Characterization of the molecular properties of surfaces under ambient or chemically reactive conditions is a fundamental scientific challenge. Moreover, many traditional analytical techniques used for probing surfaces often lack dynamic or molecular selectivity, which limits their applicability for mechanistic and kinetic studies under realistic chemical conditions. Nuclear magnetic resonance spectroscopy (NMR) is a widely used technique and would be ideal for probing interfaces due to the molecular information it provides noninvasively. However, it lacks the sensitivity to probe the small number of spins at surfaces. Here, we use nitrogen vacancy (NV) centers in diamond as quantum sensors to optically detect nuclear magnetic resonance signals from chemically modified aluminum oxide surfaces, prepared with atomic layer deposition (ALD). With the surface NV-NMR technique, we are able to monitor in real-time the formation kinetics of a self assembled monolayer (SAM) based on phosphonate anchoring chemistry to the surface. This demonstrates the capability of quantum sensors as a new surface-sensitive tool with sub-monolayer sensitivity for in-situ NMR analysis with the additional advantage of a strongly reduced technical complexity.
Nuclear magnetic resonance (NMR) spectroscopy is a widely used tool for chemical analysis and molecular structure identification. Because it typically relies on the weak magnetic fields produced by a small thermal nuclear spin polarization, NMR suffers from poor molecule-number sensitivity compared to other analytical techniques. Recently, a new class of NMR sensors based on optically-probed nitrogen-vacancy (NV) quantum defects in diamond have allowed molecular spectroscopy from sample volumes several orders of magnitude smaller than the most sensitive inductive detectors. To date, however, N…
Nitrogen-vacancy (NV) quantum defects in diamond are sensitive detectors of magnetic fields. Due 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 nuclear magnetic resonance (NMR) and electron spin resonance (ESR) spectroscopy in nanoscale volumes. The instrument is based on a commercially-available diamond chip, with an ion-implanted NV-e…
Nanoscale NMR of DNA-Functionalized Diamond Using Individual NV Centers
ETH Zürich（苏黎世联邦理工学院）；University of Calgary（卡尔加里大学）；National Institute of Standards and Technology（美国国家标准与技术研究院）；University of Colorado, Boulder（科罗拉多大学博尔德分校）；University of Fribourg（弗里堡大学）
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, a…
Atomic-scale magnetic field sensors based on nitrogen vacancy (NV) defects in diamonds are an exciting platform for nanoscale nuclear magnetic resonance (NMR) spectroscopy. The detection of NMR signals from a few zeptoliters to single molecules or even single nuclear spins has been demonstrated using NV-centers close to the diamond surface. However, fast molecular diffusion of sample molecules in and out of nanoscale detection volumes impedes their detection and limits current experiments to solid-state or highly viscous samples. Here, we show that restricting diffusion by confinement enables …
The past 15 years have seen an astonishing increase in Nuclear Magnetic Resonance (NMR) sensitivity and accessible pressure range in high-pressure NMR experiments, owing to a series of new developments of NMR spectroscopy applied to the diamond anvil cell (DAC). Recently, with the application of electro-magnetic lenses, so-called Lenz lenses, in toroidal diamond indenter cells, pressures of up to 72 GPa with NMR spin sensitivities of about 10^12 spins/(Hz^1/2) has been achieved. Here, we describe the implementation of a refined NMR resonator structure using a pair of double stage Lenz lenses d…
The nitrogen vacancy (NV) center in diamond has emerged as a leading solid-state quantum sensor for applications including magnetometry, electrometry, thermometry, and chemical sensing. However, an outstanding challenge for practical applications is that existing NV-based sensing techniques require bulky and discrete instruments for spin control and detection. Here, we address this challenge by integrating NV based quantum sensing with complementary metal-oxide-semiconductor (CMOS) technology. Through tailored CMOS-integrated microwave generation and photodetection, this work dramatically redu…
Precise measurement of temperature distribution and thermal behavior in microscopic regions is critical in many research fields. We demonstrate lock-in thermography using nitrogen-vacancy centers in diamond nanoparticles. We successfully visualize thermal diffusion in glass coverslip and Teflon with micrometer resolution and deduce their thermal diffusivity. By spreading diamond nanoparticles over the sample surface, temperature variation can be measured directly without any physical contact, such as lead wires, making it possible to visualize the micrometer-scale thermal behavior of various m…
Sensing small magnetic fields is relevant for many applications ranging from geology to medical diagnosis. We present a fiber-coupled diamond magnetometer with a sensitivity of (310 $\pm$ 20) pT$/\sqrt{\text{Hz}}$ in the frequency range of 10-150 Hz. This is based on optically detected magnetic resonance of an ensemble of nitrogen vacancy centers in diamond at room temperature. Fiber coupling means the sensor can be conveniently brought within 2 mm of the object under study.
