Near-surface Nitrogen-vacancy Centers Research Articles

Photoinduced Charge Injection from Shallow Point Defects in Diamond into Water.

Thanks to its low or negative surface electron affinity and chemical inertness, diamond is attracting broad attention as a source material of solvated electrons produced by optical excitation of the solid-liquid interface. Unfortunately, its wide bandgap typically imposes the use of wavelengths in the ultraviolet range, hence complicating practical applications. Here, we probe the photocurrent response of water surrounded by single-crystal diamond surfaces engineered to host shallow nitrogen-vacancy (NV) centers. We observe clear signatures of diamond-induced photocurrent generation throughout the visible range and for wavelengths reaching up to 594 nm. Experiments as a function of laser power suggest that NV centers and other coexisting defects─likely in the form of surface traps─contribute to carrier injection, though we find that NVs dominate the system response in the limit of high illumination intensities. Given our growing understanding of near-surface NV centers and adjacent point defects, these results open new perspectives in the application of diamond-liquid interfaces to photocarrier-initiated chemical and spin processes in fluids.

High Spatial Resolution 2D Imaging of Current Density and Pressure for Graphene Devices under High Pressure Using Nitrogen-Vacancy Centers in Diamond.

Current density imaging is helpful for discovering interesting electronic phenomena and understanding carrier dynamics, and by combining pressure distributions, several pressure-induced novel physics may be comprehended. In this work, noninvasive, high-resolution two-dimensional images of the current density and pressure gradient for graphene ribbon and hBN-graphene-hBN devices are explored using nitrogen-vacancy (NV) centers in diamond under high pressure. The two-dimensional vector current density is reconstructed by the vector magnetic field mapped by the near-surface NV center layer in the diamond. The current density images accurately and clearly reproduce the complicated structure and current flow of graphene under high pressure. Additionally, the spatial distribution of the pressure is simultaneously mapped, rationalizing the nonuniformity of the current density under high pressure. The current method opens a significant new avenue to investigate electronic transport and conductance variations in two-dimensional materials and electrical devices under high pressure as well as for nondestructive evaluation of semiconductor circuits.

Stability of Near-Surface Nitrogen Vacancy Centers Using Dielectric Surface Passivation.

We study the photophysical stability of ensemble near-surface nitrogen vacancy (NV) centers in diamond under vacuum and air. The optically detected magnetic resonance contrast of the NV centers was measured following exposure to laser illumination, showing opposing trends in air compared to vacuum (increasing by up to 9% and dropping by up to 25%, respectively). Characterization using X-ray photoelectron spectroscopy (XPS) suggests a surface reconstruction: In air, atmospheric oxygen adsorption on a surface leads to an increase in NV- fraction, whereas in vacuum, net oxygen desorption increases the NV0 fraction. NV charge state switching is confirmed by photoluminescence spectroscopy. Deposition of ∼2 nm alumina (Al2O3) over the diamond surface was shown to stabilize the NV charge state under illumination in either environment, attributed to a more stable surface electronegativity. The use of an alumina coating on diamond is therefore a promising approach to improve the resilience of NV sensors.

The Role of Electrolytes in the Relaxation of Near-Surface Spin Defects in Diamond.

Quantum sensing with spin defects in diamond, such as the nitrogen vacancy (NV) center, enables the detection of various chemical species on the nanoscale. Molecules or ions with unpaired electronic spins are typically probed by their influence on the NV center's spin relaxation. Whereas it is well-known that paramagnetic ions reduce the NV center's relaxation time (T1), here we report on the opposite effect for diamagnetic ions. We demonstrate that millimolar concentrations of aqueous diamagnetic electrolyte solutions increase the T1 time of near-surface NV center ensembles compared to pure water. To elucidate the underlying mechanism of this surprising effect, single and double quantum NV experiments are performed, which indicate a reduction of magnetic and electric noise in the presence of diamagnetic electrolytes. In combination with ab initio simulations, we propose that a change in the interfacial band bending due to the formation of an electric double layer leads to a stabilization of fluctuating charges at the interface of an oxidized diamond. This work not only helps to understand noise sources in quantum systems but could also broaden the application space of quantum sensors toward electrolyte sensing in cell biology, neuroscience, and electrochemistry.

Diamond surface electric-field noise detection using shallow nitrogen-vacancy centers

Detection of diamond surface electric-field noise is of importance for studying the coherence properties of shallow nitrogen-vacancy (NV) centers. Using the double quantum relaxation method, we demonstrated that the noise has a power-law frequency dependence, and it increases slowly from 295 K to 420 K but reduces quickly at higher temperatures. As the Dutta-Horn model described, the noise is created by ensembles of two-level systems with activation energies ranging from 0.3 eV to 0.6 eV. For diamond surface passivation, we found that the solid covering material (PMMA) outperforms the liquid one (glycerol) in reducing the electric-field noise, which was attributed to the presence of surface-modified phononic coupling noise. We anticipate that our findings will contribute to a better understanding of the origins of surface 1/f electric-field noise, as well as identify optimal covering materials for enhancing the coherence time of near-surface NV centers.

