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

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

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.

Controlled Surface Modification to Revive Shallow NV- Centers.

Near-surface negatively charged nitrogen vacancy (NV) centers hold excellent promise for nanoscale magnetic imaging and quantum sensing. However, they often experience charge-state instabilities, leading to strongly reduced fluorescence and NV coherence time, which negatively impact magnetic imaging sensitivity. This occurs even more severely at 4 K and ultrahigh vacuum (UHV, p = 2 × 10-10 mbar). We demonstrate that in situ adsorption of H2O on the diamond surface allows the partial recovery of the shallow NV sensors. Combining these with band-bending calculations, we conclude that controlled surface treatments are essential for implementing NV-based quantum sensing protocols under cryogenic UHV conditions.

A Telecom O-Band Emitter in Diamond.

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

Resonant Versus Nonresonant Spin Readout of a Nitrogen-Vacancy Center in Diamond under Cryogenic Conditions.

The last decade has seen an explosive growth in the use of color centers for metrology applications, the paradigm example arguably being the nitrogen-vacancy (NV) center in diamond. Here, we focus on the regime of cryogenic temperatures and examine the impact of spin-selective, narrow-band laser excitation on NV readout. Specifically, we demonstrate a more than fourfold improvement in sensitivity compared to that possible with nonresonant (green) illumination, largely due to a boost in readout contrast and integrated photon count. We also leverage nuclear spin relaxation under resonant excitation to polarize the ^{14}N host, which we then prove beneficial for spin magnetometry. These results open opportunities in the application of NV sensing to the investigation of condensed matter systems, particularly those exhibiting superconducting, magnetic, or topological phases selectively present at low temperatures.

Single-spin resonance in a van der Waals embedded paramagnetic defect.

A plethora of single-photon emitters have been identified in the atomic layers of two-dimensional van der Waals materials1-8. Here, we report on a set of isolated optical emitters embedded in hexagonal boron nitride that exhibit optically detected magnetic resonance. The defect spins show an isotropic ge-factor of ~2 and zero-field splitting below 10 MHz. The photokinetics of one type of defect is compatible with ground-state electron-spin paramagnetism. The narrow and inhomogeneously broadened magnetic resonance spectrum differs significantly from the known spectra of in-plane defects. We determined a hyperfine coupling of ~10 MHz. Its angular dependence indicates an unpaired, out-of-plane delocalized π-orbital electron, probably originating from substitutional impurity atoms. We extracted spin-lattice relaxation times T1 of 13-17 µs with estimated spin coherence times T2 of less than 1 µs. Our results provide further insight into the structure, composition and dynamics of single optically active spin defects in hexagonal boron nitride.

Strong Zero-Phonon Transition from Point Defect-Stacking Fault Complexes in Silicon Carbide Nanowires.

Crystallographic defects such as vacancies and stacking faults engineer electronic band structure at the atomic level and create zero- and two-dimensional quantum structures in crystals. The combination of these point and planar defects can generate a new type of defect complex system. Here, we investigate silicon carbide nanowires that host point defects near stacking faults. These point-planar defect complexes in the nanowire exhibit outstanding optical properties of high-brightness single photons (>360 kcounts/s), a fast recombination time (<1 ns), and a high Debye-Waller factor (>50%). These distinct optical properties of coupled point-planar defects lead to an unusually strong zero-phonon transition, essential for achieving highly efficient quantum interactions between multiple qubits. Our findings can be extended to other defects in various materials and therefore offer a new perspective for engineering defect qubits.

Identification of a Telecom Wavelength Single Photon Emitter in Silicon.

We identify the exact microscopic structure of the G photoluminescence center in silicon by first-principles calculations with including a self-consistent many-body perturbation method, which is a telecommunication wavelength single photon source. The defect constitutes of C_{s}C_{i} carbon impurities in its C_{s}─Si_{i}─C_{s} configuration in the neutral charge state, where s and i stand for the respective substitutional and interstitial positions in the Si lattice. We reveal that the observed fine structure of its optical signals originates from the athermal rotational reorientation of the defect. We attribute the monoclinic symmetry reported in optically detected magnetic resonance measurements to the reduced tunneling rate at very low temperatures. We discuss the thermally activated motional averaging of the defect properties and the nature of the qubit state.

