Tunneling Density Research Articles

Electronically Seamless Domain Wall of Chiral Charge Density Wave in 1T-TiSe2.

Domain walls (DWs) have been recognized to play crucial roles in various interesting properties and functionalities in quantum materials. A notable example is DWs in charge density wave (CDW), which are believed to provide metallic electron channels for emerging superconductivity. However, electronic states of DWs and the microscopic mechanism toward superconductivity have been elusive. Here, we clarify the atomic/electronic structure of DWs of the chiral CDW emerging in 1T-TiSe2, using scanning tunneling microscopy and density functional calculations. We reveal unambiguously the microscopic origin of chiral CDW as the C2 distortion in Se layers and its interlayer coupling. We further identify unique DWs connecting CDW domains of opposite chirality. The DWs are endowed with no in-gap state due to the characteristic multibands around the band gap, which defies the widely believed notion for CDW DWs. These results provide an important insight into the role of DWs in emerging superconductivity.

Magnetic coupled electronic landscape in bilayer-distorted titanium-based kagome metals

Quantum materials whose atoms are arranged on a lattice of corner-sharing triangles, i.e., the kagome lattice, have recently emerged as a captivating platform for investigating exotic correlated and topological electronic phenomena. Here, we combine ultralow temperature angle-resolved photoemission spectroscopy (ARPES) with scanning tunneling microscopy and density functional theory calculations to reveal the fascinating electronic structure of the bilayer-distorted kagome material LnTi3Bi4, where stands for Nd and Yb. Distinct from other kagome materials, LnTi3Bi4 exhibits twofold, rather than sixfold, symmetries, stemming from the distorted kagome lattice, which leads to a unique electronic structure. Combining experiment and theory we map out the electronic structure and discover double flat bands as well as multiple Van Hove singularities (VHSs), with one VHS exhibiting higher-order characteristics near the Fermi level. Notably, in the magnetic version NdTi3Bi4, the ultralow base temperature ARPES measurements unveil an unconventional band splitting in the band dispersions which is induced by the ferromagnetic ordering. These findings reveal the potential of bilayer-distorted kagome metals LnTi3Bi4 as a promising platform for exploring novel emergent phases of matter at the intersection of strong correlation and magnetism. Published by the American Physical Society 2024

Growth of an Fe buckled honeycomb lattice on Be(0001)

The growth of Fe on a clean Be(0001) surface is investigated on the atomic scale by a combined scanning tunneling microscopy and density functional theory study. At low Fe coverage, the nucleation of terraced nanoislands with a disordered surface is observed experimentally. Increasing the Fe coverage results in the growth of extended films exhibiting a well-ordered p(2×2) superstructure. Density functional theory is applied to investigate the growth of Fe on a Be(0001) surface from individual atoms to extended films. Our studies provide strong evidence for the formation of a buckled honeycomb Fe lattice that is embedded in two Be planes with Kagome and triangular symmetry, respectively.

The Conductance and Thermopower Behavior of Pendent Trans-Coordinated Palladium(II) Complexes in Single-Molecule Junctions.

The present work provides insight into the effect of connectivity within isomeric 1,2-bis(2-pyridylethynyl)benzene (bpb) palladium complexes on their electron transmission properties within gold|single-molecule|gold junctions. The ligands 2,2'-((4,5-bis(hexyloxy)-1,2-phenylene)bis(ethyne-2,1-diyl))bis(4-(methylthio)pyridine) (Lm ) and 6,6'-((4,5-bis(hexyloxy)-1,2-phenylene)bis(ethyne-2,1-diyl))bis(3-(methylthio)pyridine) (Lp ) were synthesized and coordinated with PdCl2 to give the trans-Pd(Lmorp )Cl2 complexes. X-ray photoelectron spectroscopy (XPS) measurements shed light on the contacting modes of the molecules in the junctions. A combination of scanning tunneling microscopy-break junction (STM-BJ) measurements and density functional theory (DFT) calculations demonstrate that the typical lower conductance of meta- compared with para-connected isomers in a molecular junction was suppressed upon metal coordination. Simultaneously there was a modest increase in both conductance and Seebeck coefficient due to the contraction of the HOMO-LUMO gap upon metal coordination. It is shown that the low Seebeck coefficient is primarily a consequence of how the resonances shift relative to the Fermi energy.

