Roadmap on nanoscale magnetic resonance imaging.

The field of nanoscale magnetic resonance imaging (NanoMRI) was started 30 years ago. It was motivated by the desire to image single molecules and molecular assemblies, such as proteins and virus particles, with near-atomic spatial resolution and on a length scale of 100 nm. Over the years, the NanoMRI field has also expanded to include the goal of useful high-resolution nuclear magnetic resonance (NMR) spectroscopy of molecules under ambient conditions, including samples up to the micron-scale. The realization of these goals requires the development of spin detection techniques that are many orders of magnitude more sensitive than conventional NMR and MRI, capable of detecting and controlling nanoscale ensembles of spins. Over the years, a number of different technical approaches to NanoMRI have emerged, each possessing a distinct set of capabilities for basic and applied areas of science. The goal of this roadmap article is to report the current state of the art in NanoMRI technologies, outline the areas where they are poised to have impact, identify the challenges that lie ahead, and propose methods to meet these challenges. This roadmap also shows how developments in NanoMRI techniques can lead to breakthroughs in emerging quantum science and technology applications. .

Dynamical Coulomb Blockade as a Local Probe for Quantum Transport.

Quantum fluctuations are imprinted with valuable information about transport processes. Experimental access to this information is possible, but challenging. We introduce the dynamical Coulomb blockade (DCB) as a local probe for fluctuations in a scanning tunneling microscope (STM) and show that it provides information about the conduction channels. In agreement with theoretical predictions, we find that the DCB disappears in a single-channel junction with increasing transmission following the Fano factor, analogous to what happens with shot noise. Furthermore we demonstrate local differences in the DCB expected from changes in the conduction channel configuration. Our experimental results are complemented by ab initio transport calculations that elucidate the microscopic nature of the conduction channels in our atomic-scale contacts. We conclude that probing the DCB by STM provides a technique complementary to shot noise measurements for locally resolving quantum transport characteristics.

Quantum Brownian Motion at Strong Dissipation Probed by Superconducting Tunnel Junctions.

We have investigated the phase dynamics of a superconducting tunnel junction at ultralow temperatures in the presence of high damping, where the interaction with environmental degrees of freedom represents the leading energy scale. In this regime, theory predicts the dynamics to follow a generalization of the classical Smoluchowski description, the quantum Smoluchowski equation, thus, exhibiting overdamped quantum Brownian motion characteristics. For this purpose, we have performed current-biased measurements on the small-capacitance Josephson junction of a scanning tunneling microscope placed in a low impedance environment at milli-Kelvin temperatures. We can describe our experimental findings with high accuracy by using a quantum phase diffusion model based on the quantum Smoluchowski equation. In this way we experimentally demonstrate that overdamped quantum systems follow quasiclassical dynamics with significant quantum effects as the leading corrections.

Probing absolute spin polarization at the nanoscale.

Probing absolute values of spin polarization at the nanoscale offers insight into the fundamental mechanisms of spin-dependent transport. Employing the Zeeman splitting in superconducting tips (Meservey-Tedrow-Fulde effect), we introduce a novel spin-polarized scanning tunneling microscopy that combines the probing capability of the absolute values of spin polarization with precise control at the atomic scale. We utilize our novel approach to measure the locally resolved spin polarization of magnetic Co nanoislands on Cu(111). We find that the spin polarization is enhanced by 65% when increasing the width of the tunnel barrier by only 2.3 Å due to the different decay of the electron orbitals into vacuum.

Tracking a spin-polarized superconducting bound state across a quantum phase transition.

The magnetic exchange coupling between magnetic impurities and a superconductor induce so-called Yu-Shiba-Rusinov (YSR) states which undergo a quantum phase transition (QPT) upon increasing the exchange interaction beyond a critical value. While the evolution through the QPT is readily observable, in particular if the YSR state features an electron-hole asymmetry, the concomitant change in the ground state is more difficult to identify. We use ultralow temperature scanning tunneling microscopy to demonstrate how the change in the YSR ground state across the QPT can be directly observed for a spin-1/2 impurity in a magnetic field. The excitation spectrum changes from featuring two peaks in the doublet (free spin) state to four peaks in the singlet (screened spin) ground state. We also identify a transition regime, where the YSR excitation energy is smaller than the Zeeman energy. We thus demonstrate a straightforward way for unambiguously identifying the ground state of a spin-1/2 YSR state.

Graphene sublattice symmetry and isospin determined by circular dichroism in angle-resolved photoemission spectroscopy.

