Nitrogen-vacancy Defect Centers Research Articles

Resonant structure for improved directionality and extraction of single photons

Abstract Fluorescent atomic defects, particularly in dielectric materials such as diamond, are promising for several emerging quantum applications. However, efficient light extraction, directional emission, and narrow spectral emission are key challenges. We have designed a dielectric metasurface exploiting Mie-resonance and Kerker conditions to address these issues. Our designed diamond metasurface, tailored for nitrogen-vacancy (NV) defect centers in diamond, predicts up to 500x improvement in the collection of 637 nm (zero phonon line) photons over that from the bare diamond. Our design achieves highly directional emission, predominantly emitting in a 20° lobe in the forward direction. This makes the light collection more efficient, including fiber-based collection. The predicted results are stable against the position of the emitter placed in the metaelement, thus alleviating the challenging fabrication requirement of precise positioning of the defect center. Equally importantly, our design approach can be applied to enhance single photon emission also from other defects such as SiV, other materials such as hBN, and other sources such as quantum dots.

Nitrogen-vacancy centers in diamond: discovery of additional electronic states

Nitrogen-vacancy (NV) defect centers in diamond are key to applications in quantum sensing and quantum computing. They create localized electronic states in the diamond lattice with distinct population relaxation pathways following photoexcitation that ultimately enable its unique properties. The defect is known to exist in two charge states: neutral and negative, with respectively one and two known optically-active electronic transitions. Here, we report on the observation of a large number of hitherto undiscovered excited electronic states in both charge states as evidenced by distinct optical transitions in the infrared to ultraviolet part of the spectrum. These transitions are observed by monitoring the electronic relaxation of NV centers after photoexcitation using transient absorption spectroscopy, directly probing transient phenomena occurring on timescales from femtoseconds to microseconds. We also for the first time probed the electron transfer dynamics from the 3E state of NV− to nearby single-substitutional nitrogen defects (N s ) that leads to the well-known effect of NV photoluminescence quenching.

Parallel pumping of magnons in inhomogeneous spin textures probed through NV spin relaxometry

We combine micromagnetic simulations and nitrogen-vacancy (NV) defect center spin relaxometry measurements to study magnon modes in inhomogeneous spin textures. A thin, micrometer-scale ferromagnetic disk is magnetized in a vortex state in which the magnetization curls around a central core. Micromagnetic simulations show that at zero applied field, the magnetization dynamics of the disk consist of a low frequency gyrotropic mode and higher frequency azimuthal magnon modes, all far detuned from the NV spin transition frequencies. An in-plane static magnetic field breaks the azimuthal symmetry of the vortex state, resulting in the magnon modes transforming in frequency and spatial profile as the field increases. Experimentally, we probe the dynamics of vortex magnetization as a function of applied in-plane static field and ac driving frequency by optically monitoring a nearby NV defect center spin. At certain values of the applied magnetic field, we observe enhanced spin relaxation when driving at twice the frequency of the NV ground state spin transition in optically detected magnetic resonance measurements. We attribute this effect to parallel pumping of a magnon mode in the disk producing magnons at half the excitation frequency. Micromagnetic simulations support this finding, showing spatial and spectral overlap of a confined magnon mode and an NV spin transition, with sufficient interaction strength to explain the observed signal.

Quantitative Evaluation of the Cellular Uptake of Nanodiamonds by Monocytes and Macrophages.

Fluorescent nanodiamonds (FNDs) with negative nitrogen-vacancy (NV- ) defect centers are great probes for biosensing applications, with potential to act as biomarkers for cell differentiation. To explore this concept, uptake of FNDs (≈120 nm) by THP-1 monocytes and monocyte-derived M0-macrophages is studied. The time course analysis of FND uptake by monocytes confirms differing FND-cell interactions and a positive time-dependence. No effect on cell viability, proliferation, and differentiation potential into macrophages is observed, while cells saturated with FNDs, unload the FNDs completely by 25 cell divisions and subsequently take up a second dose effectively. FND uptake variations by THP-1 cells at early exposure-times indicate differing phagocytic capability. The cell fraction that exhibits relatively enhanced FND uptake is associated to a macrophage phenotype which derives from spontaneous monocyte differentiation. In accordance, chemical-differentiation of the THP-1 cells into M0-macrophages triggers increased and homogeneous FND uptake, depleting the fraction of cells that werenon-responsive to FNDs. These observations imply that FND uptake allows for distinction between the two cell subtypes based on phagocytic capacity. Overall, FNDs demonstrate effective cell labeling of monocytes and macrophages, and are promising candidates for sensing biological processes that involve cell differentiation.

