Scanning Tunneling Spectra Research Articles

Inelastic electron tunneling spectroscopy for probing strongly correlated many-body systems by scanning tunneling microscopy

We present an extension of the tunneling theory for scanning tunneling microcopy (STM) to include different types of vibrational-electronic couplings responsible for inelastic contributions to the tunnel current in the strong-coupling limit. It allows for a better understanding of more complex scanning tunneling spectra of molecules on a metallic substrate in separating elastic and inelastic contributions. The starting point is the exact solution of the spectral functions for the electronic active local orbitals in the absence of the STM tip. This includes electron-phonon coupling in the coupled system comprising the molecule and the substrate to arbitrary order including the anti-adiabatic strong coupling regime as well as the Kondo effect on a free electron spin of the molecule. The tunneling current is derived in second order of the tunneling matrix element which is expanded in powers of the relevant vibrational displacements. We use the results of an ab-initio calculation for the single-particle electronic properties as an adapted material-specific input for a numerical renormalization group approach for accurately determining the electronic properties of a NTCDA molecule on Ag(111) as a challenging sample system for our theory. Our analysis shows that the mismatch between the ab-initio many-body calculation of the tunnel current in the absence of any electron-phonon coupling to the experiment scanning tunneling spectra can be resolved by including two mechanisms: (i) a strong unconventional Holstein term on the local substrate orbital leads to reduction of the Kondo temperature and (ii) a different electron-vibrational coupling to the tunneling matrix element is responsible for inelastic steps in the $dI/dV$ curve at finite frequencies.

Contrast Reversal in Scanning Tunneling Microscopy and Its Implications for the Topological Classification of SmB6.

SmB6 has recently attracted considerable interest as a candidate for the first strongly correlated topological insulator. Such materials promise entirely new properties such as correlation-enhanced bulk bandgaps or a Fermi surface from spin excitations. Whether SmB6 and its surface states are topological or trivial is still heavily disputed however, and a solution is hindered by major disagreement between angle-resolved photoemission (ARPES) and scanning tunneling microscopy (STM) results. Here, a combined ARPES and STM experiment is conducted. It is discovered that the STM contrast strongly depends on the bias voltage and reverses its sign beyond 1 V. It is shown that the understanding of this contrast reversal is the clue to resolving the discrepancy between ARPES and STM results. In particular, the scanning tunneling spectra reflect a low-energy electronic structure at the surface, which supports a trivial origin of the surface states and the surface metallicity of SmB6 .

Epitaxial growth and electronic properties of few-layer stanene on InSb (1 1 1)

Stanene has been theoretically predicted to be a 2D topological insulator with a large band gap, potentially hosting quantum spin Hall effect at room temperature. Here, few-layer stanene films have been epitaxially grown on Sb-terminated InSb (1 1 1) surface and their structural and electrical properties are characterized. Scanning tunneling spectrum results reveal a large bulk bandgap in single-layer stanene (over 0.2 eV). Moreover, spectroscopy evidence for a filled edge state near the steps was observed. The gap decreases dramatically with increasing number of layers, and multilayer stanene should become a Dirac semimetal in the bulk limit. The changeover may involve nontrivial topological phase transitions. Clear and reproducible Shubnikov–de Haas oscillations were observed on the single-layer stanene films that were exposed to atmospheric conditions for an extended period of time, showing the possibility for device experiments using nanofabrication and magneto-transport. Our results demonstrate that the single-layer stanene is a promising topological material for exploring fundamental physics and quantum applications.

Bidirectional multiple negative differential resistance (BM-NDR): An interplay between interface resistance and redox reaction

Abstract Bidirectional multiple negative differential resistance (BM-NDR) was observed from a single 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) molecule at room temperature when the device was studied by using density functional theory (DFT) in association with non-equilibrium Green's function (NEGF). The BM-NDR effect was also verified experimentally by studying the scanning tunneling spectra (STS) of single DDQ molecule. The carrier transport in the device occurs mainly through the transmission channel corresponding to the highest occupied molecular orbital (HOMO) of the molecule and a commensurate change in the magnitude of transmission peak was observed at the peak and valley voltages. The reason for the NDR is proposed to be due to the two competing factors involved namely, the reduction of the molecule and the interface resistance between the molecule and the electrodes. The involvement of both the factors is validated from the molecular projected self-consistent Hamiltonian (MPSH) and the local device density of states (LDDOS) of the device at the corresponding peak and valley voltages.

