Scanning Tunneling Spectroscopy Measurements Research Articles

Magnetic Weyl semimetal phase in a Kagomé crystal.

Weyl semimetals are crystalline solids that host emergent relativistic Weyl fermions and have characteristic surface Fermi-arcs in their electronic structure. Weyl semimetals with broken time reversal symmetry are difficult to identify unambiguously. In this work, using angle-resolved photoemission spectroscopy, we visualized the electronic structure of the ferromagnetic crystal Co3Sn2S2 and discovered its characteristic surface Fermi-arcs and linear bulk band dispersions across the Weyl points. These results establish Co3Sn2S2 as a magnetic Weyl semimetal that may serve as a platform for realizing phenomena such as chiral magnetic effects, unusually large anomalous Hall effect and quantum anomalous Hall effect.

Magnetic Weyl semimetals

Topological Matter Weyl semimetals (WSMs)—materials that host exotic quasiparticles called Weyl fermions—must break either spatial inversion or time-reversal symmetry. A number of WSMs that break inversion symmetry have been identified, but showing unambiguously that a material is a time-reversal-breaking WSM is tricky. Three groups now provide spectroscopic evidence for this latter state in magnetic materials (see the Perspective by da Silva Neto). Belopolski et al. probed the material Co2MnGa using angle-resolved photoemission spectroscopy, revealing exotic drumhead surface states. Using the same technique, Liu et al. studied the material Co3Sn2S2, which was complemented by the scanning tunneling spectroscopy measurements of Morali et al. These magnetic WSM states provide an ideal setting for exotic transport effects. Science , this issue p. [1278][1], p. [1282][2], p. [1286][3]; see also p. [1248][4] [1]: /lookup/doi/10.1126/science.aav2327 [2]: /lookup/doi/10.1126/science.aav2873 [3]: /lookup/doi/10.1126/science.aav2334 [4]: /lookup/doi/10.1126/science.aax6190

Anisotropic strain effects in small-twist-angle graphene on graphite

The direct experimental probing of locally varying lattice parameters and anisotropic lattice deformations in atomic multilayers is extremely challenging. Here, we develop a new combined numerical/graphical method for the analysis of irregular moir\'e superstructures measured by scanning tunneling microscopy (STM) on a small-twist-angle ($\sim$0.6$^{\circ}$) graphene on highly oriented pyrolytic graphite (gr/HOPG). We observe distorted moir\'e patterns with a spatially varying period in annealed gr/HOPG. The nanoscale modulation of the moir\'e period observed by STM reflects a locally strained (and sheared) graphene with anisotropic variation of the lattice parameters. We use a specific algorithm based on a rigid lattice Fourier method, which is able to reconstruct the irregular and distorted moir\'e patterns emerging from strain-induced lattice deformations. Our model is universal and can be used to study different moir\'e patterns occurring in two-dimensional van der Waals heterostructures. Additionally, room temperature scanning tunneling spectroscopy measurements show electronic states at the Dirac point, localized on moir\'e hills, which increase significantly the apparent corrugation of the moir\'e pattern. The measured topography is compared to classical molecular dynamics simulations. Density functional theory (DFT) calculations confirm that an AAB stacked trilayer region itself can contribute electronic states near the Fermi-level, in agreement with the measured peak in the local density of states. Furthermore, CMD calculations reveal direction-dependent bond alternations ($\sim$0.5$\%$) around the stacking regions, induced by shear strain, which could influence electronic properties.

Hexagonal Nanopits with the Zigzag Edge State on Graphite Surfaces Synthesized by Hydrogen-Plasma Etching

We studied, by scanning tunneling microscopy, the morphology of nanopits of monolayer depth created at graphite surfaces by hydrogen plasma etching under various conditions such as H$_2$ pressure, temperature, etching time, and RF power of the plasma generation. In addition to the known pressure-induced transition of the nanopit morphology, we found a sharp temperature-induced transition from many small rather round nanopits of ~150 nm size to few large hexagonal ones of 300-600 nm within a narrow temperature range. The remote and direct plasma modes switching mechanism, which was proposed to explain the pressure-induced transition, is not directly applicable to this newly found transition. Scanning tunneling spectroscopy (STS) measurements of edges of the hexagonal nanopits fabricated at graphite surfaces by this method show clear signatures of the peculiar electronic state localized at the zigzag edge (edge state), i.e., a prominent peak near the Fermi energy accompanied by suppressions on either side in the local density of states. These observations indicate that the hexagonal nanopits consist of a high density of zigzag edges. The STS data also revealed a domain structure of the edge state in which the electronic state varies over a length scale of ~3 nm along the edge. The present study will pave the way for microscopic understanding of the anisotropic etching mechanism and of spin polarization in zigzag nanoribbons which are promising key elements for future graphene nanoelectronics.