Mixed type Ib-IIa diamond from a Fe–Mg2Si3O8·5H2O–C system under high pressure and high temperature

The composition of the crystalline medium has an essential effect on the formation and properties of diamonds. Large single-crystal diamonds grown in a Fe–Mg2Si3O8·5H2O–C system by the temperature gradient method (TGM) at 5.8–6.3 GPa and 1400–1480 °C were investigated. It was found that as the Mg2Si3O8·5H2O content increased from 0 to 4 wt%, the synthesis pressure and temperature both increased, and more nitrogen-vacancy (NV) defect centers appeared in the diamond crystal. The nitrogen impurity concentration in type Ib diamonds synthesized in the pure FeC system was about 90 ppm, and the distribution of nitrogen impurities was uniform from core to rim. Furthermore, with a Mg2Si3O8·5H2O content of approximately 4.0 wt%, type Ib-IIa diamond was successfully synthesized. The infrared spectra (IR) results showed that the nitrogen content of the type Ib-IIa diamond was higher in the central zone of the crystal (79 ppm), decreased in the intermediate zone (42 ppm), and decreased further at the periphery (< 1 ppm). Thus, the type Ib-IIa diamond had significant heterogeneity in the distribution of nitrogen.

Mapping current profiles of point-contacted graphene devices using single-spin scanning magnetometer

We demonstrate two-dimensional mapping of current flow in graphene devices by using a single-spin scanning magnetometer based on a nitrogen-vacancy defect center in diamond. We first image the stray magnetic field generated by the current and then reconstruct the current density map from the field data. We focus on the visualization of current flow around a small sized current source of ∼500 nm diameter, which works as an effective point contact. In this paper, we study two types of point-contacted graphene devices and find that the overall current profiles agree with the expected behavior of electron flow in the diffusive transport regime. This work could offer a route to explore interesting carrier dynamics of graphene including ballistic and hydrodynamic transport regimes.

Enhanced Optical 13C Hyperpolarization in Diamond Treated by High‐Temperature Rapid Thermal Annealing

Abstract Methods of optical dynamic nuclear polarization open the door to the replenishable hyperpolarization of nuclear spins, boosting their nuclear magnetic resonance/imaging signatures by orders of magnitude. Nanodiamond powder rich in negatively charged nitrogen vacancy defect centers has recently emerged as one such promising platform, wherein 13C nuclei can be hyperpolarized through the optically pumped defects completely at room temperature. Given the compelling possibility of relaying this 13C polarization to nuclei in external liquids, there is an urgent need for the engineered production of highly “hyperpolarizable” diamond particles. Here, a systematic study of various material dimensions affecting optical 13C hyperpolarization in diamond particles is reported on. It is discovered surprisingly that diamond annealing at elevated temperatures ∼1720 °C has remarkable effects on the hyperpolarization levels enhancing them by above an order of magnitude over materials annealed through conventional means. It is demonstrated these gains arise from a simultaneous improvement in NV− electron relaxation/coherence times, as well as the reduction of paramagnetic content, and an increase in 13C relaxation lifetimes. This work suggests methods for the guided materials production of fluorescent, 13C hyperpolarized, nanodiamonds and pathways for their use as multimodal (optical and magnetic resonance) imaging and hyperpolarization agents.

Laser-induced heating in a high-density ensemble of nitrogen-vacancy centers in diamond and its effects on quantum sensing

Among quantum sensors, the single nitrogen-vacancy (NV) defect in diamond has the highest sensitivity-to-size factor. For instance, a single-NV spin when used as a magnetometer could achieve sensitivities of the order of nT/Hz, while the dimensions of the sensor are merely atomic in size. The sensitivity is limited only by the photon shot noise. One method to boost the magnetometer sensitivity to pico-tesla scales is to use many NV defect centers as an ensemble sensor [Phys. Rev. X5, 041001 (2015)PRXHAE2160-330810.1103/PhysRevX.5.041001]. However, during the absorption-emission (fluorescence) optical cycles, the NV centers transfer a portion of the irradiation laser energy into phonons and heat the diamond matrix. This results in unintended fluorescence decrease, spin resonance lines shifts, and fluctuations. Hence, the advantages gained by packing a high density of NV centers are significantly reduced. Here we investigate the heat generation of ensemble NV centers in micrometer-sized diamond under 532 nm laser irradiation and its effects pertaining to sensing applications. These investigations help us to find strategies that mitigate the detrimental effects of heating and yet permits the use of ensemble NV defects for improved metrology applications.

