Substitutional Nitrogen Impurity Research Articles

Dynamic Nuclear Polarization with P1 Centers in Diamond.

Substitutional nitrogen impurities within the diamond lattice, known as P1 centers, have unpaired electrons that can mediate microwave driven dynamic nuclear polarization (DNP). In this paper we explore DNP of the bulk 13C spins in micrometer-sized P1 diamond particles and demonstrate a 550-fold DNP enhancement of the bulk 13C spins at room temperature in a 9 T magnetic field or 250 GHz for g ≈ 2 electrons. We study the DNP mechanisms, exploring their dependence on sample spinning frequency and microwave irradiation frequency using both continuous wave and frequency swept microwave irradiation, and discuss the results alongside recent DNP studies in the literature. Even with a modest microwave irradiation power of 160 mW from our frequency swept solid-state microwave source, we achieve a significant 13C signal enhancement, ε = 270 at room temperature. The enhancements were found to increase with the magic angle spinning (MAS) frequency, ωr/2π, and the results provide mechanistic insights into how different electron populations contribute to the observed DNP efficiency. These findings are inherently interesting and of practical importance in view of the recently reported diamond rotors fabricated from P1 high-pressure, high-temperature (HPHT) diamond.

Productivity of Concentration-Dependent Conversion of Substitutional Nitrogen Atoms into Nitrogen-Vacancy Quantum Emitters in Synthetic-Diamond by Ultrashort Laser Pulses.

Tightly focused 515-nm, 0.3-ps laser pulses modify in a laser filamentation regime the crystalline structure of an Ib-type high-pressure, high-temperature (HPHT) synthesized diamond in a thin-plate form. The modified microregions (micromarks) in the yellow and colorless crystal zones, possessing different concentrations of elementary substitutional nitrogen (N) impurity atoms (C-centers), exhibit their strongly diminished local IR absorption (upon correction to the thickness scaling factor). Simultaneously, local visible-range (400-550 nm) absorption coefficients were increased, and photoluminescence (PL) yield was strongly enhanced in the broad range of 450-800 nm. The strong yellow-red PL enhancement saturates with laser exposure, implying the complete conversion of C-centers into nitrogen-vacancy (NV0,-) ones due to the laser-induced generation of Frenkel "interstitial-vacancy" I-V carbon pairs. The other emerging blue-green (>470 nm) and green-yellow (>500 nm) PL bands were also simultaneously saturated versus the laser exposure. The observed IR/optical absorption and PL spectral changes enlighten the ultrashort pulse laser inscription of NV0--based quantum-emitter centers in synthetic diamonds and enable the evaluation of the productivity of their inscription along with the corresponding I-V generation rates.

Probing many-body dynamics in a two-dimensional dipolar spin ensemble

The most direct approach for characterizing the quantum dynamics of a strongly interacting system is to measure the time evolution of its full many-body state. Despite the conceptual simplicity of this approach, it quickly becomes intractable as the system size grows. An alternate approach is to think of the many-body dynamics as generating noise, which can be measured by the decoherence of a probe qubit. Here we investigate what the decoherence dynamics of such a probe tells us about the many-body system. In particular, we utilize optically addressable probe spins to experimentally characterize both static and dynamical properties of strongly interacting magnetic dipoles. Our experimental platform consists of two types of spin defects in nitrogen delta-doped diamond: nitrogen-vacancy colour centres, which we use as probe spins, and a many-body ensemble of substitutional nitrogen impurities. We demonstrate that the many-body system’s dimensionality, dynamics and disorder are naturally encoded in the probe spins’ decoherence profile. Furthermore, we obtain direct control over the spectral properties of the many-body system, with potential applications in quantum sensing and simulation.

Enhancement of the creation yield of NV ensembles in a chemically vapour deposited diamond

In this work we investigate the properties of negatively charged nitrogen-vacancy (NV−) centres created during single crystal diamond growth by chemical vapour deposition (CVD) on [113]-oriented substrates and with N2O as a dopant gas. The use of spin echo and double electron-electron resonance (DEER) allows us to assess NV− ratio with respect to substitutional nitrogen impurities (Ns0) incorporated during growth, a critical figure of merit for quantum technologies. We demonstrate that, at moderate growth temperatures (800 °C), dense NV− ensembles of several hundreds of ppb (800 ppb for 50 ppm of added N2O) and with exceptionally high NV−/ Ns0 ratios of up to 25% can be achieved. This NV− creation yield is higher by at least an order of magnitude to that typically obtained on standard [100]-grown diamonds and comparable to the best values reported for electron-irradiated diamonds. The material obtained here thus advantageously combines a high NV− density, high creation yield, long coherence times of several tens of μs together with a partial preferential orientation. These are highly desirable requirements for diamond-based quantum sensors that may spur new developments with this crystalline orientation leading to improved performance and sensitivity.

