Diamond-based quantum sensors have enabled high-resolution NMR spectroscopy at the microscale in scenarios where fast molecular motion averages out dipolar interactions among target nuclei. However, in samples with low-diffusion, ubiquitous dipolar couplings challenge the extraction of relevant spectroscopic information. In this work we present a protocol that enables the scanning of nuclear spins in dipolarly-coupled samples at high magnetic fields with a sensor based on nitrogen vacancy (NV) ensembles. Our protocol is based on the synchronized delivery of radio frequency (RF) and microwave (MW) radiation to eliminate couplings among nuclei in the scanned sample and to efficiently extract target energy-shifts from the sample's magnetization dynamics. In addition, the method is designed to operate at high magnetic fields leading to a larger sample thermal polarization, thus to an increased NMR signal. The precision of our method is ultimately limited by the coherence time of the sample, allowing for accurate identification of relevant energy shifts in solid-state systems.
Diamond-based quantum sensors have enabled high-resolution NMR spectroscopy at the microscale in scenarios where fast molecular motion averages out dipolar interactions among target nuclei. However, in samples with low-diffusion, ubiquitous dipolar couplings challenge the extraction of relevant spectroscopic information. In this work we present a protocol that enables the scanning of nuclear spins in dipolarly-coupled samples at high magnetic fields with a sensor based on nitrogen vacancy (NV) ensembles. Our protocol is based on the synchronized delivery of radio frequency (RF) and microwave (MW) radiation to eliminate couplings among nuclei in the scanned sample and to efficiently extract target energy-shifts from the sample's magnetization dynamics. In addition, the method is designed to operate at high magnetic fields leading to a larger sample thermal polarization, thus to an increased NMR signal. The precision of our method is ultimately limited by the coherence time of the sample, allowing for accurate identification of relevant energy shifts in solid-state systems.
Advances in sensing devices that utilize nitrogen-vacancy (NV) center ensembles in diamond are driving progress in microscale nuclear magnetic resonance spectroscopy. Utilizing quantum sensing techniques in the high-field regime significantly boosts sensitivity by increasing thermal polarization and improves spectral quality via enhanced energy shifts. Compatible with the latter, a straightforward manner to further raise sensor sensitivity is to increase NV concentration, although this intensifies detrimental dipole-dipole interactions among NVs. In this Letter, we present a method for detecting NMR signals in high-field scenarios while effectively suppressing dipole-dipole couplings in the NV ensemble. Thus, this approach enhances sensitivity by combining highly doped diamond substrates and elevated magnetic fields.
Nuclear magnetic resonance (NMR) schemes can be applied to micron-, and nanometer-sized samples by the aid of quantum sensors such as nitrogen vacancy (NV) color centers in diamond. These minute devices allow for magnetometry of nuclear spin ensembles with high spatial and frequency resolution at ambient conditions, thus having a clear impact in different areas such as chemistry, biology, medicine, and material sciences. In practice, NV quantum sensors are driven by microwave (MW) control fields with a twofold objective: On the one hand, MW fields bridge the energy gap between NV and nearby nuclei which enables a coherent and selective coupling among them while, on the other hand, MW fields remove environmental noise on the NV leading to enhanced interrogation time. In this work we review distinct MW radiation patterns, or dynamical decoupling techniques, for nanoscale NMR applications.
Nitrogen vacancy centers in diamond (NVs) are point defects well suited to quantum sensing of magnetic fields. NV spin states can be initialized and read out optically with high spatial resolution, enabling detection of pL-scale volumes of nuclear spins. Using Coherently Averaged Synchronized Readout (CASR), standard NMR spectroscopy techniques such as free decay, spin echo, and PGSE have been performed with Hz-scale spectral resolution using NV-diamond sensors. However, using NV detection for conventional high-resolution NMR at multi-tesla fields is challenging due to the need to manipulate NV electronic spins at resonance frequencies 100 GHz or higher. Low-field J-coupling spectroscopy provides an alternative path to chemical resolution in a regime more easily accessible to NVs. Here, we demonstrate homonuclear and heteronuclear J-coupling spectroscopy using an NV-NMR spectrometer based on permanent magnets operating at $\sim$890 kHz proton Larmor frequency (bias magnetic field $\sim21mT).ThisfieldstrengthenableschemicalcharacterizationbasedonJ−couplingusingsequencessuchasSynchronizedEcho(SyncE)andSpin−EchoDoubleResonance(SEDOR),whichdonotrequirethestrongchemicalshiftdispersionandpristinefieldhomogeneityofhigh−fieldNMR.ThefrequencyrangeiseasilydetectedbyNVsusingstandardXYdynamicaldecouplingsequencesandiswell−suitedforapplyingOverhauserDNP,whichcanboostprotonsignalbytwoordersofmagnitude.WeacquireinitialNV−NMRmeasurementsofT_1,T_2,andOverhauserDNPinglycerolbeforeadvancingtoSEDORspectroscopyofmethanol−^{13}Candamethanol−^{13}C/acetonitrile−2−^{13}$C mixture at sample volumes $\sim$50 pL, in which we demonstrate measurement of 1JCH couplings and resolution between species. We also acquire a homonuclear J-coupling spectrum of a natural-abundance propylene carbonate sample.