Spin‐State Switching of Spin‐Crossover Complexes on Cu(111) Evidenced by Spin‐Flip Spectroscopy

Spin‐crossover compounds can be switched between two stable states with different magnetic moments, conformations, electronic, and optical properties, which opens appealing perspectives for technological applications including miniaturization down to the scale of single molecules. Although control of the spin states is crucial their direct identification is challenging in single‐molecule experiments. Here we investigate the spin‐crossover complex [Fe(HB(1,2,4‐triazol‐1‐yl)3)2] on a Cu(111) surface with scanning tunneling microscopy and density functional theory calculations. Spin crossover of single molecules in dense islands is achieved via electron injection. Spin‐flip excitations are resolved in scanning tunneling spectra in a magnetic field enabling the direct identification of the molecular spin state, and revealing the existence of magnetic anisotropy in the HS molecules.

Spin-State Switching of Spin-Crossover Complexes on Cu(111) Evidenced by Spin-Flip Spectroscopy.

Spin-crossover compounds can be switched between two stable states with different magnetic moments, conformations, electronic, and optical properties, which opens appealing perspectives for technological applications including miniaturization down to the scale of single molecules. Although control of the spin states is crucial their direct identification is challenging in single-molecule experiments. Here we investigate the spin-crossover complex [Fe(HB(1,2,4-triazol-1-yl)3)2] on a Cu(111) surface with scanning tunneling microscopy and density functional theory calculations. Spin crossover of single molecules in dense islands is achieved via electron injection. Spin-flip excitations are resolved in scanning tunneling spectra in a magnetic field enabling the direct identification of the molecular spin state, and revealing the existence of magnetic anisotropy in the HS molecules.

LEED-IV analyses of tellurium adsorbate structures on iridium and gold surfaces

The determination of the configuration of atomic adsorbates on clean metal surfaces has been a key issue in surface science 60 years ago and still is today. We demonstrate that despite the prevalence of combined scanning tunneling microscopy and density functional theory studies of adsorbate systems the pitfalls are plentiful calling for accurate, reliable structure analyses that can be delivered by diffraction methods. We analyze and compare the ordered phases of Te on Ir(111), Ir(100), and Au(100) demonstrating the accuracy, the in-depth information and physical insight that can nowadays be obtained by quantitative low-energy electron diffraction structural analyses.

Signature of anyonic statistics in the integer quantum Hall regime

Anyons are exotic low-dimensional quasiparticles whose unconventional quantum statistics extend the binary particle division into fermions and bosons. The fractional quantum Hall regime provides a natural host, with the first convincing anyon signatures recently observed through interferometry and cross-correlations of colliding beams. However, the fractional regime is rife with experimental complications, such as an anomalous tunneling density of states, which impede the manipulation of anyons. Here we show experimentally that the canonical integer quantum Hall regime can provide a robust anyon platform. Exploiting the Coulomb interaction between two copropagating quantum Hall channels, an electron injected into one channel splits into two fractional charges behaving as abelian anyons. Their unconventional statistics is revealed by negative cross-correlations between dilute quasiparticle beams. Similarly to fractional quantum Hall observations, we show that the negative signal stems from a time-domain braiding process, here involving the incident fractional quasiparticles and spontaneously generated electron-hole pairs. Beyond the dilute limit, a theoretical understanding is achieved via the edge magnetoplasmon description of interacting integer quantum Hall channels. Our findings establish that, counter-intuitively, the integer quantum Hall regime provides a platform of choice for exploring and manipulating quasiparticles with fractional quantum statistics.

On-Surface Self-Assembly Kinetic Study of Cu-Hexaazatriphenylene 2D Conjugated Metal-Organic Frameworks on Coinage Metals and MoS2 Substrates.

Supramolecular coordination self-assembly on solid surfaces provides an effective route to form two-dimensional (2D) metal-organic frameworks (MOFs). In such processes, surface-adsorbate interaction plays a key role in determining the MOFs' structural and chemical properties. Here, we conduct a systematic study of Cu-HAT (HAT = 1,4,5,8,9,12-hexaazatriphenylene) 2D conjugated MOFs (c-MOFs) self-assembled on Cu(111), Au(111), Ag(111), and MoS2 substrates. Using scanning tunneling microscopy and density functional theory calculations, we found that the as-formed Cu3HAT2 c-MOFs on the four substrates exhibit distinctive structural features including lattice constant and molecular conformation. The structural variations can be attributed to the differentiated substrate effects on the 2D c-MOFs, including adsorption energy, lattice commensurability, and surface reactivity. Specifically, the framework grown on MoS2 is nearly identical to its free-standing counterpart. This suggests that the 2D van der Waals (vdW) materials are good candidate substrates for building intrinsic 2D MOFs, which hold promise for next-generation electronic devices.