Topological surface states above the Fermi level in Hf2Te2P

We report a detailed experimental study of the band structure of the recently discovered topological material $\textrm{Hf}_{2}\textrm{Te}_2\textrm{P}$. Using the combination of scanning tunneling spectroscopy and angle-resolved photo-emission spectroscopy with surface K-doping, we probe the band structure of $\textrm{Hf}_{2}\textrm{Te}_2\textrm{P}$ with energy and momentum resolution above the Fermi level. Our experiments show the presence of multiple surface states with a linear Dirac-like dispersion, consistent with the predictions from previously reported band structure calculations. In particular, scanning tunneling spectroscopy measurements provide the first experimental evidence for the strong topological surface state predicted at 460 meV, which stems from the band inversion between Hf-d and Te-p orbitals. This band inversion comprised of more localized d-states could result in a better surface-to-bulk conductance ratio relative to more traditional topological insulators.

Switching the Spin on a Ni Trimer within a Metal-Organic Motif by Controlling the On-Top Bromine Atom.

Controlling the spin of metal atoms embedded in molecular systems is a key step toward the realization of molecular electronics and spintronics. Many efforts have been devoted to explore the influencing factors dictating the survival or quenching of a magnetic moment in a metal-organic molecule, and among others, the spin control by axial ligand attachments is the most promising. Herein, from the interplay of high-resolution scanning tunneling microscopy imaging/manipulation and scanning tunneling spectroscopy measurements together with density functional theory calculations, we successfully demonstrate that a Ni trimer within a metal-organic motif acquires a net spin promoted by the adsorption of an on-top Br atom. The spin localization in the trimetal centers bonded to Br was monitored via the Kondo effect. The removal of the Br ligand resulted in the switch from a Kondo ON to a Kondo OFF state. The magnetic state induced by the Br ligand is theoretically attributed to the enhanced Br 4pz and Ni 3dz2 states due to the charge redistribution. The manipulation strategy reported here provides the possibility to explore potential applications of spin-tunable structures in spintronic devices.

Negatively Curved Warped Nanographene Self-Assembled on Metal Surfaces.

We report the investigation of a conjugated polycyclic hydrocarbon containing multiple nonbenzenoid rings and exhibiting negative curvature-the warped nanographene C80H30-adsorbed on several noble metal surfaces in an ultrahigh vacuum environment. From a detailed analysis of the molecular self-assembly at different molecular coverages via scanning tunneling microscopy and spectroscopy measurements in combination with theoretical modeling, the nature of the intermolecular interactions is unraveled. For high molecular coverages on Cu(111), the formation of homochiral porous networks is observed, which is rationalized by (i) intermolecular π-π interactions between neighboring C80H30 molecules that promote the formation of molecular dimers and (ii) enantioselective intermolecular CH···π interactions between the dimers. Such interactions are also observed after deposition of C80H30 molecules on Au(111) and Ag(111) substrates. Our results provide perspectives for the on-surface study of negatively curved nanographenes whichopen new avenuestothe design of novel and functional chiral structures with potential use in the field of organic optoelectronics.

Manipulating Topological Domain Boundaries in the Single-Layer Quantum Spin Hall Insulator 1T'-WSe2.

We report the creation and manipulation of structural phase boundaries in the single-layer quantum spin Hall insulator 1T'-WSe2 by means of scanning tunneling microscope tip pulses. We observe the formation of one-dimensional interfaces between topologically nontrivial 1T' domains having different rotational orientations, as well as induced interfaces between topologically nontrivial 1T' and topologically trivial 1H phases. Scanning tunneling spectroscopy measurements show that 1T'/1T' interface states are localized at domain boundaries, consistent with theoretically predicted unprotected interface modes that form dispersive bands in and around the energy gap of this quantum spin Hall insulator. We observe a qualitative difference in the experimental spectral line shape between topologically "unprotected" states at 1T'/1T' domain boundaries and protected states at 1T'/1H and 1T'/vacuum boundaries in single-layer WSe2.

