Diamond surface functionalization via visible light-driven C-H activation for nanoscale quantum sensing.

Nitrogen-vacancy (NV) centers in diamond are a promising platform for nanoscale NMR sensing. Despite significant progress toward using NV centers to detect and localize nuclear spins down to the single spin level, NV-based spectroscopy of individual, intact, arbitrary target molecules remains elusive. Such sensing requires that target molecules are immobilized within nanometers of NV centers with long spin coherence. The inert nature of diamond typically requires harsh functionalization techniques such as thermal annealing or plasma processing, limiting the scope of functional groups that can be attached to the surface. Solution-phase chemical methods can be readily generalized to install diverse functional groups, but they have not been widely explored for single-crystal diamond surfaces. Moreover, realizing shallow NV centers with long spin coherence times requires highly ordered single-crystal surfaces, and solution-phase functionalization has not yet been shown with such demanding conditions. In this work, we report a versatile strategy to directly functionalize C-H bonds on single-crystal diamond surfaces under ambient conditions using visible light, forming C-F, C-Cl, C-S, and C-N bonds at the surface. This method is compatible with NV centers within 10 nm of the surface with spin coherence times comparable to the state of the art. As a proof-of-principle demonstration, we use shallow ensembles of NV centers to detect nuclear spins from surface-bound functional groups. Our approach to surface functionalization opens the door to deploying NV centers as a tool for chemical sensing and single-molecule spectroscopy.

Control of Neuronal Survival and Development Using Conductive Diamond.

This study demonstrates the control of neuronal survival and development using nitrogen-doped ultrananocrystalline diamond (N-UNCD). We highlight the role of N-UNCD in regulating neuronal activity via near-infrared illumination, demonstrating the generation of stable photocurrents that enhance neuronal survival and neurite outgrowth and foster a more active, synchronized neuronal network. Whole transcriptome RNA sequencing reveals that diamond substrates improve cellular-substrate interaction by upregulating extracellular matrix and gap junction-related genes. Our findings underscore the potential of conductive diamond as a robust and biocompatible platform for noninvasive and effective neural tissue engineering.

Miniature fluorescence sensor for quantitative detection of brain tumour.

Fluorescence-guided surgery has emerged as a vital tool for tumour resection procedures. As well as intraoperative tumour visualisation, 5-ALA-induced PpIX provides an avenue for quantitative tumour identification based on ratiometric fluorescence measurement. To this end, fluorescence imaging and fibre-based probes have enabled more precise demarcation between the cancerous and healthy tissues. These sensing approaches, which rely on collecting the fluorescence light from the tumour resection site and its "remote" spectral sensing, introduce challenges associated with optical losses. In this work, we demonstrate the viability of tumour detection at the resection site using a miniature fluorescence measurement system. Unlike the current bulky systems, which necessitate remote measurement, we have adopted a millimetre-sized spectral sensor chip for quantitative fluorescence measurements. A reliable measurement at the resection site requires a stable optical window between the tissue and the optoelectronic system. This is achieved using an antifouling diamond window, which provides stable optical transparency. The system achieved a sensitivity of 92.3% and specificity of 98.3% in detecting a surrogate tumour at a resolution of 1 × 1 mm2. As well as addressing losses associated with collecting and coupling fluorescence light in the current 'remote' sensing approaches, the small size of the system introduced in this work paves the way for its direct integration with the tumour resection tools with the aim of more accurate interoperative tumour identification.

A Telecom O-Band Emitter in Diamond.

Color centers in diamond are promising platforms for quantum technologies. Most color centers in diamond discovered thus far emit in the visible or near-infrared wavelength range, which are incompatible with long-distance fiber communication and unfavorable for imaging in biological tissues. Here, we report the experimental observation of a new color center that emits in the telecom O-band, which we observe in silicon-doped bulk single crystal diamonds and microdiamonds. Combining absorption and photoluminescence measurements, we identify a zero-phonon line at 1221 nm and phonon replicas separated by 42 meV. Using transient absorption spectroscopy, we measure an excited state lifetime of around 270 ps and observe a long-lived baseline that may arise from intersystem crossing to another spin manifold.

Electrical control of quantum emitters in a Van der Waals heterostructure.