The Dirac-like electronic structure of graphene originates from the equivalence of the two basis atoms in the honeycomb lattice. We show that the characteristic parameters of the initial state wave function (sublattice symmetry and isospin) can be determined using angle-resolved photoemission spectroscopy (ARPES) with circularly polarized synchrotron radiation. At a photon energy of hν = 52 eV, transition matrix element effects can be neglected allowing us to determine sublattice symmetry and isospin with high accuracy using a simple theoretical model.

Electric control of spin transitions at the atomic scale.

Electric control of spins has been a longstanding goal in the field of solid state physics due to the potential for increased efficiency in information processing. This efficiency can be optimized by transferring spintronics to the atomic scale. We present electric control of spin resonance transitions in single TiH molecules by employing electron spin resonance scanning tunneling microscopy (ESR-STM). We find strong bias voltage dependent shifts in the ESR signal of about ten times its line width. We attribute this to the electric field in the tunnel junction, which induces a displacement of the spin system changing the g-factor and the effective magnetic field of the tip. We demonstrate direct electric control of the spin transitions in coupled TiH dimers. Our findings open up new avenues for fast coherent control of coupled spin systems and expands on the understanding of spin electric coupling.

Microwave excitation of atomic scale superconducting bound states.

Magnetic impurities on superconductors lead to bound states within the superconducting gap, so called Yu-Shiba-Rusinov (YSR) states. They are parity protected, which enhances their lifetime, but makes it more difficult to excite them. Here, we realize the excitation of YSR states by microwaves facilitated by the tunnel coupling to another superconducting electrode in a scanning tunneling microscope (STM). We identify the excitation process through a family of anomalous microwave-assisted tunneling peaks originating from a second-order resonant Andreev process, in which the microwave excites the YSR state triggering a tunneling event transferring a total of two charges. We vary the amplitude and the frequency of the microwave to identify the energy threshold and the evolution of this excitation process. Our work sets an experimental basis and proof-of-principle for the manipulation of YSR states using microwaves with an outlook towards YSR qubits.

Combining electron spin resonance spectroscopy with scanning tunneling microscopy at high magnetic fields.

The continuous increase in storage densities and the desire for quantum memories and computers push the limits of magnetic characterization techniques. Ultimately, a tool that is capable of coherently manipulating and detecting individual quantum spins is needed. Scanning tunneling microscopy (STM) is the only technique that unites the prerequisites of high spatial and energy resolution, low temperature, and high magnetic fields to achieve this goal. Limitations in the available frequency range for electron spin resonance STM (ESR-STM) mean that many instruments operate in the thermal noise regime. We resolve challenges in signal delivery to extend the operational frequency range of ESR-STM by more than a factor of two and up to 100 GHz, making the Zeeman energy the dominant energy scale at achievable cryogenic temperatures of a few hundred millikelvin. We present a general method for augmenting existing instruments into ESR-STM to investigate spin dynamics in the high-field limit. We demonstrate the performance of the instrument by analyzing inelastic tunneling in a junction driven by a microwave signal and provide proof of principle measurements for ESR-STM.

Reactive chemical doping of the Bi2Se3 topological insulator.

Using angular resolved photoemission spectroscopy we studied the evolution of the surface electronic structure of the topological insulator Bi(2)Se(3) as a function of water vapor exposure. We find that a surface reaction with water induces a band bending, which shifts the Dirac point deep into the occupied states and creates quantum well states with a strong Rashba-type splitting. The surface is thus not chemically inert, but the topological state remains protected. The band bending is traced back to Se abstraction, leaving positively charged vacancies at the surface. Because of the presence of water vapor, a similar effect takes place when Bi(2)Se(3) crystals are left in vacuum or cleaved in air, which likely explains the aging effect observed in the Bi(2)Se(3) band structure.

Band Engineering of Dirac Semimetals Using Charge Density Waves.

New developments in the field of topological matter are often driven by materials discovery, including novel topological insulators, Dirac semimetals, and Weyl semimetals. In the last few years, large efforts have been made to classify all known inorganic materials with respect to their topology. Unfortunately, a large number of topological materials suffer from non-ideal band structures. For example, topological bands are frequently convoluted with trivial ones, and band structure features of interest can appear far below the Fermi level. This leaves just a handful of materials that are intensively studied. Finding strategies to design new topological materials is a solution. Here, a new mechanism is introduced, which is based on charge density waves and non-symmorphic symmetry, to design an idealized Dirac semimetal. It is then shown experimentally that the antiferromagnetic compound GdSb0.46 Te1.48 is a nearly ideal Dirac semimetal based on the proposed mechanism, meaning that most interfering bands at the Fermi level are suppressed. Its highly unusual transport behavior points to a thus far unknown regime, in which Dirac carriers with Fermi energy very close to the node seem to gradually localize in the presence of lattice and magnetic disorder.

