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Register a new userTwo-dimensional nuclear magnetic resonance spectroscopy with a microfluidic diamond quantum sensor
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Quantum sensors based on nitrogen-vacancy centers in diamond have emerged as a promising detection modality for nuclear magnetic resonance (NMR) spectroscopy owing to their micron-scale detection volume and non-inductive based detection. A remaining challenge is to realize sufficiently high spectral resolution and concentration sensitivity for multidimensional NMR analysis of picoliter sample volumes. Here, we address this challenge by spatially separating the polarization and detection phases of the experiment in a microfluidic platform. We realize a spectral resolution of 0.65 +/- 0.05 Hz, an order-of-magnitude improvement over previous diamond NMR studies. We use the platform to perform two-dimensional correlation spectroscopy of liquid analytes within an effective ~20 picoliter detection volume. The use of diamond quantum sensors as in-line microfluidic NMR detectors is a significant step towards applications in mass-limited chemical analysis and single cell biology.
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Current density distributions in active integrated circuits (ICs) result in patterns of magnetic fields that contain structural and functional information about the IC. Magnetic fields pass through standard materials used by the semiconductor industry and provide a powerful means to fingerprint IC activity for security and failure analysis applications. Here, we demonstrate high spatial resolution, wide field-of-view, vector magnetic field imaging of static (DC) magnetic field emanations from an IC in different active states using a Quantum Diamond Microscope (QDM). The QDM employs a dense layer of fluorescent nitrogen-vacancy (NV) quantum defects near the surface of a transparent diamond substrate placed on the IC to image magnetic fields. We show that QDM imaging achieves simultaneous $sim10$ $mu$m resolution of all three vector magnetic field components over the 3.7 mm $times$ 3.7 mm field-of-view of the diamond. We study activity arising from spatially-dependent current flow in both intact and decapsulated field-programmable gate arrays (FPGAs); and find that QDM images can determine pre-programmed IC active states with high fidelity using machine-learning classification methods.
Magnetometers based on nitrogen-vacancy (NV) centers in diamond are promising room-temperature, solid-state sensors. However, their reported sensitivity to magnetic fields at low frequencies (<1 kHz) is presently >10 pT s^{1/2}, precluding potential applications in medical imaging, geoscience, and navigation. Here we show that high-permeability magnetic flux concentrators, which collect magnetic flux from a larger area and concentrate it into the diamond sensor, can be used to improve the sensitivity of diamond magnetometers. By inserting an NV-doped diamond membrane between two ferrite cones in a bowtie configuration, we realize a ~250-fold increase of the magnetic field amplitude within the diamond. We demonstrate a sensitivity of ~0.9 pT s^{1/2} to magnetic fields in the frequency range between 10 and 1000 Hz, using a dual-resonance modulation technique to suppress the effect of thermal shifts of the NV spin levels. This is accomplished using 200 mW of laser power and 20 mW of microwave power. This work introduces a new dimension for diamond quantum sensors by using micro-structured magnetic materials to manipulate magnetic fields.
Nuclear magnetic resonance (NMR) spectroscopy has approached the limit of single molecule sensitivity, however the spectral resolution is currently insufficient to obtain detailed information on chemical structure and molecular interactions. Here we demonstrate more than two orders of magnitude improvement in spectral resolution by performing correlation spectroscopy with shallow nitrogen-vacancy (NV) magnetic sensors in diamond. In principle, the resolution is sufficient to observe chemical shifts in $sim$1 T magnetic fields, and is currently limited by molecular diffusion at the surface. We measure oil diffusion rates of $D = 0.15 - 0.2$,nm$^2/mathrm{mu}$s within (5 nm)$^3$ volumes at the diamond surface.
We present Auger-electron-detected magnetic resonance (AEDMR) experiments on phosphorus donors in silicon, where the selective optical generation of donor-bound excitons is used for the electrical detection of the electron spin state. Because of the long dephasing times of the electron spins in isotopically purified $^{28}$Si, weak microwave fields are sufficient, which allow to realize broadband AEDMR in a commercial ESR resonator. Implementing Auger-electron-detected ENDOR, we further demonstrate the optically-assisted control of the nuclear spin under conditions where the hyperfine splitting is not resolved in the optical spectrum. Compared to previous studies, this significantly relaxes the requirements on the sample and the experimental setup, e.g. with respect to strain, isotopic purity and temperature. We show AEDMR of phosphorus donors in silicon with natural isotope composition, and discuss the feasibility of ENDOR measurements also in this system.
We demonstrate nuclear magnetic resonance (NMR) spectroscopy of picoliter-volume solutions with a nanostructured diamond chip. Using optical interferometric lithography, diamond surfaces were nanostructured with dense, high-aspect-ratio nanogratings, enhancing the surface area by more than a factor of 15 over mm^2 regions of the chip. The nanograting sidewalls were doped with nitrogen-vacancy (NV) centers so that more than 10 million NV centers in a (25 micrometer)^2 laser spot are located close enough to the diamond surface (5 nm) to detect the NMR spectrum of 1 pL of fluid lying within adjacent nanograting grooves. The platform was used to perform 1H and 19F NMR spectroscopy at room temperature in magnetic fields below 50 mT. Using a solution of CsF in glycerol, we demonstrate that 4 +/- 2 x 10^12 19F spins in a 1 pL volume, can be detected with a signal-to-noise ratio of 3 in 1 s integration. This represents nearly two orders of magnitude improvement in concentration sensitivity over previous NV and picoliter NMR studies.
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