Single-Nitrogen-Vacancy NMR of Amine-Functionalized Diamond Surfaces.

Nuclear magnetic resonance (NMR) imaging with shallow nitrogen-vacancy (NV) centers in diamond offers an exciting route toward sensitive and localized chemical characterization at the nanoscale. Remarkable progress has been made to combat the degradation in coherence time and stability suffered by near-surface NV centers using suitable chemical surface termination. However, approaches that also enable robust control over adsorbed molecule density, orientation, and binding configuration are needed. We demonstrate a diamond surface preparation for mixed nitrogen- and oxygen-termination that simultaneously improves NV center coherence times for <10 nm-deep emitters and enables direct and recyclable chemical functionalization via amine-reactive cross-linking. Using this approach, we probe single NV centers embedded in nanopillar waveguides to perform 19F NMR sensing of covalently bound fluorinated molecules with detection on the order of 100 molecules. This work signifies an important step toward nuclear spin localization and structure interrogation at the single-molecule level.

Experimental Constraint on an Exotic Parity-Odd Spin- and Velocity-Dependent Interaction with a Single Electron Spin Quantum Sensor.

Improved laboratory limits on the exotic spin- and velocity-dependent interaction at the micrometer scale are established with a single electron spin quantum sensor. The single electron spin of a near-surface nitrogen-vacancy center in diamond is used as the quantum sensor, and a fused-silica half-sphere lens is taken as the source of the moving nucleons. The exotic interaction between the polarized electron and the moving nucleon source is explored by measuring the possible magnetic field sensed by the electron spin quantum sensor. Our experiment sets improved constraints on the exotic spin- and velocity-dependent interaction within the force range from 1.4 to 330 μm. The upper limit of the coupling g_{A}^{e}g_{V}^{N} at 200 μm is |g_{A}^{e}g_{V}^{N}|≤5.3×10^{-19}, significantly improving the current laboratory limit by more than 4 orders of magnitude.

Resonant Excitation and Purcell Enhancement of Coherent Nitrogen-Vacancy Centers Coupled to a Fabry-Perot Microcavity

The nitrogen-vacancy (NV) center in diamond has been established as a prime building block for quantum networks. However, scaling beyond a few network nodes is currently limited by low spin-photon entanglement rates, resulting from the NV center's low probability of coherent photon emission and collection. Integration into a cavity can boost both values via the Purcell effect, but poor optical coherence of near-surface NV centers has so far prevented their resonant optical control, as would be required for entanglement generation. Here, we overcome this challenge, and demonstrate resonant addressing of individual, fiber-cavity-coupled NV centers, and collection of their Purcell-enhanced coherent photon emission. Utilizing off-resonant and resonant addressing protocols, we extract Purcell factors of up to 4, consistent with a detailed theoretical model. This model predicts that the probability of coherent photon detection per optical excitation can be increased to 10% for realistic parameters - an improvement over state-of-the art solid immersion lens collection systems by two orders of magnitude. The resonant operation of an improved optical interface for single coherent quantum emitters in a closed-cycle cryogenic system at T $\sim$ 4 K is an important result towards extensive quantum networks with long coherence.

Nanoscale localization of the near-surface nitrogen vacancy center assisted by a silicon atomic force microscopy probe

The nitrogen vacancy (NV) center in diamond has wide applications in sensing, imaging and quantum information processing. One of the bases of these applications is to localize the NV center in diamond with high precision. In this work we demonstrate a method for nanoscale imaging and locating near-surface NV centers on diamond waveguides based on an atomic force microscopy (AFM) combined confocal system. The resulted lateral resolution for imaging the NV center is 31.6 nm and the precision of locating the NV center in diamond is 0.7 nm. Finally, the position of the NV center is indicated in AFM images of the diamond waveguide. These results provide a useful characterization tool for optimizing the diamond nanostructure for quantum information processing and quantum sensing.

