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Optical activation and detection of charge transport between individual colour centres in diamond

Abstract

Understanding the capture of charge carriers by colour centres in semiconductors is important for the development of novel forms of sensing and quantum information processing, but experiments typically involve ensemble measurements, often impacted by defect proximity. Here we show that confocal fluorescence microscopy and magnetic resonance can be used to induce and probe charge transport between individual nitrogen-vacancy centres in diamond at room temperature. In our experiments, a ‘source’ nitrogen vacancy undergoes optically driven cycles of ionization and recombination to produce a stream of photogenerated carriers, one of which is subsequently captured by a ‘target’ nitrogen vacancy several micrometres away. We use a spin-to-charge conversion scheme to encode the spin state of the source colour centre into the charge state of the target, which allows us to set an upper bound to carrier injection from other background defects. We attribute our observations to the action of unscreened Coulomb potentials producing giant carrier capture cross-sections, orders of magnitude greater than those measured in ensembles.

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Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

References

1. 1.

Degen, C. L., Reinhard, F. & Cappellaro, P. Quantum sensing. Rev. Mod. Phys. 89, 035002 (2017).

2. 2.

Awschalom, D. D., Hanson, R., Wrachtrup, J. & Zhou, B. B. Quantum technologies with optically interfaced solid-state spins. Nat. Photon. 12, 516–527 (2018).

3. 3.

Atatüre, M., Englund, D., Vamivakas, N., Lee, S.-Y. & Wrachtrup, J. Material platforms for spin-based photonic quantum technologies. Nat. Rev. Mater. 3, 38–51 (2018).

4. 4.

Doherty, M. W. et al. The nitrogen-vacancy colour centre in diamond. Phys. Rep. 528, 1–45 (2013).

5. 5.

Koehl, W. F., Buckley, B. B., Heremans, F. J., Calusine, G. & Awschalom, D. D. Room temperature coherent control of defect spin qubits in silicon carbide. Nature 479, 84–87 (2011).

6. 6.

Tran, T. T., Bray, K., Ford, M. J., Toth, M. & Aharonovich, I. Quantum emission from hexagonal boron nitride monolayers. Nat. Nanotechnol. 11, 37–41 (2015).

7. 7.

Aslam, N., Waldherr, G., Neumann, P., Jelezko, F. & Wrachtrup, J. Photo-induced ionization dynamics of the nitrogen vacancy defect in diamond investigated by single-shot charge state detection. New J. Phys. 15, 013064 (2013).

8. 8.

Jayakumar, H. et al. Optical patterning of trapped charge in nitrogen-doped diamond. Nat. Commun. 7, 12660 (2016).

9. 9.

Dhomkar, S., Zangara, P., Henshaw, J. & Meriles, C. A. On-demand generation of neutral and negatively charged silicon-vacancy centres in diamond. Phys. Rev. Lett. 120, 117401 (2018).

10. 10.

Wolfowicz, G. et al. Optical charge state control of spin defects in 4H-SiC. Nat. Commun. 8, 1876 (2017).

11. 11.

Widmann, M. et al. Electrical charge state manipulation of single silicon vacancies in a silicon carbide quantum optoelectronic device. Nano Lett. 19, 7173–7180 (2019).

12. 12.

Dhomkar, S., Jayakumar, H., Zangara, P. R. & Meriles, C. A. Charge dynamics in near-surface, variable-density ensembles of nitrogen-vacancy centres in diamond. Nano Lett. 18, 4046–4052 (2018).

13. 13.

Bluvstein, D., Zhang, Z. & Bleszynski Jayich, A. C. Identifying and mitigating charge instabilities in shallow diamond nitrogen-vacancy centres. Phys. Rev. Lett. 122, 076101 (2019).

14. 14.

Siyushev, P. et al. Optically controlled switching of the charge state of a single nitrogen-vacancy centre in diamond at cryogenic temperatures. Phys. Rev. Lett. 110, 167402 (2013).

15. 15.

Anderson, C. P. et al. Electrical and optical control of single spins integrated in scalable semiconductor devices. Science 366, 1225–1230 (2019).

16. 16.

Wolfowicz, G., Whiteley, S. J. & Awschalom, D. D. Electrometry by optical charge conversion of deep defects in 4H-SiC. Proc. Natl Acad. Sci. USA 115, 7879–7883 (2018).

17. 17.

Han, K. Y., Kim, S. K., Eggeling, C. & Hell, S. W. Metastable dark states enable ground state depletion microscopy of nitrogen vacancy centres in diamond with diffraction-unlimited resolution. Nano Lett. 10, 3199–3203 (2010).

