Controlled Surface Modification to Revive Shallow NV- Centers.

Near-surface negatively charged nitrogen vacancy (NV) centers hold excellent promise for nanoscale magnetic imaging and quantum sensing. However, they often experience charge-state instabilities, leading to strongly reduced fluorescence and NV coherence time, which negatively impact magnetic imaging sensitivity. This occurs even more severely at 4 K and ultrahigh vacuum (UHV, p = 2 × 10-10 mbar). We demonstrate that in situ adsorption of H2O on the diamond surface allows the partial recovery of the shallow NV sensors. Combining these with band-bending calculations, we conclude that controlled surface treatments are essential for implementing NV-based quantum sensing protocols under cryogenic UHV conditions.

Landing Proteins on Graphene Trampoline Preserves Their Gas-Phase Folding on the Surface.

Molecule-surface collisions are known to initiate dynamics that lead to products inaccessible by thermal chemistry. These collision dynamics, however, have mostly been examined on bulk surfaces, leaving vast opportunities unexplored for molecular collisions on nanostructures, especially on those that exhibit mechanical properties radically different from those of their bulk counterparts. Probing energy-dependent dynamics on nanostructures, particularly for large molecules, has been challenging due to their fast time scales and high structural complexity. Here, by examining the dynamics of a protein impinging on a freestanding, single-atom-thick membrane, we discover molecule-on-trampoline dynamics that disperse the collision impact away from the incident protein within a few picoseconds. As a result, our experiments and ab initio calculations show that cytochrome c retains its gas-phase folded structure when it collides onto freestanding single-layer graphene at low energies (∼20 meV/atom). The molecule-on-trampoline dynamics, expected to be operative on many freestanding atomic membranes, enable reliable means to transfer gas-phase macromolecular structures onto freestanding surfaces for their single-molecule imaging, complementing many bioanalytical techniques.

In-situ atomic level observation of the strain response of graphene lattice.

Strain is inevitable in two-dimensional (2D) materials, regardless of whether the film is suspended or supported. However, the direct measurement of strain response at the atomic scale is challenging due to the difficulties of maintaining both flexibility and mechanical stability at low temperature under UHV conditions. In this work, we have implemented a compact nanoindentation system with a size of [Formula: see text] 160 mm[Formula: see text] [Formula: see text] 5.2 mm in a scanning tunneling microscope (STM) sample holder, which enables the reversible control of strain and gate electric field. A combination of gearbox and piezoelectric actuator allowed us to modulate the depth of the indentation continuously with nanometer precision. The 2D materials were transferred onto the polyimide film. Pd clamp was used to enhance the strain transfer from the polyimide from to the 2D layers. Using this unique technique, strain response of graphene lattice were observed at atomic precision. In the relaxed graphene, strain is induced mainly by local curvature. However, in the strained graphene with tented structure, the lattice parameters become more sensitive to the indentor height change and stretching strain is increased additionally. Moreover, the gate controllability is confirmed by measuring the dependence of the STM tip height on gate voltage.

Seeding and Emergence of Composite Skyrmions in a van der Waals Magnet.

Topological charge plays a significant role in a range of physical systems. In particular, observations of real-space topological objects in magnetic materials have been largely limited to skyrmions - states with a unitary topological charge. Recently, more exotic states with varying topology, such as antiskyrmions, merons, or bimerons and 3D states such as skyrmion strings, chiral bobbers, and hopfions, have been experimentally reported. Along these lines, the realization of states with higher-order topology has the potential to open new avenues of research in topological magnetism and its spintronic applications. Here, real-space imaging of such spin textures, including skyrmion, skyrmionium, skyrmion bag, and skyrmion sack states, observed in exfoliated flakes of the van der Waals magnet Fe3-x GeTe2 (FGT) is reported. These composite skyrmions may emerge from seeded, loop-like states condensed into the stripe domain structure, demonstrating the possibility to realize spin textures with arbitrary integer topological charge within exfoliated flakes of 2D magnets. The general nature of the formation mechanism motivates the search for composite skyrmion states in both well-known and new magnetic materials, which may yet reveal an even richer spectrum of higher-order topological objects.