Atomically precise bottom-up synthesis of π-extended [5]triangulene.

The zigzag-edged triangular graphene molecules (ZTGMs) have been predicted to host ferromagnetically coupled edge states with the net spin scaling with the molecular size, which affords large spin tunability crucial for next-generation molecular spintronics. However, the scalable synthesis of large ZTGMs and the direct observation of their edge states have been long-standing challenges because of the molecules' high chemical instability. Here, we report the bottom-up synthesis of π-extended [5]triangulene with atomic precision via surface-assisted cyclodehydrogenation of a rationally designed molecular precursor on metallic surfaces. Atomic force microscopy measurements unambiguously resolve its ZTGM-like skeleton consisting of 15 fused benzene rings, while scanning tunneling spectroscopy measurements reveal edge-localized electronic states. Bolstered by density functional theory calculations, our results show that [5]triangulenes synthesized on Au(111) retain the open-shell π-conjugated character with magnetic ground states.

Atomic-Scale Observation of Reversible Thermally Driven Phase Transformation in 2D In2Se3

Phase transformation in emerging two-dimensional (2D) materials is crucial for understanding and controlling the interplay between structure and electronic properties. In this work, we investigate 2D In2Se3 synthesized via chemical vapor deposition, a recently discovered 2D ferroelectric material. We observed that In2Se3 layers with thickness ranging from a single layer to ∼20 layers stabilized at the β phase with a superstructure at room temperature. At around 180 K, the β phase converted to a more stable β' phase that was distinct from previously reported phases in 2D In2Se3. The kinetics of the reversible thermally driven β-to-β' phase transformation was investigated by temperature-dependent transmission electron microscopy and Raman spectroscopy, corroborated with the expected minimum-energy pathways obtained from our first-principles calculations. Furthermore, density functional theory calculations reveal in-plane ferroelectricity in the β' phase. Scanning tunneling spectroscopy measurements show that the indirect bandgap of monolayer β' In2Se3 is 2.50 eV, which is larger than that of the multilayer form with a measured value of 2.05 eV. Our results on the reversible thermally driven phase transformation in 2D In2Se3 with thickness down to the monolayer limit and the associated electronic properties will provide insights to tune the functionalities of 2D In2Se3 and other emerging 2D ferroelectric materials and shed light on their numerous potential applications (e.g., nonvolatile memory devices).

Modulating Epitaxial Atomic Structure of Antimonene through Interface Design.

Antimonene, a new semiconductor with fundamental bandgap and desirable stability, has been experimentally realized recently. However, epitaxial growth of wafer-scale single-crystalline monolayer antimonene preserving its buckled configuration remains a daunting challenge. Here, Cu(111) and Cu(110) are chosen as the substrates to fabricate high-quality, single-crystalline antimonene via molecular beam epitaxy (MBE). Surface alloys form spontaneously after the deposition and postannealing of Sb on two substrates that show threefold and twofold symmetry with different lattice constants. Increasing the coverage leads to the epitaxial growth of two atomic types of antimonene, both exhibiting a hexagonal lattice but with significant difference in lattice constants, which are observed by scanning tunneling microscopy. Scanning tunneling spectroscopy measurements reveal the strain-induced tunable bandgap, in agreement with the first-principles calculations. The results show that epitaxial growth of antimonene on different substrates allow the electronic properties of these films to be tuned by substrate-induced strain and stress.

Low-Dimensional Metal-Organic Coordination Structures on Graphene.

We report the formation of one- and two-dimensional metal–organic coordination structures from para-hexaphenyl-dicarbonitrile (NC–Ph6–CN) molecules and Cu atoms on graphene epitaxially grown on Ir(111). By varying the stoichiometry between the NC–Ph6–CN molecules and Cu atoms, the dimensionality of the metal–organic coordination structures could be tuned: for a 3:2 ratio, a two-dimensional hexagonal porous network based on threefold Cu coordination was observed, while for a 1:1 ratio, one-dimensional chains based on twofold Cu coordination were formed. The formation of metal–ligand bonds was supported by imaging the Cu atoms within the metal–organic coordination structures with scanning tunneling microscopy. Scanning tunneling spectroscopy measurements demonstrated that the electronic properties of NC–Ph6–CN molecules and Cu atoms were different between the two-dimensional porous network and one-dimensional molecular chains.