High mobility in a van der Waals layered antiferromagnetic metal.

Van der Waals (vdW) materials with magnetic order have been heavily pursued for fundamental physics as well as for device design. Despite the rapid advances, so far, they are mainly insulating or semiconducting, and none of them has a high electronic mobility-a property that is rare in layered vdW materials in general. The realization of a high-mobility vdW material that also exhibits magnetic order would open the possibility for novel magnetic twistronic or spintronic devices. Here, we report very high carrier mobility in the layered vdW antiferromagnet GdTe3. The electron mobility is beyond 60,000 cm2 V-1 s-1, which is the highest among all known layered magnetic materials, to the best of our knowledge. Among all known vdW materials, the mobility of bulk GdTe3 is comparable to that of black phosphorus. By mechanical exfoliation, we further demonstrate that GdTe3 can be exfoliated to ultrathin flakes of three monolayers.

Single-Crystal Growth and Characterization of the Chalcopyrite Semiconductor CuInTe2 for Photoelectrochemical Solar Fuel Production.

Transition-metal chalcogenides are a promising family of materials for applications as photocathodes in photoelectrochemical (PEC) H2 generation. A long-standing challenge for chalcopyrite semiconductors is characterizing their electronic structure, both experimentally and theoretically, because of their relatively high-energy band gaps and spin-orbit coupling (SOC), respectively. In this work, we present single crystals of CuInTe2, whose relatively small optically measured band gap of 0.9 ± 0.03 eV enables electronic structure characterization by angle-resolved photoelectron spectroscopy (ARPES) in conjunction with first-principles calculations incorporating SOC. ARPES measurements reveal bands that are steeply dispersed in energy with a band velocity of 2.5-5.4 × 105 m/s, almost 50% of the extremely conductive material graphene. Additionally, CuInTe2 single crystals are fabricated into electrodes to experimentally determine the valence band edge energy and confirm the thermodynamic suitability of CuInTe2 for water redox chemistry. The electronic structure characterization and band edge position presented in this work provide kinetic and thermodynamic factors that support CuInTe2 as a strong candidate for water reduction.

Tunable Weyl and Dirac states in the nonsymmorphic compound CeSbTe.

Recent interest in topological semimetals has led to the proposal of many new topological phases that can be realized in real materials. Next to Dirac and Weyl systems, these include more exotic phases based on manifold band degeneracies in the bulk electronic structure. The exotic states in topological semimetals are usually protected by some sort of crystal symmetry, and the introduction of magnetic order can influence these states by breaking time-reversal symmetry. We show that we can realize a rich variety of different topological semimetal states in a single material, CeSbTe. This compound can exhibit different types of magnetic order that can be accessed easily by applying a small field. Therefore, it allows for tuning the electronic structure and can drive it through a manifold of topologically distinct phases, such as the first nonsymmorphic magnetic topological phase with an eightfold band crossing at a high-symmetry point. Our experimental results are backed by a full magnetic group theory analysis and ab initio calculations. This discovery introduces a realistic and promising platform for studying the interplay of magnetism and topology. We also show that we can generally expand the numbers of space groups that allow for high-order band degeneracies by introducing antiferromagnetic order.

An ultrahigh-vacuum cryostat for simultaneous scanning tunneling microscopy and magneto-transport measurements down to 400 mK.

We present the design and calibration measurements of a scanning tunneling microscope setup in a 3He ultrahigh-vacuum cryostat operating at 400 mK with a hold time of 10 days. With 2.70 m in height and 4.70 m free space needed for assembly, the cryostat fits in a one-story lab building. The microscope features optical access, an xy table, in situ tip and sample exchange, and enough contacts to facilitate atomic force microscopy in tuning fork operation and simultaneous magneto-transport measurements on the sample. Hence, it enables scanning tunneling spectroscopy on microstructured samples which are tuned into preselected transport regimes. A superconducting magnet provides a perpendicular field of up to 14 T. The vertical noise of the scanning tunneling microscope amounts to 1 pmrms within a 700 Hz bandwidth. Tunneling spectroscopy using one superconducting electrode revealed an energy resolution of 120 µeV. Data on tip-sample Josephson contacts yield an even smaller feature size of 60 µeV, implying that the system operates close to the physical noise limit.

