Scanning Tunneling Microscopy Images Research Articles

Distance and Potential Dependence of Charge Transport Through the Reaction Center of Individual Photosynthetic Complexes

AbstractCharge separation and transport through the reaction center of photosystem I (PSI) is an essential part of the photosynthetic electron transport chain. A strategy is developed to immobilize and orient PSI complexes on gold electrodes allowing to probe the complex's electron acceptor side, the chlorophyll special pair P700. Electrochemical scanning tunneling microscopy (ECSTM) imaging and current–distance spectroscopy of single protein complex shows lateral size in agreement with its known dimensions, and a PSI apparent height that depends on the probe potential revealing a gating effect in protein conductance. In current–distance spectroscopy, it is observed that the distance‐decay constant of the current between PSI and the ECSTM probe depends on the sample and probe electrode potentials. The longest charge exchange distance (lowest distance‐decay constant β) is observed at sample potential 0 mV/SSC (SSC: reference electrode silver/silver chloride) and probe potential 400 mV/SSC. These potentials correspond to hole injection into an electronic state that is available in the absence of illumination. It is proposed that a pair of tryptophan residues located at the interface between P700 and the solution and known to support the hydrophobic recognition of the PSI redox partner plastocyanin, may have an additional role as hole exchange mediator in charge transport through PSI.

Eliminating Edge Electronic and Phonon States of Phosphorene Nanoribbon by Unique Edge Reconstruction.

Edge termination plays a vital role in determining the properties of 2D materials. By performing compelling ab initio simulations, a lowest-energy U-edge [ZZ(U)] reconstruction is revealed in the bilayer phosphorene. Such reconstruction reduces 60% edge energy compared with the pristine one and occurs almost without an energy barrier, implying it should be the dominating edge in reality. The electronic band structure of phosphorene nanoribbon with such reconstruction resembles that of an intrinsic 2D layer, exhibiting nearly edgeless band characteristics. Although ZZ(U) changes the topology of phosphorene nanoribbons, simulated transmission electron microscope, scanning transmission electron microscope and scanning tunneling microscope images indicate it is very hard to be identified. One possible identified method is infrared/Raman analyses because the ZZ(U) edge alters vibrational modes dramatically. In addition, it also increases the thermal conductivity of PNR 1.4 and 2.3 times than the pristine and Klein edges.

Absence of in-gap modes in charge density wave edge dislocations of the Weyl semimetal (TaSe4)2I

Axion electrodynamics in condensed matter could emerge from the formation of charge density waves (CDWs) in Weyl semimetals. (TaSe$_4$)$_2$I was proposed to be the first material platform for realizing axionic CDW that may host topological defects with one-dimensional in-gap modes. The real-space modulation of the CDW phase and the existence of in-gap modes remain elusive. Here, we present a comprehensive scanning tunneling microscopic and spectroscopic study of a CDW on a (TaSe$_4$)$_2$I (110) surface. The tunneling spectroscopic measurements reveal a CDW gap of $\sim 200$ meV, in good agreement with prior studies, while the spectroscopy of CDW edge dislocation shows no indication of in-gap states. The bias-dependent scanning tunneling microscopy images indicate that the CDW in(TaSe$_4$)$_2$I is dominated by a large periodic lattice distortion instead of charge modulation, suggesting a non-Peierls mechanism of the CDW instability.

Simulation of STM Images of Hematite α-Fe2O3(0001) Surfaces: Dependence on Distance and Bias

Experimental scanning tunneling microscopy (STM) images of the hematite (0001) surface exhibit long-range superstructures formed by coexisting domains consisting of different terminations (α, β, γ) of the α-Fe2O3(0001) surface. In this work extensive simulations of STM images of different terminations of hematite (0001) surfaces are performed and compared with measured ones in order to identify the nature of the superstructure unit meshes. Based on DFT calculations of α-Fe2O3(0001) surfaces, the STM images are simulated using Chen’s derivative rules approach. Different bias voltages and tip–sample distances as well as the role of the tip type are considered and discussed. For some terminations an extreme dependence of the simulated image on the distance and bias voltage is found. The difference between simulations of metal and insulator/semiconductor surfaces is discussed. The condition of simultaneous agreement between simulation and experiment for all terminations within a narrow STM parameter range leads to the assignment of the α, β and γ terminations to the ferryl, Fe-Fe–O3– or Fe–O3–Fe–, and O3–Fe–Fe– terminations, respectively.