Phase Reconstruction of Low-Energy Electron Holograms of Individual Proteins.

Low-energy electron holography (LEEH) is one of the few techniques capable of imaging large and complex three-dimensional molecules, such as proteins, on the single-molecule level at subnanometer resolution. During the imaging process, the structural information about the object is recorded both in the amplitude and in the phase of the hologram. In low-energy electron holography imaging of proteins, the object's amplitude distribution, which directly reveals molecular size and shape on the single-molecule level, can be retrieved via a one-step reconstruction process. However, such a one-step reconstruction routine cannot directly recover the phase information encoded in the hologram. In order to extract the full information about the imaged molecules, we thus implemented an iterative phase retrieval algorithm and applied it to experimentally acquired low-energy electron holograms, reconstructing the phase shift induced by the protein along with the amplitude data. We show that phase imaging can map the projected atomic density of the molecule given by the number of atoms in the electron path. This directly implies a correlation between reconstructed phase shift and projected mean inner potential of the molecule, and thus a sensitivity to local changes in potential, an interpretation that is further substantiated by the strong phase signatures induced by localized charges.

Single Skyrmion Generation via a Vertical Nanocontact in a 2D Magnet-Based Heterostructure.

Skyrmions have been well studied in chiral magnets and magnetic thin films due to their potential application in practical devices. Recently, monochiral skyrmions have been observed in two-dimensional van der Waals magnets. Their atomically flat surfaces and capability to be stacked into heterostructures offer new prospects for skyrmion applications. However, the controlled local nucleation of skyrmions within these materials has yet to be realized. Here, we utilize real-space X-ray microscopy to investigate a heterostructure composed of the 2D ferromagnet Fe3GeTe2 (FGT), an insulating hexagonal boron nitride layer, and a graphite top electrode. Upon a stepwise increase of the voltage applied between the graphite and FGT, a vertically conducting pathway can be formed. This nanocontact allows the tunable creation of individual skyrmions via single nanosecond pulses of low current density. Furthermore, time-resolved magnetic imaging highlights the stability of the nanocontact, while our micromagnetic simulations reproduce the observed skyrmion nucleation process.

Berry curvature-induced local spin polarisation in gated graphene/WTe2 heterostructures.

Experimental control of local spin-charge interconversion is of primary interest for spintronics. Van der Waals (vdW) heterostructures combining graphene with a strongly spin-orbit coupled two-dimensional (2D) material enable such functionality by design. Electric spin valve experiments have thus far provided global information on such devices, while leaving the local interplay between symmetry breaking, charge flow across the heterointerface and aspects of topology unexplored. Here, we probe the gate-tunable local spin polarisation in current-driven graphene/WTe2 heterostructures through magneto-optical Kerr microscopy. Even for a nominal in-plane transport, substantial out-of-plane spin accumulation is induced by a corresponding out-of-plane current flow. We present a theoretical model which fully explains the gate- and bias-dependent onset and spatial distribution of the intense Kerr signal as a result of a non-linear anomalous Hall effect in the heterostructure, which is enabled by its reduced point group symmetry. Our findings unravel the potential of 2D heterostructure engineering for harnessing topological phenomena for spintronics, and constitute an important step toward nanoscale, electrical spin control.

Ultrashort Pulse Excited Tip-Enhanced Raman Spectroscopy in Molecules.

Vibrational fingerprints of molecules and low-dimension materials can be traced with subnanometer resolution by performing Tip-enhanced Raman spectroscopy (TERS) in a scanning tunneling microscope (STM). Strong atomic-scale localization of light in the plasmonic nanocavity of the STM enables high spatial resolution in STM-TERS; however, the temporal resolution is so far limited. Here, we demonstrate stable TERS measurements from subphthalocyanine (SubPc) molecules excited by ∼500 fs long laser pulses in a low-temperature (LT) ultrahigh-vacuum (UHV) STM. The intensity of the TERS signal excited with ultrashort pulses scales linearly with the increasing flux of the laser pulses and exponentially with the decreasing gap-size of the plasmonic nanocavity. Furthermore, we compare the characteristic features of TERS excited with ultrashort pulses and with a continuous-wave (CW) laser. Our work lays the foundation for future experiments of time-resolved femtosecond TERS for the investigation of molecular dynamics with utmost spatial, temporal, and energy resolutions simultaneously.