Wide dynamic range magnetic field cycler: Harnessing quantum control at low and high fields.

We describe the construction of a fast field cycling device capable of sweeping a 4-order-of-magnitude range of magnetic fields, from ∼1 mT to 7 T, in under 700 ms, and which is further extendable to a 1 nT-7 T range. Central to this system is a high-speed sample shuttling mechanism between a superconducting magnet and a magnetic shield, with the capability to access arbitrary fields in between with high resolution. Our instrument serves as a versatile platform to harness the inherent dichotomy of spin dynamics on offer at low and high fields-in particular, the low anisotropy, fast spin manipulation, and rapid entanglement growth at low field as well as the long spin lifetimes, spin specific control, and efficient inductive measurement possible at high fields. Exploiting these complementary capabilities in a single device opens up applications in a host of problems in quantum control, sensing, and information storage, besides in nuclear hyperpolarization, relaxometry, and imaging. In particular, in this paper, we focus on the ability of the device to enable low-field hyperpolarization of 13C nuclei in diamond via optically pumped electronic spins associated with nitrogen vacancy defect centers.

Cross-entangling electronic and nuclear spins of distant nitrogen-vacancy centers in noisy environments by means of quantum microwave radiation

Nitrogen-vacancy (NV) defect centers in diamond are strong candidates to generate entangled states in solid-state environments even at room temperature. Quantum correlations in spatially separated NV systems, for distances between NVs ranging from a few nanometers to a few kilometers, have been recently reported. In the present work we consider the entanglement transfer from two- mode microwave squeezed (entangled) photons, which are in resonance with the two lowest NV electron spin states, to initially unentangled NV centers. We first demonstrate that the entanglement transfer process from quantum microwaves to isolated NV electron spins is feasible. We then proceed to extend the previous results to more realistic scenarios where 13 C nuclear spin baths surrounding each NV are included, quantifying the entanglement transfer efficiency and robustness under the effects of dephasing/dissipation noisy nuclear baths. Finally, we address the issue of assessing the possibility of entanglement transfer from the squeezed microwave light to two remote nuclear spins closely linked to different NV centers.

Magnetic imaging of a single ferromagnetic nanowire using diamond atomic sensors

Recent advances in nanorobotic manipulation of ferromagnetic nanowires bring new avenues for applications in the biomedical area, such as targeted drug delivery, diagnostics or localized surgery. However, probing a single nanowire and monitoring its dynamics remains a challenge since it demands high precision sensing, high-resolution imaging, and stable operations in fluidic environments. Here, we report on a novel method of imaging and sensing magnetic fields from a single ferromagnetic nanowire with an atomic-scale sensor in diamond, i.e. diamond nitrogen-vacancy (NV) defect center. The distribution of static magnetic fields around a single Co nanowire is mapped out by spatially distributed NV centers and the obtained image is further compared with numerical simulation for quantitative analysis. DC field measurements such as continuous-wave ODMR and Ramsey sequence are used in the paper and sub Gauss level of field sensing is demonstrated. By imaging magnetic fields at a single nanowire level, this work represents an important step toward tracking and probing of ferromagnetic nanowires in biomedical applications.

Coupling a Single Nitrogen-Vacancy Center in Nanodiamond to Superparamagnetic Nanoparticles

Single nitrogen-vacancy (NV) defect centers in diamond have been exploited as single photon sources and spin qubits due to their room-temperature robust quantum light emission and long electron spin coherence times. They were coupled to a manifold of structures, such as optical cavities, plasmonic waveguides, and even injected into living cells to study fundamental interactions of various nature at the nanoscale. Of particular interest are applications of NVs as quantum sensors for local nanomagnetometry. Here, we employ a nanomanipulation approach to couple a single NV center in a nanodiamond to a single few-nm superparamagnetic iron oxide nanoparticle in a controlled way. After measuring via relaxometry the magnetic particle spin-noise, we take advantage of the crystal strain ms = ± 1 spin level separation to detect the superparamagnetic particle’s effect in presence of a driving AC magnetic field. Our experiments provide detailed insight in the behavior of such particles with respect to high frequency fields. The approach can be extended to the investigation of increasingly complex, but controlled nanomagnetic hybrid particle assemblies. Moreover, our results suggest that superparamagnetic nanoparticles can amplify local magnetic interactions in order to improve the sensitivity of diamond nanosensors for specific measurement scenarios.

High-Density Quantum Sensing with Dissipative First Order Transitions.

