Nitrogen-vacancy Centers In Nanodiamonds Research Articles

Probing Abrikosov vortices in niobium with single nitrogen-vacancy centers in nanodiamonds

Abrikosov vortices play a fundamental role in the magnetic and electric properties of superconductors. The study of their pinning forces is essential to better understand the stability of vortex lattices, with the aim of increasing critical currents in superconductors. However, the study of vortices is challenging because of their nanometric sizes and the large variation in the pinning forces. In this Letter, we use a single nitrogen-vacancy center in a nanodiamond as a nanoscale magneto sensor to locally probe single vortices and their pinning effects in a thin niobium film. This simple, far-field optical approach also offers the possibility of manipulating a single spin with a single flux quantum.

Probing the electronic ground state of the nitrogen-vacancy center in nanodiamonds at room temperature

The color centers in diamonds are promising candidates in the context of quantum information science, quantum computation, and spin-based quantum sensors due to their spin-dependent optical transitions. The manipulation and optical readout of electronic spin state is measured using a technique known as optically detected magnetic resonance (ODMR). Here, we discuss the indigenous development of ODMR setup to coherently manipulate and precise readout of spin state of nitrogen-vacancy centers (NV) in nanodiamond at room-temperature. The study involves the confocal mapping of an ensemble of NV centers to measure spin state-dependent optical transition by applying an optical excitation and microwave field simultaneously. The spin state control appears as a dip at 2.87 GHz in the measured emission intensity spectra as a function of microwave frequency. An ODMR contrast of 3.4 % is achieved at the NV center emission maximum of 660 nm and an inhomogeneous dephasing time of 0.03 microseconds. We find an inherent small split in the ODMR dip which is induced by local strain in nanodiamonds. The split becomes stronger while applying an external magnetic field, which forms the basis of NV center-based magnetometry. The results are useful for spin-based microwave-optical quantum transducers, quantum sensing, and quantum memory devices.

Thermoelectric measurements of nanomaterials by nanodiamond quantum thermometry

In this study, the Seebeck coefficient of a single-walled carbon nanotube (SWCNT) was evaluated using a nitrogen vacancy center in nanodiamonds as a thermometer. A temperature gradient was established across the SWCNT, and the temperatures of the nanodiamonds on the electrodes, along with the electromotive force between these electrodes, were measured. The Seebeck coefficient for a metallic SWCNT was determined to be 14.0 ± 1.1 μV K−1, which is consistent with results reported in previous studies. This methodology offers a promising approach for evaluating the thermoelectric properties of various nanomaterials.

Creation, Control, and Modeling of NV Centers in Nanodiamonds

AbstractSensing based on Nitrogen‐Vacancy (NV) centers in nanodiamonds (NDs) represents a potentially groundbreaking technology with broad applications. Nevertheless, the optimization of their quantum‐optical properties is still a challenging issue. The present work aims at enhancing and controlling NV centers optical properties in NDs by combining their surface chemistry tuning and proton beam irradiation. Systematic thermal oxidations are carried out to study the evolution of surface chemical groups (IR spectroscopy), as well as their influence on optical properties (photoluminescence spectroscopy, PL decay measurements). Proton irradiation is performed by exploring a wide range of fluences (1014 – 1017 cm−2) in order to precisely control the amount of NV centers, thus defining the conditions that maximize their creation and emission intensity. In addition, NV centers charge state control is achieved by assessing NV−/NV0 ratio upon different surface termination tuning and NV centers amount. Finally, a novel predictive mathematical model is developed, allowing for the evaluation of the efficiencies of the formation of both NV− and NV0. Although the model is tested in the specific case study with proton irradiated NDs, it offers a broad applicability, thus representing a key landmark in the prediction of the outcome of ion‐beam‐based color centers generation in diamond.

Near-zero-field microwave-free magnetometry with nitrogen-vacancy centers in nanodiamonds

We study the fluorescence of nanodiamond ensembles as a function of static external magnetic field and observe characteristic dip features close to the zero field with potential for magnetometry applications. We analyze the dependence of the feature’s width and the contrast of the feature on the size of the diamond (in the range 30 nm–3000 nm) and on the strength of a bias magnetic field applied transversely to the field being scanned. We also perform optically detected magnetic resonance (ODMR) measurements to quantify the strain splitting of the zero-field ODMR resonance across various nanodiamond sizes and compare it with the width and contrast measurements of the zero-field fluorescence features for both nanodiamonds and bulk samples. The observed properties provide compelling evidence of cross-relaxation effects in the NV system occurring close to zero magnetic fields. Finally, the potential of this technique for use in practical magnetometry is discussed.