Controlling and manipulating individual quantum systems in solids underpins the growing interest in the development of scalable quantum technologies. Recently, hexagonal boron nitride (hBN) has garnered significant attention in quantum photonic applications due to its ability to host optically stable quantum emitters. However, the large bandgap of hBN and the lack of efficient doping inhibits electrical triggering and limits opportunities to study the electrical control of emitters. Here, we show an approach to electrically modulate quantum emitters in an hBN-graphene van der Waals heterostructure. We show that quantum emitters in hBN can be reversibly activated and modulated by applying a bias across the device. Notably, a significant number of quantum emitters are intrinsically dark and become optically active at non-zero voltages. To explain the results, we provide a heuristic electrostatic model of this unique behavior. Finally, employing these devices we demonstrate a nearly-coherent source with linewidths of ~160 MHz. Our results enhance the potential of hBN for tunable solid-state quantum emitters for the growing field of quantum information science.

Large Area Ultrathin InN and Tin Doped InN Nanosheets Featuring 2D Electron Gases.

Indium nitride (InN) has been of significant interest for creating and studying two-dimensional electron gases (2DEG). Herein we demonstrate the formation of 2DEGs in ultrathin doped and undoped 2D InN nanosheets featuring high carrier mobilities at room temperature. The synthesis is carried out via a two-step liquid metal-based printing method followed by a microwave plasma-enhanced nitridation reaction. Ultrathin InN nanosheets with a thickness of ∼2 ± 0.2 nm were isolated over large areas with lateral dimensions exceeding centimeter scale. Room temperature Hall effect measurements reveal carrier mobilities of ∼216 and ∼148 cm2 V-1 s-1 for undoped and doped InN, respectively. Further analysis suggests the presence of defined quantized states in these ultrathin nitride nanosheets that can be attributed to a 2D electron gas forming due to strong out-of-plane confinement. Overall, the combination of electronic and plasmonic features in undoped and doped ultrathin 2D InN holds promise for creating advanced optoelectronic devices and functional 2D heterostructures.

Polycrystalline diamond coating on 3D printed titanium scaffolds: Surface characterisation and foreign body response.

Titanium-based implants are the leading material for orthopaedic surgery, due to their strength, versatility, fabrication via additive manufacturing and invoked biological response. However, the interface between the implant and the host tissue requires improvement to better integrate the implant material and mitigate foreign body response. The interface can be manipulated by changing the surface energy, chemistry, and topography of the Titanium-based implant. Recently, polycrystalline diamond (PCD) has emerged as an exciting coating material for 3D printed titanium scaffolds showing enhanced mammalian cell functions while inhibiting bacterial attachment in vitro. In this study, we performed in-depth characterisation of PCD coatings investigating the surface topography, thickness, surface energy, and compared its foreign body response in vivo with uncoated titanium scaffold. Coating PCD onto titanium scaffolds resulted in a similar microscale surface roughness (RMS(PCD-coated) = 24 µm; RMS(SLM-Ti) = 28 µm), increased nanoscale roughness (RMS(PCD-coated) = 35 nm; RMS(SLM-Ti) = 66 nm) and a considerable decrease in surface free energy (E(PCD-coated) = 4 mN m-1; E(SLM-Ti) = 16 mN m-1). These surface property changes were supported by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy as corresponding to observed surface chemistry changes induced by the coating. The underlying mechanism of how the diamond coatings chemical and physical properties changes the wettability of implants was examined. In vivo, the coated scaffolds induced similar level of fibrous encapsulation with uncoated scaffolds. This study thus provides further insight into the physicochemical characteristics of PCD coatings, adding evidence to the promising potential of PCD-coatings of medical implants.

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.

Hybrid diamond/ carbon fiber microelectrodes enable multimodal electrical/chemical neural interfacing.

Implantable medical devices are now in regular use to treat or ameliorate medical conditions, including movement disorders, chronic pain, cardiac arrhythmias, and hearing or vision loss. Aside from offering alternatives to pharmaceuticals, one major advantage of device therapy is the potential to monitor treatment efficacy, disease progression, and perhaps begin to uncover elusive mechanisms of diseases pathology. In an ideal system, neural stimulation, neural recording, and electrochemical sensing would be conducted by the same electrode in the same anatomical region. Carbon fiber (CF) microelectrodes are the appropriate size to achieve this goal and have shown excellent performance, in vivo. Their electrochemical properties, however, are not suitable for neural stimulation and electrochemical sensing. Here, we present a method to deposit high surface area conducting diamond on CF microelectrodes. This unique hybrid microelectrode is capable of recording single-neuron action potentials, delivering effective electrical stimulation pulses, and exhibits excellent electrochemical dopamine detection. Such electrodes are needed for the next generation of miniaturized, closed-loop implants that can self-tune therapies by monitoring both electrophysiological and biochemical biomarkers.

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.