Anionic character of the conduction band of sodium chloride.

The alkali halides are ionic compounds. Each alkali atom donates an electron to a halogen atom, leading to ions with full shells. The valence band is mainly located on halogen atoms, while, in a traditional picture, the conduction band is mainly located on alkali atoms. Scanning tunnelling microscopy of NaCl at 4 K actually shows that the conduction band is located on Cl- because the strong Madelung potential reverses the order of the Na+ 3s and Cl- 4s levels. We verify this reversal is true for both atomically thin and bulk NaCl, and discuss implications for II-VI and I-VII compounds.

Synthesis of High-Performance Monolayer Molybdenum Disulfide at Low Temperature.

The large-area synthesis of high-quality MoS2 plays an important role in realizing industrial applications of optoelectronics, nanoelectronics, and flexible devices. However, current techniques for chemical vapor deposition (CVD)-grown MoS2 require a high synthetic temperature and a transfer process, which limits its utilization in device fabrications. Here, the direct synthesis of high-quality monolayer MoS2 with the domain size up to 120 µm by metal-organic CVD (MOCVD) at a temperature of 320 °C is reported. Owing to the low-substrate temperature, the MOCVD-grown MoS2 exhibits low impurity doping and nearly unstrained properties on the growth substrate, demonstrating enhanced electronic performance with high electron mobility of 68.3 cm2 V-1 s-1 at room temperature. In addition, by tuning the precursor ratio, a better understanding of the MoS2 growth process via a geometric model of the MoS2 flake shape, is developed, which can provide further guidance for the synthesis of 2D materials.

Low-energy electron holography imaging of conformational variability of single-antibody molecules from electrospray ion beam deposition.

Imaging of proteins at the single-molecule level can reveal conformational variability, which is essential for the understanding of biomolecules. To this end, a biologically relevant state of the sample must be retained during both sample preparation and imaging. Native electrospray ionization (ESI) can transfer even the largest protein complexes into the gas phase while preserving their stoichiometry and overall shape. High-resolution imaging of protein structures following native ESI is thus of fundamental interest for establishing the relation between gas phase and solution structure. Taking advantage of low-energy electron holography's (LEEH) unique capability of imaging individual proteins with subnanometer resolution, we investigate the conformational flexibility of Herceptin, a monoclonal IgG antibody, deposited by native electrospray mass-selected ion beam deposition (ES-IBD) on graphene. Images reconstructed from holograms reveal a large variety of conformers. Some of these conformations can be mapped to the crystallographic structure of IgG, while others suggest that a compact, gas-phase-related conformation, adopted by the molecules during ES-IBD, is retained. We can steer the ratio of those two types of conformations by changing the landing energy of the protein on the single-layer graphene surface. Overall, we show that LEEH can elucidate the conformational heterogeneity of inherently flexible proteins, exemplified here by IgG antibodies, and thereby distinguish gas-phase collapse from rearrangement on surfaces.

Ultrafast Photon-Induced Tunneling Microscopy.

Unification of the techniques of ultrafast science and scanning tunneling microscopy (STM) has the potential of tracking electronic motion in molecules simultaneously in real space and real time. Laser pulses can couple to an STM junction either in the weak-field or in the strong-field interaction regime. The strong-field regime entails significant modification (dressing) of the tunneling barrier of the STM junction, whereas the weak-field or the photon-driven regime entails perturbative interaction. Here, we describe how photons carried in an ultrashort pulse interact with an STM junction, defining the basic fundamental framework of ultrafast photon-induced tunneling microscopy. Selective dipole coupling of electronic states by photons is shown to be controllable by adjusting the DC bias at the STM junction. An ultrafast tunneling microscopy involving photons is established. Consolidation of the technique calls for innovative approaches to detect photon-induced tunneling currents at the STM junction. We introduce and characterize here three techniques involving dispersion, polarization, and frequency modulation of the laser pulses to lock-in detect the laser-induced tunneling current. We show that photon-induced tunneling currents can simultaneously achieve angstrom scale spatial resolution and sub-femtosecond temporal resolution. Ultrafast photon-induced tunneling microscopy will be able to directly probe electron dynamics in complex molecular systems, without the need of reconstruction techniques.

