Nitrogen-vacancy (NV) quantum defects in diamond are sensitive detectors of magnetic fields. Owing to their atomic size and optical readout capability, they have been used for magnetic resonance spectroscopy of nanoscale samples on diamond surfaces. Here, we present a protocol for fabricating NV diamond chips and for constructing and operating a simple, low-cost ‘quantum diamond spectrometer’ for performing NMR and electron spin resonance (ESR) spectroscopy in nanoscale volumes. The instrument is based on a commercially available diamond chip, into which an NV ensemble is ion-implanted at a depth of ~10 nm below the diamond surface. The spectrometer operates at low magnetic fields (~300 G) and requires standard optical and microwave (MW) components for NV spin preparation, manipulation, and readout. We demonstrate the utility of this device for nanoscale proton and fluorine NMR spectroscopy, as well as for the detection of transition metals via relaxometry. We estimate that the full protocol requires 2–3 months to implement, depending on the availability of equipment, diamond substrates, and user experience.
This is a preview of subscription content, access via your institution
Open Access articles citing this article.
npj Quantum Information Open Access 19 February 2021
Subscribe to Nature+
Get immediate online access to Nature and 55 other Nature journal
Subscribe to Journal
Get full journal access for 1 year
only $8.25 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Get time limited or full article access on ReadCube.
All prices are NET prices.
The primary data of this study are available from the corresponding authors upon reasonable request.
The qdSpectro package is available to download from https://gitlab.com/dplaudecraik/qdSpectro and is licensed under the MIT License. The most recent version at the time of writing is v.1.0.1, but the user is encouraged to download the latest version and refer to the readme file for any patches and updates. The package is registered at https://doi.org/10.5281/zenodo.1478113, which points to the latest version.
Rule, G. S. and Hitchens, K. T. Fundamentals of Protein NMR Spectroscopy. (Springer, 2006).
Schweiger, A. and Jeschke, G. Principles of Pulse Electron Paramagnetic Resonance. (Oxford University Press, 2001).
Zalesskiy, S. S., Danieli, E., Blümich, B. & Ananikov, V. P. Miniaturization of NMR systems: desktop spectrometers, microcoil spectroscopy, and “NMR on a Chip” for chemistry, biochemistry, and industry. Chem. Rev. 114, 5641–5694 (2014).
Fratila, R. M. & Velders, A. H. Small-volume nuclear magnetic resonance spectroscopy. Annu. Rev. Anal. Chem. 4, 227–249 (2011).
Ardenkjaer-Larsen, J.-H. et al. Facing and overcoming sensitivity challenges in biomolecular NMR spectroscopy. Angew. Chem. Int. Ed. 54, 9162–9185 (2015).
Staudacher, T. et al. Nuclear magnetic resonance spectroscopy on a (5-Nanometer)3 sample volume. Science 339, 561–563 (2013).
Mamin, H. J. et al. Nanoscale nuclear magnetic resonance with a nitrogen-vacancy spin sensor. Science 339, 557–560 (2013).
Lovchinsky, I. et al. Nuclear magnetic resonance detection and spectroscopy of single proteins using quantum logic. Science 351, 836–841 (2016).
Shi, F. et al. Single-protein spin resonance spectroscopy under ambient conditions. Science 347, 1135–1138 (2015).
Sushkov, A. O. et al. Magnetic resonance detection of individual proton spins using quantum reporters. Phys. Rev. Lett. 113, 197601 (2014).
Lovchinsky, I. et al. Magnetic resonance spectroscopy of an atomically thin material using a single-spin qubit. Science 355, 503–507 (2017).
Aharonovich, I. et al. Diamond-based single-photon emitters. Rep. Prog. Phys. 74, 076501 (2011).
Schirhagl, R., Chang, K., Loretz, M. & Degen, C. L. Nitrogen-vacancy centers in diamond: nanoscale sensors for physics and biology. Annu. Rev. Phys. Chem. 65, 83–105 (2014).
Doherty, M. W. et al. The nitrogen-vacancy colour centre in diamond. Phys. Rep. 528, 1–45 (2013).
Rondin, L. et al. Magnetometry with nitrogen-vacancy defects in diamond. Rep. Prog. Phys. 77, 056503 (2014).