Excellent HER and OER Catalyzing Performance of Se‐Vacancies in Defects‐Engineered PtSe2: From Simulation to Experiment

AbstractFaced with grave climate change and enormous energy demands, effective catalysts have become more and more important due to their significant effects on reducing fossil fuels consumption. The hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) by water splitting are feasible ways to produce clean sustainable energy. Here, atomic structures and related scanning tunneling microscope images of Se defects in PtSe2 are systematically explored. The equilibrium fractions of vacancies under variable conditions are predicted in detail. In addition, it is found that the vacancies are highly kinetically stable, without recovering or aggregation. The Se vacancies in PtSe2 can dramatically enhance the HER performance, comparing to Pt(111). It is also revealed that a PtSe2 monolayer with Se vacancies is also a good OER catalyst. The excellent bipolar catalysis of Se vacancies is further confirmed by experimental measurements. A defective PtSe2 made via direct selenization of Pt foil at 773 K using a chemical vapor deposition process is produced. It is shown that the HER and OER performance of defective PtSe2 is much more efficient than Pt foils by a series of measurements. This work, with its compelling theoretical and experimental studies indicates PtSe2 with Se defects is an ideal bipolar candidate for HER and OER.

Experimental and theoretical investigation of the formation of two-dimensional Fe silicate on Pd(111)

A single layer of Fe silicate was grown on Pd(111) and analyzed experimentally and theoretically. Following sequential deposition of SiO and Fe and annealing above 900 K in O2, an incommensurate but well-ordered, low-defect density layer was observed with low-energy electron diffraction and scanning tunneling microscopy (STM). The STM images revealed a moiré pattern due to the lattice mismatch between the relaxed oxide layer and the substrate, while high-resolution images showed a honeycomb structure consistent with a silicate layer with six-membered rings of corner-sharing SiO4 tetrahedra at its surface. Reflection-absorption infrared spectroscopy revealed a single peak at 1050 cm−1 due to Si–O–Fe linkages, while x-ray photoelectron spectroscopy data indicated a Si/Fe ratio of one, that the Fe were all 3+, and that the Si atoms were closest to the surface. Consistent with these experimental observations, first principles theory identified a layer with an overall stoichiometry of Fe2Si2O9 with the six-membered rings of SiO4 tetrahedra at the surface. One of the oxygen atoms appears as a chemisorbed atom on the Pd surface, and, thus, the layer is better described as Fe2Si2O8 atop an oxygen-covered Pd surface. The Fe2Si2O8 is chemically bound to the Pd surface through its oxygen atoms; and the passivation of these bonds by hydrogen was investigated theoretically. Upon hydrogenation, the adsorbed O atom joins the Fe silicate layer and thermodynamic analysis indicates that, at room temperature and H2 pressures below 1 atm, Fe2Si2O9H4 becomes favored. The hydrogenation is accompanied by a substantial increase in the equilibrium distance between the oxide layer and the Pd surface and a drop in the adhesion energy to the surface. Together the results indicate that a highly ordered 2D Fe silicate can be grown on Pd(111) and that subsequent hydrogenation of this layer offers potential to release the 2D material from the growth substrate.

Distorted 3Q state driven by topological-chiral magnetic interactions

We demonstrate that topological-chiral magnetic interactions can play a key role for magnetic ground states in ultrathin films at surfaces. Based on density functional theory we show that significant chiral-chiral interactions occur in hexagonal Mn monolayers due to large topological orbital moments which interact with the emergent magnetic field. Due to the competition with higher-order exchange interactions superposition states of spin spirals such as the 2Q state or a distorted 3Q state arise. Simulations of spin-polarized scanning tunneling microscopy images suggest that the distorted 3Q state could be the magnetic ground state of a Mn monolayer on Re(0001).

