Benefiting from both molecular tunability and versatile methods for deployment, optically interfaced molecular spins are a promising platform for quantum technologies such as sensing and imaging. Room-temperature optically detected coherent spin control is a key enabler for many applications, combining sensitive readout, versatile spin manipulation, and ambient operation. Here we demonstrate such functionality in a molecular spin system. Using the photoexcited triplet state of organic chromophores (pentacene doped in a para-terphenyl host), we optically detect coherent spin manipulation with photoluminescence contrasts exceeding 10% and microsecond coherence times at room temperature. We further demonstrate how coherent control of multiple triplet sublevels can significantly enhance optical spin contrast, and extend optically detected coherent control to a thermally evaporated thin film, retaining high photoluminescence contrast and coherence times of order one microsecond. These results open opportunities for room-temperature quantum technologies that can be systematically tailored through synthetic chemistry.
A coherent superposition of rotational states in D$_2$ has been excited by nonresonant ultrafast (12 femtosecond) intense (2 $\times$ 10$^{14}$ Wcm$^{-2}$) 800 nm laser pulses leading to impulsive dynamic alignment. Field-free evolution of this rotational wavepacket has been mapped to high temporal resolution by a time-delayed pulse, initiating rapid double ionization, which is highly sensitive to the angle of orientation of the molecular axis with respect to the polarization direction, $θ$. The detailed fractional revivals of the neutral D$_2$ wavepacket as a function of $θ$ and evolution tim…
Optically addressable spins in materials are important platforms for quantum technologies, such as repeaters and sensors. Identification of such systems in two-dimensional (2d) layered materials offers advantages over their bulk counterparts, as their reduced dimensionality enables more feasible on-chip integration into devices. Here, we report optically detected magnetic resonance (ODMR) from previously identified carbon-related defects in 2d hexagonal boron nitride (hBN). We show that single-defect ODMR contrast can be as strong as 6% and displays a magnetic-field dependence with both positi…
We propose a scanning magnetic microscope which has a photoluminescence nanoprobe implanted in the tip of an AFM or STM, or NSOM, and exhibits optically detected magnetic resonance (ODMR). The proposed spin microscope has nanoscale lateral resolution and the single spin sensitivity for AFM and STM.
We report bulk, room-temperature hyperpolarization of 13C nuclear spins observed via high-field nuclear magnetic resonance (NMR). The hyperpolarization is achieved by optical pumping (OP) of nitrogen vacancy defect centers in diamond accompanied by dynamic nuclear polarization (DNP). The technique harnesses the large optically-induced spin polarization of NV- centers at room temperature, which is many orders of magnitude greater than thermal equilibrium polarization and typically achievable only at sub-Kelvin temperatures. Transfer of the spin polarization to the 13C nuclear spins is accomplis…
Optically pumped magnetometers are becoming a promising alternative to cryogenically-cooled superconducting magnetometers for detecting and imaging biomagnetic fields. Magnetic field detection is a completely non-invasive method, which allows one to study the function of excitable human organs with a sensor placed outside the human body. For instance, magnetometers can be used to detect brain activity or to study the activity of the heart. We have developed a highly sensitive miniature optically pumped magnetometer based on cesium atomic vapor kept in a paraffin-coated glass container. The mag…
Using pulsed optically detected magnetic resonance techniques, we directly probe electron-spin resonance transitions in the excited-state of single Nitrogen-Vacancy color centers in diamond. Unambiguous assignment of excited state fine structure is made, based on changes of NV defect photoluminescence lifetime. This study provides significant insight into the structure of the emitting 3E excited state, which is invaluable for the development of diamond-based quantum information processing.
