Production of High Yield, Ultra‐Shallow Nitrogen‐Vacancy Centre Ensembles Through High Purity Forming gas Annealing
Alexander J. Healey, Alexander Jakob, Daniel J. McCloskey, Philipp Reineck, Dhilan T. Vallury, Brant C. Gibson, David Simpson, Alastair D. Stacey, Nikolai Dontschuk
ABSTRACT Dense, ultra‐shallow (<10 nm from the surface) ensembles of nitrogen‐vacancy (NV) centers in diamond are sought‐after for realising practical quantum sensing at the nanoscale. However, these ensembles typically suffer from reduced NV creation efficiency and spin coherence compared to their deeper and bulk counterparts. Consequently, most demonstrations in the literature to date have been restricted to using single NV centers with atypical coherence and charge stability properties not achievable across entire ensembles. In this work, we demonstrate that controlled annealing in a high purity forming gas atmosphere improves near‐surface NV formation efficiency to over 20%. This environment preserves a high quality hydrogen termination throughout the anneal, avoiding material etching over many hours at temperatures up to 1100°C and possibly helping to suppress vacancy out‐diffusion. We show that high temperature annealing is especially vital for improving spin properties in high density, ultra‐shallow implanted samples due to the localised damage profiles produced. By allowing the formation of high yield NV ensembles with improved spin properties, the optimised forming gas anneal can facilitate the reliable production of more sensitive diamond sensors than have previously been accessible.
ABSTRACT Dense, ultra‐shallow (<10 nm from the surface) ensembles of nitrogen‐vacancy (NV) centers in diamond are sought‐after for realising practical quantum sensing at the nanoscale. However, these ensembles typically suffer from reduced NV creation efficiency and spin coherence compared to their deeper and bulk counterparts. Consequently, most demonstrations in the literature to date have been restricted to using single NV centers with atypical coherence and charge stability properties not achievable across entire ensembles. In this work, we demonstrate that controlled annealing in a high purity forming gas atmosphere improves near‐surface NV formation efficiency to over 20%. This environment preserves a high quality hydrogen termination throughout the anneal, avoiding material etching over many hours at temperatures up to 1100°C and possibly helping to suppress vacancy out‐diffusion. We show that high temperature annealing is especially vital for improving spin properties in high density, ultra‐shallow implanted samples due to the localised damage profiles produced. By allowing the formation of high yield NV ensembles with improved spin properties, the optimised forming gas anneal can facilitate the reliable production of more sensitive diamond sensors than have previously been accessible.
Efficient creation of shallow NV− ensembles by high-angle ion implantation
Negatively charged nitrogen-vacancy (NV−) centers located a few nanometers below the diamond surface are key quantum defects for nanoscale sensing of external spins. However, the creation of shallow NV− centers with high yield remains a materials challenge. Here, we demonstrate that high-angle ion implantation enhances the creation efficiency of shallow NV− centers. By implanting 15N ions at angles exceeding 60∘, we achieve high NV− yields approaching 10% with effective NV− depths below 10 nm. These yields are significantly higher than those typically reported for shallow NV− creation. The enhanced NV− yield is consistent with an increased vacancy-to-nitrogen ratio in the near-surface region, which is expected to promote NV formation during annealing. The created NV− ensembles show coherence properties comparable to those of single shallow NV− centers at similar depths, and allow detection of nuclear spins in van der Waals materials attached to the diamond surface. Our results establish geometric control of ion implantation as a simple and broadly applicable approach to engineer shallow vacancy-related quantum defects.
The nanometer‐scale engineering of single nitrogen‐vacancy (NV) centres in diamond can be obtained by low‐energy (keV) nitrogen implantation with limited straggling. However, shallow NV centres (a few nanometres deep) generally have inferior overall properties than deeply implanted or deep native NV centres, due to the surface proximity. It has already been shown that the spin coherence time of shallow NVs is improved by overgrowth of a thin diamond layer. However the influence of the overgrowth on the survival, the optical properties and the charge state of the centres has not been studied in detail. In this article, we have overgrown three diamond samples (containing NV centres implanted at different depths) using different procedures. We show the successful overgrowth of a pattern of very shallow (2 nm) implanted NV centres using an optimised overgrowth process. Furthermore, the charge state of ensembles and single NV centres was found to be shifted from NV0 to NV− and stabilised in the negative charge state after overgrowth. The combination of low‐energy high‐resolution ion implantation and high‐purity chemical vapour deposition (CVD) overgrowth procedures opens the way towards the fabrication of scalable and efficient quantum devices based on single defects in diamond. Left: implanted pattern of very shallow NV centres (depth ∼2 nm) using a pierced AFM tip. Right: same pattern after CVD overgrowth of a 4 μm‐thick diamond layer.
