We investigate native nitrogen vacancy (NV) and silicon vacancy (SiV) color centers in a commercially available, heteroepitaxial, wafer-sized, mm thick, single-crystal diamond. We observe single, native NV centers with a density of roughly 1 NV per μm3 and moderate coherence time (T2 = 5 μs) embedded in an ensemble of SiV centers. Using low temperature luminescence of SiV centers as a probe, we prove the high crystalline quality of the diamond especially close to the growth surface, consistent with a reduced dislocation density. Using ion implantation and plasma etching, we verify the possibility to fabricate nanostructures with shallow color centers rendering our material promising for fabrication of nanoscale sensing devices. As this diamond is available in wafer-sizes up to 100 mm, it offers the opportunity to up-scale diamond-based device fabrication.
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.
Silicon-vacancy (SiV) centers in diamond are gaining an increased interest for application, such as in quantum technologies and sensing. Due to the strong luminescence concentrated in its sharp zero-phonon line at room temperature, SiV centers are being investigated as single-photon sources for quantum communication, and also as temperature probes for sensing. Here, we discussed strategies for the fabrication of SiV centers in diamond based on Si-ion implantation followed by thermal activation. SiV color centers in high-quality single crystals have the best optical properties, but polycrystalline micro and nanostructures are interesting for applications in nano-optics. Moreover, we discuss the photoluminescence properties of SiV centers in phosphorous-doped diamond, which are relevant for the creation of electroluminescent devices, and nanophotonics strategies to improve the emission characteristics of the SiV centers. Finally, the optical properties of such centers at room and high temperatures show the robustness of the center and give perspectives for temperature-sensing applications.
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.
Abstract Providing high-quality, single-crystal diamond (SCD) with a large area is desirable for up-scaling quantum technology applications that rely on color centers in diamond. Growth methods aiming to increase the area of SCD are an active research area. Native color centers offer a sensitive probe for local crystal quality in such novel materials e.g. via their reaction to stress. In this work, we investigate individual native nitrogen-vacancy (NV) centers in SCD layers manufactured via laterally overgrowing hole arrays in a heteroepitaxially grown large-scale substrate. Heteroepitaxy has become a common tool for growing large SCDs; however, achieving the high crystal quality needed for quantum applications remains a challenge. In the overgrown layer, we identify NV centers with spin-decoherence times in the order of hundreds of µs, comparable to high-purity homoepitaxial SCD. We quantify the effective crystal stress in different regions of the overgrown layer, indicating a low stress overall and a stress reduction in the diamond layer above the holes.
The development of material-processing techniques that can be used to generate optical diamond nanostructures containing a single-color center is an important problem in quantum science and technology. In this work, we present the combination of ion implantation and top-down diamond nanofabrication in two scenarios: diamond nanopillars and diamond nanowires. The first device consists of a 'shallow' implant (∼20 nm) to generate nitrogen-vacancy (NV) color centers near the top surface of the diamond crystal prior to device fabrication. Individual NV centers are then mechanically isolated by etching a regular array of nanopillars in the diamond surface. Photon anti-bunching measurements indicate that a high yield (>10%) of the devices contain a single NV center. The second device demonstrates 'deep' (∼1 μm) implantation of individual NV centers into diamond nanowires as a post-processing step. The high single-photon flux of the nanowire geometry, combined with the low background fluorescence of the ultrapure diamond, allowed us to observe sustained photon anti-bunching even at high pump powers.