Optically detected and radio wave-controlled spin chemistry in flavoproteins
Technical University of Munich, TUM School of Natural Sciences, Chemistry Department（慕尼黑工业大学）；Munich Center for Quantum Science and Technology (MCQST)（慕尼黑量子科学与技术中心）；Albert Ludwigs-Universität Freiburg, Institute of Physical Chemistry（弗赖堡大学）；Marburg University, Chemistry Department（马尔堡大学）
We present an experimental and theoretical study of the optically detected magnetic resonance signals for ensembles of negatively charged nitrogen-vacancy (NV) centers in 13C isotopically enriched single-crystal diamond. We observe four broad transition peaks with superimposed sharp features at zero magnetic field and study their dependence on applied magnetic field. A theoretical model that reproduces all qualitative features of these spectra is developed. Understanding the magnetic-resonance spectra of NV centers in isotopically enriched diamond is important for emerging applications in nucl…
We employ the technique of optical detection of magnetic resonance to study dipolar interaction in diamond between nitrogen-vacancy color centers of different crystallographic orientations and substitutional nitrogen defects. We demonstrate optical measurements of resonant spin flips-flips (second Larmor line), and flip-flops between different spin ensembles in diamond. In addition, the strain coupling between the nitrogen-vacancy color centers and bulk acoustic modes is studied using optical detection. Our findings may help optimizing cross polarization protocols, which, in turn, may allow im…
We present the development of an optically detected magnetic resonance (ODMR) system, which enables us to perform the ODMR measurements of a single defect in solids at high frequencies and high magnetic fields. Using the high-frequency and high-field ODMR system, we demonstrate 115 GHz continuous-wave and pulsed ODMR measurements of a single nitrogen-vacancy (NV) center in a diamond crystal at the magnetic field of 4.2 Tesla as well as investigation of field dependence ($0-8$ Tesla) of the longitudinal relaxation time ($T_1$) of NV centers in nanodiamonds.
Optically addressable spins in widebandgap semiconductors have become one of the most prominent platforms for exploring fundamental quantum phenomena. While several candidates in 3D crystals including diamond and silicon carbide have been extensively studied, the identification of spindependent processes in atomically thin 2D materials has remained elusive. Although optically accessible spin states in hBN are theoretically predicted, they have not yet been observed experimentally. Here, employing rigorous electron paramagnetic resonance techniques and photoluminescence spectroscopy, we identif…
Nitrogen-vacancy (NV) centers in diamond can be used for nanoscale sensing with atomic resolution and sensitivity; however, it has been observed that their properties degrade as they approach the diamond surface. Here we report that in addition to degraded spin coherence, NV centers within nanometers of the surface can also exhibit decreased fluorescence contrast for optically detected electron spin resonance (OD-ESR). We demonstrate that this decreased OD-ESR contrast arises from charge state dynamics of the NV center, and that it is strongly surface-dependent, indicating that surface enginee…
We experimentally demonstrate the temporary removal of thermal photons from a microwave mode at 1.45 GHz through its interaction with the spin-polarized triplet states of photo-excited pentacene molecules doped within a p-terphenyl crystal at room temperature. The crystal functions electromagnetically as a narrow-band cryogenic load, removing photons from the otherwise room-temperature mode via stimulated absorption. The noise temperature of the microwave mode dropped to $50^{+18}_{-32}$ K (as directly inferred by noise-power measurements) while the metal walls of the cavity enclosing the mode…
We report a mixed-signal data acquisition (DAQ) system for optically detected magnetic resonance (ODMR) of solid-state spins. This system is designed and implemented based on a Field-Programmable-Gate-Array (FPGA) chip assisted with high-speed peripherals. The ODMR experiments often require high-speed mixed-signal data acquisition and processing for general and specific tasks. To this end, we realized a mixed-signal DAQ system which can acquire both analog and digital signals with precise hardware synchronization. The system consist of 4 analog channels (2 inputs and 2 outputs) and 16 optional…