Impact of Surface Functionalization on the Quantum Coherence of Nitrogen-Vacancy Centers in Nanodiamonds.

Nanoscale quantum probes such as the nitrogen-vacancy (NV) center in diamonds have demonstrated remarkable sensing capabilities over the past decade as control over fabrication and manipulation of these systems has evolved. The biocompatibility and rich surface chemistry of diamonds has added to the utility of these probes but, as the size of these nanoscale systems is reduced, the surface chemistry of diamond begins to impact the quantum properties of the NV center. In this work, we systematically study the effect of the diamond surface chemistry on the quantum coherence of the NV center in nanodiamonds (NDs) 50 nm in size. Our results show that a borane-reduced diamond surface can on average double the spin relaxation time of individual NV centers in nanodiamonds when compared to thermally oxidized surfaces. Using a combination of infrared and X-ray absorption spectroscopy techniques, we correlate the changes in quantum relaxation rates with the conversion of sp2 carbon to C-O and C-H bonds on the diamond surface. These findings implicate double-bonded carbon species as a dominant source of spin noise for near surface NV centers. The link between the surface chemistry and quantum coherence indicates that through tailored engineering of the surface, the quantum properties and magnetic sensitivity of these nanoscale systems may approach that observed in bulk diamond.

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.

Polycrystalline Diamond Coating of Additively Manufactured Titanium for Biomedical Applications.

Additive manufacturing using selective laser melted titanium (SLM-Ti) is used to create bespoke items across many diverse fields such as medicine, defense, and aerospace. Despite great progress in orthopedic implant applications, such as for "just in time" implants, significant challenges remain with regards to material osseointegration and the susceptibility to bacterial colonization on the implant. Here, we show that polycrystalline diamond coatings on these titanium samples can enhance biological scaffold interaction improving medical implant applicability. The highly conformable coating exhibited excellent bonding to the substrate. Relative to uncoated SLM-Ti, the diamond coated samples showed enhanced mammalian cell growth, enriched apatite deposition, and reduced microbial S. aureus activity. These results open new opportunities for novel coatings on SLM-Ti devices in general and especially show promise for improved biomedical implants.

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.

Germanium terminated (1 0 0) diamond.

An ordered germanium terminated (1 0 0) diamond surface has been formed and characterised using a combination of low energy electron diffraction and synchrotron-based core level photoemission spectroscopy. A number of preparation methods are explored, in each case inducing a two domain [Formula: see text] surface reconstruction. The surface becomes saturated with bonded germanium such that each [Formula: see text] unit cell hosts 1.26 Ge atoms on average, and possesses a negative electron affinity of -0.71 eV.

Diamond Devices for High Acuity Prosthetic Vision.

Retinal implants restore a sense of vision, for a growing number of users worldwide. Nevertheless, visual acuities provided by the current generation of devices are low. The quantity of information transferable to the retina using existing implant technologies is limited, far below receptor cells' capabilities. Many agree that increasing the information density deliverable by a retinal prosthesis requires devices with stimulation electrodes that are both dense and numerous. This work describes a new generation of retinal prostheses capable of upscaling the information density conveyable to the retina. Centered on engineered diamond materials, the implant is very well tolerated and long-term stable in the eye's unique physiological environment and capable of delivering highly versatile stimulation waveforms - both key attributes in providing useful vision. Delivery of high-density information, close to the retina with the flexibility to alter stimulation parameters in situ provides the best chance for success in providing high acuity prosthetic vision.

Optimizing growth and post treatment of diamond for high capacitance neural interfaces.

Electrochemical and biological properties are two crucial criteria in the selection of the materials to be used as electrodes for neural interfaces. For neural stimulation, materials are required to exhibit high capacitance and to form intimate contact with neurons for eliciting effective neural responses at acceptably low voltages. Here we report on a new high capacitance material fabricated using nitrogen included ultrananocrystalline diamond (N-UNCD). After exposure to oxygen plasma for 3 h, the activated N-UNCD exhibited extremely high electrochemical capacitance greater than 1 mF/cm(2), which originates from the special hybrid sp(2)/sp(3) structure of N-UNCD. The in vitro biocompatibility of the activated N-UNCD was then assessed using rat cortical neurons and surface roughness was found to be critical for healthy neuron growth, with best results observed on surfaces with a roughness of approximately 20 nm. Therefore, by using oxygen plasma activated N-UNCD with appropriate surface roughness, and considering the chemical and mechanical stability of diamond, the fabricated neural interfaces are expected to exhibit high efficacy, long-term stability and a healthy neuron/electrode interface.