Atomic-Scale Structural Fluctuations of a Plasmonic Cavity.

Optical spectromicroscopies, which can reach atomic resolution due to plasmonic enhancement, are perturbed by spontaneous intensity modifications. Here, we study such fluctuations in plasmonic electroluminescence at the single-atom limit profiting from the precision of a low-temperature scanning tunneling microscope. First, we investigate the influence of a controlled single-atom transfer from the tip to the sample on the plasmonic properties of the junction. Next, we form a well-defined atomic contact of several quanta of conductance. In contact, we observe changes of the electroluminescence intensity that can be assigned to spontaneous modifications of electronic conductance, plasmonic excitation, and optical antenna properties all originating from minute atomic rearrangements at or near the contact. Our observations are relevant for the understanding of processes leading to spontaneous intensity variations in plasmon-enhanced atomic-scale spectroscopies such as intensity blinking in picocavities.

Local stiffness and work function variations of hexagonal boron nitride on Cu(111).

Combined scanning tunnelling and atomic force microscopy using a qPlus sensor enables the measurement of electronic and mechanic properties of two-dimensional materials at the nanoscale. In this work, we study hexagonal boron nitride (h-BN), an atomically thin 2D layer, that is van der Waals-coupled to a Cu(111) surface. The system is of interest as a decoupling layer for functional 2D heterostructures due to the preservation of the h-BN bandgap and as a template for atomic and molecular adsorbates owing to its local electronic trapping potential due to the in-plane electric field. We obtain work function (Φ) variations on the h-BN/Cu(111) superstructure of the order of 100 meV using two independent methods, namely the shift of field emission resonances and the contact potential difference measured by Kelvin probe force microscopy. Using 3D force profiles of the same area we determine the relative stiffness of the Moiré region allowing us to analyse both electronic and mechanical properties of the 2D layer simultaneously. We obtain a sheet stiffness of 9.4 ± 0.9 N·m-1, which is one order of magnitude higher than the one obtained for h-BN/Rh(111). Using constant force maps we are able to derive height profiles of h-BN/Cu(111) showing that the system has a corrugation of 0.6 ± 0.2 Å, which helps to demystify the discussion around the flatness of the h-BN/Cu(111) substrate.

Identifying the origin of local flexibility in a carbohydrate polymer.

Correlating the structures and properties of a polymer to its monomer sequence is key to understanding how its higher hierarchy structures are formed and how its macroscopic material properties emerge. Carbohydrate polymers, such as cellulose and chitin, are the most abundant materials found in nature whose structures and properties have been characterized only at the submicrometer level. Here, by imaging single-cellulose chains at the nanoscale, we determine the structure and local flexibility of cellulose as a function of its sequence (primary structure) and conformation (secondary structure). Changing the primary structure by chemical substitutions and geometrical variations in the secondary structure allow the chain flexibility to be engineered at the single-linkage level. Tuning local flexibility opens opportunities for the bottom-up design of carbohydrate materials.

Gigahertz Frame Rate Imaging of Charge-Injection Dynamics in a Molecular Light Source.

Light sources on the scale of single molecules can be addressed and characterized at their proper sub-nanometer scale by scanning tunneling microscopy-induced luminescence (STML). Such a source can be driven by defined short charge pulses while the luminescence is detected with sub-nanosecond resolution. We introduce an approach to concurrently image the molecular emitter, which is based on an individual defect, with its local environment along with its luminescence dynamics at a resolution of a billion frames per second. The observed dynamics can be assigned to the single electron capture occurring in the low-nanosecond regime. While the emitter's location on the surface remains fixed, the scanning of the tip modifies the energy landscape for charge injection into the defect. The principle of measurement is extendable to fundamental processes beyond charge transfer, like exciton diffusion.