A novel approach for automated high throughput NMR spectroscopy with improved mass-sensitivity is accomplished by integrating microfluidic technologies and micro-NMR resonators. A flow system is utilized to transport a sample of interest from outside the NMR magnet through the NMR detector, circumventing the relatively vast dead volume in the supplying tube by loading a series of individual sample plugs separated by an immiscible fluid. This dual-phase flow demands a real-time robust sensing system to track the sample position and velocities and synchronize the NMR acquisition. In this contrib…
Recent advancements in radio-frequency resonator designs have led to the implementation of nuclear magnetic resonance in diamond anvil cells (DACs) at pressures well above 100 GPa. However, a relatively low resolution and the absence of decoupling sequences complicate the analysis of the results of solid state NMR in DACs. Here, we present the first application of homo-nuclear Lee-Goldburg (LG) decoupling at extreme conditions on high density molecular hydrogen. Lenz lens based two-dimensional resonator structures were found to generate a homogeneous B1 field across sample cavities as small as…
Efficient Detection of Statistical RF Fields at High Magnetic Field with a Quantum Sensor
University of Stuttgart（斯图加特大学）；Max Planck Institute for Solid State Research（马克斯·普朗克固体研究所）；Center for Integrated Quantum Science and Technology（集成量子科学与技术中心）；Sumitomo Electric Industries Ltd.（住友电工株式会社）；Takasaki Institute for Advance Quantum Science（高崎高级量子科学研究所）；University of Tsukuba（筑波大学）
One of the biggest challenges to implement quantum protocols and quantum information processing (QIP) is achieving long coherence times, usually requiring systems at ultra-low temperatures. The nitrogen-vacancy (NV) center in diamond is a promising alternative to this problem. Due to its spin properties, easy manipulation, and the possibility of doing optical state initialization and readout, it quickly became one of the best solid-state spin systems for QIP at room temperature. Here, we present the characterization of the spin-coherence of an ensemble of NV centers in an engineered sample of …
To efficiently align the creation of defect center with photonics structure in nanoscale precision is one of the outstanding challenges for realizing high-performance photonic devices and the application in quantum technology such as quantum sensing, scalable quantum systems, and quantum computing network. Here, we propose a facile self-aligned patterning technique wholly based on conventional engineering technology, with the doping precision can reach ~15nm. Specifically, we demonstrate this technique by fabricating diamond nanopillar sensor arrays, which show high consistency and near-optima…
We present a microwave B-field scanning imaging technique using diamond micro-crystal containing nitrogen vacancy center that is attached to a fiber tip. We propose a pulsed modulation technique, enabling the implementation of a variety of pulsed quantum algorithm for state manipulation and fast readout of spin state. A detailed mapping of the magnetic B-field distribution of a helical antenna with sub-100 micron resolution is presented and compared with numerical simulations. This fiber based microwave B-field probe has the advantage of minimized invasiveness, small overall size, will boost b…
The ability to perform noninvasive, non-contact measurements of electric signals produced by action potentials is essential in biomedicine. A key method to do this is to remotely sense signals by the magnetic field they induce. Existing methods for magnetic field sensing of mammalian tissue, used in techniques such as magnetoencephalography of the brain, require cryogenically cooled superconducting detectors. These have many disadvantages in terms of high cost, flexibility and limited portability as well as poor spatial and temporal resolution. In this work we demonstrate an alternative techni…