Inverse-designed photon extractors for optically addressable defect qubits

Solid-state defect qubit systems with spin-photon interfaces show great promise for quantum information and metrology applications. Photon collection efficiency, however, presents a major challenge for defect qubits in high refractive index host materials. Inverse-design optimization of photonic devices enables unprecedented flexibility in tailoring critical parameters of a spin-photon interface including spectral response, photon polarization, and collection mode. Further, the design process can incorporate additional constraints, such as fabrication tolerance and material processing limitations. Here, we design and demonstrate a compact hybrid gallium phosphide on diamond inverse-design planar dielectric structure coupled to single near-surface nitrogen-vacancy centers formed by implantation and annealing. We observe up to a 14-fold broadband enhancement in photon extraction efficiency, in close agreement with simulations. We expect that such inverse-designed devices will enable realization of scalable arrays of single-photon emitters, rapid characterization of new quantum emitters, efficient sensing, and heralded entanglement schemes.

Spin coherence and depths of single nitrogen-vacancy centers created by ion implantation into diamond via screening masks

We characterize single nitrogen-vacancy (NV) centers created by 10-keVN+ ion implantation into diamond via thin SiO2 layers working as screening masks. Despite the relatively high acceleration energy compared with standard ones (&amp;lt;5keV) used to create near-surface NV centers, the screening masks modify the distribution of N+ ions to be peaked at the diamond surface [Ito et al., Appl. Phys. Lett. 110, 213105 (2017)]. We examine the relation between coherence times of the NV electronic spins and their depths, demonstrating that a large portion of NV centers are located within 10 nm from the surface, consistent with Monte Carlo simulations. The effect of the surface on the NV spin coherence time is evaluated through noise spectroscopy, surface topography, and x-ray photoelectron spectroscopy.

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.

Extending the Quantum Coherence of a Near-Surface Qubit by Coherently Driving the Paramagnetic Surface Environment.

Surfaces enable useful functionalities for quantum systems, e.g., as interfaces to sensing targets, but often result in surface-induced decoherence where unpaired electron spins are common culprits. Here we show that the coherence time of a near-surface qubit is increased by coherent radio-frequency driving of surface electron spins, where we use a diamond nitrogen-vacancy (NV) center as a model qubit. This technique is complementary to other methods of suppressing decoherence and, importantly, requires no additional materials processing or control of the qubit. Further, by combining driving with the increased magnetic susceptibility of the double-quantum basis, we realize an overall fivefold sensitivity enhancement in NV magnetometry. Informed by our results, we discuss a path toward relaxation-limited coherence times for near-surface NV centers. The surface-spin driving technique presented here is broadly applicable to a wide variety of qubit platforms afflicted by surface-induced decoherence.

Selective measurement of charge dynamics in an ensemble of nitrogen-vacancy centers in nanodiamond and bulk diamond

Nitrogen-vacancy (NV) centers in diamond have attracted considerable interest in sensing of weak magnetic fields, such as those created by biological systems. Detecting such feeble signals requires near-surface NV centers, to reduce the distance between NVs and sources. Moreover, dense ensembles of NVs are highly desirable to reduce measurement time. However, robust charge state switching is often observed in these systems, resulting in a complex interplay between charge and spin dynamics that can reduce the attainable level of spin polarization, and consequently, sensitivity. Understanding the mechanisms behind charge state switching is, therefore, crucial to developing NV based sensors. Here, we demonstrate a novel method to selectively measure charge dynamics in an ensemble of NVs by quenching the spin polarization using an off-axis magnetic field. Utilizing this technique, we show that, in nanodiamonds, charge state instability increases with increasing NV density. In the case of bulk single crystal diamond, we show that NV centers located near the surface are more stable in the neutral (NV$^{0}$) charge state, while the negatively charged (NV$^{-}$) form is more stable in bulk.

Identifying and Mitigating Charge Instabilities in Shallow Diamond Nitrogen-Vacancy Centers

The charge degree of freedom in solid-state defects fundamentally underpins the electronic spin degree of freedom, a workhorse of quantum technologies. Here we measure, analyze, and control charge-state behavior in individual near-surface nitrogen-vacancy (NV) centers in diamond, where NV^{-} hosts the metrologically relevant electron spin. We find that NV^{-} initialization fidelity varies between individual centers and over time; we alleviate the deleterious effects of reduced NV^{-} initialization fidelity via logic-based initialization. Importantly, we also show that NV^{-} can ionize in the dark on experimentally relevant timescales, and we introduce measurement protocols that mitigate the compromising effects of charge conversion on spin measurements. We identify tunneling to a single local electron trap as the mechanism for ionization in the dark, and we develop novel NV-assisted techniques to control and read out the trap charge state. Our understanding and command of the NV's local electrostatic environment will simultaneously guide materials design and provide unique functionalities with NV centers.