Fast Molecular Compression by a Hyperthermal Collision Gives Bond-Selective Mechanochemistry.

Using electrospray ion beam deposition, we collide the complex molecule Reichardt's dye (C_{41}H_{30}NO^{+}) at low, hyperthermal translational energy (2-50 eV) with a Cu(100) surface and image the outcome at single-molecule level by scanning tunneling microscopy. We observe bond-selective reaction induced by the translational kinetic energy. The collision impulse compresses the molecule and bends specific bonds, prompting them to react selectively. This dynamics drives the system to seek thermally inaccessible reactive pathways, since the compression timescale (subpicosecond) is much shorter than the thermalization timescale (nanosecond), thereby yielding reaction products that are unobtainable thermally.

Catalyzing Bond-Dissociation in Graphene via Alkali-Iodide Molecules.

Atomic design of a 2D-material such as graphene can be substantially influenced by etching, deliberately induced in a transmission electron microscope. It is achieved primarily by overcoming the threshold energy for defect formation by controlling the kinetic energy and current density of the fast electrons. Recent studies have demonstrated that the presence of certain species of atoms can catalyze atomic bond dissociation processes under the electron beam by reducing their threshold energy. Most of the reported catalytic atom species are single atoms, which have strong interaction with single-layer graphene (SLG). Yet, no such behavior has been reported for molecular species. This work shows by experimentally comparing the interaction of alkali and halide species separately and conjointly with SLG, that in the presence of electron irradiation, etching of SLG is drastically enhanced by the simultaneous presence of alkali and iodine atoms. Density functional theory and first principles molecular dynamics calculations reveal that due to charge-transfer phenomena the CC bonds weaken close to the alkali-iodide species, which increases the carbon displacement cross-section. This study ascribes pronounced etching activity observed in SLG to the catalytic behavior of the alkali-iodide species in the presence of electron irradiation.

Readout and control of an endofullerene electronic spin.

Atomic spins for quantum technologies need to be individually addressed and positioned with nanoscale precision. C60 fullerene cages offer a robust packaging for atomic spins, while allowing in-situ physical positioning at the nanoscale. However, achieving single-spin level readout and control of endofullerenes has so far remained elusive. In this work, we demonstrate electron paramagnetic resonance on an encapsulated nitrogen spin (14N@C60) within a C60 matrix using a single near-surface nitrogen vacancy (NV) center in diamond at 4.7 K. Exploiting the strong magnetic dipolar interaction between the NV and endofullerene electronic spins, we demonstrate radio-frequency pulse controlled Rabi oscillations and measure spin-echos on an encapsulated spin. Modeling the results using second-order perturbation theory reveals an enhanced hyperfine interaction and zero-field splitting, possibly caused by surface adsorption on diamond. These results demonstrate the first step towards controlling single endofullerenes, and possibly building large-scale endofullerene quantum machines, which can be scaled using standard positioning or self-assembly methods.

Exploring the Molecular Conformation Space by Soft Molecule-Surface Collision.

Biomolecules function by adopting multiple conformations. Such dynamics are governed by the conformation landscape whose study requires characterization of the ground and excited conformation states. Here, the conformational landscape of a molecule is sampled by exciting an initial gas-phase molecular conformer into diverse conformation states, using soft molecule-surface collision (0.5-5.0 eV). The resulting ground and excited molecular conformations, adsorbed on the surface, are imaged at the single-molecule level. This technique permits the exploration of oligosaccharide conformations, until now, limited by the high flexibility of oligosaccharides and ensemble-averaged analytical methods. As a model for cellulose, cellohexaose chains are observed in two conformational extremes, the typical "extended" chain and the atypical "coiled" chain-the latter identified as the gas-phase conformer preserved on the surface. Observing conformations between these two extremes reveals the physical properties of cellohexaose, behaving as a rigid ribbon that becomes flexible when twisted. The conformation space of any molecule that can be electrosprayed can now be explored.