Scanning Tunneling Spectroscopy Experiments Research Articles

Coverage-dependent anisotropy of the NTCDA/Ag(111) interface state dispersion

We employ density functional theory (DFT) to analyze the dispersion of the electronic state that exists at the commensurate interface between a monolayer of 1,4,5,8-naphthalene-tetracarboxylic acid dianhydride (NTCDA) and the Ag(111) surface. First, we present and verify a hydrogen-termination approach which allows a meaningful DFT description of the interface state with relatively thin silver slabs. Complemented with a projection technique which maps the interface electronic structure onto the original Ag(111) Shockley state, the DFT calculations enable us to analyze the evolution of the dispersion of the NTCDA/Ag(111) interface state when changing of the molecular coverage. Our calculations yield a difference between the interface state energy and the Shockley state energy that scales linearly with coverage. Furthermore, they predict a pronounced anisotropy of the dispersion of the interface state at long wavelengths which also depends linearly on the molecular coverage. The dispersion anisotropy is fully confirmed by our Fourier transform (FT) scanning tunneling spectroscopy (STS) experiments performed on a relaxed phase NTCDA/Ag(111) monolayer. Using feature detection STS (FD-STS), we moreover measure a band gap in the interface state band structure at the Brillouin zone boundary which indicates Bragg scattering of the interface state electrons in the periodic potential of the molecular layer. We thus observe an influence of the molecular layer on the interface state both at long (DFT, STS) and short wavelengths (STS).

Josephson effect in the strontium titanate/lanthanum aluminate junction**Project supported by the National Natural Science Foundation of China (Grant No. 11675051) and China Scholarship Council (Grant No. 201506130054).

We report theoretical studies on the newly discovered novel Josephson effect and scanning tunneling spectroscopy (STS) at the interface of strontium titanate/lanthanum aluminate (STO/LAO). With a phenomenological boson–fermion model, the density of states is calculated and the results are consistent with the STS experiments. A typical calculation of Josephson effect is performed, and it is in qualitative agreement with the experiments. The calculations indicate that the gap states come from the pairing of quasi-particles with a finite total momentum and the Josephson current comes from the tunneling of quasi-particle pairs with zero momentum. The quasi-particles are Bogoliubov quasi-particles. Moreover, the fits using Kulikʼs formula imply that the Josephson junction at the STO/LAO interface has a point contact with the clean superconductor limit.

Designing flat bands by strain

We study the effects of heterostrain on moir\'e bands in twisted bilayer graphene and bilayer transition metal dichalcogenide (TMD) systems. For bilayer graphene with twist angle near $1^\circ$, we show that heterostrain significantly increases the energy separation between conduction and valence bands as well as the Dirac velocity at charge neutrality, which resolves several puzzles in scanning tunneling spectroscopy and quantum oscillation experiments at once. For bilayer TMD, we show that applying small heterostrain generally leads to flat moir\'e bands that are highly tunable.

Strongly Hole-Doped and Highly Decoupled Graphene on Platinum by Water Intercalation.

Scanning tunneling microscopy and spectroscopy experiments under ultrahigh vacuum and low-temperature conditions have been performed on water-intercalated graphene on Pt(111). We find that the confined water layer, with a thickness around 0.35 nm, induces a strong hole doping in graphene, i.e., the Dirac point locates at round 0.64 eV above the Fermi level. This can be explained by the presence of a single "puckered bilayer" of ice-Ih, which has not been experimentally found on bare Pt(111), being confined in between graphene and Pt(111) surface. Moreover, the water intercalation makes graphene highly decoupled from the substrate, allowing us to reveal the intrinsic graphene phonons and double Rydberg series of even and odd symmetry image-potential states. Our work not only demonstrates that the electronic properties of graphene can be tuned by the confined water layer between graphene and the substrate, but also provides a generally applicable method to study the intrinsic properties of graphene as well as of other supported two-dimensional materials.