We demonstrate electrical detection of the $^{14}$N nuclear spin coherence of NV centers at room temperature. Nuclear spins are candidates for quantum memories in quantum-information devices and quantum sensors, and hence the electrical detection of nuclear spin coherence is essential to develop and integrate such quantum devices. In the present study, we used a pulsed electrically detected electron-nuclear double resonance technique to measure the Rabi oscillations and coherence time ($T_2$) of $^{14}$N nuclear spins in NV centers at room temperature. We observed $T_2 \approx$ 0.9 ms at room …
Optically addressable spins associated with defects in wide-bandgap semiconductors are versatile platforms for quantum information processing and nanoscale sensing, where spin-dependent inter-system crossing (ISC) transitions facilitate optical spin initialization and readout. Recently, the van der Waals material hexagonal boron nitride (h-BN) has emerged as a robust host for quantum emitters (QEs), but spin-related effects have yet to be observed. Here, we report room-temperature observations of strongly anisotropic photoluminescence (PL) patterns as a function of applied magnetic field for s…
We study features in the optically detected magnetic resonance (ODMR) signals associated with negatively charged nitrogen-vacancy (NV) centers coupled to other paramagnetic impurities in diamond. Our results are important for understanding ODMR line shapes and for optimization of devices based on NV centers. We determine the origins of several side features to the unperturbed NV magnetic resonance by studying their magnetic field and microwave power dependences. Side resonances separated by around 130 MHz are due to hyperfine coupling between NV centers and nearest-neighbor C-13 nuclear spins.…
Recent experiments demonstrated the cooling of a microwave mode of a high-quality dielectric resonator coupled to optically cooled nitrogen-vacancy (NV) spins in diamond. Our recent theoretical study [arXiv:2110.10950] pointed out the cooled NV spins can be used to realize cavity quantum electrodynamics effects (C-QED) at room temperature. In this article, we propose to modify the setup used in a recent diamond maser experiment [Nature 55, 493-496 (2018)], which features a higher spin transition frequency, a lower spin-dephasing rate and a stronger NV spins-resonator coupling, to realize bette…
Neutral silicon vacancy (SiV0) centers in diamond are promising candidates for quantum networks because of their excellent optical properties and long spin coherence times. However, spin-dependent fluorescence in such defects has been elusive due to poor understanding of the excited state fine structure and limited off-resonant spin polarization. Here we report the realization of optically detected magnetic resonance and coherent control of SiV0 centers at cryogenic temperatures, enabled by efficient optical spin polarization via previously unreported higher-lying excited states. We assign the…
The application of magnetic resonance (MR) spectroscopy at progressively smaller length scales may eventually permit "chemical imaging" of spins at the surfaces of materials and biological complexes. In particular, the negatively charged nitrogen-vacancy (NV-) centre in diamond has been exploited as an optical transducer for nanoscale nuclear magnetic resonance. However, the spectra of detected spins are generally broadened by their interaction with proximate paramagnetic NV- centres through coherent and incoherent mechanisms. Here we demonstrate a detection technique that can resolve the spec…
Nitrogen-vacancy (NV) centers in diamond are considered sensors for detecting magnetic fields. Pulsed optically detected magnetic resonance (ODMR) is typically used to detect AC magnetic fields; however, this technique can only be implemented after careful calibration that involves aligning an external static magnetic field, measuring continuous-wave (CW) ODMR, determining the Rabi frequency, and setting the microwave phase. In contrast, CW-ODMR can be simply implemented by continuous application of green CW laser and a microwave filed. In this letter, we report a method that uses NV centers a…
The negatively-charged nitrogen-vacancy (NV) center in diamond is at the frontier of quantum nano-metrology and bio-sensing. Recent attention has focused on the application of high-sensitivity thermometry using the spin resonances of NV centers in nano-diamond to sub-cellular biological and biomedical research. Here, we report a comprehensive investigation of the thermal properties of the center's spin resonances and demonstrate an alternate all-optical NV thermometry technique that exploits the temperature dependence of the center's optical Debye-Waller factor.