Local electronic structure of doping defects on Tl/Si(111)1x1

The Tl/Si(111)1 × 1 surface is a representative of a 2D layer with Rashba-type spin-split electronic bands. To utilize the spin polarization, doping of the system should be understood on atomic level. We present a study of two types of atomic defects predicted to dope the considered electronic system – Si-induced vacancies and defects associated with the presence of extra Tl atoms. Structural calculations based on density functional theory (DFT) confirm the stability of the proposed defect structure consisting of an extra Si atom and missing seven Tl atoms as proposed in an earlier experimental study. The calculated spatial charge distributions indicate an enhancement of the charge around the extra Si atom, which correctly reproduces topographies of the corresponding scanning tunneling microscopy images while the calculated local densities of states of this system explain obtained scanning tunneling spectra. The DFT structural calculations let us determine the atomic structure of the defect caused by the presence of an extra Tl atom. The calculated spatial charge distributions show a ring-like feature around the extra Tl atom. The obtained results indicate a charge transfer from the central extra Tl atom to its vicinity in the agreement with earlier photoemission measurements.

Modulating the Electronic Properties of Graphene by Self-Organized Sulfur Identical Nanoclusters and Atomic Superlattices Confined at an Interface.

Ordered atomic-scale superlattices on a surface hold great interest both for basic science and for potential applications in advanced technology. However, controlled fabrication of superlattices down to the atomic scale has proven exceptionally challenging. Here we develop a segregation method to realize self-organization of S superlattices at the interface of graphene and S-rich Cu substrates. Via scanning tunneling microscope measurements, we directly image well-ordered identical nanocluster superlattices and atomic superlattices under the cover of graphene. Scanning tunneling spectra show that the superlattices in turn could modulate the electronic structure of top-layer graphene. Importantly, a special-ordered S monatomic superlattice commensurate with a graphene lattice is found to drive semimetal graphene into a symmetry-broken phase-the electronic Kekulé distortion phase-which opens a bandgap of ∼245 meV.

Bandgap opening in hydrogenated germanene

We have studied the hydrogenation of germanene synthesized on Ge2Pt crystals using scanning tunneling microscopy and spectroscopy. The germanene honeycomb lattice is buckled and consists of two hexagonal sub-lattices that are slightly displaced with respect to each other. The hydrogen atoms adsorb exclusively on the Ge atoms of the upward buckled hexagonal sub-lattice. At a hydrogen exposure of about 100 L, the (1 × 1) buckled honeycomb structure of germanene converts to a (2 × 2) structure. Scanning tunneling spectra recorded on this (2 × 2) structure reveal the opening of a bandgap of about 0.2 eV. A fully (half) hydrogenated germanene surface is obtained after an exposure of about 9000 L hydrogen. The hydrogenated germanene, also referred to as germanane, has a sizeable bandgap of about 0.5 eV and is slightly n-type.

Modeling of the gate-controlled Kondo effect at carbon point defects in graphene

We study the magnetic properties in the vicinity of a single carbon defect in a monolayer of graphene. We include the unbound $\sigma$ orbital and the vacancy induced bound $\pi$ state in an effective two-orbital single impurity model. The local magnetic moments are stabilized by the Coulomb interaction as well as a significant ferromagnetic Hund's rule coupling between the orbitals predicted by a density functional theory calculation. A hybridization between the orbitals and the Dirac fermions is generated by the curvature of the graphene sheet in the vicinity of the vacancy. We present results for the local spectral function calculated using Wilson's numerical renormalization group approach for a realistic graphene band structure and find three different regimes depending on the filling, the controlling chemical potential, and the hybridization strength. These different regions are characterized by different magnetic properties. The calculated spectral functions qualitatively agree with recent scanning tunneling spectra on graphene vacancies.