The sensing of external fields using quantum systems is a prime example of an emergent quantum technology. Generically, the sensitivity of a quantum sensor consisting of N independent particles is proportional to sqrt[N]. However, interactions invariably occurring at high densities lead to a breakdown of the assumption of independence between the particles, posing a severe challenge for quantum sensors operating at the nanoscale. Here, we show that interactions in quantum sensors can be transformed from a nuisance into an advantage when strong interactions trigger a dissipative phase transition in an open quantum system. We demonstrate this behavior by analyzing dissipative quantum sensors based upon nitrogen-vacancy defect centers in diamond. Using both a variational method and a numerical simulation of the master equation describing the open quantum many-body system, we establish the existence of a dissipative first order transition that can be used for quantum sensing. We investigate the properties of this phase transition for two- and three-dimensional setups, demonstrating that the transition can be observed using current experimental technology. Finally, we show that quantum sensors based on dissipative phase transitions are particularly robust against imperfections such as disorder or decoherence, with the sensitivity of the sensor not being limited by the T_{2} coherence time of the device. Our results can readily be applied to other applications in quantum sensing and quantum metrology where interactions are currently a limiting factor.

Facile preparation of fluorescent nanodiamond-based polymer composites through a metal-free photo-initiated RAFT process and their cellular imaging

Nanodiamond (ND)-based fluorescent probes have been extensively researched in cell imaging applications. Several outstanding properties of fluorescent NDs (FNDs), such as their excellent biocompatibility, intensive fluorescence and chemical stability in organisms, have made them the most promising carbon materials in biomedicine. However, the production of FNDs with nitrogen-vacancy defect centers was rather complicated and costly, which limited their wide application in the biomedical field. Moreover, the particle size of these types of FNDs was much larger than that of NDs produced by the detonation method; thus, it is difficult for them to penetrate the cell membrane. In this present work, a facile and ultrafast photo-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization was introduced for the fabrication of FND-based polymer composites. The photo-initiated RAFT polymerization is time saving, environmentally friendly and highly efficient. To prepare these FNDs, fluorescein was converted into diacryloyl fluorescein (AcFl), which was used not only as the photocatalyst but also a fluorescent comonomer. The functional monomer 2-methacryloyloxyethyl phosphorylcholine (MPC) was introduced to improve the water dispersibility of the FNDs. The successful fabrication of FNDs-polyMPC composites was proven by a series of characterization methods. These FNDs-polyMPC composites show high water dispersibility, strong fluorescence and low toxicity. The cell uptake behavior suggested that FNDs-polyMPC composites can be facilely internalized by cells. Taken together, FNDs-polyMPC composites can be fabricated by a photo-initiated RAFT polymerization. These FNDs-polyMPC composites possess excellent physicochemical and biological properties and are promising candidates for cell imaging applications.

Impact of carrier gas flow rate on the synthesis of nanodiamonds via microplasma technique

Nanodiamonds (NDs) have been fabricated utilizing micro plasma facility. The mixture of argon as carrier gas and ethanol as precursor has been dissociated in micro plasma. The argon flow rate was varied from 4 to 9l/min. The influence of argon gas flow rates on structural, surface and optical properties of NDs was compared. An increased amount of diamond has been reported with the increase in flow rate, obtaining the maximum value at 6l/min. Further increase in flow rate starts decreasing the quality of NDs. Raman and XRD confirm that the smallest size and stress free NDs are obtained at 6l/min argon flow rate. AFM micrograph also reveals the smallest size of NDs ~27nm for 6l/min argon flow rate. The hydrophobicity of NDs increases with increasing argon flow rate as confirmed by FTIR. Photoluminescence indicates the presence of nitrogen vacancy defect centers such as N3, H3 and NV for all the flow rates. The smallest PL peak intensity at 6l/min argon flow rate indicates the lowest density of vacancy defects in the diamond. UV–Visible spectroscopy indicates the presence of nitrogen-hydrogen defect and nitrogen vacancy defect centers (N4 and N5). The largest band gap at 6l/min argon flow rate also confirms the highest quality of NDs. The centers offer promising applications as, active laser material, fluorescent markers, quantum information, nanoscale magnetic and electric filed sensors.