Defect spins in silicon carbide have become promising platforms with respect to quantum information processing and quantum sensing. Indeed, the optically detected magnetic resonance (ODMR) of defect spins is the cornerstone of the applications. In this work, we systematically investigate the contrast and linewidth of laser-and microwave power-dependent ODMR with respect to ensemble-divacancy spins in silicon carbide at room temperature. The results suggest that magnetic field sensing sensitivity can be improved by a factor of 10 for the optimized laser and microwave power range. The experiment…
We develop a parallel optically detected magnetic resonance (PODMR) spectrometer to address, manipulate and read out an array of single nitrogen-vacancy (NV) centers in diamond in parallel. In this spectrometer, we use an array of micro-lens to generate 20 * 20 laser-spot lattice (LSL) on the objective focal plane, and then align the LSL with an array of single NV centers. The quantum states of NV centers are manipulated by a uniform microwave field from a Ω-shape coplanar coil. As an experimental demonstration, we observe 80 NV centers in the field of view. Among them, magnetic resonance (MR)…
We report sensitive detection of the nuclear quadrupolar interaction of the 14N nuclear spin of the nitrogen-vacancy (NV) center using the electron spin echo envelope modulation technique. We applied a weak transverse magnetic field to the spin system so that certain forbidden transitions became weakly allowed due to second-order effects involving the nonsecular terms of the hyperfine interaction. The weak transitions cause modulation of the electron spin-echo signal, and a theoretical analysis suggests that the modulation frequency is primarily determined by the nuclear quadrupolar frequency;…
Silicon vacancies in silicon carbide have been proposed as an alternative to nitrogen vacancy centers in diamonds for spintronics and quantum technologies. An important precondition for these applications is the initialization of the qubits into a specific quantum state. In this work, we study the optical alignment of the spin 3/2 negatively charged silicon vacancy in 6H-SiC. Using a time-resolved optically detected magnetic resonance technique, we coherently control the silicon vacancy spin ensemble and measure Rabi frequencies and spin-lattice relaxation time of all three transitions. Then t…
Temperature sensing with nitrogen vacancy (NV) centers using quantum techniques is very promising and further development is expected. Recently, the optically detected magnetic resonance (ODMR) spectrum of a high-density ensemble of the NV centers was reproduced with noise parameters [inhomogeneous magnetic field, inhomogeneous strain (electric field) distribution, and homogeneous broadening] of the NV center ensemble. In this study, we use ODMR to estimate the noise parameters of the NV centers in several diamonds. These parameters strongly depend on the spin concentration. This knowledge is …
Optically detected magnetic resonance (ODMR) is a way to characterize the NV centers. Recently, a remarkably sharp dip was observed in the ODMR with a high-density ensemble of NV centers, and this was reproduced by a theoretical model in [Zhu et al., Nature Communications 5, 3424 (2014)], showing that the dip is a consequence of the spin-1 properties of the NV centers. Here, we present much more details of analysis to show how this model can be applied to investigate the properties of the NV centers. By using our model, we have reproduced the ODMR with and without applied magnetic fields. Also…
The electron and nuclear spins of the shallow donor 31P are promising qubit candidates invoked in many proposed Si-based quantum computing schemes. We have recently shown that the near-elimination of inhomogeneous broadening in highly isotopically enriched 28Si enables an optical readout of both the donor electron and nuclear spins by resolving the donor hyperfine splitting in the near-gap donor bound exciton transitions. We have also shown that pumping these same transitions can very quickly produce large electron and nuclear hyperpolarizations at low magnetic fields, where the equilibrium el…
Recently, vacancy-related spin defects in silicon carbide (SiC) have been demonstrated to be potentially suitable for versatile quantum interface building and scalable quantum network construction. Significant efforts have been undertaken to identify spin systems in SiC and to extend their quantum capabilities using large-scale growth and advanced nanofabrication methods. Here we demonstrated a type of spin defect in the 4H polytype of SiC generated via hydrogen ion implantation with high-temperature post-annealing, which is different from any known defects. These spin defects can be optically…
We investigate the real-time estimation protocols for the frequency shift of optically detected magnetic resonance (ODMR) of nitrogen-vacancy (NV) centers in nanodiamonds (NDs). Efficiently integrating multipoint ODMR measurements and ND particle tracking into fluorescence microscopy has recently demonstrated stable monitoring of the temperature inside living animals. We analyze the multipoint ODMR measurement techniques (3-, 4-, and 6-point methods) in detail and quantify the amount of measurement artifact owing to several systematic errors derived from instrumental errors of experimental har…