Gallenene epitaxially grown on Si(1 1 1)

Gallenene, an analogue of graphene composed of gallium, is epitaxially grown on Si(1 1 1) surface and studied by low temperature scanning tunneling microscopy (LT-STM). The STM images display that the buffer layer has a superstructure with respect to the substrate lattice and the gallenene layer has a hexagonal honeycomb structure. The scanning tunneling spectra (STS) of the gallenene show that it behaves as a metallic layer. First-principles calculations give the proposed configuration. Our results provide a method to synthesize the gallenene and shed important light on the growth mechanism of it.

Fingerprints of a position-dependent Fermi velocity on scanning tunnelling spectra of strained graphene

Nonuniform strain in graphene induces a position dependence of the Fermi velocity, as recently demonstrated by scanning tunnelling spectroscopy experiments. In this work, we study the effects of a position-dependent Fermi velocity on the local density of states (LDOS) of strained graphene, with and without the presence of a uniform magnetic field. The variation of LDOS obtained from tight-binding calculations is successfully explained by analytical expressions derived within the Dirac approach. These expressions also rectify a rough Fermi velocity substitution used in the literature that neglects the strain-induced anisotropy. The reported analytical results could be useful for understanding the nonuniform strain effects on scanning tunnelling spectra of graphene, as well as when it is exposed to an external magnetic field.

Shell Thickness-Dependent Tunable Threshold Voltage Single Quantum Dot Rectification Diode

Ambient atmosphere single colloidal quantum dot (QD) rectifying diode with tunable threshold voltage has been fabricated by using a type-II heterojunction core/shell structure with a device geometry ITO/ZnO/QDs. Specifically, in our work we have used ZnTe/CdS core/shell QDs in which hole wave function strongly confined to the core, whereas the lowest-lying conduction band state resides in the shell. Current–voltage (I–V) characterization of this device has been done using an ambient atmosphere scanning tunneling microscope. The scanning tunneling spectra (STS) shows high rectification with a ratio of 103. The rectification is found to arise because of the bias-dependent band alignment of ZnO/QDs heterojunction and the effect of shell of each QD that presents a barrier for hole tunneling into the substrate. This barrier is overcome by the externally applied bias. This mechanism is distinct from the rectification observed in conventional p–n junction diodes. In particular, we find that even for QDs with opt...

Ligand-Induced Energy Shift and Localization of Kondo Resonances in Cobalt-Based Complexes on Cu(111).

Magnetic sandwich complexes are of particular interest for molecular spintronics. Using scanning tunneling microscopy, we evidence the successful deposition of 1,3,5-tris(η6-borabenzene-η5-cyclopentadienylcobalt) benzene, a molecule composed of three connected magnetic sandwich units, on Cu(111). Scanning tunneling spectra reveal two distinct spatial-dependent narrow resonances close to the Fermi level for the trimer molecules as well as for molecular fragments composed of one and two magnetic units. With the help of density functional theory, these resonances are interpreted as two Kondo resonances originating from two distinct nondegenerate d-like orbitals. These Kondo resonances are found to have defined spatial extents dictated by the hybridization of the involved orbitals with that of the ligands. These results opens promising perspectives for investigating complex Kondo systems composed of several "Kondo" orbitals.

Molecular Beam Epitaxy Growth of Tetragonal FeS Films on SrTiO3 (001) Substrates**Supported by the National Natural Science Foundation of China, the Ministry of Science and Technology of China, and the Specialized Research Fund for the Doctoral Program of Higher Education under Grant No 20130002120033.

We report the successful growth of the tetragonal FeS film with one or two unit-cell (UC) thickness on SrTiO3(001) substrates by molecular beam epitaxy. Large lattice constant mismatch with the substrate leads to high density of defects in single-UC FeS, while it has been significantly reduced in the double-UC thick film due to the lattice relaxation. The scanning tunneling spectra on the surface of the FeS thin film reveal the electronic doping effect of single-UC FeS from the substrate. In addition, at the Fermi level, the energy gaps of approximately 1.5 meV are observed in the films of both thicknesses at 4.6 K and below. The absence of coherence peaks of gap spectra may be related to the preformed Cooper-pairs without phase coherence.