Quantum systems composed of solid-state electronic spins can be sensitive detectors of narrowband magnetic fields. A prominent example is the nitrogen-vacancy (NV) center in diamond, which has been employed for magnetic spectroscopy with high spatial and spectral resolution. However, NV-diamond spectroscopy protocols are typically based on dynamical decoupling sequences, which are limited to low-frequency signals ( ≲ 20 MHz) due to the technical requirements on microwave (MW) pulses used to manipulate NV electronic spins. In this work, we experimentally demonstrate a high-resolution magnetic spectroscopy protocol that integrates a quantum frequency mixing (QFM) effect in a dense NV ensemble with coherently averaged synchronized readout (CASR) to provide both a wide range of signal frequency detection and sub-Hz spectral resolution. We assess the sensitivity of this QFM-CASR protocol across a frequency range of 10 MHz to 4 GHz. By measuring the spectra of multi-frequency signals near 0.6, 2.4 and 4 GHz, we demonstrate sub-Hz spectral resolution with a nT-scale noise floor for the target signal, and precise phase measurement with error < 1 ∘ . Compared to state-of-the-art NV-diamond techniques for high-resolution magnetic spectroscopy, the QFM-CASR protocol extends the signal frequency range by more than an order of magnitude, enabling applications in radio frequency (RF) and MW signal microscopy and analysis, as well as tesla-scale nuclear magnetic resonance (NMR) spectroscopy of small samples.
Abstract Quantum systems composed of solid-state electronic spins can be sensitive detectors of narrowband magnetic fields. A prominent example is the nitrogen-vacancy (NV) center in diamond, which has been employed for magnetic spectroscopy with high spatial and spectral resolution. However, NV-diamond spectroscopy protocols are typically based on dynamical decoupling sequences, which are limited to low-frequency signals (≲ 20 MHz) due to the technical requirements on microwave (MW) pulses used to manipulate NV electronic spins. In this work, we experimentally demonstrate a high-resolution magnetic spectroscopy protocol that integrates a quantum frequency mixing (QFM) effect in a dense NV ensemble with coherently averaged synchronized readout (CASR) to provide both a wide range of signal frequency detection and sub-Hz spectral resolution. We assess the sensitivity of this QFM-CASR protocol across a frequency range of 10 MHz to 4 GHz. By measuring the spectra of multi-frequency signals near 0.6, 2.4 and 4 GHz, we demonstrate sub-Hz spectral resolution with a nT-scale noise floor for the target signal, and precise phase measurement with error <1°. Compared to state-of-the-art NV-diamond techniques for narrowband magnetic spectroscopy, the QFM-CASR protocol greatly extends the detectable frequency range, enabling applications in high-frequency radio frequency (RF) and MW signal microscopy and analysis, as well as tesla-scale nuclear magnetic resonance (NMR) spectroscopy of small samples.
Nuclear magnetic resonance (NMR) spectroscopy is widely used in fields ranging from chemistry, materials science to neuroscience. Nanoscale NMR spectroscopy using Nitrogen-vacancy (NV) centers in diamond has emerged as a promising platform due to an unprecedented sensitivity down to the single spin level. At the nanoscale, high nuclear spin polarization through spin fluctuations (statistical polarization) far outweighs thermal polarization. However, until now efficient NMR detection using coherent averaging techniques could not be applied to the detection of statistical polarization, leading to long measurement times. Here we present two protocols to enable coherent averaging of statistically oscillating signals through rectification. We demonstrate these protocols on an artificial radiofrequency signal detected with a single NV center at 2.7 T. The signal-to-noise scaling with number of measurements 𝑁 increases from 𝑁0.5 to 𝑁1, improving the measurement time significantly. The relevance of rectification for the detection of statistically polarized nuclear spins using ensembles of NV centers is outlined, paving the way for efficient nanoscale NMR spectroscopy.