Evolution of PTCDA-derived seeds prior to graphene nanoribbon growth on Ge(001)

The synthesis of graphene nanoribbons (GNRs) can be realized via CH4 chemical vapor deposition (CVD) on substrates such as Ge(001) that promote highly anisotropic growth. Small polycyclic aromatic hydrocarbons (PAHs) are first sublimed onto Ge at relatively low temperature to form graphene-like seeds that subsequently initiate GNR growth with CH4 exposure at 1173 K. The behaviors of PAHs between their sublimation onto Ge and GNR growth are unclear. Here, we study an archetypical PAH – perylene-3,4,9,10-tetracarboxyl acid dianhydride (PTCDA) – on Ge(001) using both scanning tunneling microscopy (STM) and density functional theory (DFT) to characterize PAH configuration, surface diffusivity, and clustering. PTCDA becomes mobile above 673 K, consistent with a DFT diffusion barrier of 1.74 eV. The mobile PTCDA molecules meet, cluster, and fuse at Ge step edges, dehydrogenating at higher temperatures. These clusters have a height of 0.4 nm, similar to small graphene islands, and grow laterally with increasing temperature – reaching 1.2–2.1 nm in width at 1173 K, consistent with extrapolated CVD experiments. These results provide a plausible picture for how PTCDA forms seeds for anisotropic GNR CVD and show that PAHs with reduced surface diffusivity and inter-molecular reactivity are needed to enable more monodisperse PAH-seeded GNR synthesis.

Orientation transitions and chiral assemblies of para-terphenyl molecules on Cd(0001).

The interplay between orientation transition and chiral self-assemblies of para-terphenyl (P3P) molecules on the Cd(0001) surface has been investigated using low temperature scanning tunneling microscopy and density functional theory calculations. Three distinct molecular orientations have been discerned from the self-assembled thin films of P3P. At the low coverage, flat-lying molecules appear in the homochiral domains with the incommensurate registry to the substrate. With the coverage increasing, the incoming molecules are incorporated into the first layer with edge-on orientation and form the self-assembled zigzag chains. The alternative arrangement of zigzag chains with opposite chirality leads to the formation of a c(4 × 2) superstructure, in which the tilted molecules exhibit orientational frustration and fuzzy noises. The analysis of the tunneling spectra reveals that the electronic structure of P3P layers is contingent upon the hybridization between the electronic states of P3P molecules and the Cd(0001) surface. These results provide important insights into the interplay between orientational transition and chiral assembly of P3P molecules on metal substrates.

Construction of Two-Dimensional Organometallic Coordination Networks with Both Organic Kagome and Semiregular Metal Lattices on Au(111).

Two-dimensional metal-organic networks (2D MONs) having heterogeneous coordination nodes (HCNs) could exhibit excellent performance in catalysis and optoelectronics because of the unbalanced electron distribution of the coordinating metals. Therefore, the design and construction of 2D MONs with HCNs are highly desirable but remain challenging. Here, we report the construction of 2D organometallic coordination networks with an organic Kagome lattice and a semiregular metal lattice on Au(111) via the in situ formation of HCNs. Using a bifunctional precursor 1,4-dibromo-2,5-diisocyanobenzene, the coordination of isocyano with Au adatom on a room-temperature Au(111) yielded metal-organic coordination chains with isocyano-Au-isocyano nodes. In contrast, on a high-temperature Au(111), a selective debromination/coordination cascade reaction occurred, affording 2D organometallic coordination networks with phenyl-Au-isocyano nodes. By combining scanning tunneling microscopy and density functional theory calculations, we determined the structures of coordination products and the nature of coordination nodes, demonstrating a thermodynamically favorable pathway for forming the phenyl-Au-isocyano nodes.

Revealing the Influence of Molecular Chemisorption Direction on the Reaction Selectivity of Dehalogenative Coupling on Au(111): Polymerization versus Cyclization.