Indium coverage of the Si(111)- 7×3 -In surface

The indium coverage of the Si(111)-$\sqrt{7}\ifmmode\times\else\texttimes\fi{}\sqrt{3}$-In surface is investigated by means of x-ray photoelectron spectroscopy and first-principles density functional theory calculations. Both experimental and theoretical results indicate that the In coverage is a double layer rather than a single layer. Moreover, the atomic structure of the Si(111)-$\sqrt{7}\ifmmode\times\else\texttimes\fi{}\sqrt{3}$-In surface is discussed by comparing experimental with simulated scanning tunneling microscopy (STM) images and scanning tunneling spectra with the calculated density of states. Our structural assignment agrees with previous studies, except for the interpretation of experimental STM images.

Towards a quantitative description of tunneling conductance of superconductors: Application to LiFeAs

Since the discovery of iron-based superconductors, a number of theories have been put forward to explain the qualitative origin of pairing, but there have been few attempts to make quantitative, material-specific comparisons to experimental results. The spin-fluctuation theory of electronic pairing, based on first-principles electronic structure calculations, makes predictions for the superconducting gap. Within the same framework, the surface wave functions may also be calculated, allowing, e.g., for detailed comparisons between theoretical results and measured scanning tunneling topographs and spectra. Here we present such a comparison between theory and experiment on the Fe-based superconductor LiFeAs. Results for the homogeneous surface as well as impurity states are presented as a benchmark test of the theory. For the homogeneous system, we argue that the maxima of topographic image intensity may be located at positions above either the As or Li atoms, depending on tip height and the setpoint current of the measurement. We further report the experimental observation of transitions between As and Li-registered lattices as functions of both tip height and setpoint bias, in agreement with this prediction. Next, we give a detailed comparison between the simulated scanning tunneling microscopy images of transition-metal defects with experiment. Finally, we discuss possible extensions of the current framework to obtain a theory with true predictive power for scanning tunneling microscopy in Fe-based systems.

Electronic Structure and Band Gap of Fullerenes on Tungsten Surfaces: Transition from a Semiconductor to a Metal Triggered by Annealing.

The understanding and control of molecule-metal interfaces is critical to the performance of molecular electronics and photovoltaics devices. We present a study of the interface between C60 and W, which is a carbide-forming transition metal. The complex solid-state reaction at the interface can be exploited to adjust the electronic properties of the molecule layer. Scanning tunneling microscopy/spectroscopy measurements demonstrate the progression of this reaction from wide band gap (>2.5 eV) to metallic molecular surface during annealing from 300 to 800 K. Differential conduction maps with 104 scanning tunneling spectra are used to quantify the transition in the density of states and the reduction of the band gap during annealing with nanometer spatial resolution. The electronic transition is spatially homogeneous, and the surface band gap can therefore be adjusted by a targeted annealing step. The modified molecules, which we call nanospheres, are quite resistant to ripening and coalescence, unlike any other metallic nanoparticle of the same size. Densely packed C60 and isolated C60 molecules show the same transition in electronic structure, which confirms that the transformation is controlled by the reaction at the C60-W interface. Density functional theory calculations are used to develop possible reaction pathways in agreement with experimentally observed electronic structure modulation. Control of the band gap by the choice of annealing temperature is a unique route to tailoring molecular-layer electronic properties.