Robust nuclear hyperpolarization driven by strongly coupled nitrogen vacancy centers

Nuclear magnetic resonance techniques are widely used in the natural sciences but they lack sensitivity. Therefore, large sample volumes or long measurement times are necessary. In this work, we investigate the polarization of bulk 13C nuclei in a diamond above the thermal equilibrium at room temperature. Previously studied mechanisms utilize direct coupling to nitrogen vacancy centers or the additional assistance of substitutional nitrogen impurities for this purpose. We exploit strongly coupled nitrogen vacancy centers as polarization sources. We study two approaches to transfer the optically induced polarization of the electron spins of the nitrogen vacancy centers to nearby nuclear spins. First, the electron-nuclear polarization transfer is achieved by energy matching conditions or, second, by magnetic field sweeps inducing Landau–Zener-like transitions. Simulations according to a quantum mechanical system consisting of two coupled nitrogen vacancy centers and a weakly coupled 13C spin show an excellent agreement with the experimental data. Both approaches allow a reduction of the measurement time by roughly three orders of magnitude.

Carbon-13 dynamic nuclear polarization in diamond via a microwave-free integrated cross effect

Color-center-hosting semiconductors are emerging as promising source materials for low-field dynamic nuclear polarization (DNP) at or near room temperature, but hyperfine broadening, susceptibility to magnetic field heterogeneity, and nuclear spin relaxation induced by other paramagnetic defects set practical constraints difficult to circumvent. Here, we explore an alternate route to color-center-assisted DNP using nitrogen-vacancy (NV) centers in diamond coupled to substitutional nitrogen impurities, the so-called P1 centers. Working near the level anticrossing condition-where the P1 Zeeman splitting matches one of the NV spin transitions-we demonstrate efficient microwave-free 13C DNP through the use of consecutive magnetic field sweeps and continuous optical excitation. The amplitude and sign of the polarization can be controlled by adjusting the low-to-high and high-to-low magnetic field sweep rates in each cycle so that one is much faster than the other. By comparing the 13C DNP response for different crystal orientations, we show that the process is robust to magnetic field/NV misalignment, a feature that makes the present technique suitable to diamond powders and settings where the field is heterogeneous. Applications to shallow NVs could capitalize on the greater physical proximity between surface paramagnetic defects and outer nuclei to efficiently polarize target samples in contact with the diamond crystal.

Multispin-assisted optical pumping of bulk C13 nuclear spin polarization in diamond

The nitrogen-vacancy (NV) center in diamond is known to spin-polarize under optical illumination, but how is this polarization transferred to carbon spins in the bulk of the crystal? Here, the authors use field-cycled nuclear magnetic resonance to study the formation of light-driven ${}^{13}$C spin polarization in NV-rich diamond at room temperature. By considering the system's response to various magnetic fields, it is shown that ${}^{13}$C spins polarize via a cross-relaxation process involving the NV center and the electron and nuclear spins of the substitutional nitrogen impurities. Furthermore, it is shown that high levels of ${}^{13}$C spin polarization can be attained for almost any magnetic field orientation.

Optically induced cross relaxation via nitrogen-related defects for bulk diamond C13 hyperpolarization

In this Rapid Communication we utilize nuclear magnetic resonance to investigate the hyperpolarization effect of negatively charged nitrogen vacancy (NV) centers on bulk $^{13}\mathrm{C}$ nuclei in a diamond single crystal. We were able to identify several polarization peaks of a different sign at different magnetic fields in a region of some tens of Gauss centered around $50\phantom{\rule{0.28em}{0ex}}\mathrm{mT}$. The bulk $^{13}\mathrm{C}$ hyperpolarization in the investigated field range is usually attributed to the excited state level anticrossing of the NV center. However, we found that this bulk hyperpolarization is caused by optically induced cross relaxation and that it takes place in the NV center ground state. The four-spin coupling between the polarized NV electron spin, the electron spin of a substitutional nitrogen impurity (P1), as well as its $^{14}\mathrm{N}$ nuclei and the $^{13}\mathrm{C}$ nuclear spin have to be considered. We introduce a simple theoretical model which completely fits with the experimental data and which clearly shows that the P1 centers are involved in the polarization process. We expect that the current work has a significant impact on future NV-based polarization applications.

Effect of Nitrogen Impurities on the Raman Line Width in Diamond, Revisited

The results of a high-resolution Raman scattering study of a diamond crystal with a high content of single substitutional nitrogen impurities (550 ppm) in the temperature range from 50 to 673 K are presented and compared with the data for defect-free diamond. It is established that the increase of the nitrogen concentration in diamond leads to the temperature-independent increase of the Raman line width. Analysis of the experimental data allows us to conclude that this broadening should be attributed to the defect-induced shortening of the Raman phonon lifetime. We believe that this mechanism is responsible for the increase of the Raman line width caused by most point-like defects in diamond. No pronounced effects of the nitrogen defects on the Raman line position and phonon anharmonicity are observed.