An important tool in the investigation of the early stages of neurodegenerative disease is the study of dissected living tissue from the brain of an animal model. Such investigations allow the physical structure of individual neurons and neural circuits to be probed alongside neuronal electrical activity, disruption of which can shed light on the mechanisms of emergence of disease. Existing techniques for recording activity rely on potentially damaging direct interaction with the sample, either mechanically as point electrical probes or via intense focused laser light combined with highly spec…
Patterning of diamond-like carbon (DLC) and DLC:metal nanocomposites is of interest for an increasing number of applications. We demonstrate a nanoimprint lithography process based on silicon containing thermoplastic resist combined with plasma etching for straightforward patterning of such films. A variety of different structures with few hundred nanometer feature size and moderate aspect ratios were successfully realized. The quality of produced patterns was directly investigated by the means of optical and scanning electron microscopy (SEM). Such structures were further assessed by employin…
Unconditional full vector magnetometry using spin selectivity in Nitrogen Vacancy centers in diamond
University of the Basque Country（巴斯克大学）；Centro de Fisica de Materiales (CFM), CSIC-UPV/EHU（材料物理中心，西班牙国家研究委员会/巴斯克大学）；Donostia International Physics Center（圣塞巴斯蒂安国际物理中心）；IKERBASQUE, Basque Foundation for Science（伊卡巴斯基克，巴斯克科学基金会）
Versatile nanoscale sensors that are susceptible to changes in a variety of physical quantities often exhibit limited selectivity. This paper reports a novel scheme based on microwave-dressed spin states for optically probed nanoscale temperature detection using diamond quantum sensors, which provides selective sensitivity to temperature changes. By combining this scheme with a continuous pump-probe scheme using ensemble nitrogen-vacancy centers in nanodiamonds, a sub-microsecond temporal resolution with thermal sensitivity of 3.7 K$\cdot$Hz$^{-1/2}$ that is insensitive to variations in extern…
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 …
Sensing vector magnetic fields is critical to many applications in fundamental physics, bioimaging, and material science. Magnetic-field sensors exploiting nitrogen-vacancy (NV) centers are particularly compelling as they offer high sensitivity and spatial resolution even at nanoscale. Achieving vector magnetometry has, however, often required applying microwaves sequentially or simultaneously, limiting the sensors' applications under cryogenic temperature. Here we propose and demonstrate a microwave-free vector magnetometer that simultaneously measures all Cartesian components of a magnetic f…
Diamond containing the negatively charged nitrogen-vacancy (NV) center is emerging as a significant new system for magnetometry. However, most NV sensors require microscopes to collect the fluorescence signals and are therefore limited to laboratory settings. By incorporating micron-scale diamond particles at an annular interface within the cross section of a silicate glass fiber, a high-sensitivity and robust fiber platform for magnetic field sensing is demonstrated here. The fluorescence and spin properties of NV centers embedded in the diamond crystals are well preserved during the fiber dr…
The sensitivity of magnetic and electric field sensors based on nitrogen-vacancy (NV) center in diamond strongly depends on the available concentration of NV and their coherence properties. Achieving high coherence times simultaneously with high concentration is a challenging experimental task. Here, we demonstrate that by using a high-pressure, high-temperature growing technique, one can achieve nearly maximally possible effective coherence T2* times, limited only by carbon nuclear spins at low nitrogen concentrations or nitrogen electron spin at high nitrogen concentrations. Hahn-echo T2 coh…