18. 18.

Chen, X. et al. Subdiffraction optical manipulation of the charge state of nitrogen vacancy centre in diamond. Light Sci. Appl. 4, e230 (2015).

19. 19.

Bassett, L. C., Heremans, F. J., Yale, C. G., Buckley, B. B. & Awschalom, D. D. Electrical tuning of single nitrogen-vacancy centre optical transitions enhanced by photo-induced fields. Phys. Rev. Lett. 107, 266403 (2011).

20. 20.

Mizuochi, N. et al. Electrically driven single-photon source at room temperature in diamond. Nat. Photon. 6, 299–303 (2012).

21. 21.

Shields, B. J., Unterreithmeier, Q. P., De Leon, N. P., Park, H. & Lukin, M. D. Efficient readout of a single spin state in diamond via spin-to-charge conversion. Phys. Rev. Lett. 114, 136402 (2015).

22. 22.

Hopper, D. A., Lauigan, J. D., Huang, T.-Y. & Bassett, L. C. Real-time charge initialization of diamond nitrogen-vacancy centers for enhanced spin readout. Phys. Rev. Appl. 13, 024016 (2020).

23. 23.

Hopper, D. A., Grote, R. R., Parks, S. M. & Bassett, L. C. Amplified sensitivity of nitrogen-vacancy spins in nanodiamonds using all-optical charge readout. ACS Nano 12, 4678–4686 (2018).

24. 24.

Pfender, M. et al. Protecting a diamond quantum memory by charge state control. Nano Lett. 17, 5931–5937 (2017).

25. 25.

Dhomkar, S., Henshaw, J., Jayakumar, H. & Meriles, C. A. Long-term data storage in diamond. Sci. Adv. 2, e1600911 (2016).

26. 26.

Bourgeois, E. et al. Photoelectric detection of electron spin resonance of nitrogen-vacancy centres in diamond. Nat. Commun. 6, 8577 (2015).

27. 27.

Siyushev, P. et al. Photoelectrical imaging and coherent spin-state readout of single nitrogen-vacancy centers in diamond. Science 363, 728–731 (2019).

28. 28.

Hrubesch, F. M., Braunbeck, G., Stutzmann, M., Reinhard, F. & Brandt, M. S. Efficient electrical spin readout of NV centers in diamond. Phys. Rev. Lett. 118, 037601 (2017).

29. 29.

Niethammer, M. et al. Coherent electrical readout of defect spins in silicon carbide by photo-ionization at ambient conditions. Nat. Commun. 10, 5569 (2019).

30. 30.

Dolde, F. et al. Nanoscale detection of a single fundamental charge in ambient conditions using the NV centre in diamond. Phys. Rev. Lett. 112, 097603 (2014).

31. 31.

Doherty, M. W. et al. Towards a room-temperature spin quantum bus in diamond via optical spin injection, transport and detection. Phys. Rev. X 6, 041035 (2016).

32. 32.

Chu, Y. et al. Coherent optical transitions in implanted nitrogen vacancy centres. Nano Lett. 14, 1982–1986 (2014).

33. 33.

Pezzagna, S., Naydenov, B., Jelezko, F., Wrachtrup, J. & Meijer, J. Creation efficiency of nitrogen-vacancy centres in diamond. New J. Phys. 12, 065017 (2010).

34. 34.

Lozovoi, A., Daw, D., Jayakumar, H. & Meriles, C. A. Dark defect charge dynamics in bulk chemical-vapor-deposition-grown diamonds probed via nitrogen vacancy centres. Phys. Rev. Mater. 4, 053602 (2020).

35. 35.

Jayakumar, H., Dhomkar, S., Henshaw, J. & Meriles, C. A. Spin readout via spin-to-charge conversion in bulk diamond nitrogen-vacancy ensembles. Appl. Phys. Lett. 113, 122404 (2018).

36. 36.

Lozovoi, A., Jayakumar, H., Daw, D., Lakra, A. & Meriles, C. A. Probing metastable space-charge potentials in a wide bandgap semiconductor. Phys. Rev. Lett. 125, 256602 (2020).

37. 37.

Hopper, D. A., Grote, R. R., Exarhos, A. L. & Bassett, L. C. Near-infrared-assisted charge control and spin readout of the nitrogen-vacancy centre in diamond. Phys. Rev. B 94, 241201 (2016).

38. 38.

Jayakumar, H., Lozovoi, A., Daw, D. & Meriles, C. A. Long-term spin state storage using ancilla charge memories. Phys. Rev. Lett. 125, 236601 (2020).

39. 39.