Pseudodoping of a metallic two-dimensional material by the supporting substrate

Charge transfers resulting from weak bondings between two-dimensional materials and the supporting substrates are often tacitly associated with their work function differences. In this context, two-dimensional materials could be normally doped at relatively low levels. Here, we demonstrate how even weak hybridization with substrates can lead to an apparent heavy doping, using the example of monolayer 1H-TaS2 grown on Au(111). Ab-initio calculations show that sizable changes in Fermi areas can arise, while the transferred charge between substrate and two-dimensional material is much smaller than the variation of Fermi areas suggests. This mechanism, which we refer to as pseudodoping, is associated with non-linear energy-dependent shifts of electronic spectra, which our scanning tunneling spectroscopy experiments reveal for clean and defective TaS2 monolayer on Au(111). The influence of pseudodoping on the formation of many-body states in two-dimensional metallic materials is analyzed, shedding light on utilizing pseudodoping to control electronic phase diagrams.

Autocorrelation of quasiparticle spectral intensities and its connection with quasiparticle scattering interference in cuprate superconductors

ABSTRACTThe quasiparticle excitation is one of the most fundamental and ubiquitous physical observables in cuprate superconductors, carrying information about the bosonic glue forming electron pairs. Here the autocorrelation of the quasiparticle excitation spectral intensities in cuprate superconductors and its connection with the quasiparticle scattering interference are investigated based on the framework of the kinetic-energy driven superconducting mechanism by taking into account the pseudogap effect. It is shown that the octet scattering model of the quasiparticle scattering processes with the scattering wave vectors connecting the hot spots on the constant energy contours is intrinsically related to the emergence of the highly anisotropic momentum-dependence of the pseudogap. Concomitantly, the sharp peaks in the autocorrelation of the quasiparticle excitation spectral intensities with the wave vectors are directly correlated to the regions of the highest joint density of states. Moreover, the momentum-space structure of the autocorrelation patterns of the quasiparticle excitation spectral intensities is well consistent with the momentum-space structure of the quasiparticle scattering interference patterns observed from Fourier-transform scanning tunnelling spectroscopy experiments. The theory therefore confirms an intimate connection between the angle-resolved photoemission spectroscopy autocorrelation and quasiparticle scattering interference in cuprate superconductors.

Realistic Large‐Scale Modeling of Rashba and Induced Spin–Orbit Effects in Graphene/High‐Z‐Metal Systems

AbstractGraphene, as a material with a small intrinsic spin–orbit interaction of approximately 1 µeV, has a limited application in spintronics. Adsorption of graphene on the surfaces of heavy metals was proposed to induce the strong spin splitting of the graphene π bands either via Rashba effect or due to the induced spin–orbit effects via hybridization of the valence band states of graphene and metal. Spin‐resolved photoelectron spectroscopy experiments performed on graphene adsorbed on the substrates containing heavy elements demonstrate the “giant” spin splitting of the π states of the order of 100 meV in the vicinity of the Fermi level (EF) and the K point. However, recent scanning tunneling spectroscopy experiments did not confirm these findings, leaving the fact of the observation of the “giant” Rashba effect or induced spin–orbit interaction in graphene still open. Thus, a detailed understanding of the physics in such systems is indispensable. From the theory side, this requires, first of all, correct modeling of the graphene/metal interfaces under study. Here, realistic super‐cell density‐functional theory calculations are presented, including dispersion interaction and spin–orbit interaction, for several graphene/high‐Z‐metal interfaces. While correctly reproducing the spin‐splitting features of the metallic surfaces, their modifications under graphene adsorption and doping level of graphene, it is revealed that neither “giant” Rashba‐ nor spin–orbit‐induced splitting of the graphene π states around EF take place.

Topological Insulator GMR Straintronics for Low-Power Strain Sensors.