Sensing the Spin State of Room-Temperature Switchable Cyanometallate Frameworks with Nitrogen-Vacancy Centers in Nanodiamonds.

Room-temperature magnetically switchable materials play a vital role in current and upcoming quantum technologies, such as spintronics, molecular switches, and data storage devices. The increasing miniaturization of device architectures produces a need to develop analytical tools capable of precisely probing spin information at the single-particle level. In this work, we demonstrate a methodology using negatively charged nitrogen vacancies (NV-) in fluorescent nanodiamond (FND) particles to probe the magnetic switching of a spin crossover (SCO) metal-organic framework (MOF), [Fe(1,6-naphthyridine)2(Ag(CN)2)2] material (1), and a single-molecule photomagnet [X(18-crown-6)(H2O)3]Fe(CN)6·2H2O, where X = Eu and Dy (materials 2a and 2b, respectively), in response to heat, light, and electron beam exposure. We employ correlative light-electron microscopy using transmission electron microscopy (TEM) finder grids to accurately image and sense spin-spin interacting particles down to the single-particle level. We used surface-sensitive optically detected magnetic resonance (ODMR) and magnetic modulation (MM) of FND photoluminescence (PL) to sense spins to a distance of ca. 10-30 nm. We show that ODMR and MM sensing was not sensitive to the temperature-induced SCO of FeII in 1 as formation of paramagnetic FeIII through surface oxidation (detected by X-ray photoelectron spectroscopy) on heating obscured the signal of bulk SCO switching. We found that proximal FNDs could effectively sense the chemical transformations induced by the 200 keV electron beam in 1, namely, AgI → Ag0 and FeII → FeIII. However, transformations induced by the electron beam are irreversible as they substantially disrupt the structure of MOF particles. Finally, we demonstrate NV- sensing of reversible photomagnetic switching, FeIII + (18-crown-6) ⇆ FeII + (18-crown-6)+ •, triggered in 2a and 2b by 405 nm light. The photoredox process of 2a and 2b proved to be the best candidate for room-temperature single-particle magnetic switching utilizing FNDs as a sensor, which could have applications into next-generation quantum technologies.

Atomically Precise Detection and Manipulation of Nitrogen-Vacancy Centers in Nanodiamonds.

Nitrogen-vacancy (NV) centers in nanodiamonds are a promising quantum communication system offering robust and discrete single photon emission, but a more thorough understanding of properties of the NV centers is critical for real world implementation in functional devices. The first step to understanding how factors such as surface, depth, and charge state affect NV center properties is to directly characterize these defects on the atomic scale. Here we use Angstrom-resolution scanning transmission electron microscopy (STEM) to identify a single NV center in a ∼4 nm natural nanodiamond through simultaneous acquisition of electron energy loss and energy dispersive X-ray spectra, which provide a characteristic NV center peak and a nitrogen peak, respectively. In addition, we identify NV centers in larger, ∼15 nm synthetic nanodiamonds, although without the single-defect resolution afforded by the lower background of the smaller natural nanodiamonds. We have further demonstrated the potential to directly position these technologically relevant defects at the atomic scale using the scanning electron beam to "herd" NV centers and nitrogen atoms across their host nanodiamonds.

