Increasing the coherence time of single electron spins in diamond by high temperature annealing
Boris Naydenov, Friedemann Reinhard, Anke Lämmle, V. Richter, Rafi Kalish, Ulrika F. S. D'Haenens-Johansson, Mark Newton, Fedor Jelezko, Jörg Wrachtrup
Negatively charged Nitrogen-Vacancy (NV$^-$) centers in diamond produced by ion implantation often show properties different from NVs created during the crystal growth. We observe that NVs created from nitrogen ions with four different energies (30-300 keV) show much shorter electron spin coherence time $T_2$ compared to the "natural" NVs and we could find any dependence of $T_2$ on the implantation energy. Moreover, we also find out that about 10% of them show switching from NV$^-$to NV$^0$. We develop a method to increase $T_2$ of single NV$^-$ centers by annealing the sample at $t=1200 {\circ}$C whereas at the same time the fraction of the NVs showing discharging is greatly reduced.
Spins of negatively charged nitrogen-vacancy (NV$^-$) defects in diamond are among the most promising candidates for solid-state qubits. The fabrication of quantum devices containing these spin-carrying defects requires position-controlled introduction of NV$^-$ defects having excellent properties such as spectral stability, long spin coherence time, and stable negative charge state. Nitrogen ion implantation and annealing enable the positioning of NV$^-$ spin qubits with high precision, but to date, the coherence times of qubits produced this way are short, presumably because of the presence …
Etching experiments were performed that reveal the vertical distribution of optically active nitrogen-vacancy (NV) centers in diamond created in close proximity to a surface through ion implantation and annealing. The NV distribution depends strongly on the native nitrogen concentration, and spectral measurements of the neutral and negatively-charged NV peaks give evidence for electron depletion effects in lower-nitrogen material. The results are important for potential quantum information and magnetometer devices where NV centers must be created in close proximity to a surface for coupling to…
It has been reported that conversion yield and coherence time of ion-implanted NV centers improve if the Fermi level is raised or lowered during the annealing step following implantation. Here we investigate whether surface transfer doping and surface charging, by UV light, can be harnessed to induce this effect. We analyze the coherence times and the yield of NV centers created by ion implantation and annealing, applying various conditions during annealing. Specifically, we study coating the diamond with nickel, palladium or aluminum oxide, to induce positive surface transfer doping, as well …
In the recent years graphitization of ion-beam induced amorphous layers became the basic tool for device fabrication in diamond. The etchable graphitic layers can be removed to form free-standing membranes into which the desired structures can be sculpted using FIB milling. The optical properties of the devices fabricated using this method are assumed on the model of sharp diamond-air interface. The real quality of this interface could depend on degree of graphitization of the amorphous damage layers after annealing. In the present work the graphitization process was studied using conventional…
Due to their outstanding mechanical properties, diamond and diamond-like materials find significant technological applications ranging from well-established industrial fields (cutting tools, coatings, etc.) to more advanced mechanical devices as micro- and nano-electromechanical systems. The use of energetic ions is a powerful and versatile tool to fabricate three-dimensional micro-mechanical structures. In this context, it is of paramount importance to have an accurate knowledge of the effects of ion-induced structural damage on the mechanical properties of this material, firstly to predict p…
Knowledge of the nitrogen-vacancy center formation kinetics in diamond is critical to engineering sensors and quantum information devices based on this defect. Here we utilize the longitudinal tracking of single NV centers to elucidate NV defect kinetics during high-temperature annealing from 800-1100 $^\circ$C in high-purity chemical-vapor-deposition diamond. We observe three phenomena which can coexist: NV formation, NV quenching, and NV orientation changes. Of relevance to NV-based applications, a 6 to 24-fold enhancement in the NV density, in the absence of sample irradiation, is observed …