A quantum spin Hall insulator, i.e., topological insulator (TI), is a natural candidate for low-power electronics and spintronics because of its intrinsic dissipationless feature. Recent density functional theory and scanning tunneling spectroscopy experiments show that the mechanical strain allows dynamic, continuous, and reversible modulations of the topological surface states within the topological phase and hence opens prospects for TI straintronics. Here, we combine the mechanical strain and the giant magnetoresistance (GMR) of a ferromagnet-TI (FM-TI) junction to construct a novel TI GMR straintronics device. Such a FM-strained-FM-TI junction permits several energy spectral ranges for 100% GMR and a robust strain-controllable magnetic switch. Beyond the 100% GMR energy range, we observe a strain-modulated oscillating GMR, which is an alternative hallmark of the Fabry-Pérot quantum interference of Dirac surface states. These strain-sensitive GMR responses indicate that FM-strained-FM-TI junctions are very favorable for practical applications for low-power nanoscale strain sensors.

Concentration Dependence of Dopant Electronic Structure in Bottom-up Graphene Nanoribbons.

Bottom-up fabrication techniques enable atomically precise integration of dopant atoms into the structure of graphene nanoribbons (GNRs). Such dopants exhibit perfect alignment within GNRs and behave differently from bulk semiconductor dopants. The effect of dopant concentration on the electronic structure of GNRs, however, remains unclear despite its importance in future electronics applications. Here we use scanning tunneling microscopy and first-principles calculations to investigate the electronic structure of bottom-up synthesized N = 7 armchair GNRs featuring varying concentrations of boron dopants. First-principles calculations of freestanding GNRs predict that the inclusion of boron atoms into a GNR backbone should induce two sharp dopant states whose energy splitting varies with dopant concentration. Scanning tunneling spectroscopy experiments, however, reveal two broad dopant states with an energy splitting greater than expected. This anomalous behavior results from an unusual hybridization between the dopant states and the Au(111) surface, with the dopant-surface interaction strength dictated by the dopant orbital symmetry.

Quasiparticle density of states, localization, and distributed disorder in the cuprate superconductors

We explore the effects of various kinds of random disorder on the quasiparticle density of states of two-dimensional $d$-wave superconductors using an exact real-space method, incorporating realistic details known about the cuprates. Random on-site energy and pointlike unitary impurity models are found to give rise to a vanishing DOS at the Fermi energy for narrow distributions and low concentrations, respectively, and lead to a finite, but suppressed, DOS at unrealistically large levels of disorder. Smooth disorder arising from impurities located away from the copper-oxide planes meanwhile gives rise to a finite DOS at realistic impurity concentrations. For the case of smooth disorder whose average potential is zero, a resonance is found at zero energy for the quasiparticle DOS at large impurity concentrations. We discuss the implications of these results on the computed low-temperature specific heat, the behavior of which we find is strongly affected by the amount of disorder present in the system. We also compute the localization length as a function of disorder strength for various types of disorder and find that intermediate- and high-energy states are quasiextended for low disorder, and that states near the Fermi energy are strongly localized and have a localization length that exhibits an unusual dependence on the amount of disorder. We comment on the origin of disorder in the cuprates and provide constraints on these based on known results from scanning tunneling spectroscopy and specific heat experiments.

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.

Superconductivity proximate to antiferromagnetism in a copper-oxide monolayer grown on Bi2Sr2CaCu2O8+δ

A nodeless superconducting (SC) gap was reported in a recent scanning tunneling spectroscopy experiment of a copper-oxide monolayer grown on the Bi$_2$Sr$_2$CaCu$_2$O$_{8+\delta}$ (Bi2212) substrate [Y. Zhong {\it et al.}, Sci. Bull. {\bf 61}, 1239 (2016)], which is in stark contrast to the nodal d-wave pairing gap in the bulk cuprates. Motivated by this experiment, we first show with first-principles calculations that the tetragonal CuO (T-CuO) monolayer on the Bi2212 substrate is more stable than the commonly postulated CuO$_{2}$ structure. The T-CuO monolayer is composed of two CuO$_2$ layers sharing the same O atoms. The band structure is obtained by first-principles calculations, and its strong electron correlation is treated with the renormalized mean-field theory. We argue that one CuO$_2$ sublattice is hole doped while the other sublattice remains half filled and may have antiferromagnetic (AF) order. The doped Cu sublattice can show d-wave SC; however, its proximity to the AF Cu sublattice induces a spin-dependent hopping, which splits the Fermi surface and may lead to a full SC gap. Therefore, the nodeless SC gap observed in the experiment could be accounted for by the d-wave SC proximity to an AF order, thus it is extrinsic rather than intrinsic to the CuO$_2$ layers.