Density Functional Theory Study of Ethylene Carbonate Adsorption on the (0001) Surface of Aluminum Oxide α-Al2O3.

Surface coating is one of the techniques used to improve the electrochemical performance and enhance the resistance against decomposition of cathode materials in lithium-ion batteries. Despite several experimental studies addressing the surface coating of secondary Li-ion batteries using α-Al2O3, the reactivity of the material toward the electrolyte components is not yet fully understood. Here, we have employed calculations based on the density functional theory to investigate the adsorption of the organic solvent ethylene carbonate (EC) on the major α-Al2O3(0001) surface. During adsorption of a single EC molecule, it was found that it prefers to bind parallel to the surface through its carboxyl oxygen. As the surface coverage (θ) was increased up to a monolayer, we observed larger adsorption energies per EC molecule (Eads/NEC) for parallel interactions and a reduction for perpendicular interactions. We also noted that increasing the surface coverage with both parallel and perpendicularly interacting EC molecules led to a decrease of the surface free energies and hence increased stability of the α-Al2O3(0001) surface. Despite the larger Eads/NEC observed when the molecule was placed parallel to the surface, minimal charge transfer was calculated for single EC interactions and at higher surface coverages. The simulated scanning tunneling microscopy images are also presented for a clean corundum α-Al2O3 surface and after adsorption with different coverages of parallel and perpendicularly placed EC molecules.

Point and complex defects in monolayer PdSe2 : Evolution of electronic structure and emergence of magnetism

Layered transition-metal dichalcogenides (TMDs) constitute an emerging class of materials that provide researchers a platform to realize fundamental studies and to design promising optoelectronic devices. While defects are an almost unavoidable part of TMDs, they bring additional interesting properties absent in defect-free layers. Moreover, the controlled introduction of defects in TMDs makes it possible to tailor the electromagnetic properties of the materials. Here we report defect-induced properties of single-layer $\mathrm{Pd}{\mathrm{Se}}_{2}$ and demonstrate the emergence of magnetism at the nanoscale. Our first-principle calculations indicate that Se vacancies create in-gap defect states, which can be responsible for trapping of carriers. The complex square ${V}_{\mathrm{Pd}+4\mathrm{Se}}$ vacancy induces spin-polarized states with a total local magnetic moment of $2\phantom{\rule{0.16em}{0ex}}{\ensuremath{\mu}}_{\mathrm{B}}$ per defect, making it possible to introduce magnetization into $\mathrm{Pd}{\mathrm{Se}}_{2}$ and therefore expand the family of two-dimensional (2D) magnets. The defect formation energies are much lower compared to many other TMD materials that can explain the presence of a large number of Se defects after mechanical exfoliation of $\mathrm{Pd}{\mathrm{Se}}_{2}$ layers, while the central location of the Pd atoms preserves them from exfoliation-induced defect formation. The negatively charged vacancies are prone to form and in many cases demonstrate spin-polarized states. The small diffusion barrier of ${\mathrm{V}}_{\mathrm{Se}}$ in 2D $\mathrm{Pd}{\mathrm{Se}}_{2}$ leads to an easy room-temperature migration, while ${\mathrm{V}}_{\mathrm{Pd}}$ demonstrates a high diffusion barrier preventing its spontaneous migration. As a guide for experimentalists, we simulate and characterize scanning tunneling microscope images in valence and conduction states and estimate the electron-beam energy for a controllable production of various defect patterns. These intriguing findings make $\mathrm{Pd}{\mathrm{Se}}_{2}$ an ideal platform to study defect-induced phenomena.

