. We expect that numerous biotechnological and medical applications will emerge as this nanomaterial satisfies all criteria for short-term in vivo imaging.

Rapid, High-Resolution Magnetic Microscopy of Single Magnetic Microbeads.

Magnetic microparticles or "beads" are used in a variety of research applications from cell sorting through to optical force traction microscopy. The magnetic properties of such particles can be tailored for specific applications with the uniformity of individual beads critical to their function. However, the majority of magnetic characterization techniques quantify the magnetic properties from large bead ensembles. Developing new magnetic imaging techniques to evaluate and visualize the magnetic fields from single beads will allow detailed insight into the magnetic uniformity, anisotropy, and alignment of magnetic domains. Here, diamond-based magnetic microscopy is applied to image and characterize individual magnetic beads with varying magnetic and structural properties: ferromagnetic and superparamagnetic/paramagnetic, shell (coated with magnetic material), and solid (magnetic material dispersed in matrix). The single-bead magnetic images identify irregularities in the magnetic profiles from individual bead populations. Magnetic simulations account for the varying magnetic profiles and allow to infer the magnetization of individual beads. Additionally, this work shows that the imaging technique can be adapted to achieve illumination-free tracking of magnetic beads, opening the possibility of tracking cell movements and mechanics in photosensitive contexts.

Proximity-Induced Artefacts in Magnetic Imaging with Nitrogen-Vacancy Ensembles in Diamond.

Magnetic imaging with ensembles of nitrogen-vacancy (NV) centres in diamond is a recently developed technique that allows for quantitative vector field mapping. Here we uncover a source of artefacts in the measured magnetic field in situations where the magnetic sample is placed in close proximity (a few tens of nm) to the NV sensing layer. Using magnetic nanoparticles as a test sample, we find that the measured field deviates significantly from the calculated field, in shape, amplitude and even in sign. By modelling the full measurement process, we show that these discrepancies are caused by the limited measurement range of NV sensors combined with the finite spatial resolution of the optical readout. We numerically investigate the role of the stand-off distance to identify an artefact-free regime, and discuss an application to ultrathin materials. This work provides a guide to predict and mitigate proximity-induced artefacts that can arise in NV-based wide-field magnetic imaging, and also demonstrates that the sensitivity of these artefacts to the sample can make them a useful tool for magnetic characterisation.

Quantum probe hyperpolarisation of molecular nuclear spins.

Hyperpolarisation of nuclear spins is important in overcoming sensitivity and resolution limitations of magnetic resonance imaging and nuclear magnetic resonance spectroscopy. Current hyperpolarisation techniques require high magnetic fields, low temperatures, or catalysts. Alternatively, the emergence of room temperature spin qubits has opened new pathways to achieve direct nuclear spin hyperpolarisation. Employing a microwave-free cross-relaxation induced polarisation protocol applied to a nitrogen vacancy qubit, we demonstrate quantum probe hyperpolarisation of external molecular nuclear spins to ~50% under ambient conditions, showing a single qubit increasing the polarisation of ~106 nuclear spins by six orders of magnitude over the thermal background. Results are verified against a detailed theoretical treatment, which also describes how the system can be scaled up to a universal quantum hyperpolarisation platform for macroscopic samples. Our results demonstrate the prospects for this approach to nuclear spin hyperpolarisation for molecular imaging and spectroscopy and its potential to extend beyond into other scientific areas.

Microwave-free nuclear magnetic resonance at molecular scales.

The implementation of nuclear magnetic resonance (NMR) at the nanoscale is a major challenge, as the resolution of conventional methods is limited to mesoscopic scales. Approaches based on quantum spin probes, such as the nitrogen-vacancy (NV) centre in diamond, have achieved nano-NMR under ambient conditions. However, the measurement protocols require application of complex microwave pulse sequences of high precision and relatively high power, placing limitations on the design and scalability of these techniques. Here we demonstrate NMR on a nanoscale organic environment of proton spins using the NV centre while eliminating the need for microwave manipulation of either the NV or the environmental spin states. We also show that the sensitivity of our significantly simplified approach matches that of existing techniques using the NV centre. Removing the requirement for coherent manipulation while maintaining measurement sensitivity represents a significant step towards the development of robust, non-invasive nanoscale NMR probes.

Quantum imaging of current flow in graphene.

Since its first discovery in 2004, graphene has been found to host a plethora of unusual electronic transport phenomena, making it a fascinating system for fundamental studies in condensed matter physics as well as offering tremendous opportunities for future electronic and sensing devices. Typically, electronic transport in graphene has been investigated via resistivity measurements; however, these measurements are generally blind to spatial information critical to observing and studying landmark transport phenomena in real space and in realistic imperfect devices. We apply quantum imaging to the problem and demonstrate noninvasive, high-resolution imaging of current flow in monolayer graphene structures. Our method uses an engineered array of near-surface, atomic-sized quantum sensors in diamond to map the vector magnetic field and reconstruct the vector current density over graphene geometries of varying complexity, from monoribbons to junctions, with spatial resolution at the diffraction limit and a projected sensitivity to currents as small as 1 µA. The measured current maps reveal strong spatial variations corresponding to physical defects at the submicrometer scale. The demonstrated method opens up an important new avenue to investigate fundamental electronic and spin transport in graphene structures and devices and, more generally, in emerging two-dimensional materials and thin-film systems.

Environmentally Mediated Coherent Control of a Spin Qubit in Diamond.