Jelezko, F. & Wrachtrup, J. Single defect centres in diamond: a review. Phys. Status Solidi A 203, 3207–3225 (2006).
Doherty, M. W. et al. Theory of the ground-state spin of the NV- center in diamond. Phys. Rev. B 85, 205203 (2012).
Hincks, I., Granade, C. & Cory, D. G. Statistical inference with quantum measurements: methodologies for nitrogen vacancy centers in diamond. New J. Phys. 20, 013022 (2018).
Meriles, C. A. et al. Imaging mesoscopic nuclear spin noise with a diamond magnetometer. J. Chem. Phys. 133, 124105 (2010).
DeVience, S. J. et al. Nanoscale NMR spectroscopy and imaging of multiple nuclear species. Nat. Nanotechnol. 10, 129–134 (2015).
Pham, L. M. et al. NMR technique for determining the depth of shallow nitrogen-vacancy centers in diamond. Phys. Rev. B 93, 045425 (2016).
Herzog, B. E., Cadeddu, D., Xue, F., Peddibhotla, P. & Poggio, M. Boundary between the thermal and statistical polarization regimes in a nuclear spin ensemble. Appl. Phys. Lett. 105, 043112 (2014).
Degen, C. L., Reinhard, F. & Cappellaro, P. Quantum sensing. Rev. Mod. Phys. 89, 035002 (2017).
Abe, E. & Sasaki, K. Tutorial: magnetic resonance with nitrogen-vacancy centers in diamond—microwave engineering, materials science, and magnetometry. J. Appl. Phys. 123, 161101 (2018).
Gullion, T., Baker, D. B. & Conradi, M. S. New, compensated Carr-Purcell sequences. J. Magn. Reson. 89, 479–484 (1990).
Ryan, C. A., Hodges, J. S. & Cory, D. G. Robust decoupling techniques to extend quantum coherence in diamond. Phys. Rev. Lett. 105, 200402 (2010).
Loretz, M. et al. Spurious harmonic response of multipulse quantum sensing sequences. Phys. Rev. X 5, 021009 (2015).
Laraoui, A. et al. High-resolution correlation spectroscopy of 13C spins near a nitrogen-vacancy centre in diamond. Nat. Commun. 4, 1651 (2013).
Kong, X., Stark, A., Du, J., McGuinness, L. P. & Jelezko, F. Towards chemical structure resolution with nanoscale nuclear magnetic resonance spectroscopy. Phys. Rev. Appl. 4, 024004 (2015).
Staudacher, T. et al. Probing molecular dynamics at the nanoscale via an individual paramagnetic centre. Nat. Commun. 6, 8527 (2015).
Kehayias, P. et al. Solution nuclear magnetic resonance spectroscopy on a nanostructured diamond chip. Nat. Commun. 8, 188 (2017).
Aslam, N. et al. Nanoscale nuclear magnetic resonance with chemical resolution. Science 357, 67–71 (2017).
Glenn, D. R. et al. High-resolution magnetic resonance spectroscopy using a solid-state spin sensor. Nature 555, 351–354 (2018).
Bucher, D. B., Glenn, D. R., Park, H., Lukin, M. D. & Walsworth, R. L. Hyperpolarization-enhanced NMR spectroscopy with femtomole sensitivity using quantum defects in diamond. Preprint at https://arxiv.org/abs/1810.02408 (2018).
Steinert, S. et al. Magnetic spin imaging under ambient conditions with sub-cellular resolution. Nat. Commun. 4, 1607 (2013).
Sushkov, A. O. et al. All-optical sensing of a single-molecule electron spin. Nano Lett. 14, 6443–6448 (2014).
Simpson, D. A. et al. Electron paramagnetic resonance microscopy using spins in diamond under ambient conditions. Nat. Commun. 8, 458 (2017).
Ermakova, A. et al. Detection of a few metallo-protein molecules using color centers in nanodiamonds. Nano Lett. 13, 3305–3309 (2013).
Schlipf, L. et al. A molecular quantum spin network controlled by a single qubit. Sci. Adv. 3, e1701116 (2017).
Tetienne, J.-P. et al. Spin properties of dense near-surface ensembles of nitrogen-vacancy centers in diamond. Phys. Rev. B 97, 085402 (2018).
Myers, B. A. et al. Probing surface noise with depth-calibrated spins in diamond. Phys. Rev. Lett. 113, 027602 (2014).