Boron, nitrogen, and nickel impurities in GeC nanoribbons: A first-principles investigation

Using first-principles calculations based on the density functional theory we investigated the structural, electronic and magnetic properties of substitutional boron, nitrogen, and nickel impurities in germanium carbide (GeC) nanoribbons. Hydrogen terminated GeC ribbons with armchair and zigzag edges are considered here. We observed that all three impurities preferentially substitutes the Ge atom at the ribbon edge. In addition, the electronic band structures of the doped systems indicate that (i) the impurities could introduce impurity bands in the band gap and resulting in a reduction of the band gap of 7-AGeCNR, (ii) the metallic behavior of 4-ZGeCNR turns into semiconductor because of the incorporation of the impurities, (iii) the impurities could change the magnetic moment of 4-ZGeCNR and even introduce magnetic moment into the non-magnetic 7-AGeCNR.

Electron spin resonance spectroscopy of small ensemble paramagnetic spins using a single nitrogen-vacancy center in diamond

A nitrogen-vacancy (NV) center in diamond is a promising sensor for nanoscale magnetic sensing. Here, we report on electron spin resonance (ESR) spectroscopy using a single NV center in diamond. First, using a 230 GHz ESR spectrometer, we performed ensemble ESR of a type-Ib sample crystal and identified a substitutional single nitrogen impurity as a major paramagnetic center in the sample crystal. Then, we carried out free-induction decay and spin echo measurements of the single NV center to study static and dynamic properties of nanoscale bath spins surrounding the NV center. We also measured ESR spectrum of the bath spins using double electron-electron resonance spectroscopy with the single NV center. The spectrum analysis of the NV-based ESR measurement identified that the detected spins are the nitrogen impurity spins. The experiment was also performed with several other single NV centers in the diamond sample and demonstrated that the properties of the bath spins are unique to the NV centers indicating the probe of spins in the microscopic volume using NV-based ESR. Finally, we discussed the number of spins detected by the NV-based ESR spectroscopy. By comparing the experimental result with simulation, we estimated the number of the detected spins to be ≤50 spins.

Sublattice imbalance of substitutionally doped nitrogen in graphene

Motivated by the recently observed sublattice asymmetry of substitutional nitrogen impurities in CVD grown graphene, we show, in a mathematically transparent manner, that oscillations in the local density of states driven by the presence of substitutional impurities are responsible for breaking the sublattice symmetry. While these oscillations are normally averaged out in the case of randomly dispersed impurities, in graphene they have either the same, or very nearly the same, periodicity as the lattice. As a result, the total interaction energy of randomly distributed impurities embedded in the conduction-electron-filled medium does not vanish and is lowered when their configuration is sublattice-asymmetric. We also identify the presence of a critical concentration of nitrogen above which one should expect the sublattice asymmetry to disappear. This feature is not particular to nitrogen dopants, but should be present in other impurities.

Entanglement of electron spins and geometric phases in the diamond color center coupled to the P1 center

Impurity spins in semiconductors are potential quantum bits. Entanglement and topological phases are key resources in quantum computation. We prove that the coupled electron spins carried by a diamond nitrogen-vacancy color center (NV${}^{\ensuremath{-}}$) and a single substitutional nitrogen impurity (P1 center) are entangled in the immediate vicinity of the level anticrossing that appears in the Zeeman energy diagram at about 500 G. We also determine the Aharonov-Anandan, Berry, and marginal geometric phases that can be accumulated by the state vectors of this spin system when it is magnetically transported around a closed path. At the resonance where the gap between two energy levels is minimum, the geometric phases undergo discontinuities, and the entanglement of the two electron spins is maximal.

Temperature-scanned magnetic resonance and the evidence of two-way transfer of a nitrogen nuclear spin hyperfine interaction in coupled NV-N pairs in diamond

New method for the detection of magnetic resonance signals versus temperature is developed on the basis of the temperature dependence of the spin Hamiltonian parameters of the paramagnetic system under investigation. The implementation of this technique is demonstrated on the nitrogen-vacancy (NV) centers in diamonds. Single NV defects and their ensembles are suggested to be almost inertialess temperature sensors. The hyperfine structure of the 14N nitrogen nuclei of the nitrogen-vacancy center appears to be resolved in the hyperfine structure characteristic of the hyperfine interaction between NV and an Ns center (substitutional nitrogen impurity) in the optically detected magnetic resonance spectra of the molecular NV-Ns complex. Thus, we show that a direct evidence of the two-way transfer of a nitrogen nuclear spin hyperfine interaction in coupled NV-Ns pairs was observed. It is shown that more than 3-fold enhancement of the NV optically detected magnetic resonance signal can be achieved by using water as a collection optics medium.