The effect of shape and size in the stability of triangular Janus MoSSe quantum dots

Asymmetric Janus transition metal dichalcogenide MoSSe is a promising catalytic material due to the intrinsic in-plane dipole of its opposite faces. The atomic description of the structures observed by experimental techniques is relevant to tuning and optimizing its surface reaction processes. Furthermore, the experimentally observed triangular morphologies in MoSSe suggest that an analysis of the chemical environment of its edges is vital to understand its reactivity. Here we analyze the size-shape stability among different triangular structures-quantum- dots proposed from the ideal S(-1010) and Mo(10-10) terminations. Our stability analysis evidenced that the S–Se termination is more stable than Mo; moreover, as the size of the quantum dot increases, its stability increases as well. Besides, a trend is observed, with the appearance of elongated Mo-S/Se bonds at symmetric positions of the edges. Tersoff–Hamann scanning tunneling microscopy images for both faces of the stablest models are presented. Electrostatic potential isosurfaces denote that the basal plane on the S face of both configurations remains the region with more electron density concentration. These results point toward the differentiated activity over both faces. Finally, our study denotes the exact atomic arrangement on the edges of MoSSe quantum dots corresponding with the formation of S/Se dimers who decorates the edges and their role along with the faces as catalytic sites.

Collaborative Low-Rank Matrix Approximation-Assisted Fast Hyperspectral Raman Imaging and Tip-Enhanced Raman Spectroscopic Imaging.

Fast acquisition of Raman images is essential for accurately characterizing the analytes' information. In this paper, we developed a collaborative low-rank matrix approximation method for fast hyperspectral Raman imaging as well as tip-enhanced Raman spectroscopy (TERS) imaging. This method combines high signal-to-noise ratio (SNR) data with the target data to perform collaborative singular value decomposition. The high-quality reference data can impose constraints on factorization, which will force its components to approximate the true signal or noise components. The simulation demonstrated that this method offers state-of-the-art signal extraction performance and, thus, can be used to accelerate data acquisition. Specifically, the results indicate that the CLRMA can largely decrease the root-mean-square error by 20.92-54.12% compared with the baseline method of our previous study. We then applied this method to the fast TERS imaging of a Au/Pd bimetallic surface and significantly decreased the integration time down to 0.1 s/pixel, which is about 10 times faster than that of conventional experiments. High-SNR TERS spectra and clear TERS images that are well consistent with scanning tunneling microscopy (STM) images can be obtained even under such a weak signal condition. We further applied this method to the fast Raman imaging of HeLa cells and obtained clear Raman images at a short integration time of 2 s/line, which is about 5 times faster than that of conventional experiments. This method offers a promising tool for TERS imaging as well as conventional Raman imaging where fast data acquisition is required.

Multiband charge density wave exposed in a transition metal dichalcogenide

In the presence of multiple bands, well-known electronic instabilities may acquire new complexity. While multiband superconductivity is the subject of extensive studies, the possibility of multiband charge density waves (CDWs) has been largely ignored so far. Here, combining energy dependent scanning tunnelling microscopy (STM) topography with a simple model of the charge modulations and a self-consistent calculation of the CDW gap, we find evidence for a multiband CDW in 2H-NbSe2. This CDW not only involves the opening of a gap on the inner band around the K-point, but also on the outer band. This leads to spatially out-of-phase charge modulations from electrons on these two bands, which we detect through a characteristic energy dependence of the CDW contrast in STM images.

Compressed sensing for scanning tunnel microscopy imaging of defects and disorder

Compressed sensing (CS) is a valuable technique for reconstructing measurements in numerous domains. CS has not yet gained widespread adoption in scanning tunneling microscopy (STM), despite potentially offering the advantages of lower acquisition time and enhanced tolerance to noise. Here we applied a simple CS framework, using a weighted iterative thresholding algorithm for CS reconstruction, to representative high-resolution STM images of superconducting surfaces and adsorbed molecules. We calculated reconstruction diagrams for a range of scanning patterns, sampling densities, and noise intensities, evaluating reconstruction quality for the whole image and chosen defects. Overall we find that typical STM images can be satisfactorily reconstructed down to 30\% sampling - already a strong improvement. We furthermore outline limitations of this method, such as sampling pattern artifacts, which become particularly pronounced for images with intrinsic long-range disorder, and propose ways to mitigate some of them. Finally we investigate compressibility of STM images as a measure of intrinsic noise in the image and a precursor to CS reconstruction, enabling a priori estimation of the effectiveness of CS reconstruction with minimal computational cost.