Detecting the metabolism of individual yeast mutant strain cells when aged, stressed or treated with antioxidants with diamond magnetometry

Free radicals play a key role in the ageing process. However, free radicals are small, reactive and short lived and thus challenging to measure. We utilize a new technique called diamond magnetometry for this purpose. We make use of nitrogen vacancy centers in nanodiamonds. Via a quantum effect these defects convert a magnetic resonance signal into an optical signal. While this method is increasingly popular for its unprecedented sensitivity in physics, we use this technique here for the first time to measure free radicals in living cells. Our signals are equivalent to T1 signals in conventional MRI but from nanoscale voxels from single cells with sub-cellular resolution. With this powerful tool we are able to follow free radical generation after chemically inducing stress. In addition, we can observe free radical reduction in presence of an antioxidant. We were able to clearly differentiate between mutant strains with altered metabolism. Finally, the excellent stability of our diamond particles allowed us to follow the ageing process and differentiate between young and old cells. We could confirm the expected increase of free radical load in old wild type and sod1Δ mutants. We further applied this new technique to investigate tor1Δ and pex19Δ cells. For these mutants an increased lifespan has been reported but the exact mechanism is unclear. We find a decreased free radical load in, which might offer an explanation for the increased lifespan in these cells.

Tailored light emission from color centers in nanodiamond using self-assembled photonic crystals

The defect centers in solid-state materials especially the nitrogen-vacancy (NV) centers in diamond have shown a tremendous potential for their utilization in quantum technology applications. However, they exhibit certain drawbacks such as the feeble zero phonon line with huge phonon contribution and the higher lifetime values. Here, we present a novel approach to control the spontaneous emission from NV centers in nanodiamond using engineered self-assembled photonic crystals. Using two complimentary emission measuring geometries at room temperature, we show a 63% suppression and 17% enhancement of NV center emission intensity using photonic stopgap, supported with simulations. The emission rates are modified in a broad spectral range of NV center emission and are consistent with the Barnett–Loudon sum rule. The results are crucial for emerging quantum technologies using NV centers in diamond.

Nanodiamond-Quantum Sensors Reveal Temperature Variation Associated to Hippocampal Neurons Firing.

Temperature is one of the most relevant parameters for the regulation of intracellular processes. Measuring localized subcellular temperature gradients is fundamental for a deeper understanding of cell function, such as the genesis of action potentials, and cell metabolism. Notwithstanding several proposed techniques, at the moment detection of temperature fluctuations at the subcellular level still represents an ongoing challenge. Here, for the first time, temperature variations (1 °C) associated with potentiation and inhibition of neuronal firing is detected, by exploiting a nanoscale thermometer based on optically detected magnetic resonance in nanodiamonds. The results demonstrate that nitrogen‐vacancy centers in nanodiamonds provide a tool for assessing various levels of neuronal spiking activity, since they are suitable for monitoring different temperature variations, respectively, associated with the spontaneous firing of hippocampal neurons, the disinhibition of GABAergic transmission and the silencing of the network. Conjugated with the high sensitivity of this technique (in perspective sensitive to < 0.1 °C variations), nanodiamonds pave the way to a systematic study of the generation of localized temperature gradients under physiological and pathological conditions. Furthermore, they prompt further studies explaining in detail the physiological mechanism originating this effect.

Revealing Capillarity in AFM Indentation of Cells by Nanodiamond-Based Nonlocal Deformation Sensing.

Nanoindentation based on atomic force microscopy (AFM) can measure the elasticity of biomaterials and cells with high spatial resolution and sensitivity, but relating the data to quantitative mechanical properties depends on information on the local contact, which is unclear in most cases. Here, we demonstrate nonlocal deformation sensing on biorelevant soft matters upon AFM indentation by using nitrogen-vacancy centers in nanodiamonds, providing data for studying both the elasticity and capillarity without requiring detailed knowledge about the local contact. Using fixed HeLa cells for demonstration, we show that the apparent elastic moduli of the cells would have been overestimated if the capillarity was not considered. In addition, we observe that both the elastic moduli and the surface tensions are reduced after depolymerization of the actin cytoskeleton in cells. This work demonstrates that the nanodiamond sensing of nonlocal deformation with nanometer precision is particularly suitable for studying mechanics of soft biorelevant materials.

