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.
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.
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.
Quantum sensors using solid-state spin defects excel in the detection of radiofrequency (RF) fields, serving various applications in communication, ranging, and sensing. For this purpose, pulsed dynamical decoupling (PDD) protocols are typically applied, which enhance sensitivity to RF signals. However, these methods are limited to frequencies of a few megahertz, which poses a challenge for sensing higher frequencies. We introduce an alternative approach based on a continuous dynamical decoupling (CDD) scheme involving dressed states of nitrogen vacancy (NV) ensemble spins driven within a microwave resonator. We compare the CDD methods to established PDD protocols and demonstrate the detection of RF signals up to ~85 MHz, about ten times the current limit imposed by the PDD approach under identical conditions. Implementing the CDD method in a heterodyne/synchronized protocol combines the high-frequency detection with high spectral resolution. This advancement extends to various domains requiring detection in the high frequency (HF) and very high frequency (VHF) ranges of the RF spectrum, including spin sensor-based magnetic resonance spectroscopy at high magnetic fields.
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.
High-resolution wide-spectrum measurement techniques have important applications in fields such as astronomy, wireless communication, and medical imaging. Nitrogen-vacancy (NV) center in diamond is well known for its high stability, high sensitivity, real-time monitoring, single-point detection, and suitability for long-term measurement, and has an outstanding choice for spectrum analyzers. Currently, spectrum analyzers based on NV centers as detectors can perform real-time spectrum analysis in the range of several tens of gigahertz, but their frequency resolution is limited to a MHz level. In this study, we construct a quantum diamond microwave spectrum imaging system by combining continuous wave-mixing techniques. According to the spin-related properties of the NV center in diamond, we implement optical pumping by 532 nm green laser light illuminating the diamond NV center. A spherical magnet is used to produce a magnetic field gradient along the direction of the diamond crystal. By adjusting the size and direction of the magnetic field gradient, spatial encoding of the resonance frequency of the NV center is achieved. The magnetic field gradient induces the Zeeman effect on the diamond surface at different positions, generating corresponding ODMR signals. Through accurate programming, we coordinate the frequency scanning step size of the microwave source with the camera exposure and image storage time, and synchronize them circularly according to the order of image acquisition. Ultimately, after algorithmic processing, we successfully obtain comprehensive spectrum data in a range from 900 MHz to 6.0 GHz. Within the measurable spectrum range, the system employs continuous wave-mixing, simultaneously applying resonant microwaves and slightly detuning auxiliary microwaves to effectively excite the NV center. This method triggers off microwave interference effects, disrupting the balance between laser-induced polarization and microwave-induced spontaneous relaxation. Specifically, microwave interference causes the phase and amplitude of the fluorescence signal to change, leading to the generation of alternating current fluorescence signals. This further enhances the response of the NV magnetometer to weak microwave signals. The method enables the system to achieve a frequency resolution of 1 Hz in the measurable spectrum range, and it can separately measure the frequency resolution of multiple frequency points with a frequency step size of 1 MHz. The research results indicate that the wide-spectrum measurement based on NV centers can achieve sub-hertz frequency resolution, providing robust technical support for future spectrum analysis and applications.
Magnetic field fluctuations on nanometer length scales manifest in a diverse range of phenomena -- electron and spin dynamics in materials and devices, quantum many-body systems, and molecular chemistry. Measuring these phenomena requires sensors with a challenging combination of broad spectral bandwidth, high sensitivity, and nanoscale spatial resolution. Nitrogen-vacancy (NV) centers, atom-like quantum sensors in diamond, possess the requisite sensitivity and nanoscale sensing volume, but are typically limited in bandwidth by the practical speed of the applied quantum control sequence. Here, we overcome this limitation by exposing the NV qubit to a microwave dressing field during a dynamical decoupling sequence, which both amplifies and frequency-mixes target signals at arbitrary frequencies into the detection band of the dynamical decoupling protocol. We demonstrate this approach by using NV centers to detect both coherent and noisy nanoscale spin wave dynamics in a magnetic yttrium-iron-garnet (YIG) thin film over a broad frequency range. Our technique generalizes to other qubit platforms, providing a versatile framework for nanoscale spectroscopy across diverse physical and chemical systems.
Wide-field quantum magnetometry using nitrogen-vacancy (NV) center in diamond can be a breakthrough for a nuclear magnetic resonance (NMR) in a small volume, which is important for biological applications. Although the coherence time of the electron spin of the NV center results in a limited frequency resolution for diamond magnetometry in the range 10–100 kHz, recent studies have shown that a phase-sensitive protocol can circumvent this limit using a confocal setup. We proposed a new measurement protocol, “iQdyne,” which facilitates an improved frequency resolution of wide-field imaging, unencumbered by the coherence limit imposed by the NV center. We demonstrated wide-field magnetometry with a frequency resolution of 238 mHz and a magnetic sensitivity of 65 nT/Hz1/2, which are superior to those obtained using a conventional XY8-based technique, and showed the potential of the iQdyne protocol for the wide-field NMR imaging.