Substitutional Tin Acceptor States in Black Phosphorus

Nominally-pure black phosphorus (BP) is commonly found to be a p-type semiconductor, suggesting the ubiquitious presence of impurity species or intrinsic, charged defects. Moreover, scanning tunnelling microscopy (STM) images of black phosphorus reveal the presence of long-ranged double-lobed defect features superimposed onto the surface atomic lattice. We show that both the p-type doping of BP and the defect features observed in STM images can be attributed to substitutional tin impurities. We show that black phosphorus samples produced through two common synthesis pathways contain tin impurities, and we demonstrate that the ground state of substitutional tin impurities is negatively charged for a wide range of Fermi level positions within the BP bandgap. The localised negative charge of the tin impurities induces hydrogenic states in the bandgap and it is the 2p level that sits at the valence band edge that gives rise to the double-lobed features observed in STM images.

A time-shared switching scheme designed for multi-probe scanning tunneling microscope.

We report the designof a time-shared switching scheme, aiming to realize the manipulation and working modes (imaging mode and transport measurement mode) switching between multiple scanning tunneling microscope (STM) probes one by one with a shared STM control system (STM CS) and an electrical transport characterization system. This scheme comprises three types of switch units, switchable preamplifiers (SWPAs), high voltage amplifiers, and a main control unit. Together with the home-made software kit providing the graphical user interface, this scheme achieves a seamless switching process between different STM probes. Compared with the conventional scheme using multiple independent STM CSs, this scheme possesses more compatibility, flexibility, and expansibility for lower cost. The overall architecture and technique issues are discussed in detail. The performances of the system are demonstrated, including the millimeter scale moving range and atomic scale resolution of a single STM probe, safely approached multiple STM probes beyond the resolution of the optical microscope (1.1 µm), qualified STM imaging, and accurate electrical transport characterization. The combinational technique of imaging and transport characterization is also shown, which is supported by SWPA switches with ultra-high open circuit resistance (909TΩ). These successful experiments prove the effectiveness and the usefulness of the scheme. In addition, the scheme can be easily upgraded with more different functions and numbers of probe arrays, thus opening a new way to build an extremely integrated and high throughput characterization platform.

Single germanene phase formed by segregation through Al(111) thin films on Ge(111)

We have obtained single phase monolayer germanene on aluminum (111) thin films grown on a germanium (111) template by atomic segregation epitaxy, a preparation method differing from molecular beam epitaxy used in previous works. This 2 × 2 reconstructed germanene phase matching an Al(111)3 × 3 supercell has been prepared in large areas upon annealing at 430 °C. Detailed studies have been carried out using scanning tunneling microscopy (STM), low-energy electron diffraction, Auger electron spectroscopy, and synchrotron radiation photoemission spectroscopy. First-principles calculations based on the density function theory along with atomic-scale STM images reveal the atomic structure with one protruding Ge atom per 2 × 2 germanene supercell and a characteristic dispersing band originating from the germanene sheet slightly coupled to the first layer Al atoms underneath. Instead, upon annealing at lower temperatures, multi-phase regions comprise twisted germanene domains in correspondence with an Al(111)√7×√7 R ± 19.1° superstructure as obtained in previous studies.

Theoretical study of ethyl alcohol adsorbed on a germanium (100) surface

AbstractThe chemical reaction of ethyl alcohol on a germanium surface was investigated through density functional theory analysis. The most stable product containing the HOGeGeCH2CH3 linkage was formed via OC‐dissociative adsorption. Kinetic studies revealed that the OH‐dissociative reaction pathways have relatively low activation barriers and may, respectively, occur at room temperature. Configurationally, the oxygen atom of the ethoxy fragment was bonded to the germanium atom, and the ethyl group was oriented either perpendicular or parallel to the germanium surface. The two configurations had similar adsorption energies and activation barriers. Further reaction of the dissociated hydrogen with a nearby electron‐rich germanium atom passivated the dangling bond. Theoretical scanning tunneling microscopy images simulated based on the OH‐dissociative adsorption revealed a better agreement with the experimentally observed adsorption features than those of other possible structures.

