Doping of carbon nanoparticles with impurity atoms is central to their application. However, doping has proven elusive for very small carbon nanoparticles because of their limited availability and a lack of fundamental understanding of impurity stability in such nanostructures. Here, we show that isolated diamond nanoparticles as small as 1.6 nm, comprising only ∼400 carbon atoms, are capable of housing stable photoluminescent colour centres, namely the silicon vacancy (SiV). Surprisingly, fluorescence from SiVs is stable over time, and few or only single colour centres are found per nanocrystal. We also observe size-dependent SiV emission supported by quantum-chemical simulation of SiV energy levels in small nanodiamonds. Our work opens the way to investigating the physics and chemistry of molecular-sized cubic carbon clusters and promises the application of ultrasmall non-perturbative fluorescent nanoparticles as markers in microscopy and sensing.

Atomic-size spin defects in solids are unique quantum systems. Most applications require nanometre positioning accuracy, which is typically achieved by low-energy ion implantation. A drawback of this technique is the significant residual lattice damage, which degrades the performance of spins in quantum applications. Here we show that the charge state of implantation-induced defects drastically influences the formation of lattice defects during thermal annealing. Charging of vacancies at, for example, nitrogen implantation sites suppresses the formation of vacancy complexes, resulting in tenfold-improved spin coherence times and twofold-improved formation yield of nitrogen-vacancy centres in diamond. This is achieved by confining implantation defects into the space-charge layer of free carriers generated by a boron-doped diamond structure. By combining these results with numerical calculations, we arrive at a quantitative understanding of the formation and dynamics of the implanted spin defects. These results could improve engineering of quantum devices using solid-state systems.

In recent years, solid-state spin systems have emerged as promising candidates for quantum information processing (QIP). Prominent examples are the nitrogen-vacancy (NV) center in diamond [1][2][3], phosphorous dopants in silicon (Si:P) [4][5][6], rare-earth ions in solids [7][8][9] and VSi-centers in silicon-carbide (SiC) [10][11][12]. The Si:P system has demonstrated that its nuclear spins can yield exceedingly long spin coherence times by eliminating the electron spin of the dopant. For NV centers, however, a proper charge state for storage of nuclear spin qubit coherence has not been identified yet [13]. Here, we identify and characterize the positively-charged NV center as an electron-spin-less and optically inactive state by utilizing the nuclear spin qubit as a probe [13]. We control the electronic charge and spin utilizing nanometer scale gate electrodes. We achieve a lengthening of the nuclear spin coherence times by a factor of 20. Surprisingly, the new charge state allows switching the optical response of single nodes facilitating full individual addressability.Spin defects are excellent quantum systems. Particularly, defects that possess an electron spin together with a set of well-defined nuclear spins make up excellent, small quantum registers [3,14]. They have been used for demonstrations in quantum information processing [3,15], long distance entanglement [16] and sensing [17]. In such systems the electron spin is used for efficient readout (sensing or interaction with photons) whereas the nuclear spins are used as local quantum bits. Owing to their different magnetic and orbital angular momentum, electron and nuclear spins exhibit orders of magnitude different spin relaxation times. As an example, NV electron spins typically relax on a timescale of ms under ambient conditions [18], while nuclear spins do have at least minutes-long spin relaxation times [19]. However, the hyperfine coupling of nuclear spins to the fast relaxing electron spins in most cases significantly deteriorates the nuclear spin coherence, and eventually its relaxation time, down to time scales similar to the electron spin. For NV centers at room-temperature, this limits coherence times to about 10 ms [17,19,20]. For other hybrid spin ensembles e.g. in Si:P, this strict limit was overcome by ionizing the electron spin donors and thereby removing the electron spin. The resulting T 2 times were on the order of minutes for Si:P ensembles [5] and less than a second for single spins [6,21].It is known that the NV center in diamond exists in various charge states. Besides the widely employed negative charge state (NV − ), it is known to have a stable NV 0 and eventually NV + configurations. NV − has a spin triplet ground state with total spin angular momentum S = 1. Calculations as well as spectroscopic data suggest that the NV 0 ground state is S = 1/2 while NV + is believed to be S = 0, i.e. diamagnetic. Several experiments have demonstrated the optical ionization from NV − to the neutral NV 0 charge-state [13,[22][23][24][25][26...

The negatively charged nitrogen-vacancy (NV) center in diamond has been shown recently as an excellent sensor for external spins. Nevertheless, their optimum engineering in the near-surface region still requires quantitative knowledge in regard to their activation by vacancy capture during thermal annealing. To this aim, we report on the depth profiles of near-surface helium-induced NV centers (and related helium defects) by step-etching with nanometer resolution. This provides insights into the efficiency of vacancy diffusion and recombination paths concurrent to the formation of NV centers. It was found that the range of efficient formation of NV centers is limited only to approximately 10 to 15 nm (radius) around the initial ion track of irradiating helium atoms. Using this information we demonstrate the fabrication of nanometric-thin (δ) profiles of NV centers for sensing external spins at the diamond surface based on a three-step approach, which comprises (i) nitrogen-doped epitaxial CVD diamond overgrowth, (ii) activation of NV centers by low-energy helium irradiation and thermal annealing, and (iii) controlled layer thinning by low-damage plasma etching. Spin coherence times (Hahn echo) ranging up to 50 μs are demonstrated at depths of less than 5 nm in material with 1.1% of (13)C (depth estimated by spin relaxation (T1) measurements). At the end, the limits of the helium irradiation technique at high ion fluences are also experimentally investigated.