We studied the parameters to optimize the production of negatively-charged nitrogen-vacancy color centers (NV-) in type~1b single crystal diamond using proton irradiation followed by thermal annealing under vacuum. Several samples were treated under different irradiation and annealing conditions and characterized by slow positron beam Doppler-broadening and photoluminescence (PL) spectroscopies. At high proton fluences another complex vacancy defect appears limiting the formation of NV-. Concentrations as high as 2.3 x 10^18 cm^-3 of NV- have been estimated from PL measurements. Furthermore, w…
We report a systematic photoluminescence (PL) investigation of the spectral emission properties of individual optical defects fabricated in diamond upon ion implantation and annealing. Three spectral lines at 620 nm, 631 nm, and 647 nm are identified and attributed to the SnV center due to their occurrence in the PL spectra of the very same single-photon emitting defects. We show that the relative occurrence of the three spectral features can be modified by oxidizing the sample surface following thermal annealing. We finally report the relevant emission properties of each class of individual e…
Exposure to beams of low energy electrons (2 to 30 keV) in a scanning electron microscope locally induces formation of NV-centers without thermal annealing in diamonds that have been implanted with nitrogen ions. We find that non-thermal, electron beam induced NV-formation is about four times less efficient than thermal annealing. But NV-center formation in a consecutive thermal annealing step (800C) following exposure to low energy electrons increases by a factor of up to 1.8 compared to thermal annealing alone. These observations point to reconstruction of nitrogen-vacancy complexes induced …
A high-current annealing technique is used to fabricate nanogaps and hybrid diamond/graphite structures in boron-doped nanocrystalline diamond films. Nanometer-sized gaps down to 1 nm are produced using a feedback-controlled current annealing procedure. The nanogaps are characterized using scanning electron microscopy and electronic transport measurements. The structural changes produced by the elevated temperature, achieved by Joule heating during current annealing, are characterized using Raman spectroscopy. The formation of hybridized diamond/graphite structure is observed at the point of m…
Results of Small-Angle Scattering study of diamonds with various types of point and extended defects and different degrees of annealing are presented. It is shown that thermal annealing and/or mechanical deformation cause formation of nanosized planar and threedimensional defects giving rise to Small-Angle Scattering. The defects are often facetted by crystallographic planes 111, 100, 110, 311, 211 common for diamond. The scattering defects likely consist of clusters of intrinsic and impurity-related defects; boundaries of mechanical twins also contribute to the SAS signal. There is no clear c…
We exposed nitrogen-implanted diamonds to beams of swift uranium and gold ions (~1 GeV) and find that these irradiations lead directly to the formation of nitrogen vacancy (NV) centers, without thermal annealing. We compare the photoluminescence intensities of swift heavy ion activated NV- centers to those formed by irradiation with low-energy electrons and by thermal annealing. NV- yields from irradiations with swift heavy ions are 0.1 of yields from low energy electrons and 0.02 of yields from thermal annealing. We discuss possible mechanisms of NV-center formation by swift heavy ions such a…
Theoretical study of nitrogen-vacancy spin coherence enhanced by vacancy aggregation in diamond using cluster-correlation expansion
University of Tsukuba（筑波大学）；Institute of Pure and Applied Sciences（纯理与应用科学研究院）；Japanese-French Laboratory for Semiconductor Physics and Technology J-FAST（日法半导体物理与技术实验室（J-FAST））；CNRS（法国国家科学研究中心）；University Grenoble Alpes（格勒诺布尔阿尔卑斯大学）；Grenoble INP（格勒诺布尔国立理工学院）
We characterize single nitrogen-vacancy (NV) centers created by 10-keV N+ ion implantation into diamond via thin SiO$_2$ layers working as screening masks. Despite the relatively high acceleration energy compared with standard ones (< 5 keV) used to create near-surface NV centers, the screening masks modify the distribution of N$^+$ ions to be peaked at the diamond surface [Ito et al., Appl. Phys. Lett. 110, 213105 (2017)]. We examine the relation between coherence times of the NV electronic spins and their depths, demonstrating that a large portion of NV centers are located within 10 nm from …
Nitrogen Vacancy Centers in Hexagonal Diamond Exhibit Long Coherence Times