The Atomic and Electronic Structure of 0° and 60° Grain Boundaries in MoS2

We have investigated atomic and electronic structure of grain boundaries in monolayer MoS2, where relative angles between two different grains are 0 and 60 degree. The grain boundaries with specific relative angle have been formed with chemical vapor deposition growth on graphite and hexagonal boron nitride flakes; van der Waals interlayer interaction between MoS2 and the flakes restricts the relative angle. Through scanning tunneling microscopy and spectroscopy measurements, we have found that the perfectly stitched structure between two different grains of MoS2 was realized in the case of the 0 degree grain boundary. We also found that even with the perfectly stitched structure, valence band maximum and conduction band minimum shows significant blue shift, which probably arise from lattice strain at the boundary.

Dirac States of 2D Topological Insulators: Effect of Heterovalent Dopant-Content.

We have studied Bi2Se3 at its 2D-limit using scanning tunneling spectroscopy (STS). Bulk Bi2Se3 is a well-known topological insulator having gapless surface states. In the 2D limit, the interior of the material exhibits a band gap, whereas the periphery shows a gapless metallic state having a Dirac point. We demonstrate a method to tune the Fermi energy and hence the Dirac point of Bi2Se3 nanoplates through doping at the anionic site. For this purpose, STS measurements were carried out on the Bi2Se3 system. We have used bromide as a dopant, which turns the material to n-type in nature. As a result, STS studies infer that the Fermi energy (EF) shifted toward the conduction band and consequently the Dirac point could be found to move away from Fermi energy. Through STS measurements, we have demonstrated a correlation between the shift of Dirac point position and the dopant content. The size, shape, and compositions of Bi2Se3 nanoflakes and concentration of bromine in the doped nanostructures were determined using transmission electron microscopy, associated energy dispersive X-ray spectroscopy analysis, and X-ray diffraction.

Directly visualizing the sign change of d-wave superconducting gap in Bi2Sr2CaCu2O8+\u03b4 by phase-referenced quasiparticle interference

The superconducting state is formed by the condensation of Cooper pairs and protected by the superconducting gap. The pairing interaction between the two electrons of a Cooper pair determines the gap function. Thus, it is pivotal to detect the gap structure for understanding the mechanism of superconductivity. In cuprate superconductors, it has been well established that the gap may have a d-wave function. This gap function has an alternative sign change in the momentum space. It is however hard to visualize this sign change. Here we report the measurements of scanning tunneling spectroscopy in Bi2Sr2CaCu2O8+δ and conduct the analysis of phase-referenced quasiparticle interference (QPI). We see the seven basic scattering vectors that connect the octet ends of the banana-shaped contour of Fermi surface. The phase-referenced QPI clearly visualizes the sign change of the d-wave gap. Our results illustrate an effective way for determining the sign change of unconventional superconductors.

Evidence of direct electronic band gap in two-dimensional van der Waals indium selenide crystals

Metal monochalcogenide compounds offer a large variety of electronic properties depending on chemical composition, number of layers, and stacking order. Among them, the InSe has attracted much attention due to the promise of outstanding electronic properties, attractive quantum physics, and high photoresponse. Precise experimental determination of the electronic structure of InSe is sorely needed for better understanding of potential properties and device applications. Here, combining scanning tunneling spectroscopy (STS) and two-photon photoemission spectroscopy, we demonstrate that InSe exhibits a direct band gap of about 1.25 eV located at the \ensuremath{\Gamma} point of the Brillouin zone. STS measurements underline the presence of a finite and almost constant density of states (DOS) near the conduction-band minimum. This particular DOS is generated by a poorly dispersive nature of the top valence band, as shown by angle-resolved photoemission spectroscopy (ARPES) investigation. In fact, a hole effective mass of about ${m}^{*}/{m}_{0}=\ensuremath{-}0.95$ ($\overline{\mathrm{\ensuremath{\Gamma}}K}$ direction) was measured. Moreover, using ARPES measurements a spin-orbit splitting of the deeper-lying bands of about 0.35 eV was evidenced. These findings allow a deeper understanding of the InSe electronic properties underlying the potential of III-VI semiconductors for electronic and photonic technologies.