Local Electronic Structure of a Single-Layer Porphyrin-Containing Covalent Organic Framework.

We have characterized the local electronic structure of a porphyrin-containing single-layer covalent organic framework (COF) exhibiting a square lattice. The COF monolayer was obtained by the deposition of 2,5-dimethoxybenzene-1,4-dicarboxaldehyde (DMA) and 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (TAPP) onto a Au(111) surface in ultrahigh vacuum followed by annealing to facilitate Schiff-base condensations between monomers. Scanning tunneling spectroscopy (STS) experiments conducted on isolated TAPP precursor molecules and the covalently linked COF networks yield similar transport (HOMO-LUMO) gaps of 1.85 ± 0.05 eV and 1.98 ± 0.04 eV, respectively. The COF orbital energy alignment, however, undergoes a significant downward shift compared to isolated TAPP molecules due to the electron-withdrawing nature of the imine bond formed during COF synthesis. Direct imaging of the COF local density of states (LDOS) via dI/dV mapping reveals that the COF HOMO and LUMO states are localized mainly on the porphyrin cores and that the HOMO displays reduced symmetry. DFT calculations reproduce the imine-induced negative shift in orbital energies and reveal that the origin of the reduced COF wave function symmetry is a saddle-like structure adopted by the porphyrin macrocycle due to its interactions with the Au(111) substrate.

Revisiting quasiparticle scattering interference in high-temperature superconductors: The problem of narrow peaks

We revisit the interpretation of quasiparticle scattering interference in cuprate high-$T_c$ superconductors. This phenomenon has been very successful in reconstructing the dispersions of d-wave Bogoliubov excitations, but the successful identification and interpretation of QPI in scanning tunneling spectroscopy (STS) experiments rely on theoretical results obtained for the case of isolated impurities. We introduce a highly flexible technique to simulate STS measurements by computing the local density of states using real-space Green's functions defined on two-dimensional lattices with as many as 100,000 sites. We focus on the following question: to what extent can the experimental results be reproduced when various forms of distributed disorder are present? We consider randomly distributed point-like impurities, smooth "Coulombic" disorder, and disorder arising from random on-site energies and superconducting gaps. We find an apparent paradox: the QPI peaks in the Fourier-transformed local density of states appear to be sharper and better defined in experiment than those seen in our simulations. We arrive at a no-go result for smooth-potential disorder since this does not reproduce the QPI peaks associated with large-momentum scattering. An ensemble of point-like impurities gets closest to experiment, but this goes hand in hand with impurity cores that are not seen in experiment. We also study the effects of possible measurement artifacts (the "fork mechanism"), which turn out to be of relatively minor consequence. It appears that there is an unknown mechanism at work which renders the QPI peaks much sharper than they are based on present theoretical understanding.

Tuneling Spectroscopy Study Of The Local Conductivity Features Of The Solid State Surface

The procedure of the scanning tunneling spectroscopy experiments on the base of air multimicroscope SMM2000T is developed. Highly oriented pyrolytic graphite single crystal was chosen as model sample. Proposed approach allows investigation of the local nonuniformity of the surface properties. The statistical confirmed difference of volt-ampere curves recorded over pyrolytic graphite terrace and steps determined by the structure features is shown

Correlating electronic and magnetic coupling in large magnetic molecules via scanning tunneling microscopy

In an effort to improve the spin coupling in single-molecule magnets, we rationally designed a new building-block molecule with significantly enhanced spin coupling compared to a previously established molecule. We relate this to a stabilization of aromaticity in the central connecting carbon ring, promoting the spin-polarization mechanism. This correlation between magnetic and electronic properties is supported by bulk measurements as well as submolecularly resolved scanning tunneling microscopy and spectroscopy experiments, where we found distinct differences in the local density of states distribution of the two molecules, especially at the central carbon ring. While the established molecule exhibits localized, spatially decoupled and even switchable states, the improved building block exhibits symmetric local density of states delocalized over the entire molecule, also revealing that this main characteristic electronic property is preserved upon adsorption on a metal surface. Due to their planar geometry, these molecules can serve as model systems for scanning-probe based studies of molecular magnetism.