Ofori-Okai, B. K. et al. Spin properties of very shallow nitrogen vacancy defects in diamond. Phys. Rev. B 86, 081406 (2012).
Romach, Y. et al. Spectroscopy of surface-induced noise using shallow spins in diamond. Phys. Rev. Lett. 114, 017601 (2015).
Ziegler, J. F., Ziegler, M. D. & Biersack, J. P. SRIM - the stopping and range of ions in matter (2010). Nucl. Instrum. Methods Phys. Res. B 268, 1818–1823 (2010).
Lehtinen, O. et al. Molecular dynamics simulations of shallow nitrogen and silicon implantation into diamond. Phys. Rev. B 93, 035202 (2016).
Yamamoto, T. et al. Extending spin coherence times of diamond qubits by high-temperature annealing. Phys. Rev. B 88, 075206 (2013).
Haque, A. & Sumaiya, S. An overview on the formation and processing of nitrogen-vacancy photonic centers in diamond by ion implantation. J. Manuf. Mater. Process. 1, 6 (2017).
Pezzagna, S., Naydenov, B., Jelezko, F., Wrachtrup, J. & Meijer, J. Creation efficiency of nitrogen-vacancy centres in diamond. New J. Phys. 12, 065017 (2010).
Kim, M. et al. Decoherence of near-surface nitrogen-vacancy centers due to electric field noise. Phys. Rev. Lett. 115, 087602 (2015).
Fávaro de Oliveira, F. et al. Tailoring spin defects in diamond by lattice charging. Nat. Commun. 8, 15409 (2017).
Rosskopf, T. et al. Investigation of surface magnetic noise by shallow spins in diamond. Phys. Rev. Lett. 112, 147602 (2014).
Sangtawesin, S. et al. Origins of diamond surface noise probed by correlating single spin measurements with surface spectroscopy. Preprint at https://arxiv.org/abs/1811.00144 (2018).
Atikian, H. A. et al. Superconducting nanowire single photon detector on diamond. Appl. Phys. Lett. 104, 122602 (2014).
Tisler, J. et al. Fluorescence and spin properties of defects in single digit nanodiamonds. ACS Nano 3, 1959–1965 (2009).
Pham, L. M. et al. Enhanced solid-state multispin metrology using dynamical decoupling. Phys. Rev. B 86, 045214 (2012).
Aude Craik, D. P. L. qdSpectro. Zenodo. https://doi.org/10.5281/zenodo.1478113. (2019).
Fischer, R., Jarmola, A., Kehayias, P. & Budker, D. Optical polarization of nuclear ensembles in diamond. Phys. Rev. B 87, 125207 (2013).
Jacques, V. et al. Dynamic polarization of single nuclear spins by optical pumping of nitrogen-vacancy color centers in diamond at room temperature. Phys. Rev. Lett. 102, 057403 (2009).
This article is based on work supported by, or supported in part by, the US Army Research Laboratory and the US Army Research Office under contract/grant no. W911NF1510548. D.B.B. was partially supported by the German Research Foundation (BU 3257/1-1). D.P.L.A.C. was partially supported by the NSF STC ‘Center for Integrated Quantum Materials’ under cooperative agreement no. DMR-1231319.
The authors declare no competing interests.
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Key references using this protocol
DeVience, S. J. et al. Nat. Nanotechnol. 10, 129–134 (2015): https://www.nature.com/articles/nnano.2014.313
Kehayias, P. et al. Nat. Commun. 8, 188 (2017): https://www.nature.com/articles/s41467-017-00266-4
Steinert, S. et al. Nat. Commun. 4, 1607 (2013): https://www.nature.com/articles/ncomms2588
Staudacher, T. et al. Science 339, 561–563 (2013): https://science.sciencemag.org/content/339/6119/561
About this article
Cite this article
Bucher, D.B., Aude Craik, D.P.L., Backlund, M.P. et al. Quantum diamond spectrometer for nanoscale NMR and ESR spectroscopy. Nat Protoc 14, 2707–2747 (2019). https://doi.org/10.1038/s41596-019-0201-3
This article is cited by
Frontiers of Materials Science (2022)
Journal of the Indian Institute of Science (2022)
npj Quantum Information (2021)