Pritzker School of Molecular Engineering, The University of Chicago（芝加哥大学普里茨克分子工程学院）；Materials Science Division, Argonne National Laboratory（阿贡国家实验室材料科学部）；Department of Chemistry, The University of Chicago（芝加哥大学化学系）
The Hydrogenated Diamond Like Carbon (HDLC) thin films are deposited on Silicon substrate at room temperature using asymmetric capacitively coupled RF plasma with varying flow rates of methane. These films are undergone annealing at high vacuum and high temperature furnace. The as-prepared and annealed HDLC films have been depth profiled for hydrogen using the resonance at 6.44 MeV in nuclear reaction between fluoride ion beam and HDLC. The as prepared films exhibit non-uniform depth distribution of hydrogen: it decreases with depth. Annealing in vacuum brings about a significant desorption of…
Boron implantation with in-situ dynamic annealing is used to produce highly conductive sub-surface layers in type IIa (100) diamond plates for the search of a superconducting phase transition. Here we demonstrate that high-fluence MeV ion-implantation, at elevated temperatures avoids graphitization and can be used to achieve doping densities of 6 at.%. In order to quantify the diamond crystal damage associated with implantation Raman spectroscopy was performed, demonstrating high temperature annealing recovers the lattice. Additionally, low-temperature electronic transport measurements show ev…
We report on the systematic characterization of conductive micro-channels fabricated in single-crystal diamond with direct ion microbeam writing. Focused high-energy (~MeV) helium ions are employed to selectively convert diamond with micrometric spatial accuracy to a stable graphitic phase upon thermal annealing, due to the induced structural damage occurring at the end-of-range. A variable-thickness mask allows the accurate modulation of the depth at which the microchannels are formed, from several μm deep up to the very surface of the sample. By means of cross-sectional transmission electron…
Engineering coherent systems is a central goal of quantum science. Color centers in diamond are a promising approach, with the potential to combine the coherence of atoms with the scalability of a solid state platform. However, the solid environment can adversely impact coherence. For example, phonon- mediated spin relaxation can induce spin decoherence, and electric field noise can change the optical transition frequency over time. We report a novel color center with insensitivity to both of these sources of environmental decoherence: the neutral charge state of silicon vacancy (SiV0). Throug…
High concentration of negatively charged nitrogen-vacancy ($\text{NV}^{-}$) centers was created in diamond single crystals containing approximately 100 ppm nitrogen using electron and neutron irradiation and subsequent thermal annealing in a stepwise manner. Continuous wave electron paramagnetic resonance (EPR) was used to determine the transformation efficiency from isolated N atoms to $\text{NV}^{-}$ centers in each production step and its highest value was as high as 17.5 %. Charged vacancies are formed after electron irradiation as shown by EPR spectra, but the thermal annealing restores t…
The longest spin coherence times for nitrogen-vacancy (NV) centers at room temperature have been achieved in phosphorus-doped n-type diamond. However, difficulty controlling impurity incorporation and the utilization of highly toxic phosphine gas in the chemical vapor deposition (CVD) technique pose problems for the growth of n-type diamond. In the present study, n-type diamond samples were synthesized by CVD using tert-butylphosphine, which is much less toxic than phosphine. The unintentional incorporation of nitrogen was found to be suppressed by incrementally increasing the gas flow rates o…
We show a marked reduction in the emission from nitrogen-vacancy (NV) color centers in single crystal diamond due to exposure of the diamond to hydrogen plasmas ranging from 700°C to 1000°C. Significant fluorescence reduction was observed beneath the exposed surface to at least 80mm depth after ~10 minutes, and did not recover after post-annealing in vacuum for seven hours at 1100°C. We attribute the fluorescence reduction to the formation of NVH centers by the plasma induced diffusion of hydrogen. These results have important implications for the formation of nitrogen-vacancy centers for quan…
