Friedemann Reinhard

Electric-field sensing using single diamond spins.

The ability to sensitively detect charges under amb ient conditions would be a fascinating new tool benefitting a wide range of researchers ac ross disciplines. However, most current techniques are limited to low-temperature methods l ike single-electron transistors (SET)[1,2], single–electron electrostatic force microscopy[3] a nd scanning tunnelling microscopy [4]. Here we open up a new quantum metrology technique demons trating precision electric field measurement using a single nitrogen-vacancy defect entre(NV) spin in diamond. An AC electric field sensitivity reaching ~ 140V/cm/ √Hz has been achieved. This corresponds to the electric field produced by a single elementary char ge located at a distance of ~ 150 nm from our spin sensor with averaging for one second. By caref ul analysis of the electronic structure of the defect centre, we show how an applied magnetic fiel d influences the electric field sensing properties. By this we demonstrate that diamond defct centre spins can be switched between electric and magnetic field sensing modes and ident ify suitable parameter ranges for both detector schemes. By combining magnetic and electri c field sensitivity, nanoscale detection and ambient operation our study opens up new frontiers in imaging and sensing applications ranging from material science to bioimaging.

Nuclear magnetic resonance spectroscopy on a (5-nanometer)3 sample volume.

Nanoscale NMR with Diamond Defects Although nuclear magnetic resonance (NMR) methods can be used for spatial imaging, the low sensitivity of detectors limits the minimum sample size. Two reports now describe the use of near-surface nitrogen-vacancy (NV) defects in diamond for detecting nanotesla magnetic fields from very small volumes of material (see the Perspective by Hemmer). The spin of the defect can be detected by changes in its fluorescence, which allows proton NMR of organic samples only a few nanometers thick on the diamond surface. Mamin et al. (p. 557) used a combination of electron spin echoes and pulsed NMR manipulation of the proton spins to detect the very weak fields. Staudacher et al. (p. 561) measured statistical polarization of a population of about 104 spins near the NV center with a dynamical decoupling method. The optical response of the spin of a near-surface atomic defect in diamond can be used to sense proton magnetic fields. [Also see Perspective by Hemmer] Application of nuclear magnetic resonance (NMR) spectroscopy to nanoscale samples has remained an elusive goal, achieved only with great experimental effort at subkelvin temperatures. We demonstrated detection of NMR signals from a (5-nanometer)3 voxel of various fluid and solid organic samples under ambient conditions. We used an atomic-size magnetic field sensor, a single nitrogen-vacancy defect center, embedded ~7 nanometers under the surface of a bulk diamond to record NMR spectra of various samples placed on the diamond surface. Its detection volume consisted of only 104 nuclear spins with a net magnetization of only 102 statistically polarized spins.

Chemical control of the charge state of nitrogen-vacancy centers in diamond

We investigate the effect of surface termination on the charge state of nitrogen vacancy centers, which have been ion-implanted few nanometers below the surface of diamond. We find that, when changing the surface termination from oxygen to hydrogen, previously stable NV- centers convert into NV0 and, subsequently, into an unknown non-fluorescent state. This effect is found to depend strongly on the implantation dose. Simulations of the electronic band structure confirm the dissappearance of NV- in the vicinity of the hydrogen-terminated surface. The band bending, which induces a p-type surface conductive layer leads to a depletion of electrons in the nitrogen vacancies close to the surface. Therefore, hydrogen surface termination provides a chemical way for the control of the charge state of nitrogen-vacancy centers in diamond. Furthermore, it opens the way to an electrostatic control of the charge state with the use of an external gate electrode.

Charge state manipulation of qubits in diamond

The nitrogen-vacancy (NV) centre in diamond is a promising candidate for a solid-state qubit. However, its charge state is known to be unstable, discharging from the qubit state NV− into the neutral state NV0 under various circumstances. Here we demonstrate that the charge state can be controlled by an electrolytic gate electrode. This way, single centres can be switched from an unknown non-fluorescent state into the neutral charge state NV0, and the population of an ensemble of centres can be shifted from NV0 to NV−. Numerical simulations confirm the manipulation of the charge state to be induced by the gate-controlled shift of the Fermi level at the diamond surface. This result opens the way to a dynamic control of transitions between charge states and to explore hitherto inaccessible states, such as NV+.

Single-protein spin resonance spectroscopy under ambient conditions

Single-protein spectroscopy The spin of a single nitrogen-vacancy (NV) center in diamond is a highly sensitive magnetic-field sensor. Shi et al. used the NV center to detect a nitroxidelabeled protein through electron spin resonance under ambient conditions (see the Perspective by Hemmer and Gomes). The strength of the interaction and the details of the hyperfine interaction between the electron and nitrogen spin revealed the position and orientation of the spin label relative to the NV center. The findings also elucidate the dynamical motions of the protein on the diamond surface. Science, this issue p. 1135; see also p. 1072 Electron spin resonance (ESR) signals from a single labeled protein were detected with diamond nitrogen-vacancy centers. [Also see Perspective by Hemmer and Gomes] Magnetic resonance is essential in revealing the structure and dynamics of biomolecules. However, measuring the magnetic resonance spectrum of single biomolecules has remained an elusive goal. We demonstrate the detection of the electron spin resonance signal from a single spin-labeled protein under ambient conditions. As a sensor, we use a single nitrogen vacancy center in bulk diamond in close proximity to the protein. We measure the orientation of the spin label at the protein and detect the impact of protein motion on the spin label dynamics. In addition, we coherently drive the spin at the protein, which is a prerequisite for studies involving polarization of nuclear spins of the protein or detailed structure analysis of the protein itself.