Optically Detected Magnetic Resonance in Neutral Silicon Vacancy Centers in Diamond via Bound Exciton States.

Neutral silicon vacancy (SiV^{0}) 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 SiV^{0} centers at cryogenic temperatures, enabled by efficient optical spin polarization via previously unreported higher-lying excited states. We assign these states as bound exciton states using group theory and density functional theory. These bound exciton states enable new control schemes for SiV^{0} as well as other emerging defect systems.

Electrical Charge State Manipulation of Single Silicon Vacancies in a Silicon Carbide Quantum Optoelectronic Device.

Color centers with long-lived spins are established platforms for quantum sensing and quantum information applications. Color centers exist in different charge states, each of them with distinct optical and spin properties. Application to quantum technology requires the capability to access and stabilize charge states for each specific task. Here, we investigate charge state manipulation of individual silicon vacancies in silicon carbide, a system which has recently shown a unique combination of long spin coherence time and ultrastable spin-selective optical transitions. In particular, we demonstrate charge state switching through the bias applied to the color center in an integrated silicon carbide optoelectronic device. We show that the electronic environment defined by the doping profile and the distribution of other defects in the device plays a key role for charge state control. Our experimental results and numerical modeling evidence that control of these complex interactions can, under certain conditions, enhance the photon emission rate. These findings open the way for deterministic control over the charge state of spin-active color centers for quantum technology and provide novel techniques for monitoring doping profiles and voltage sensing in microscopic devices.

First-Principles Study of Charge Diffusion between Proximate Solid-State Qubits and Its Implications on Sensor Applications.

Solid-state qubits from paramagnetic point defects in solids are promising platforms to realize quantum networks and novel nanoscale sensors. Recent advances in materials engineering make it possible to create proximate qubits in solids that might interact with each other, leading to electron spin or charge fluctuation. Here we develop a method to calculate the tunneling-mediated charge diffusion between point defects from first principles and apply it to nitrogen-vacancy (NV) qubits in diamond. The calculated tunneling rates are in quantitative agreement with previous experimental data. Our results suggest that proximate neutral and negatively charged NV defect pairs can form a NV-NV molecule. A tunneling-mediated model for the source of decoherence of the near-surface NV qubits is developed based on our findings on the interacting qubits in diamond.

Identification of the binding site between bovine serum albumin and ultrasmall SiC fluorescent biomarkers.

Ultrasmall silicon carbide nanoparticles (SiC USNPs) are very promising biomarkers for developing new applications in diagnostics, cell monitoring or drug delivery, even though their interaction with biological molecules such as different proteins has not yet been investigated in detail. In this study, the biological behaviour of SiC USNPs in a medium modeling a living organism was investigated in detail through the dependence of the fluorescence on interactions between bovine serum albumin (BSA) and SiC USNPs. The interaction shows transient nanoparticle-protein associations due to the restricted diffusion behaviour of the nanoparticles in the vicinity of a protein. The transient association manifests in a complex fluorescence quenching mechanism where the dynamic component was dominated by Förster resonance energy transfer. By studying SiC nanoparticles of different sizes, it can be concluded that the transient effect is an ultrasmall nanoparticle behaviour.

Photoluminescence, infrared, and Raman spectra of co-doped Si nanoparticles from first principles.

Co-doped silicon nanoparticles (NPs) are promising for the realization of novel biological and optoelectronic applications. Despite the scientific and technological interest, the structure of heavily co-doped Si NPs is still not very well understood. By means of first principles simulations, various spectroscopic quantities can be computed and compared to the corresponding experimental data. In this paper, we demonstrate that the calculated infrared spectra, photoluminescence spectra, and Raman spectra can provide valuable insights into the atomistic structure of co-doped Si NPs.

Nitrogen-Terminated Diamond (111) Surface for Room-Temperature Quantum Sensing and Simulation.