A method for obtaining a smooth, single crystal diamond surface is presented, whereby a sacrificial defective layer is created by implantation and graphitized by annealing before being selectively etched. We have used O+ at 240 keV, the main process variables being the ion fluence (ranging from 3x10^15 cm^-2 to 3x10^17 cm^-2) and the final etching process (wet etch, H2 plasma and annealing in air). The substrates were characterized by atomic force microscopy, optical profilometry and white beam X-ray topography. The influence of the various process parameters on the resulting lift-off efficien…
Optical coherence lifetimes and decoherence processes in erbium-doped lithium niobate (Er$^{3+}$:LiNbO$_3$) crystalline powders are investigated for materials that underwent different mechanical and thermal treatments. Several complimentary methods are used to assess the coherence lifetimes for these highly scattering media. Direct intensity or heterodyne detection of two-pulse photon echo techniques was employed for samples with longer coherence lifetimes and larger signal strengths, while time-delayed optical free induction decays were found to work well for shorter coherence lifetimes and w…
The nitrogen vacancy (NV) center in diamond exhibits spin-dependent fluorescence and long spin coherence times under ambient conditions, enabling applications in quantum information processing and sensing. NV centers near the surface can have strong interactions with external materials and spins, enabling new forms of nanoscale spectroscopy. However, NV spin coherence degrades within 100 nanometers of the surface, suggesting that diamond surfaces are plagued with ubiquitous defects. Prior work on characterizing near-surface noise has primarily relied on using NV centers themselves as probes; w…
We examine the quantum spin state of a single nitrogen-vacancy (NV) center in diamond at room temperature as it makes a transition from the orbital ground-state (GS) to the orbital excited-state (ES) during non-resonant optical excitation. While the fluorescence read-out of NV-center spins relies on conservation of the longitudinal spin projection during optical excitation, the question of quantum phase preservation has not been examined. Using Ramsey measurements and quantum process tomography, we establish limits on NV center spin decoherence induced during optical excitation. Treating the o…
We assess independently the impact of high-temperature substrate annealing and metal deposition conditions on the coherence of transmon qubits in the standard 2D circuit-QED architecture. We restrict our study to devices made with aluminum interdigital capacitors on sapphire substrates. We record more than an order-of-magnitude improvement in the relaxation time of devices made with an annealed substrate, independent of whether a conventional evaporator or molecular beam epitaxy chamber was used to deposit the aluminum. We also infer similar levels of flux noise and photon shot noise through d…
Nuclear magnetic resonance (NMR) imaging with shallow nitrogen-vacancy (NV) centers in diamond offers an exciting route toward sensitive and localized chemical characterization at the nanoscale. Remarkable progress has been made to combat the degradation in coherence time and stability suffered by near-surface NV centers using suitable chemical surface termination. However, approaches that also enable robust control over adsorbed molecule density, orientation, and binding configuration are needed. We demonstrate a diamond surface preparation for mixed nitrogen- and oxygen-termination that simu…
Ion implantation is widely used to modify the structural, electrical and optical properties of materials. By appropriate masking, this technique can be used to define nano- and micro-structures. However, depending on the type of mask used, experiments have shown that vacancy-related substrate modification can be inferred tens of microns away from the edge of the mask used to define the implanted region. This could be due to fast diffusion of vacancies from the implanted area during annealing or to a geometric effect related to ion scattering around the mask edges. For quantum and single-atom d…
We report on wide-field optically detected magnetic resonance imaging of nitrogen-vacancy centers (NVs) in type IIa polycrystalline diamond. These studies reveal a heterogeneous crystalline environment that produces a varied density of NV centers, including preferential orientation within some individual crystal grains, but preserves long spin coherence times. Using the native NVs as nanoscale sensors, we introduce a 3-dimensional strain imaging technique with high sensitivity ( $< 10^{-5}$ Hz$^{-1/2}$) and diffraction-limited resolution across a wide field of view.