Nanoscale nuclear magnetic imaging with chemical contrast

Scanning probe microscopy is one of the most versatile windows into the nanoworld, providing imaging access to a variety of sample properties, depending on the probe employed. Tunneling probes map electronic properties of samples, magnetic and photonic probes image their magnetic and dielectric structure while sharp tips probe mechanical properties like surface topography, friction or stiffness. Most of these observables, however, are accessible only under limited circumstances. For instance, electronic properties are measurable only on conducting samples while atomic-resolution force microscopy requires careful preparation of samples in ultrahigh vacuum or liquid environments. Here we demonstrate a scanning probe imaging method that extends the range of accessible quantities to label-free imaging of chemical species operating on arbitrary samples - including insulating materials - under ambient conditions. Moreover, it provides three-dimensional depth information, thus revealing subsurface features. We achieve these results by recording nuclear magnetic resonance signals from a sample surface with a recently introduced scanning probe, a single nitrogen-vacancy center in diamond. We demonstrate NMR imaging with 10 nm resolution and achieve chemically specific contrast by separating fluorine from hydrogen rich regions. Our result opens the door to scanning probe imaging of the chemical composition and atomic structure of arbitrary samples. A method with these abilities will find widespread application in material science even on biological specimens down to the level of single macromolecules.Scanning probe microscopy is one of the most versatile windows into the nanoworld, providing imaging access to a variety of electronic, dielectric, magnetic and topographic sample properties, depending on the probe used. Here, we demonstrate a scanning probe imaging method that extends the range of accessible quantities to label-free imaging of chemical species while operating on arbitrary samples--including insulating materials--under ambient conditions. Moreover, its sensitivity extends below the surface of a sample, allowing for imaging of subsurface features. We achieve these results by recording NMR signals from a sample surface with a recently introduced scanning probe, a single nitrogen-vacancy centre in diamond. We demonstrate NMR imaging with 10 nm resolution and achieve chemically specific contrast by separating fluorine from hydrogen-rich regions. Our result opens the door to scanning probe imaging of the chemical composition and molecular structure of arbitrary samples. A method with these abilities will find widespread application in materials science, even on biological specimens down to the level of single macromolecules.

Highly efficient FRET from a single nitrogen-vacancy center in nanodiamonds to a single organic molecule.

We show highly efficient fluorescence resonance energy transfer (FRET) between negatively charged nitrogen-vacancy (NV) centers in diamond as donor and dye molecules as acceptor, respectively. The energy transfer efficiency is 86% with particles of 20 nm in size. Calculated and experimentally measured energy transfer efficiencies are in excellent agreement. Owing to the small size of the nanocrystals and careful surface preparation, energy transfer between a single nitrogen-vacancy center and a single quencher was identified by the stepwise change of energy transfer efficiencies due to bleaching of single acceptor molecules. Our studies pave the way toward FRET-based scanning probe techniques using single NV donors.

Sensing external spins with nitrogen-vacancy diamond

A single nitrogen-vacancy (NV) center is used to sense individual, as well as small ensembles of, electron spins placed outside the diamond lattice. Applying double electron–electron resonance techniques, we were able to observe Rabi nutations of these external spins as well as the coupling strength between the external spins and the NV sensor, via modulations and accelerated decay of the NV spin echo. Echo modulation frequencies as large as 600 kHz have been observed, being equivalent to a few nanometers distance between the NV and an unpaired electron spin. Upon surface modification, the coupling disappears, suggesting the spins to be localized at surface defects. The present study is important for understanding the properties of diamond surface spins so that their effects on NV sensors can eventually be mitigated. This would enable potential applications such as the imaging and tracking of single atoms and molecules in living cells or the use of NVs on scanning probe tips to entangle remote spins for scalable room temperature quantum computers.

Nanoengineered diamond waveguide as a robust bright platform for nanomagnetometry using shallow nitrogen vacancy centers.

Photonic structures in diamond are key to most of its application in quantum technology. Here, we demonstrate tapered nanowaveguides structured directly onto the diamond substrate hosting shallow-implanted nitrogen vacancy (NV) centers. By optimization based on simulations and precise experimental control of the geometry of these pillar-shaped nanowaveguides, we achieve a net photon flux up to ∼ 1.7 × 10(6) s(-1). This presents the brightest monolithic bulk diamond structure based on single NV centers so far. We observe no impact on excited state lifetime and electronic spin dephasing time (T2) due to the nanofabrication process. Possessing such high brightness with low background in addition to preserved spin quality, this geometry can improve the current nanomagnetometry sensitivity ∼ 5 times. In addition, it facilitates a wide range of diamond defects-based magnetometry applications. As a demonstration, we measure the temperature dependency of T1 relaxation time of a single shallow NV center electronic spin. We observe the two-phonon Raman process to be negligible in comparison to the dominant two-phonon Orbach process.

Increasing the coherence time of single electron spins in diamond by high temperature annealing

Negatively charged nitrogen-vacancy (NV−) centers in diamond produced by ion implantation often show properties different from NVs created during the crystal growth. We observe that NVs created from nitrogen ion implantation at 30–300 keV show much shorter electron spin coherence time T2 as compared to the “natural” NVs and about 20% of them show switching from NV− to NV0. We show that annealing the diamond at T=1200 °C substantially increases T2 and at the same time the fraction of NVs converting from NV− to NV0 is greatly reduced.