Zhang, Z.-H. et al. Optically detected magnetic resonance in neutral silicon vacancy centres in diamond via bound exciton states. Phys. Rev. Lett. 125, 237402 (2020).

40. 40.

Lax, M. Cascade capture of electrons in solids. Phys. Rev. 119, 1502 (1960).

41. 41.

Alkauskas, A., Yan, Q. & Van de Walle, C. G. First-principles theory of non-radiative carrier capture via multi-phonon emission. Phys. Rev. B 90, 075202 (2014).

42. 42.

Jacoboni, C. & Reggiani, L. The Monte Carlo method for the solution of charge transport in semiconductors with applications to covalent materials. Rev. Mod. Phys. 55, 645 (1983).

43. 43.

Suntornwipat, N. et al. A valleytronic diamond transistor: electrostatic control of valley currents and charge-state manipulation of NV centers. Nano Lett. 21, 868–874 (2021).

44. 44.

Restrepo, O. D. & Windl, W. Full first-principles theory of spin relaxation in group-IV materials. Phys. Rev. Lett. 109, 166604 (2012).

45. 45.

Tamarat, P. et al. Spin-flip and spin-conserving optical transitions of the nitrogen-vacancy centre in diamond. New J. Phys. 10, 045004 (2008).

46. 46.

Kazimierczuk, T., Fröhlich, D., Scheel, S., Stolz, H. & Bayer, M. Giant Rydberg excitons in the copper oxide Cu2O. Nature 514, 343–347 (2014).

47. 47.

Irber, D. M. et al. Robust all-optical single-shot readout of NV centers in diamond. Nat. Commun. 12, 532 (2021).

48. 48.

Williams, J. R., Low, T., Lundstrom, M. S. & Marcus, C. M. Gate-controlled guiding of electrons in graphene. Nat. Nanotechnol. 6, 222–225 (2011).

49. 49.

Sivan, U., Heiblum, M., Umbach, C. P. & Shtrikman, H. Electrostatic electron lens in the ballistic regime. Phys. Rev. B 41, 7937 (1990).

50. 50.

Chen, S., Raha, M., Phenicie, C. M., Ourari, S. & Thompson, J. D. Parallel single-shot measurement and coherent control of solid-state spins below the diffraction limit. Science 370, 592–595 (2020).

51. 51.

Rose, B. C. et al. Observation of an environmentally insensitive solid-state spin defect in diamond. Science 361, 60–63 (2018).

52. 52.

Ziegler, J. F., Ziegler, M. D. & Biersack, J. P. SRIM–the stopping and range of ions in matter (2010). Nucl. Instrum. Methods B 268, 1818–1823 (2010).

53. 53.

Albrecht, U. & Bässler, H. Langevin‐type charge carrier recombination in a disordered hopping system. Phys. Status Solidi B 191, 455–459 (1995).

54. 54.

Willatzen, M., Cardona, M. & Christensen, N. E. Linear muffin-tin-orbital and kp calculations of effective masses and band structure of semiconducting diamond. Phys. Rev. B 50, 18054 (1994).

55. 55.

Löfås, H., Grigoriev, A., Isberg, J. & Ahuja, R. Effective masses and electronic structure of diamond including electron correlation effects in first principles calculations using the GW-approximation. AIP Adv. 1, 032139 (2011).

56. 56.

Hamann, D. R. & McWhorter, A. L. Cascade capture of electrons by ionized impurities. Phys. Rev. 134, A250 (1964).

57. 57.

Mei, D.-M. et al. Impact of charge trapping on the energy resolution of Ge detectors for rare-event physics searches. J. Phys. G 47, 105106 (2020).

58. 58.

Nebel, C. E. Electronic properties of CVD diamond. Semicond. Sci. Technol. 18, S1 (2003).

59. 59.

MacQuarrie, E. R., Gosavi, T. A., Jungwirth, N. R., Bhave, S. A. & Fuchs, G. D. Mechanical spin control of nitrogen-vacancy centres in diamond. Phys. Rev. Lett. 111, 227602 (2013).

60. 60.

Klein, C. A., Hartnett, T. M. & Robinson, C. J. Critical-point phonon frequencies of diamond. Phys. Rev. B 45, 12854 (1992).

61. 61.

Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996).

62. 62.

Perdew, J., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996).

63. 63.

Krukau, A. V., Vydrov, O. A., Izmaylov, A. F. & Scuseria, G. E. Influence of the exchange screening parameter on the performance of screened hybrid functionals. J. Chem. Phys. 125, 224106 (2006).

64. 64.