We created dense ensembles of negatively charged nitrogen-vacancy (NV-) centers in diamond by neutron and electron irradiation for applications in hybrid quantum systems and magnetometry. We characterize fluorescence intensity, optical and coherence properties of the resulting defects by confocal microscopy, UV/Vis and FTIR spectroscopy, optically detected magnetic resonance and small angle X-ray scattering. We find the highest densities of NV- at neutron fluences on the order of 10^17 cm^-2 and electron doses of 10^18 cm^-2, with spin resonance linewidths of 6 MHz. Lower electron energies inc…
We present a study of the spin properties of dense layers of near-surface nitrogen-vacancy (NV) centres in diamond created by nitrogen ion implantation. The optically detected magnetic resonance contrast and linewidth, spin coherence time, and spin relaxation time, are measured as a function of implantation energy, dose, annealing temperature and surface treatment. To track the presence of damage and surface-related spin defects, we perform in situ electron spin resonance spectroscopy through both double electron-electron resonance and cross-relaxation spectroscopy on the NV centres. We find t…
Quantum information processing (QIP) with solid state spin qubits strongly depends on the efficient initialisation of the qubit's desired charge state. While the negatively charged tin-vacancy ($\text{SnV}^{-}$) centre in diamond has emerged as an excellent platform for realising QIP protocols due to long spin coherence times at liquid helium temperature and lifetime limited optical transitions, its usefulness is severely limited by termination of the fluorescence under resonant excitation [1,2,3]. Here, we unveil the underlying charge cycle of group IV-vacancy (G4V) centres and exploit it to …
We demonstrate the fabrication of sub-micron layers of single-crystal diamond suitable for subsequent processing as demonstrated by this test ring structure. This method is a significant enabling technology for nanomechanical and photonic structures incorporating colour-centres. The process uses a novel double implant process, annealing and chemical etching to produce membranes of diamond from single-crystal starting material, the thinnest layers achieved to date are 210 nm thick.
We demonstrate nanometer-precision depth control of nitrogen-vacancy (NV) center creation near the surface of synthetic diamond using an in situ nitrogen delta-doping technique during plasma-enhanced chemical vapor deposition. Despite their proximity to the surface, doped NV centers with depths (d) ranging from 5 - 100 nm display long spin coherence times, T2 > 100 \mus at d = 5 nm and T2 > 600 \mus at d \geq 50 nm. The consistently long spin coherence observed in such shallow NV centers enables applications such as atomic-scale external spin sensing and hybrid quantum architectures.
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…
Ionized nitrogen molecules ($^{15}$N$_{2}^+$) are used as efficient point sources for creating NV$^-$ pairs in diamond with nanoscale spatial separation and up to 55 kHz magnetic coupling strength. Co-implantation of $^{12}$C$^+$ increased the yield of pairs, and a $^{13}$C-depleted diamond allowed 0.65 ms coherence times to be obtained. Further coupling to a third dark spin provided a strongly coupled three spin register. These results mark an important step towards realization of multi-qubit systems and scalable NV$^-$ quantum registers.
