We demonstrate three-dimensional localization of a single nitrogen-vacancy (NV) center in diamond by combining nitrogen doping during growth with a post-growth 12C implantation technique that facilitates vacancy formation in the crystal. We show that the NV density can be controlled by the implantation dose without necessitating increase of the nitrogen incorporation. By implanting a large 12C dose through nanoscale apertures, we can localize an individual NV center within a volume of (∼180 nm)3 at a deterministic position while repeatedly preserving a coherence time (T2) > 300 μs. This deterministic position control of coherent NV centers enables integration into NV-based nanostructures to realize scalable spin-sensing devices as well as coherent spin coupling mediated by photons and phonons.
We demonstrate fully three-dimensional and patterned localization of nitrogen-vacancy (NV) centers in diamond with coherence times in excess of 1 ms. Nitrogen δ-doping during chemical vapor deposition diamond growth vertically confines nitrogen to 4 nm while electron irradiation with a transmission electron microscope laterally confines vacancies to less than 450 nm. We characterize the effects of electron energy and dose on NV formation. Importantly, our technique enables the formation of reliably high-quality NV centers inside diamond nanostructures with applications in quantum information and sensing.
Nitrogen-vacancy (NV) color centers in diamond are excellent quantum sensors possessing high sensitivity and nano-scale spatial resolution. Their integration in photonic structures is often desired, since it leads to an increased photon emission and also allows the realization of solid-state quantum technology architectures. Here, we report the fabrication of diamond nano-pillars with diameters up to 1000 nm by electron beam lithography and inductively coupled plasma reactive ion etching in nitrogen-rich diamonds (type Ib) with [100] and [111] crystal orientations. The NV centers were created by keV-He ion bombardment and subsequent annealing, and we estimate an average number of NVs per pillar to be 4300 ± 300 and 520 ± 120 for the [100] and [111] samples, respectively. Lifetime measurements of the NVs’ excited state showed two time constants with average values of τ1 ≈ 2 ns and τ2 ≈ 8 ns, which are shorter as compared to a single color center in a bulk crystal (τ ≈ 10 ns). This is probably due to a coupling between the NVs as well as due to interaction with bombardment-induced defects and substitutional nitrogen (P1 centers). Optically detected magnetic resonance measurements revealed a contrast of about 5% and average coherence and relaxation times of T2 [100] = 420 ± 40 ns, T2 [111] = 560 ± 50 ns, and T1 [100] = 162 ± 11 μs, T1 [111] = 174 ± 24 μs. These pillars could find an application for scanning probe magnetic field imaging.
Engineering shallow nitrogen-vacancy (NV) centers in diamond holds the key to unlocking new advances in nanoscale quantum sensing. We find that the creation of near-surface NVs through delta doping during diamond growth allows for tunable control over both NV depth confinement (with a twofold improvement relative to low-energy ion implantation) and NV density, ultimately resulting in highly-sensitive single defects and ensembles with coherence limited by NV-NV interactions. Additionally, we demonstrate the utility of our shallow delta-doped NVs by imaging magnetism in few-layer CrSBr, a two-dimensional magnet. We anticipate that the control afforded by near-surface delta doping will enable new developments in NV quantum sensing from nanoscale NMR to entanglement-enhanced metrology.