Growth of ordered two-dimensional cobalt phthalocyanine films on a one-dimensional substrate

The growth of Co phthalocyanine (CoPc) films on the one-dimensional Si(111)(4 × 1)-In surface is studied using scanning tunneling microscopy (STM). At low CoPc coverages, the molecules are highly mobile on the surface. Only when the coverage approaches the saturation coverage, the molecules stabilize each other and a highly ordered two-dimensional CoPc monolayer forms. Based on the STM images, a structure model for this film could be developed, with the molecules selectively adsorbing on the In chains with a (4 × 4) periodicity.

Atomic and electronic structures of the Au2Sn surface alloy on Au(111)

Atomic and electronic structure investigations of the substitutional ${\mathrm{Au}}_{2}\mathrm{Sn}$ surface alloy formed on Au(111) are presented. Low energy electron diffraction and scanning tunneling microscopy (STM) reveal a structure with a local $\sqrt{3}\ifmmode\times\else\texttimes\fi{}\sqrt{3}$ periodicity with a superimposed modulation resulting in a $26\ifmmode\times\else\texttimes\fi{}\sqrt{3}$ unit cell. STM images show a striped structure that resembles the herringbone reconstruction of clean Au(111), but with a longer periodicity compared to the $22\ifmmode\times\else\texttimes\fi{}\sqrt{3}$ unit cell of clean Au(111). Angle-resolved photoelectron spectroscopy data along the high-symmetry lines $\overline{\mathrm{\ensuremath{\Gamma}}}\ensuremath{-}{\overline{K}}^{\ensuremath{'}}\ensuremath{-}{\overline{M}}^{\ensuremath{'}}$ and $\overline{\mathrm{\ensuremath{\Gamma}}}\ensuremath{-}{\overline{M}}^{\ensuremath{'}}\ensuremath{-}\phantom{\rule{4pt}{0ex}}{\overline{\mathrm{\ensuremath{\Gamma}}}}^{\ensuremath{'}}$ of a $\sqrt{3}\ifmmode\times\else\texttimes\fi{}\sqrt{3}$ surface Brillouin zone show two bands from the ${\mathrm{Au}}_{2}\mathrm{Sn}$ surface alloy layer. The experimental bands are compared to the calculated band structure of the local $\sqrt{3}\ifmmode\times\else\texttimes\fi{}\sqrt{3}$ periodicity. Most of the experimental band dispersions are qualitatively reproduced by the theoretical band structure including a spin split of one of the alloy bands. However, our detailed data reveal a band split, not present in the calculated bands of the $\sqrt{3}\ifmmode\times\else\texttimes\fi{}\sqrt{3}$ model, which is a consequence of the striped atomic structure of the ${\mathrm{Au}}_{2}\mathrm{Sn}$ surface alloy.

The scanning tunneling microscopy and spectroscopy of GaSb1– x Bi x films of a few-nanometer thickness grown by molecular beam epitaxy

The ultrahigh vacuum scanning tunneling microscope (STM) was used to characterize the GaSb1– x Bi x films of a few nanometers thickness grown by the molecular beam epitaxy (MBE) on the GaSb buffer layer of 100 nm with the GaSb (100) substrates. The thickness of the GaSb1– x Bi x layers of the samples are 5 and 10 nm, respectively. For comparison, the GaSb buffer was also characterized and its STM image displays terraces whose surfaces are basically atomically flat and their roughness is generally less than 1 monolayer (ML). The surface of 5 nm GaSb1– x Bi x film reserves the same terraced morphology as the buffer layer. In contrast, the morphology of the 10 nm GaSb1– x Bi x film changes to the mound-like island structures with a height of a few MLs. The result implies the growth mode transition from the two-dimensional mode as displayed by the 5 nm film to the Stranski–Krastinov mode as displayed by the 10 nm film. The statistical analysis with the scanning tunneling spectroscopy (STS) measurements indicates that both the incorporation and the inhomogeneity of Bi atoms increase with the thickness of the GaSb1– x Bi x layer.