Electric Noise Spectra of a Near-Surface Nitrogen-Vacancy Center in Diamond with a Protective Layer

Surface noise is a detrimental issue for sensing devices based on shallow nitrogen vacancy (NV) color center diamonds. A recent experiment indicates that electric field noise is significant compared to magnetic field noise. They also found that the electric field noise can be reduced with a protective surface layer, though the mechanism of noise reduction is not well understood. We examine the effect of a protective surface layer on the noise spectrum, which is caused by surface charge fluctuations. We use the fluctuation-dissipation theorem to calculate and analyze the noise spectrum for six different surface layer materials typically used for NV center diamond devices. We find that four parameters largely affect the noise spectrum: effective relaxation time, effective loss tangent, power law exponent of the noise spectrum, and layer thickness. Our results suggest that a surface covering layer is indeed useful for decreasing surface noise, but which material is most suitable depends on the device operational frequency range.

Evidence for Primal sp2 Defects at the Diamond Surface: Candidates for Electron Trapping and Noise Sources

AbstractMany advanced applications of diamond materials are now being limited by unknown surface defects, including in the fields of high power/frequency electronics and quantum computing and quantum sensing. Of acute interest to diamond researchers worldwide is the loss of quantum coherence in near‐surface nitrogen‐vacancy (NV) centers and the generation of associated magnetic noise at the diamond surface. Here for the first time is presented the observation of a family of primal diamond surface defects, which is suggested as the leading cause of band‐bending and Fermi‐pinning phenomena in diamond devices. A combination of density functional theory and synchrotron‐based X‐ray absorption spectroscopy is used to show that these defects introduce low‐lying electronic trap states. The effect of these states is modeled on band‐bending into the diamond bulk and it is shown that the properties of the important NV defect centers are affected by these defects. Due to the paramount importance of near‐surface NV center properties in a growing number of fields, the density of these defects is further quantified at the surface of a variety of differently‐treated device surfaces, consistent with best‐practice processing techniques in the literature. The identification and characterization of these defects has wide‐ranging implications for diamond devices across many fields.

Lithographically engineered shallow nitrogen-vacancy centers in diamond for external nuclear spin sensing

The simultaneous control of the number and position of negatively charged nitrogen-vacancy (NV) centers in diamond was achieved. While single near-surface NV centers are known to exhibit outstanding capabilities in external spin sensing, trade-off relationships among the accuracy of the number and position, and the coherence of NV centers have made the use of such engineered NV centers difficult. Namely, low-energy nitrogen implantation with lithographic techniques enables the nanoscale position control but results in degradation of the creation yield and the coherence property. In this paper, we show that low-energy nitrogen ion implantation to a 12C (99.95%)-enriched homoepitaxial diamond layer using nanomask is applicable to create shallow NV centers with a sufficiently long coherence time for external spin sensing, at a high creation yield. Furthermore, the NV centers were arranged in a regular array so that 40% lattice sites contain single NV centers. The XY8-k measurements using the individual NV centers reveal that the created NV centers have depths from 2 to 12 nm, which is comparable to the stopping range of nitrogen ions implanted at 2.5 keV. We show that the position-controlled NV centers are capable of external spin sensing with a ultra-high spatial resolution.

Effect of ultraprecision polishing techniques on coherence times of shallow nitrogen-vacancy centers in diamond

We investigate the correlation between surface roughness and corresponding T2 times of near-surface nitrogen-vacancy centers (~10 nm/5 keV implantation energy) in diamond. For this purpose we compare five different polishing techniques, including both purely mechanical as well as chemical mechanical approaches, two different substrate sources (IIa Technologies and Element Six) and two different surface terminations (O- and H-termination) during nitrogen-vacancy forming. All coherence times are measured and compared before and after an oxygen surface treatment at 520 °C.We find that the coherence times of shallow nitrogen-vacancy centers are surprisingly independent of surface roughness.

Searching for an exotic spin-dependent interaction with a single electron-spin quantum sensor

Searching for new particles beyond the standard model is crucial for understanding several fundamental conundrums in physics and astrophysics. Several hypothetical particles can mediate exotic spin-dependent interactions between ordinary fermions, which enable laboratory searches via the detection of the interactions. Most laboratory searches utilize a macroscopic source and detector, thus allowing the detection of interactions with submillimeter force range and above. It remains a challenge to detect the interactions at shorter force ranges. Here we propose and demonstrate that a near-surface nitrogen-vacancy center in diamond can be utilized as a quantum sensor to detect the monopole–dipole interaction between an electron spin and nucleons. Our result sets a constraint for the electron–nucleon coupling, g_{{mathrm{s}}}^{mathrm{N}}g_{mathrm{p}}^{mathrm{e}}, with the force range 0.1–23 μm. The obtained upper bound of the coupling at 20 μm is g_{{mathrm{s}}}^{mathrm{N}}g_{mathrm{p}}^{mathrm{e}} < 6.24 × 10−15.