Local resilience of the 1T−TiSe2 charge density wave to Ti self-doping

In Ti-intercalated self-doped $1T$-TiSe$_2$ crystals, the charge density wave (CDW) superstructure induces two nonequivalent sites for Ti dopants. Recently, it has been shown that increasing Ti doping dramatically influences the CDW by breaking it into phase-shifted domains. Here, we report scanning tunneling microscopy and spectroscopy experiments that reveal a dopant-site dependence of the CDW gap. Supported by density functional theory, we demonstrate that the loss of the longrange phase coherence introduces an imbalance in the intercalated-Ti site distribution and restrains the CDW gap closure. This local resilient behavior of the $1T$-TiSe$_2$ CDW reveals a novel mechanism between CDW and defects in mutual influence.

Near-degeneracy of extendeds+dx2−y2anddxyorder parameters in quasi-two-dimensional organic superconductors

The symmetry of the superconducting order parameter in quasi-two-dimensional BEDT-TTF organic superconductors is a subject of ongoing debate. We report ab initio density functional theory calculations for a number of organic superconductors containing $\kappa$-type layers. Using projective Wannier functions we derive parameters of a common low-energy Hamiltonian based on individual BEDT-TTF molecular orbitals. In a random phase approximation spin-fluctuation approach we investigate the evolution of the superconducting pairing symmetry within this model and point out a phase-transition between extended $s + d_{x^2-y^2}$ and $d_{xy}$ symmetry. We discuss the origin of the mixed order parameter and the relation between the realistic molecule description and the widely used dimer approximation. Based on our ab initio calculations we position the investigated materials in the obtained molecule model phase diagram and simulate scanning tunneling spectroscopy experiments for selected cases. Our calculations show that many $\kappa$-type materials lie close to the phase transition line between the two pairing symmetry types found in our calculation, possibly explaining the multitude of contradictory experiments in this field.

Cotunneling into a Kondo lattice with odd hybridization

Cotunneling into Kondo systems, where an electron enters a $f$-electron material via a cotunneling process through the local-moment orbital, has been proposed to explain the characteristic lineshapes observed in scanning-tunneling-spectroscopy (STS) experiments. Here we extend the theory of electron cotunneling to Kondo-lattice systems where the bulk hybridization between conduction and $f$ electrons is odd under inversion, being particularly relevant to Kondo insulators. Compared to the case of even hybridization, we show that the interference between normal tunneling and cotunneling processes is fundamentally altered: it is entirely absent for layered, i.e., quasi-two-dimensional materials, while its energy dependence is strongly modified for three-dimensional materials. We discuss implications for STS experiments.

Theoretical analysis of the combined effects of sulfur vacancies and analyte adsorption on the electronic properties of single-layer MoS2

We report a first-principles theoretical investigation on the electronic structure and electron transport of defective single-layer (SL) MoS2, as well as of corresponding structures adsorbed with benzyl viologen (BV), which was shown to provide improved performance of a field effect transistor. O2 adsorption was included to gain an understanding of the response upon air-exposure. Following analysis of the structure and stability of sulfur single vacancy and line defects in SL MoS2, we investigated the local transport at the adsorbed sites via a transport model that mimics a scanning tunneling spectroscopy experiment. Distinct current–voltage characteristics were indicated for adsorbed oxygen species at a sulfur vacancy. The electronic structures of defective MoS2 indicated the emergence of impurity states in the bandgap due to sulfur defects and oxygen adsorption. Electron transport calculations for the MoS2 surface with an extended defect in a device setting demonstrated that physisorption of BV enhances the output current, while facile chemisorption by O2 upon air-exposure causes degradation of electron transport.