Enhanced Temperature Sensitivity in Ensemble NV Centers through Improved Optically Detected Magnetic Resonance Spectral Modeling
The University of Osaka（大阪大学）；Kyoto Institute of Technology（京都工艺纤维大学）；Premium Research Institute for Human Metaverse Medicine, The University of Osaka（大阪大学人类元宇宙医学高级研究所）；Institute for Chemical Research, Kyoto University（京都大学化学研究所以及）；Department of Electrical, Electronic, and Communication Engineering, Faculty of Science and Engineering, Chuo University（中央大学理工学部电气电子通信工程系）；Center for Quantum Information and Quantum Biology, The University of Osaka（大阪大学量子信息与量子生物学中心）
Optimizing Pulsed Optically Detected Magnetic Resonance Acquisition: A Digital Signal Processing Perspective
Indian Institute of Science Education and Research Kolkata（印度科学教育研究所加尔各答分校）；Boston College（波士顿学院）；University of Pittsburgh（匹兹堡大学）；Indian Institute of Space Science and Technology（印度空间科学与技术研究所）；Technical University of Munich（慕尼黑工业大学）；Ulm University（乌尔姆大学）；S. N. Bose National Centre for Basic Sciences（S.N. 玻色基础科学国家中心）
Dynamic Nuclear Polarization (DNP) is a powerful suite of techniques that deliver multifold signal enhancements in NMR and MRI. The generated athermal spin states can also be exploited for quantum sensing and as probes for many-body physics. Typical DNP methods require use of cryogens, large magnetic fields, and high power microwaves, which are expensive and unwieldy. Nanodiamond particles, rich in Nitrogen-Vacancy (NV) centers, have attracted attention as alternative DNP agents because they can potentially be optically hyperpolarized at room temperature. Indeed the realization of a miniature …
Molecular imaging refers to a class of noninvasive biomedical imaging techniques with the sensitivity and specificity to image biochemical variations in-vivo. An ideal molecular imaging technique visualizes a biochemical target according to a range of criteria, including high spatial and temporal resolution, high contrast relative to non-targeted tissues, depth-independent penetration into tissue, lack of harm to the organism under study, and low cost. Because no existing molecular imaging modality is ideal for all purposes, new imaging approaches are needed. Here we demonstrate a novel molecu…
In this paper cross-relaxation between nitrogen-vacancy (NV) centers and substitutional nitrogen in a diamond crystal was studied. It was demonstrated that optically detected magnetic resonance signals (ODMR) can be used to measure these signals successfully. The ODMR were detected at axial magnetic field values around 51.2~mT in a diamond sample with a relatively high (200~ppm) nitrogen concentration. We observed transitions that involve magnetic sublevels that are split by the hyperfine interaction. Microwaves in the frequency ranges from 1.3 GHz to 1.6 GHz ($m_S=0\longrightarrow m_S=-1$ NV …
Optically active defects in solids with accessible spin states are promising candidates for solid state quantum information and sensing applications. To employ these defects as quantum building blocks, coherent manipulation of their spin state is required. Here we realize coherent control of ensembles of boron vacancy (V$_B^-$) centers in hexagonal boron nitride (hBN). Specifically, by applying pulsed spin resonance protocols, we measure spin-lattice relaxation time ($T_1$) of 18 $μ$s and spin coherence time ($T_2$) of 2 $μ$s at room temperature. The spin-lattice relaxation time increases by t…
Quantum measurements of mechanical systems can produce optical squeezing via ponderomotive forces. Its observation requires high environmental isolation and efficient detection, typically achieved by using optical cavities and cryogenic cooling. Here we realize these conditions by measuring the position of an optically levitated nanoparticle at room temperature and without the overhead of an optical cavity. We use a fast heterodyne detection to reconstruct simultaneously orthogonal optical quadratures, and observe a noise reduction of $9\%\pm0.5\%$ below shot noise. Our experiment offers a nov…
We demonstrate room temperature detection of single 20 nm super-paramagnetic nanoparticles (SPNs) with a wide-field optical microscope platform suitable for biological integration. The particles are made of magnetite (Fe3O4) and are thus non-toxic and biocompatible. Detection is accomplished via optically detected magnetic resonance imaging using nitrogen-vacancy defect centers in diamond, resulting in a DC magnetic field detection limit of 2.3 μT. This marks a large step forward in the detection of SPNs, and we expect that it will allow for the development of magnetic-field-based biosensors c…
Optically detected nuclear magnetic resonance of carbon-13 in bulk diamond
Center for High Technology Materials, University of New Mexico（新墨西哥大学高等技术材料中心）；Department of Physics and Astronomy, University of New Mexico（新墨西哥大学物理与天文学系）；Department of Physics and Astronomy, Dartmouth College（达特茅斯学院物理与天文学系）；DEVCOM Army Research Laboratory（美国陆军研究与发展司令部陆军研究实验室）