An Overview on the Formation and Processing of Nitrogen-Vacancy Photonic Centers in Diamond by Ion Implantation

Nitrogen-vacancy (NV) in diamond possesses unique properties for the realization of novel quantum devices. Among the possibilities in the solid state, a NV defect center in diamond stands out for its robustness—its quantum state can be initialized, manipulated, and measured with high fidelity at room temperature. In this paper, we illustrated the formation kinetics of NV centers in diamond and their transformation from one charge state to another. The controlled scaling of diamond NV center-based quantum registers relies on the ability to position NV defect centers with high spatial resolution. Ion irradiation technique is widely used to control the spatial distribution of NV defect centers in diamond. This is addressed in terms of energetics and kinetics in this paper. We also highlighted important factors, such as ion struggling, ion channeling, and surface charging, etc. These factors should be considered while implanting energetic nitrogen ions on diamond. Based on observations of the microscopic structure after implantation, we further discussed post-annealing treatment to heal the damage produced during the ion irradiation process. This article shows that the ion implantation technique can be used more efficiently for controlled and efficient generation of NV color centers in diamond, which will open up new possibilities in the field of novel electronics and computational engineering, including the art of quantum cryptography, data science, and spintronics.

Topical review: spins and mechanics in diamond

There has been rapidly growing interest in hybrid quantum devices involving a solid-state spin and a macroscopic mechanical oscillator. Such hybrid devices create exciting opportunities to mediate interactions between disparate quantum bits (qubits) and to explore the quantum regime of macroscopic mechanical objects. In particular, a system consisting of the nitrogen-vacancy defect center (NV center) in diamond coupled to a high-quality-factor mechanical oscillator is an appealing candidate for such a hybrid quantum device, as it utilizes the highly coherent and versatile spin properties of the defect center. In this paper, we will review recent experimental progress on diamond-based hybrid quantum devices in which the spin and orbital dynamics of single defects are driven by the motion of a mechanical oscillator. In addition, we discuss prospective applications for this device, including long-range, phonon-mediated spin–spin interactions, and phonon cooling in the quantum regime. We conclude the review by evaluating the experimental limitations of current devices and identifying alternative device architectures that may reach the strong coupling regime.

Strain Coupling of a Mechanical Resonator to a Single Quantum Emitter in Diamond

The recent maturation of hybrid quantum devices has led to significant enhancements in the functionality of a wide variety of quantum systems. In particular, harnessing mechanical resonators for manipulation and control has expanded the use of two-level systems in quantum information science and quantum sensing. In this letter, we report on a monolithic hybrid quantum device in which strain fields associated with resonant vibrations of a diamond cantilever dynamically control the optical transitions of a single nitrogen-vacancy (NV) defect center in diamond. We quantitatively characterize the strain coupling to the orbital states of the NV center, and with mechanical driving, we observe NV-strain couplings exceeding 10 GHz. Furthermore, we use this strain-mediated coupling to match the frequency and polarization dependence of the zero-phonon lines of two spatially separated and initially distinguishable NV centers. The experiments demonstrated here mark an important step toward engineering a quantum device capable of realizing and probing the dynamics of non-classical states of mechanical resonators, spin-systems, and photons.

Determination of nitrogen spin concentration in diamond using double electron-electron resonance

Diamond has been extensively investigated recently due to a wide range of potential applications of nitrogen-vacancy (NV) defect centers existing in a diamond lattice. The applications include magnetometry and quantum information technologies, and long decoherence time $({T}_{2})$ of NV centers is critical for those applications. Although it has been known that ${T}_{2}$ highly depends on the concentration of paramagnetic impurities in diamond, precise measurement of the impurity concentration remains challenging. In the present work we show a method to determine a wide range of the nitrogen concentration $(n)$ in diamond using a wide-band high-frequency electron spin resonance and double electron-electron resonance spectrometer. Moreover, we investigate ${T}_{2}$ of the nitrogen impurities and show the relationship between ${T}_{2}$ and $n$. The method developed here is applicable for various spin systems in solid and implementable in nanoscale magnetic resonance spectroscopy with NV centers to characterize the concentration of the paramagnetic spins within a microscopic volume.

Wavelet-based fast time-resolved magnetic sensing with electronic spins in diamond

Time-resolved magnetic sensing is of great importance from fundamental studies to applications in physical and biological sciences. Recently the nitrogen-vacancy (NV) defect center in diamond has been developed as a promising sensor of magnetic field under ambient conditions. However the methods to reconstruct time-resolved magnetic field with high sensitivity are not yet fully developed. Here, we propose and demonstrate a novel sensing method based on spin echo, and Haar wavelet transform. Our method is exponentially faster in reconstructing time-resolved magnetic field with comparable sensitivity over existing methods. Further, the wavelet's unique features enable our method to extract information from the whole signal with only part of the measuring sequences. We then explore this feature for a fast detection of simulated nerve impulses. These results will be useful to time-resolved magnetic sensing with quantum probes at nano-scales.