Possible superconducting fluctuation and pseudogap state aboveTcinCsFe2As2

Resistive, magnetization, torque, specific heat and scanning tunneling microscopy measurements are carried out on the hole heavily doped CsFe$_2$As$_2$ single crystals. A characteristic temperature $T^*\sim13$ K, which is several times higher than the superconducting transition temperature $T_c=2.15$ K, is observed and possibly related to the superconducting fluctuation or the pseudogap state. A diamagnetic signal detected by torque measurements starts from the superconducting state, keeps finite and vanishes gradually until a temperature near $T^*$. Temperature dependent resistivity and specific heat also show kinks near $T^*$. An asymmetric gap-like feature with the energy of 8.4 meV and a symmetric superconducting related gap of 2.2 meV on the scanning tunneling spectra are detected, and these pseudogap-related features disappear at temperatures up to at least 9 K. These observations by different experimental tools suggest the possible existence of superconducting fluctuation or pseudogap state in the temperature range up to 4 - 6 times of $T_c$ in CsFe$_2$As$_2$.

Importance of quantum correction for the quantitative simulation of photoexcited scanning tunneling spectra of semiconductor surfaces

Photoexcited scanning tunneling spectroscopy is a promising technique for the determination of carrier concentrations, surface photovoltages, and potentials of semiconductors with atomic spatial resolution. However, extraction of the desired quantities requires computation of the electrostatic potential induced by the proximity of the tip and the tunnel current. This calculation is based on an accurate solution of the Poisson as well as the continuity equations for the tip-vacuum-semiconductor system. For this purpose, the carrier current densities are modeled by classical drift and diffusion equations. However, for small tip radii and highly doped materials, the drift and diffusion transport model significantly overestimates a semiconductor's carrier concentration near the surface, making the quantification of physical properties impossible. In this paper, we apply quantum correction to the drift and diffusion model, in order to account for the so-called quantum compressibility, i.e., reduced compressibility of the carrier gas due to the Pauli principle, in the region of the tip-induced band bending. We compare carrier concentrations, potentials, and tunnel currents derived with and without quantum correction for $\mathrm{GaN}(10\overline{1}0)$ and GaAs(110) surfaces to demonstrate its necessity.

Scanning Tunneling Microscopy and Spectroscopy of Air Exposure Effects on Molecular Beam Epitaxy Grown WSe2 Monolayers and Bilayers.

The effect of air exposure on 2H-WSe2/HOPG is determined via scanning tunneling microscopy (STM). WSe2 was grown by molecular beam epitaxy on highly oriented pyrolytic graphite (HOPG), and afterward, a Se adlayer was deposited in situ on WSe2/HOPG to prevent unintentional oxidation during transferring from the growth chamber to the STM chamber. After annealing at 773 K to remove the Se adlayer, STM images show that WSe2 layers nucleate at both step edges and terraces of the HOPG. Exposure to air for 1 week and 9 weeks caused air-induced adsorbates to be deposited on the WSe2 surface; however, the band gap of the terraces remained unaffected and nearly identical to those on decapped WSe2. The air-induced adsorbates can be removed by annealing at 523 K. In contrast to WSe2 terraces, air exposure caused the edges of the WSe2 to oxidize and form protrusions, resulting in a larger band gap in the scanning tunneling spectra compared to the terraces of air-exposed WSe2 monolayers. The preferential oxidation at the WSe2 edges compared to the terraces is likely the result of dangling edge bonds. In the absence of air exposure, the dangling edge bonds had a smaller band gap compared to the terraces and a shift of about 0.73 eV in the Fermi level toward the valence band. However, after air exposure, the band gap of the oxidized WSe2 edges became about 1.08 eV larger than that of the WSe2 terraces, resulting in the electronic passivation of the WSe2.

Scanning Tunneling Spectroscopy of Proximity Superconductivity in Epitaxial Multilayer Graphene.

We report on spatial measurements of the superconducting proximity effect in epitaxial graphene induced by a graphene-superconductor interface. Superconducting aluminum films were grown on epitaxial multilayer graphene on SiC. The aluminum films were discontinuous with networks of trenches in the film morphology reaching down to exposed graphene terraces. Scanning tunneling spectra measured on the graphene terraces show a clear decay of the superconducting energy gap with increasing separation from the graphene-aluminum edges. The spectra were well described by Bardeen-Cooper-Schrieffer (BCS) theory. The decay length for the superconducting energy gap in graphene was determined to be greater than 400 nm. Deviations in the exponentially decaying energy gap were also observed on a much smaller length scale of tens of nanometers.