The nitrogen-vacancy (NV) center in diamond has shown great promise of nanoscale sensing applications, however, near-surface NV suffer from relatively short spin coherence time that limits its sensitivity. This is presumably caused by improper surface termination. Using first-principles calculations, we propose that nitrogen-terminated (111) diamond provides electrical inactivity and surface spin noise free properties. We anticipate that the nitrogen-terminated (111) surface can be fabricated by nitrogen plasma treatment. Our findings pave the way toward an improved NV-based quantum sensing and quantum simulation operating at room temperature.

Protecting a Diamond Quantum Memory by Charge State Control.

In recent years, solid-state spin systems have emerged as promising candidates for quantum information processing. Prominent examples are the nitrogen-vacancy (NV) center in diamond, phosphorus dopants in silicon (Si:P), rare-earth ions in solids, and VSi-centers in silicon-carbide. The Si:P system has demonstrated that its nuclear spins can yield exceedingly long spin coherence times by eliminating the electron spin of the dopant. For NV centers, however, a proper charge state for storage of nuclear spin qubit coherence has not been identified yet. Here, we identify and characterize the positively charged NV center as an electron-spin-less and optically inactive state by utilizing the nuclear spin qubit as a probe. We control the electronic charge and spin utilizing nanometer scale gate electrodes. We achieve a lengthening of the nuclear spin coherence times by a factor of 4. Surprisingly, the new charge state allows switching of the optical response of single nodes facilitating full individual addressability.

Erratum: High-Fidelity Bidirectional Nuclear Qubit Initialization in SiC [Phys. Rev. Lett. 117, 220503 (2016)].

This corrects the article DOI: 10.1103/PhysRevLett.117.220503.

Surface-Mediated Energy Transfer and Subsequent Photocatalytic Behavior in Silicon Carbide Colloid Solutions.

We demonstrate that particle-particle interaction affects the photocatalytic efficiency of colloids. Colloid silicon carbide nanoparticles were examined by varying their size, size distribution, and surface chemistry, and we found that surface moieties show no effect on the individual particles but dramatically affect the collective photocatalytic efficiency of the system.

Coherent control of single spins in silicon carbide at room temperature.

Spins in solids are cornerstone elements of quantum spintronics. Leading contenders such as defects in diamond or individual phosphorus dopants in silicon have shown spectacular progress, but either lack established nanotechnology or an efficient spin/photon interface. Silicon carbide (SiC) combines the strength of both systems: it has a large bandgap with deep defects and benefits from mature fabrication techniques. Here, we report the characterization of photoluminescence and optical spin polarization from single silicon vacancies in SiC, and demonstrate that single spins can be addressed at room temperature. We show coherent control of a single defect spin and find long spin coherence times under ambient conditions. Our study provides evidence that SiC is a promising system for atomic-scale spintronics and quantum technology.

High-Fidelity Bidirectional Nuclear Qubit Initialization in SiC.

Dynamic nuclear polarization (DNP) is an attractive method for initializing nuclear spins that are strongly coupled to optically active electron spins because it functions at room temperature and does not require strong magnetic fields. In this Letter, we theoretically demonstrate that DNP, with near-unity polarization efficiency, can be generally realized in weakly coupled electron spin-nuclear spin systems. Furthermore, we theoretically and experimentally show that the nuclear spin polarization can be reversed by magnetic field variations as small as 0.8 Gauss. This mechanism offers new avenues for DNP-based sensors and radio-frequency free control of nuclear qubits.

Optical Polarization of Nuclear Spins in Silicon Carbide.

We demonstrate optically pumped dynamic nuclear polarization of (29)Si nuclear spins that are strongly coupled to paramagnetic color centers in 4H- and 6H-SiC. The 99%±1% degree of polarization that we observe at room temperature corresponds to an effective nuclear temperature of 5 µK. By combining ab initio theory with the experimental identification of the color centers' optically excited states, we quantitatively model how the polarization derives from hyperfine-mediated level anticrossings. These results lay a foundation for SiC-based quantum memories, nuclear gyroscopes, and hyperpolarized probes for magnetic resonance imaging.