Freysoldt, C., Neugebauer, J. & VandeWalle, C. G. Fully ab-initio finite-size corrections for charged-defect supercell calculations. Phys. Rev. Lett. 102, 016402 (2009).

65. 65.

Ridolfi, E., Lewenkopf, C. H. & Pereira, V. M. Excitonic structure of the optical conductivity in MoS2 monolayers. Phys. Rev. B 97, 205409 (2018).

66. 66.

Refaely-Abramson, S., Qiu, D. Y., Louie, S. G. & Neaton, J. B. Defect-induced modification of low-lying excitons and valley selectivity in monolayer transition metal dichalcogenides. Phys. Rev. Lett. 121, 167402 (2018).

Acknowledgements

We acknowledge useful discussions with Y. H. Chen. A.L., H.J. and C.A.M. acknowledge support from the National Science Foundation through grant no. NSF-1914945, and from Research Corporation for Science Advancement through a FRED award; they also acknowledge access to the facilities and research infrastructure of the NSF CREST IDEALS, grant no. NSF-HRD-1547830. M.W.D. acknowledges support from the Australian Research Council COE170100169. Ion implantation work to generate the NV and SiV centres was performed, in part, at the Centre for Integrated Nanotechnologies, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science. Sandia National Laboratories is a multimission laboratory managed and operated by the National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, for the US DOE’s National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis; any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the DOE or the US Government. The Flatiron Institute is a division of the Simons Foundation.

Author information

Authors

Contributions

A.L., H.J. and C.A.M. conceived the experiments. G.V. and E.B. ion implanted the sample. A.L. conducted the experiments and analysed the data with assistance from H.J., D.D. and C.A.M. J.F. led the theoretical and numerical modelling with assistance from M.W.D. C.A.M., A.L. and J.F. wrote the manuscript with input from all the authors. C.A.M. supervised the project.

Corresponding author

Correspondence to Carlos A. Meriles.

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The authors declare no competing interests.

Peer review information Nature Electronics thanks Sang-Yun Lee and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Engineering deep NV arrays via a high-energy focused ion beam.

(a) Schematics of the ion implanter. (b-d) Example NV patterns; fluorescence images in (b) and (c) correspond to the shaded areas in the larger NV arrays (upper schematics). (e) SRIM simulations assuming an implantation energy of 20 MeV; the top and bottom plots are the number probability distribution and lateral ion straggle as a function of depth, respectively. (f) NV fluorescence intensity as a function of depth for the source and target single NVs in Fig. 1c of the main text (top and bottom plots, respectively).

Extended Data Fig. 2 Charge control of individual NVs.

(a) Experimental protocol. Green (orange) blocks indicate laser excitation at 520 nm (594 nm). Left (right) triangles apply to the NV- recombination (ionization) measurements. APD denotes the avalanche photo-detector. (b) Relative NV- population as a function of the excitation time tEXc for 520 nm, 35 µW laser light; the solid trace is an exponential fit and the color code in the lower right corner indicates the laser color sequence. Surrounding plots are example histograms for different values of tEXc, with solid red traces indicating fits corresponding to two Poissonian distributions with differing average count rates. Black arrows indicate contributions due to NV-; both ionization and recombination rates at the excitation wavelength and power can be extracted from these fits (see text for details). During initialization, the orange laser power and duration are 7 µW and 200 ms, respectively; the readout pulse at 594 nm has a power of 7 µW and a duration of 80 ms. (c) Relative NV- population as a function of the excitation time tExc produced by a 594 nm, 4 µW laser. As in (b), NV- populations can be extracted from analysis of the recorded histograms. In this protocol, the 520 nm initialization (594 nm readout) pulse has 200 µW (4 µW) power and a duration of 500 µs (20 ms). (d) NV recombination and ionization rates krec, kion (blue and black dots, respectively) as a function of the 520 nm laser power as extracted from experiments similar to those in (b). Solid red traces indicate parabolic fits. (e) Same as in (d) but for 594 nm. All experiments are carried out in NVA (‘source’ NV in Fig. 2 of the main text). Similar results are obtained for NVB, not shown here for brevity.

Extended Data Fig. 3 Source-target carrier transport at different excitation wavelengths.

(a) Working with the NV pair presented in Fig. 2 of the main text, we modify the experimental protocol to include a 594 nm fluorescence scan over a 1.5×1.5 µm2 area around the source NV, which we use to determine its integrated fluorescence. (b) Time-averaged, integrated fluorescence of the source and target NVs (left and right panels, respectively); while the former gradually bleaches, the latter remains bright. The 520 nm laser intensity during the park is 1.0 mW; all other conditions as in Fig. 2. (c) Same as in (a) but using a 1.5 mW, 632 nm park. (d) Same as in (b) but for the protocol in (c). The source NV transitions immediately to a dark state while the target remains bright. Solid lines in (b) and (d) are guides to the eye.