Stacked metasurfaces for enhancing the emission and extraction rate of single nitrogen-vacancy centers in nanodiamond

Dielectric metasurfaces with unique possibilities of manipulating light–matter interaction lead to new insights in exploring spontaneous emission control using single quantum emitters. Here, we study the stacked metasurfaces in one- (1D) and two-dimensions (2D) to enhance the emission rate of a single quantum emitter using the associated optical resonances. The 1D structures with stacked bilayers are investigated to exhibit Tamm plasmon resonance optimized at the zero phonon line (ZPL) of the negative nitrogen-vacancy (NV−) center. The 2D stacked metasurface comprising of two-slots silicon nano-disks is studied for the Kerker condition at ZPL wavelength. The far-field radiation plots for the 1D and 2D stacked metasurfaces show an increased extraction efficiency rate for the NV− center at ZPL wavelength that reciprocates the localized electric field intensity. The modified local density of optical states results in large Purcell enhancement of 3.8 times and 25 times for the single NV− center integrated with 1D and 2D stacked metasurface, respectively. These results have implications in exploring stacked metasurfaces for applications such as single photon generation and CMOS compatible light sources for on-demand chip integration.

Comparison of back focal plane imaging of nitrogen vacancy centers in nanodiamond and core-shell CdSe/CdS quantum dots

We report on the characterization of the angular-dependent emission of two different single-photon emitters based on nitrogen-vacancy centers in nanodiamond and on core-shell CdSe/CdS quantum dot nanoparticles. The emitters were characterized in a confocal microscope setup by spectroscopy and Hanbury-Brown and Twiss interferometry. The angular-dependent emission is measured using a back focal plane imaging technique. A theoretical model of the angular emission patterns of the 2D dipoles of the emitters is developed to determine their orientation. Experiment and model agree well with each other.

Charge state depletion nanoscopy with a nitrogen-vacancy center in nanodiamonds.

The development of super-resolution imaging has driven research into biological labeling, new materials' characterization, and nanoscale sensing. Here, we studied the photoinduced charge state conversion of nitrogen-vacancy (NV) centers in nanodiamonds (NDs), which show the potential for multifunction sensing and labeling at the nanoscale. Charge state depletion (CSD) nanoscopy is subsequently demonstrated for the diffraction-unlimited imaging of NDs in biological cells. A resolution of 77 nm is obtained with 50 nm NDs. The depletion laser power of CSD nanoscopy is approximately 1/16 of stimulated emission depletion (STED) microscopy with the same resolution. The results can be used to improve the spatial resolution of biological labeling and sensing with NDs and other nanoparticles.

Sample fabrication and metrological characterization of single-photon emitters based on nitrogen vacancy centers in nanodiamonds

Quantum metrology requires a stable single-photon emission and a high single-photon purity. Since nitrogen-vacancy (NV-) centers provide both features at room temperature, they are promising candidates for the application in this field [1, 2]. The knowledge about a suitable sample preparation technique is crucial, because the quality of the single-photon emission strongly depends on the sample purity and on the spatial resolvability of the emitters. This work presents the comparison and optimization of various sample fabrication techniques of nitrogen vacancy center doped nanodiamonds on standard cover glasses. The preparation is followed by a comparative characterization of the centers of the various samples. The sample fabrication includes the removal of contaminants on the cover glass surface. This was carried out by using peroxymonosulfuric acid (piranha solution, H2SO5) in comparison to the commercially available lye Hellmanex III (by Hellma Analytics). After cleaning the cover glasses, volumes of various nanodiamond dilutions were applied via spin coating. In subsequent steps, the nanodiamonds themselves were cleaned with peroxymonosulfuric acid, too, to remove contaminants resulting from the manufacturing process, e.g. graphite. The samples were analyzed by using a confocal laser scanning microscope with an oil immersion objective. Single-photon purity was determined by measuring the second order correlation function with a Hanbury Brown and Twiss setup. Spectral analysis revealed the presence of NV−- and NV°-centers. It was shown that a suitable cleansing method has an immense impact on single-photon emission, as was proven by a comparative characterization of differently manufactured nanodiamonds.

Enhancing spontaneous emission using structural resonances of self-assembled monolayers

Self-assembled monolayers made using sub-micron dielectric spheres are analogous to atomic monolayers that have proved to be a modern workhorse in condensed matter physics. Here, we discuss the origin of optical resonances associated with sub-micron dielectric monolayers through experiments that are further supported by theory and simulation. These resonances are used to enhance the emission rate of nitrogen-vacancy centers in nanodiamonds. Emission decay rate measurements confirm a 14% decrease in the excited state lifetime, which implies an enhanced emission rate at the resonances. The increase in measured decay rates is supported by the calculated local density of optical states. Our results provide a platform to tailor light transport and emission for applications in photonics and quantum technology using these monolayers.

