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 NVensemble at a depth of ~ 10 nm below the diamond surface. The spectrometer operates at low magnetic fields (~ 300 G) and requires standard optical and microwave components for NV spin preparation, manipulation and readout. We demonstrate the utility of this device for nanoscale proton and fluorine NMR spectroscopy, as well as for the detection of transition metals via ESR noise spectroscopy. We estimate that the full protocol requires 2-3 months to implement, depending on the availability of equipment, diamond substrates, and user experience.
Introduction:Magnetic resonance spectroscopy of electrons and nuclei comprises a family of ubiquitous and essential analytical tools in modern chemical and biological research 1 . Electron spin resonance (ESR), also known as electron paramagnetic resonance (EPR), spectroscopy is a useful means for probing molecules possessing unpaired electrons, such as transition metal complexes and radicals 2 . (Bio)molecules that lack an unpaired electronic spin can be probed via ESR-active spin labels. Nuclear magnetic resonance (NMR), on the other hand, is a more widely utilized technique, as NMR-active nuclei (e.g., 1 H, 13 C, 14 N, and 31 P) are commonly encountered in organic and biological chemistry. The narrow spectral lines of NMR afford unprecedented information about molecular structure and dynamics. NMR is less sensitive than ESR, however, owing to the lower gyromagnetic ratios of nuclei compared to that of the electron. In fact, both NMR and ESR are relatively insensitive when compared to the state of the art in other analytical techniques like mass spectrometry or fluorescence microscopy. The low sensitivity of magnetic resonance is particularly challenging for life science applications, where biomolecules of interest commonly occur in small absolute quantities or concentrations. Thus, there is great interest in new techniques to increase the sensitivity of magnetic resonance spectroscopy 3-5 . One promising approach employs a magnetic sensor based on fluorescent quantum defects in diamond, such as nitrogen-vacancy (NV) color centers, enabling interrogation of sample volumes down to the nanoscale 6,7 , including single proteins 8,9 , single protons 10 and 2D materials 11 . In this protocol, we describe the procedure for generating NV-diamond sensor chips and the construction of a "quantum diamond spectrometer" for NMR and ESR of nanoscale samples placed on the diamond chip.
Physical back...