Sensing the quantum limit in scanning tunnelling spectroscopy.

The tunnelling current in scanning tunnelling spectroscopy (STS) is typically and often implicitly modelled by a continuous and homogeneous charge flow. If the charging energy of a single-charge quantum sufficiently exceeds the thermal energy, however, the granularity of the current becomes non-negligible. In this quantum limit, the capacitance of the tunnel junction mediates an interaction of the tunnelling electrons with the surrounding electromagnetic environment and becomes a source of noise itself, which cannot be neglected in STS. Using a scanning tunnelling microscope operating at 15 mK, we show that we operate in this quantum limit, which determines the ultimate energy resolution in STS. The P(E)-theory describes the probability for a tunnelling electron to exchange energy with the environment and can be regarded as the energy resolution function. We experimentally demonstrate this effect with a superconducting aluminium tip and a superconducting aluminium sample, where it is most pronounced.

Dirac cone protected by non-symmorphic symmetry and three-dimensional Dirac line node in ZrSiS.

Materials harbouring exotic quasiparticles, such as massless Dirac and Weyl fermions, have garnered much attention from physics and material science communities due to their exceptional physical properties such as ultra-high mobility and extremely large magnetoresistances. Here, we show that the highly stable, non-toxic and earth-abundant material, ZrSiS, has an electronic band structure that hosts several Dirac cones that form a Fermi surface with a diamond-shaped line of Dirac nodes. We also show that the square Si lattice in ZrSiS is an excellent template for realizing new types of two-dimensional Dirac cones recently predicted by Young and Kane. Finally, we find that the energy range of the linearly dispersed bands is as high as 2 eV above and below the Fermi level; much larger than of other known Dirac materials. This makes ZrSiS a very promising candidate to study Dirac electrons, as well as the properties of lines of Dirac nodes.

A 10 mK scanning tunneling microscope operating in ultra high vacuum and high magnetic fields.

We present design and performance of a scanning tunneling microscope (STM) that operates at temperatures down to 10 mK providing ultimate energy resolution on the atomic scale. The STM is attached to a dilution refrigerator with direct access to an ultra high vacuum chamber allowing in situ sample preparation. High magnetic fields of up to 14 T perpendicular and up to 0.5 T parallel to the sample surface can be applied. Temperature sensors mounted directly at the tip and sample position verified the base temperature within a small error margin. Using a superconducting Al tip and a metallic Cu(111) sample, we determined an effective temperature of 38 ± 1 mK from the thermal broadening observed in the tunneling spectra. This results in an upper limit for the energy resolution of ΔE = 3.5 kBT = 11.4 ± 0.3 µeV. The stability between tip and sample is 4 pm at a temperature of 15 mK as demonstrated by topography measurements on a Cu(111) surface.

Miniature active damping stage for scanning probe applications in ultra high vacuum.

Scanning probe microscope (SPM) experiments demand a low vibration level to minimize the external influence on the measured signal. We present a miniature six-degree of freedom active damping stage based on a Gough-Stewart platform (hexapod) which is positioned in ultra high vacuum as close to the SPM as possible. In this way, vibrations originating from the experimental setup can be effectively reduced providing a quiet environment for the SPM. In addition, the hexapod provides a rigid reference point, which facilitates wiring as well as sample transfer. We outline the main working principle and show that for scanning tunneling microscopy (STM) measurements of a Si(111) 7 × 7 surface, the hexapod significantly improves the stability and quality of the topographic images.

Design criteria for scanning tunneling microscopes to reduce the response to external mechanical disturbances.

We present a simple one-dimensional model to find design criteria for a scanning tunneling microscope (STM) minimizing the response of the tip-sample distance to external mechanical disturbances. The underlying concept-achieving a response that is in phase and same amplitude-goes beyond the conventional approach to construct the STM as stiff as possible. It introduces optimization conditions relating the resonance frequencies of the different components to the STM assembly, which can be implemented accordingly during the STM design process. In this way an improvement in the response to external disturbances of several orders of magnitude can be achieved. Calculations for three typical STM designs are presented along with the corresponding optimization criteria. For one of the designs an improvement in performance has been experimentally verified. The results can also be extended to other scanning probe techniques.