Engineering the collapse of lifetime distribution of nitrogen-vacancy centers in nanodiamonds

Abstract

Purcell effect of nitrogen-vacancy centers in nanodiamond coupled to propagating and localized surface plasmons revealed by photon-correlation cathodoluminescence

We measured the second-order correlation function of the cathodoluminescence intensity and investigated the Purcell effect by comparing the lifetimes of quantum emitters with and without metal structure. The increase in the electromagnetic local density of state due to the coupling of a quantum emitter with a plasmonic structure causes a shortening of the emitter lifetime, which is called the Purcell effect. Since the plasmon-enhanced electric field is confined well below the wavelength of light, the quantum emitter lifetime is changed in the nanoscale range. In this study, we combined cathodoluminescence in scanning (transmission) electron microscopy with Hanbury Brown-Twiss interferometry to measure the Purcell effect with nanometer and nanosecond resolutions. We used nitrogen-vacancy centers contained in nanodiamonds as quantum emitters and compared their lifetime in different environments: on a thin SiO2 membrane, on a thick flat silver film, and embedded in a silver film. The lifetime reductions of nitrogen-vacancy centers were clearly observed in the samples with silver. We evaluated the lifetime by analytical calculation and numerical simulations and revealed the Purcell effects of emitters coupled to propagating and localized surface plasmons. This is the first experimental result showing the Purcell effect due to the coupling between nitrogen-vacancy centers in nanodiamonds and surface plasmon polaritons with nanometer resolution.

Magnetically Modulated Fluorescence of Nitrogen-Vacancy Centers in Nanodiamonds for Ultrasensitive Biomedical Analysis.

The negatively charged nitrogen-vacancy center in fluorescent nanodiamonds (FNDs) is a point defect with unique magneto-optical properties. It emits far-red fluorescence at ∼700 nm, and its intensity can be magnetically modulated with a depth of more than 10% at a field strength of 30 mT. We have closely examined this property and illustrated its practical use in biomedicine by applying a periodic, time-varying magnetic field to FNDs deposited on a surface or dispersed in a solution with a lock-in detection method. We achieved selective and sensitive detection of 100 nm FNDs on a nitrocellulose membrane at a particle density of 0.04 ng/mm2 (or ∼2 × 104 particles/mm2) and in an aqueous solution with a particle concentration of 1 ng/mL (or ∼1 fM) in 10 s as the detection limits. The utility and versatility of the technique were demonstrated with an application to background-free detection of FNDs as reporters for FND-based lateral flow immunoassays as well as selective quantification of FNDs in tissue digests for in vivo studies.

Monitoring Dark-State Dynamics of a Single Nitrogen-Vacancy Center in Nanodiamond by Auto-Correlation Spectroscopy: Photonionization and Recharging.

In this letter, the photon-induced charge conversion dynamics of a single Nitrogen-Vacancy (NV) center in nanodiamond between two charge states, negative (NV−) and neutral (NV0), is studied by the auto-correlation function. It is observed that the ionization of NV− converts to NV0, which is regarded as the dark state of the NV−, leading to fluorescence intermittency in single NV centers. A new method, based on the auto-correlation calculation of the time-course fluorescence intensity from NV centers, was developed to quantify the transition kinetics and yielded the calculation of transition rates from NV− to NV0 (ionization) and from NV0 to NV− (recharging). Based on our experimental investigation, we found that the NV−-NV0 transition is wavelength-dependent, and more frequent transitions were observed when short-wavelength illumination was used. From the analysis of the auto-correlation curve, it is found that the transition time of NV− to NV0 (ionization) is around 0.1 μs, but the transition time of NV0 to NV− (recharging) is around 20 ms. Power-dependent measurements reveal that the ionization rate increases linearly with the laser power, while the recharging rate has a quadratic increase with the laser power. This difference suggests that the ionization in the NV center is a one-photon process, while the recharging of NV0 to NV− is a two-photon process. This work, which offers theoretical and experimental explanations of the emission property of a single NV center, is expected to help the utilization of the NV center for quantum information science, quantum communication, and quantum bioimaging.