Silicon has turned from a niche laboratory-scale material into the backbone of modern electronics. Diamond functionalized with color centers could follow a similar path and grow from proof-of-concepts experiments to application-oriented quantum technologies. Quantum sensing, communication, and information processing with color centers has been proven to work in scientific experiments and enhanced sensitivities as well as novel functionalities have been reported. While the first generation of diamond quantum devices relied on color centers formed uncontrolled in natural diamond with a high statistical variation in composition and crystallinity, the situation has changed nowadays. With the emergence of high purity monocrystals and the option for isotopic purification of the carbon matrix, technological progress in materials science on the atomic-scale enabled tailoring the spin properties in diamond. But, since many color centers typically require vacancies to combine with impurities in the carbon lattice via diffusion, the generation of color centers underlies a statistical process providing only little control on the center's final position in the crystal lattice. The negatively charged nitrogen-vacancy (NV
−) center is the most studied optically active defect in diamond and exhibits remarkable spin properties and sensing capabilities, even on the nanoscale and at room temperature. The spin properties of NV
− centers close to the surface (1\,nm - 30\,nm) have been thoroughly studied and the deeper the spins are located in diamond the less decoherence from surface defects is observed. Creating NV
− centers at the surface by nitrogen ion implantation and burying them beneath a thin diamond layer via chemical vapor deposition (CVD) of diamond is reported to enhance the coherence times significantly. By separating the color center generation from controlling the resulting depth by an additional diamond layer, narrow depth profiles can be achieved by reducing the ion energy during implantation. Although the coherence properties improve, many of the implanted NV
− center are reported to vanish in the hydrogen-rich plasma of growth CVD chambers. The mechanism responsible for the instability of NV
− centers towards the plasma remains unclear, though. One hypothesis is the formation of nitrogen-vacancy-hydrogen centers from diffusing hydrogen and implanted NV
− centers but is has not been proven, yet. Here, we demonstrate the fabrication of depth confined NV
− centers by combining low energy (1\,keV - 5\,keV) ion implantation and CVD overgrowth. By increasing the thickness of the overgrown layer (6\,nm - 100\,nm) the influence of surface noise is shown to decrease leading to bulk-like coherence properties of up to $450\,\upmu$s (Hahn-echo) and
T2∗ dephasing times around $20\,\upmu$s. Monitoring the NV
− density as a function of the overgrowth time, we analyze the kinetics of the passivation in case of implanting ion doses of 10
11 15N
+/cm
2 and 10
12 15N
+/cm
2. The passivation turns out to occur faster for lower doses offering insights into sub-surface hydrogen diffusion in diamond. Analyzing the spin bath before and after overgrowth reveals a drastic reduction in paramagnetic spins after the CVD process but no NVH
− is found around the surviving NV
− centers. Checking the chemical composition in overgrown implantation sites with secondary-ion-mass-specrometry (SIMS), however, confirms significant amounts of hydrogen in the
15N-implanted layers. Since the concentration found for hydrogen exceeds the one for nitrogen by far, we suggest that diffusing hydrogen interacts also with vacancies forming probably mostly diamagnetic defects. In the last part of this dissertation, NV
− centers are generated with sub-nanometer precision below a thin
13C-enriched layer for quantum simulation. For fabricating the spin architecture starting from a
12C base layer, we overgrow implanted nitrogen with a
13C layer and bury the spins beneath a 30\,nm-thick
12C capping layer. By measuring the coupling strength between the electron and nuclear spins, we deduce a NV
− placement accuracy reaching below one nanometer with respect to the
13C-layer. Regarding the spin properties of the electron spins, no reduction in
T2 is observed despite of the proximity to the dense
13C-bath. As a consequence, the overgrowth of NV
− centers is demonstrated as a bottom-up approach to produce buried spin architectures with sharp isotopic transitions and efficient
13C-NV
− coupling. Together with the potential for bulk-like coherence properties the synergy of implantation and overgrowth is a powerful tool to fabricate reproducible quantum systems with tailored properties and high depth confinement.
Individual, luminescent point defects in solids, so-called color centers, are atomic-sized quantum systems enabling sensing and imaging with nanoscale spatial resolution. In this overview, we introduce nanoscale sensing based on individual nitrogen vacancy (NV) centers in diamond. We discuss two central challenges of the field: first, the creation of highly-coherent, shallow NV centers less than 10 nm below the surface of a single-crystal diamond; second, the fabrication of tip-like photonic nanostructures that enable efficient fluorescence collection and can be used for scanning probe imaging based on color centers with nanoscale resolution.