Abstract Nitrogen vacancy (NV) color centers in diamond have shown great potential for various applications in quantum technology due to their long coherence times, high sensitivity to magnetic fields and atomic scale resolution. However, one major challenge in utilizing near surface NV centers is the decoherence caused by spins and charges fluctuating on the surface, which affects the spin properties of the sensors. To reduce the induced noise, various oxygen surface treatments such as low power oxygen plasma treatment and annealing under oxygen atmosphere have been explored to terminate the diamond surface and reduce its impact on NV coherence. We showed that the NV center’s coherence time can be enhanced up to a factor of 3 over a large spectral range of noise. Double electron–electron resonance measurements revealed an extra source of decoherence, scaling similarly as the P1 spin bath. The improvement in coherence times is accompanied with an increase in measured ketone/ether content and reduction of sp 2 signal in x-ray photoelectron spectroscopy measurements. Finally we compared the performance of different NV ensembles and surface treatments for sensing external proton spins. The oxygen annealing is an effective procedure of enhancing the spin coherence times and reducing broad band spin noise experienced by shallow implanted ensemble NV centers in diamond.
ABSTRACT Deploying nitrogen vacancy (NV) centers in diamond as nanoscale quantum sensors for condensed matter and materials physics requires placing the NV centers close to the sensing target. One solution is to fabricate diamond nanostructures and integrate them with materials and devices. However, diamond etching and ion milling can introduce subsurface damage and surface defects that degrade the charge stability and spin coherence of NV centers near the surface. Here, we report a procedure for fabricating low‐damage free‐standing diamond micromembranes, and we show that this fabrication scheme preserves the optical and spin properties of state‐of‐the‐art shallow NV center quantum sensors, within nanometers of the diamond surface, while providing significant photonic enhancement. Furthermore, we demonstrate a pick‐and‐place transfer method, which enables integration with diverse sensing targets.
High spatial resolution quantum sensing of near-surface nitrogen vacancy (NV) centers in diamond has enabled detection of magnetic, electrical, and thermal signals at the nanoscale. At depths of just a few nanometers, NV centers serve as localized quantum probes for external spins or low-dimensional materials, but their proximity to the surface also enhances decoherence caused by fluctuating nuclear spins. While advances in surface engineering have stabilized the charge state of NV centers at depths of tens of nanometers, achieving both ultra-shallow implantation (0.5-2 nm) and long-term spin coherence remains a central challenge. In this work, we show using first-principles modeling that, by exploiting the interaction of surface-induced strain and weak dc magnetic fields, the spin coherence times of 1-nm-deep NV centers can be greatly improved near the spin-phonon-confined regime at room temperature in 12C-rich diamonds. We also demonstrate that this protocol benefits ~ 10-nm-deep NV centers in natural diamond, enabling vector magnetometry at the nanoscale. Shallow NV centers in diamond are advantageous for quantum sensing but suffer from surface magnetic noise. Using first-principles simulations supported by experiments, the authors show that a combination of small magnetic fields and surface strain can significantly enhance spin coherence of 1 nm-deep NV centers.
The negatively-charged nitrogen-vacancy (NV) center is the most studied optical center in diamond and is very important for applications in quantum information science. Many proposals for integrating NV centers in quantum and sensing applications rely on their tailored fabrication in ultra pure host material. In this study, we use ion implantation to controllably introduce nitrogen into high purity, low nitrogen chemical vapor deposition diamond samples. The properties of the resulting NV centers are studied as a function of implantation temperature, annealing temperature, and implantation fluence. We compare the implanted NV centers with native NV centers present deep in the bulk of the as-grown samples. The results for implanted NV centers are promising but indicate, at this stage, that the deep native NV centers possess overall superior optical properties. In particular, the implanted NV centers obtained after annealing at 2000 °C under a stabilizing pressure of 8 GPa showed an ensemble linewidth of 0.17 nm compared to 0.61 nm after annealing at 1000 °C. Over the same temperature range, the ensemble NV−/NV0 ratio increased by a factor of ∼5, although this was accompanied by an overall decrease in the NV count.