Plasma surface modification was used to fabricate graphene on the top of insulating diamond-like carbon films. It is shown that by a combination of pulsed argon plasma treatment and thermal annealing at 350\degreeC is possible to achieve partial crystallization of amorphous carbon to graphene. The observed Raman spectra are typical for defected graphene - splitted D- and G-peaks and a broad 2D-peak. This result is very encouraging and we hope that by improving this technology it will be possible to fabricate defect-free graphene, which can be used in electronics without transfer to other subst…
Single-photon sources are a fundamental element for developing quantum technologies, and sources based on colour centres in diamonds are among the most promising candidates. The well-known NV centres are characterized by several limitations, thus few other defects have recently been considered. In the present work, we characterize in detail native efficient single colour centres emitting in the near infra-red in both standard IIa single-crystal and electronic-grade polycrystalline commercial CVD diamond samples. In the former case, a high-temperature annealing process in vacuum is necessary to…
We investigate the influence of plasma treatments, especially a 0V-bias, potentially low damage O$_2$ plasma as well as a biased Ar/SF$_6$/O$_2$ plasma on shallow, negative nitrogen vacancy (NV$^-$) centers. We ignite and sustain using our 0V-bias plasma using purely inductive coupling. To this end, we pre-treat surfaces of high purity chemical vapor deposited single-crystal diamond (SCD). Subsequently, we create $\sim$10 nm deep NV$^-$ centers via implantation and annealing. Onto the annealed SCD surface, we fabricate nanopillar structures that efficiently waveguide the photoluminescence (PL)…
Vacancy-mediated nitrogen diffusion and aggregation via high-fluence electron beam irradiation in HPHT synthesized diamond crystal
National Institute for Materials Science（物质材料研究机构）；University of Tsukuba（筑波大学）；National Institutes for Quantum Science and Technology（量子科学技术研究开发机构）；Tohoku University（东北大学）
We report large negative electron affinity (NEA) on diamond (100) using magnesium adsorption on a previously oxygen-terminated surface. The measured NEA is up to $(-2.01\pm0.05)$ eV, the largest reported negative electron affinity to date. Despite the expected close relationship between the surface chemistry of Mg and Li species on oxygen-terminated diamond, we observe differences in the adsorption properties between the two. Most importantly, a high-temperature annealing step is not required to activate the Mg-adsorbed surface to a state of negative electron affinity. Diamond surfaces prepare…
We investigate phonon induced electronic dynamics in the ground and excited states of the negatively charged silicon-vacancy ($\mathrm{SiV}^-$) centre in diamond. Optical transition line widths, transition wavelength and excited state lifetimes are measured for the temperature range 4-350 K. The ground state orbital relaxation rates are measured using time-resolved fluorescence techniques. A microscopic model of the thermal broadening in the excited and ground states of the $\mathrm{SiV}^-$ centre is developed. A vibronic process involving single-phonon transitions is found to determine orbita…
Diamond is a promising material for the development of emerging applications in quantum optics, quantum information and quantum sensing. The fabrication and characterization of novel luminescent defects with suitable opto-physical properties is therefore of primary importance for further advances in these research fields. In this work we report on the investigation in the formation of photoluminescent (PL) defects upon MeV He implantation in diamond. Such color centers, previously reported only in electroluminescence and cathodoluminescence regime, exhibited two sharp emission lines at 536.5 n…
Diamond nanocrystals containing highly photoluminescent color centers are attractive non-classical and near-field light sources. For near-field applications the size of the nanocrystal is crucial since it defines the optical resolution. NV (Nitrogen-Vacancy) color centers are efficiently created by proton irradiation and annealing of a nanodiamond powder. Using near-field microscopy and photon statistics measurements, we show that nanodiamond with size down to 25 nm can hold a single NV color center with bright and stable photoluminescence.
Three-dimensional arrays of silicon transistors increase the density of bits. Solid-state qubits are much larger so could benefit even more from using the third dimension given that useful fault-tolerant quantum computing will require at least 100,000 physical qubits and perhaps one billion. Here we use laser writing to create 3D arrays of nitrogen-vacancy centre (NVC) qubits in diamond. This would allow 5 million qubits inside a commercially available 4.5x4.5x0.5 mm diamond based on five nuclear qubits per NVC and allowing $(10 μm)^3$ per NVC to leave room for our laser-written electrical con…
The silicon-vacancy ($\mathrm{SiV}^-$) color center in diamond has attracted attention due to its unique optical properties. It exhibits spectral stability and indistinguishability that facilitate efficient generation of photons capable of demonstrating quantum interference. Here we show high fidelity optical initialization and readout of electronic spin in a single $\mathrm{SiV}^-$ center with a spin relaxation time of $T_1=2.4\pm0.2$ ms. Coherent population trapping (CPT) is used to demonstrate coherent preparation of dark superposition states with a spin coherence time of $T_2^\star=35\pm3$…