Berry phase induced valley level crossing in bilayer graphene quantum dots

We study the confined bound states in circular bilayer graphene quantum dots. Using the semiclassical Einstein-Brillouin-Keller quantization rule, we predict that valley levels inside the quantum dot undergo three stages: splitting, crossing, and recombining when varying the applied magnetic field. This exotic phenomenon originates from the Berry phase, which increases from zero to $2\ensuremath{\pi}$ with the magnetic field and has opposite signs for the two inequivalent valleys. To further confirm this phenomenon, we perform a fully quantum mechanical calculation based on a low-energy continuum model and a real space tight-binding model, and show that the valley effect can be explicitly observed by scanning-tunneling spectroscopy measurements. Moreover, we propose an efficient valley filter device as an application of this valley effect, which can be used to manipulate the valley degree of freedom in valleytronics.

Bifunctional Behavior of a Porphyrin in Hydrogen-Bonded Donor–Acceptor Molecular Chains on a Gold Surface

Peculiar hydrogen-bonded molecular chains are spontaneously created from the self-assembly on a gold surface of a porphyrin functionalized with four aromatic amine moieties. The molecular chains are formed by a sequence of dyads, where the same molecule behaves alternately as a hydrogen-bond acceptor or donor as a whole at all its four aromatic amino groups. This remarkable bifunctional behavior is due to the conformational flexibility of the functionalizing amino groups that switch from a planar, aniline-like conformation in donors to a pyramidal, amine-like one in acceptors. Furthermore, we show that the acceptor porphyrins can trap gold adatoms underneath their center. Combined scanning tunneling microscopy experiments and density functional theory calculations characterize the structural and electronic modifications suffered by such molecules to establish amino–amino interactions. Notably, scanning tunneling spectroscopy measurements show that the highest occupied molecular orbital–lowest unoccupied m...

Self-Assembly and Electronic Structure of Tribenzotriquinacenes on Ag(111)

The structure of two-dimensional layers of organic compounds on metal surfaces is of great interest for the fabrication of devices in the field of organic electronics. To progress in this area, a deeper understanding of intermolecular interactions and charge transfer processes between organic molecules and a metal substrate is required. Here, the two-dimensional self-assembly of tribenzotriquinacenes (TBTQs) on Ag(111) was studied by scanning tunneling microscopy under ultrahigh vacuum conditions. Highly ordered monolayers of tribenzotriquinacene (TBTQ) and centro-methyl tribenzotriquinacene (Me-TBTQ) were observed for the first time. At low to moderate coverage, both of these bowl-shaped molecules adsorb with the bowl opening faced downward, appearing in two orientations that are rotated by 14° from the high-symmetry axis of the Ag(111) surface. At high TBTQ coverage, extended islands with a self-assembled highly ordered windmill nanostructure dominate the surface, interspaced with nanometer-sized openings. This windmill structure is absent in Me-TBTQ, which immediately forms double-layered regions at high coverage. Scanning tunneling spectroscopy measurements, which probe the local density of states, identify a shift of the Ag(111) surface state in the presence of the TBTQ molecules. Investigations such as these into the self-assembly of curved aromatics provide a foundation for further work on the construction of multilayer nanostructures and the production of electronic devices.

Synergetic Enhancement of Thermoelectric Performance by Selective Charge Anderson Localization-Delocalization Transition in n-Type Bi-Doped PbTe/Ag2Te Nanocomposite.

Considerable efforts have been devoted to enhancing thermoelectric performance, by employing phonon scattering from nanostructural architecture, and material design using phonon-glass and electron-crystal concepts. The nanostructural approach helps to lower thermal conductivity but has limited effect on the power factor. Here, we demonstrate selective charge Anderson localization as a route to maximize the Seebeck coefficient while simultaneously preserving high electrical conductivity and lowering the lattice thermal conductivity. We confirm the viability of interface potential modification in an n-type Bi-doped PbTe/Ag2Te nanocomposite and the resulting enhancement in thermoelectric figure-of-merit ZT. The introduction of random potentials via Ag2Te nanoparticle distribution using extrinsic phase mixing was determined using scanning tunneling spectroscopy measurements. When the Ag2Te undergoes a structural phase transition ( T > 420 K) from monoclinic β-Ag2Te to cubic α-Ag2Te, the band gap in the α-Ag2Te increases due to the p -d hybridization. This results in a decrease in the potential barrier height, which gives rise to partial delocalization of the electrons, while wave packets of the holes are still in a localized state. Using this strategic approach, we achieved an exceptionally high thermoelectric figure-of-merit in n-type PbTe materials, a ZT greater than 2.0, suitable for waste heat power generation.