The coherent control of spin qubits forms the basis of many applications in quantum information processing and nanoscale sensing, imaging, and spectroscopy. Such control is conventionally achieved by direct driving of the qubit transition with a resonant global field, typically at microwave frequencies. Here we introduce an approach that relies on the resonant driving of nearby environment spins, whose localized magnetic field in turn drives the qubit when the environmental spin Rabi frequency matches the qubit resonance. This concept of environmentally mediated resonance (EMR) is explored experimentally using a qubit based on a single nitrogen-vacancy (NV) center in diamond, with nearby electronic spins serving as the environmental mediators. We demonstrate EMR driven coherent control of the NV spin state, including the observation of Rabi oscillations, free induction decay, and spin echo. This technique also provides a way to probe the nanoscale environment of spin qubits, which we illustrate by acquisition of electron spin resonance spectra from single NV centers in various settings.

Magneto-optical imaging of thin magnetic films using spins in diamond.

Imaging the fields of magnetic materials provides crucial insight into the physical and chemical processes surrounding magnetism, and has been a key ingredient in the spectacular development of magnetic data storage. Existing approaches using the magneto-optic Kerr effect, x-ray and electron microscopy have limitations that constrain further development, and there is increasing demand for imaging and characterisation of magnetic phenomena in real time with high spatial resolution. Here we show how the magneto-optical response of an array of negatively-charged nitrogen-vacancy spins in diamond can be used to image and map the sub-micron stray magnetic field patterns from thin ferromagnetic films. Using optically detected magnetic resonance, we demonstrate wide-field magnetic imaging over 100 × 100 µm(2) with sub-micron spatial resolution at video frame rates, under ambient conditions. We demonstrate an all-optical spin relaxation contrast imaging approach which can image magnetic structures in the absence of an applied microwave field. Straightforward extensions promise imaging with sub-µT sensitivity and sub-optical spatial and millisecond temporal resolution. This work establishes practical diamond-based wide-field microscopy for rapid high-sensitivity characterisation and imaging of magnetic samples, with the capability for investigating magnetic phenomena such as domain wall and skyrmion dynamics and the spin Hall effect in metals.

Scanning Nanospin Ensemble Microscope for Nanoscale Magnetic and Thermal Imaging.

Quantum sensors based on solid-state spins provide tremendous opportunities in a wide range of fields from basic physics and chemistry to biomedical imaging. However, integrating them into a scanning probe microscope to enable practical, nanoscale quantum imaging is a highly challenging task. Recently, the use of single spins in diamond in conjunction with atomic force microscopy techniques has allowed significant progress toward this goal, but generalization of this approach has so far been impeded by long acquisition times or by the absence of simultaneous topographic information. Here, we report on a scanning quantum probe microscope which solves both issues by employing a nanospin ensemble hosted in a nanodiamond. This approach provides up to an order of magnitude gain in acquisition time while preserving sub-100 nm spatial resolution both for the quantum sensor and topographic images. We demonstrate two applications of this microscope. We first image nanoscale clusters of maghemite particles through both spin resonance spectroscopy and spin relaxometry, under ambient conditions. Our images reveal fast magnetic field fluctuations in addition to a static component, indicating the presence of both superparamagnetic and ferromagnetic particles. We next demonstrate a new imaging modality where the nanospin ensemble is used as a thermometer. We use this technique to map the photoinduced heating generated by laser irradiation of a single gold nanoparticle in a fluid environment. This work paves the way toward new applications of quantum probe microscopy such as thermal/magnetic imaging of operating microelectronic devices and magnetic detection of ion channels in cell membranes.

Enhancement of optical processes in coupled plasmonic nanocavities [Invited].

We present detailed experimental and numerical investigations of resonances in deep nanogroove gratings in metallic substrates. These plasmonic nanocavity gratings feature enhanced fields within the grooves that enable a large enhancement of linear and nonlinear optical processes. This enhancement relies on both localized and propagating surface plasmons on the nanopatterned surface. We show that the efficiency of optical processes such as Raman scattering and four-wave mixing is dramatically enhanced by plasmonic nanocavity gratings.

Multi-wavelength mid-infrared plasmonic antennas with single nanoscale focal point.

We propose and demonstrate a novel photonic-plasmonic antenna capable of confining electromagnetic radiation at several mid-infrared wavelengths to a single sub-wavelength spot. The structure relies on the coupling between the localized surface plasmon resonance of a bow-tie nanoantenna with the photonic modes of surrounding multi-periodic particle arrays. Far-field measurements of the transmission through the central bow-tie demonstrate the presence of Fano-like interference effects resulting from the interaction of the bow-tie antenna with the surrounding nanoparticle arrays. The near-field of the multi-wavelength antenna is imaged using an aperture-less near-field scanning optical microscope. This antenna is relevant for the development of near-field probes for nanoimaging, spectroscopy and biosensing.

Light propagation with phase discontinuities: generalized laws of reflection and refraction.

Conventional optical components rely on gradual phase shifts accumulated during light propagation to shape light beams. New degrees of freedom are attained by introducing abrupt phase changes over the scale of the wavelength. A two-dimensional array of optical resonators with spatially varying phase response and subwavelength separation can imprint such phase discontinuities on propagating light as it traverses the interface between two media. Anomalous reflection and refraction phenomena are observed in this regime in optically thin arrays of metallic antennas on silicon with a linear phase variation along the interface, which are in excellent agreement with generalized laws derived from Fermat's principle. Phase discontinuities provide great flexibility in the design of light beams, as illustrated by the generation of optical vortices through use of planar designer metallic interfaces.