Controlling the quantum dynamics of a mesoscopic spin bath in diamond.

Understanding and mitigating decoherence is a key challenge for quantum science and technology. The main source of decoherence for solid-state spin systems is the uncontrolled spin bath environment. Here, we demonstrate quantum control of a mesoscopic spin bath in diamond at room temperature that is composed of electron spins of substitutional nitrogen impurities. The resulting spin bath dynamics are probed using a single nitrogen-vacancy (NV) centre electron spin as a magnetic field sensor. We exploit the spin bath control to dynamically suppress dephasing of the NV spin by the spin bath. Furthermore, by combining spin bath control with dynamical decoupling, we directly measure the coherence and temporal correlations of different groups of bath spins. These results uncover a new arena for fundamental studies on decoherence and enable novel avenues for spin-based magnetometry and quantum information processing.

Boron and nitrogen impurities in SiC nanoribbons: an ab initio investigation

Using ab initio calculations based on density-functional theory we have performed atheoretical investigation of substitutional boron and nitrogen impurities in silicon carbide(SiC) nanoribbons. We have considered hydrogen terminated SiC ribbons with zigzag andarmchair edges. In both systems we verify that the boron and nitrogen atoms energeticallyprefer to be localized at the edges of the nanoribbons. However, while boron preferentiallysubstitutes a silicon atom, nitrogen prefers to occupy a carbon site. In addition, ourelectronic-structure calculations indicate that (i) substitutional boron and nitrogenimpurities do not affect the semiconducting character of the armchair SiC nanoribbons, and(ii) the half-metallic behavior of the zigzag nanoribbons is maintained in the presenceof substitutional boron impurities. In contrast, nitrogen atoms occupying edgecarbon sites transform half-metallic zigzag nanoribbons into metallic systems.

Mobility gaps in disordered graphene‐based materials: an ab initio ‐based tight‐binding approach to mesoscopic transport

AbstractAs is common knowledge, armchair graphene nanoribbons (aGNRs) share many electronic features with carbon nanotubes (CNTs). Nevertheless, crucial differences emerge when disorder comes into play. It is thus instructive, both from a theoretical and a technological perspective, to analyze the impact of possible types of disorder on the transport properties of these graphene‐based materials.Here we report such a comparative study between CNTs and GNRs, which points out the similarities and differences emerging as a consequence of doping by substitutional boron and nitrogen impurities. The role of edge defects (absent in CNTs) is also contrasted with chemical doping disorder. All disorder models have been derived from accurate ab initio calculations of the electronic structures (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Electronic and magnetic properties of deformed and defective single wall carbon nanotubes

The combined effect of radial deformation and defects on the properties of semiconducting single wall carbon nanotubes are studied using density functional theory. A Stone–Thrower–Wales defect, a substitutional nitrogen impurity, and a mono-vacancy at the highest curvature side of a radially strained nanotube are considered. The energies characterizing the deformation and defect formation, the band gap energies, and various bond lengths are calculated. We find that there is magneto-mechanical coupling behavior in the nanotube properties which can be tailored by the degree of radial deformation and the type of defect. The carbon nanotube energetics and magnetism are also explained in terms of electronic structure changes as a function of deformation and types of defects present in the structure.

Shallow nitrogen acceptor in TiO 2 studied by β-NMR spectroscopy

The local electronic structure of substitutional nitrogen impurity in rutile TiO 2 was studied by means of the β-NMR technique. A short-lived β emitter 12N ( I=1, T 1/2=11 ms) was implanted into a rutile single crystal as a probe nucleus to detect double-quantum NMR spectrum. The result shows the existence of a small hyperfine interaction at low temperatures due to paramagnetic states localized at oxygen substitutional site, which suggests that a substitutional nitrogen atom acts as a shallow acceptor in rutile TiO 2.

Electronic structure of substitutional nitrogen impurity in TiO 2 studied by the β-NMR method

In order to study the local electronic structure of nitrogen impurity in rutile TiO2, we have measured double-quantum NMR spectra of short lived β-emitter 12N(I=1, T 1/2=11 ms) implanted into a rutile single crystal by means of the β-NMR technique. The resonance line obtained at room temperature is well accounted for by the second order shift due to the quadrupole interaction at the oxygen substitutional site. The spectrum at 25 K has shown the other lines than the central diamagnetic line shifted by 10–15 kHz to both sides, which has been already shown in the previous data obtained with a different crystal orientation and an external field. The present results supports the existence of a paramagnetic state formed by the substitutional nitrogen impurities.