Letter | Published:

High-resolution magnetic resonance spectroscopy using a solid-state spin sensor

Nature volume 555, pages 351354 (15 March 2018) | Download Citation

Abstract

Quantum systems that consist of solid-state electronic spins can be sensitive detectors of nuclear magnetic resonance (NMR) signals, particularly from very small samples. For example, nitrogen–vacancy centres in diamond have been used to record NMR signals from nanometre-scale samples1,2,3, with sensitivity sufficient to detect the magnetic field produced by a single protein4. However, the best reported spectral resolution for NMR of molecules using nitrogen–vacancy centres is about 100 hertz5. This is insufficient to resolve the key spectral identifiers of molecular structure that are critical to NMR applications in chemistry, structural biology and materials research, such as scalar couplings (which require a resolution of less than ten hertz6) and small chemical shifts (which require a resolution of around one part per million of the nuclear Larmor frequency). Conventional, inductively detected NMR can provide the necessary high spectral resolution, but its limited sensitivity typically requires millimetre-scale samples, precluding applications that involve smaller samples, such as picolitre-volume chemical analysis or correlated optical and NMR microscopy. Here we demonstrate a measurement technique that uses a solid-state spin sensor (a magnetometer) consisting of an ensemble of nitrogen–vacancy centres in combination with a narrowband synchronized readout protocol7,8,9 to obtain NMR spectral resolution of about one hertz. We use this technique to observe NMR scalar couplings in a micrometre-scale sample volume of approximately ten picolitres. We also use the ensemble of nitrogen–vacancy centres to apply NMR to thermally polarized nuclear spins and resolve chemical-shift spectra from small molecules. Our technique enables analytical NMR spectroscopy at the scale of single cells.

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Acknowledgements

This material 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 number W911NF1510548. D.B.B. was partially supported by the German Research Foundation (BU 3257/1-1). M.D.L. acknowledges support from the Gordon and Betty Moore foundation. We thank R. Fu for assisting with acquisition of the electromagnet used to apply the bias field, M. Rosen for guidance on NMR techniques and S. DeVience for assisting with SpinDynamica calculations of NMR spectra at low B0.

Author information

Author notes

    • David R. Glenn
    •  & Dominik B. Bucher

    These authors contributed equally to this work.

Affiliations

  1. Department of Physics, Harvard University, Cambridge, Massachusetts, USA

    • David R. Glenn
    • , Dominik B. Bucher
    • , Mikhail D. Lukin
    • , Hongkun Park
    •  & Ronald L. Walsworth
  2. Harvard-Smithsonian Centre for Astrophysics, Cambridge, Massachusetts, USA

    • Dominik B. Bucher
    •  & Ronald L. Walsworth
  3. Department of Physics, Massachusetts Institute of Technology, Cambridge, Massachusetts, USA

    • Junghyun Lee
  4. Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts, USA

    • Hongkun Park

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Contributions

R.L.W., D.R.G. and D.B.B. devised the synchronized readout technique. D.R.G., D.B.B. and R.L.W. conceived the application of the technique to picolitre-scale NMR measurements, designed the experiments and analysed the data. D.B.B. and D.R.G. designed and constructed the ensemble NV magnetometer and wrote the accompanying control software. J.L. carried out the single-NV synchronized readout experiments with incoherent averaging. M.D.L., H.P. and R.L.W. conceived the application of NV diamond magnetometry to NMR detection at short length scales. All authors discussed the results and participated in writing the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Ronald L. Walsworth.

Reviewer Information Nature thanks D. Budker and the other anonymous reviewer(s) for their contribution to the peer review of this work.

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    Supplementary Information

    This file contains Supplementary Methods, Notes and Data Sections 1-10 and Supplementary References.

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DOI

https://doi.org/10.1038/nature25781

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