Extended Data Fig. 4 Local spin-to-charge conversion.

(a) Fluorescence image of target and source NVs. (b) Spin-to-charge conversion (SCC) protocol. Green, red, and orange blocks indicate laser excitation at 520 nm, 632 nm, and 594 nm, respectively. During SCC, red and green excitation take place simultaneously. The grey block indicates MW excitation at variable frequency; the MW pulse length and amplitude are chosen to induce a population inversion when on-resonance with the NV ground state zero-field splitting (~2.87 GHz). (c) Fluorescence change from NVA (source) as a function of the MW frequency upon application of the SCC protocol in (b). Throughout these experiments, the power and duration of the initialization (probe) pulse are 200 µW and 500 µs (7 µW and 15 ms), respectively. The green (red) laser power during SCC is 200 µW (16 mW); the SCC pulse duration amounts to 300 ns.

Extended Data Fig. 5 Transport between few-NV islands.

(a) Fluorescence image of two proximal ion implantation spots. Time-correlated single-photon measurements at the circled sites indicate the presence of 2 or 3 NVs at each location. (b) NV- photo-luminescence at the target site upon application of the protocol in Fig. 2b of the main text for variable park times tP and different laser powers. (c) NV- fluorescence from the target site as a function of the MW frequency upon spin-to-charge conversion at the source site (protocol in Fig. 3a of the main text). As a reference, the insert the displays the optically detected magnetic resonance spectrum of the source NVs. Conditions are similar to those in Figs. 2 and 3 of the main text.

Extended Data Fig. 6 Inter-NV transport in the presence of externally applied electric fields.

(a) Schematics of the experimental setup. We pattern metal pads on the sample substrate to produce an electric field E parallel to the axis connecting the source and target NVs (respectively, NVA and NVB). The gap between the electrodes is 500 µm. (b) Pulse protocol. After NV initialization (green scan at the source and target NVs), we apply a voltage of variable (but fixed) amplitude synchronically with the green laser park at the source NV; we readout the charge state of the target NV via an orange scan. Positive voltages create an electric field pointing from NVB to NVA. (c) Integrated fluorescence of the target NV as a function of the green laser park time tP for different voltages. The green laser power during the park is 1 mW; all other conditions as in Fig. 2 of the main text.

Extended Data Fig. 7 Cascade capture of a hole by a negatively charged NV.

We consider the formation of a bound exciton state comprising a hole orbiting an NV- core. This system can be described by a hydrogenic series of states characterized by a quantum number n. Assuming the hole is in thermal equilibrium, bound exciton formation is possible for orbits nt such that $$\left( {E_{{{\mathrm{I}}}} - E_n} \right)\sim \kappa _{{{\mathrm{B}}}}T$$; subsequent capture involves the cascade emission of phonons. The corresponding trapping radius (also known as the ‘Onsager’ radius53,57) is given by $$r_{{{\mathrm{t}}}} = e^2/\left( {4\pi \varepsilon \kappa _{{{\mathrm{B}}}}T} \right) \approx 10$$ nm in room temperature diamond. The ensuing capture cross-section would then amount to $$\sigma _{{{{\mathrm{h}}}},{{{\mathrm{On}}}}}\sim 3 \times 10^{ - 4}$$ µm2, not far off from the experimental value.

Extended Data Fig. 8 DFT modeling.

(Left) PBE- and HSE06-calculated exchange-correlation functional for the (0/−1) charge transition level (blue and green dots, respectively), which corresponds to the ionization energy of the NV- center. For each functional, we show two values, the uncorrected (light) and the charge corrected64 (dark) excitation energies. Both lead to the same value for the extrapolation at infinite carbon atoms in the supercell. (Right) n = 1 bound exciton energy using the HSE06 (green) and the PBE (blue) exchange-correlation functional. The solid lines in (a) stem from fits using the formula $$\left( x \right) = a + \left( {bx + cx^3} \right)\exp \left( { - dx} \right)$$, where a, b, c and d are fitting parameters, and $$x \equiv L^{ - 1}$$ is the inverse supercell length. All values are listed in Extended Data Table 2.

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Lozovoi, A., Jayakumar, H., Daw, D. et al. Optical activation and detection of charge transport between individual colour centres in diamond. Nat Electron 4, 717–724 (2021). https://doi.org/10.1038/s41928-021-00656-z

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