The control of reaction selectivity is of great interest in chemistry and depends crucially on the revelation of key influencing factors. Based on well-defined molecule-substrate model systems, various influencing factors have been elucidated, focusing primarily on the molecular precursors and the underlying substrates themselves, while interfacial properties have recently been shown to be essential as well. However, the influence of molecular chemisorption direction on reaction selectivity, as a subtle interplay between molecules and underlying substrates, remains elusive. In this work, by a combination of scanning tunneling microscopy imaging and density functional theory calculations, we report the influence of molecular chemisorption direction on the reaction selectivity of two types of dehalogenative coupling on Au(111), i.e., polymerization and cyclization, at the atomic level. The diffusion step of a reactive dehalogenated intermediate in two different chemisorption directions was theoretically revealed to be the key to determining the corresponding reaction selectivity. Our results highlight the important role of molecular chemisorption directions in regulating the on-surface dehalogenative coupling reaction pathways and products, which provides fundamental insights into the control of reaction selectivity by exploiting some subtle interfacial parameters in on-surface reactions for the fabrication of target low-dimensional carbon nanostructures.

Origin of Distinct Insulating Domains in the Layered Charge Density Wave Material 1T-TaS2.

Vertical charge order shapes the electronic properties in layered charge density wave (CDW) materials. Various stacking orders inevitably create nanoscale domains with distinct electronic structures inaccessible to bulk probes. Here, the stacking characteristics of bulk 1T-TaS2 are analyzed using scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations. It is observed that Mott-insulating domains undergo a transition to band-insulating domains restoring vertical dimerization of the CDWs. Furthermore, STS measurements covering a wide terrace reveal two distinct band insulating domains differentiated by band edge broadening. These DFT calculations reveal that the Mott insulating layers preferably reside on the subsurface, forming broader band edges in the neighboring band insulating layers. Ultimately, buried Mott insulating layers believed to harbor the quantum spin liquid phase are identified. These results resolve persistent issues regarding vertical charge order in 1T-TaS2, providing a new perspective for investigating emergent quantum phenomena in layered CDWmaterials.

Testing functional anchor groups for the efficient immobilization of molecular catalysts on silver surfaces

Modifications of complexes by attachment of anchor groups are widely used to control molecule-surface interactions. This is of importance for the fabrication of (catalytically active) hybrid systems, viz. of surface immobilized molecular catalysts. In this study, the complex fac-Re(S-Sbpy)(CO)3Cl (S-Sbpy = 3,3′-disulfide-2,2′-bipyridine), a sulfurated derivative of the prominent Re(bpy)(CO)3Cl class of CO2 reduction catalysts, was deposited onto the clean Ag(001) surface at room temperature. The complex is thermostable upon sublimation as supported by infrared absorption and nuclear magnetic resonance spectroscopy. Its anchoring process has been analyzed using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The growth behavior was directly contrasted to the one of the parent complex fac-Re(bpy)(CO)3Cl (bpy = 2,2′-bipyridine). The sulfurated complex nucleates as single molecule at different surface sites and at molecule clusters. In contrast, for the parent complex nucleation only occurs in clusters of several molecules at specifically oriented surface steps. While this shows that surface immobilization of the sulfurated complex is more efficient as compared to the parent, symmetry analysis of the STM topographic data supported by DFT calculations indicates that more than 90% of the complexes adsorb in a geometric configuration very similar to the one of the parent complex.

Implementation of the Su-Schrieffer-Heeger Model in the Self-Assembly Si-In Atomic Chains on the Si(553)-Au Surface.

Indium-decorated Si atomic chains on a stepped Si(553)-Au substrate are proposed as an extended Su-Schrieffer-Heeger (SSH) model, revealing topological end states. An appropriate amount of In atoms on the Si(553)-Au surface induce the self-assembly formation of trimer SSH chains, where the chain unit cell comprises one In atom and two Si atoms, confirmed by scanning tunneling microscopy images and density functional calculations. The electronic structure of the system, examined through scanning tunneling spectroscopy, manifests three electron bands within the Si-In chain, accompanied by additional midgap topological states exclusively appearing at the chain's end atoms. To elucidate the emergence of these topological states, a tight-binding model for a finite-length-extended SSH chain is proposed. Analysis of the energy spectra, density of states functions, and eigenfunctions demonstrates the topological nature of these self-assembled atomic chains.

TCAD simulation study of heavy ion radiation effects on hetero junctionless tunnel field effect transistor

Semiconductor devices used in radiation environment are more prone to degradation in device performance. Junctionless Tunnel Field Effect Transistor (JLTFET) is one of the most potential candidates which overcomes the short channel effects and fabrication difficulties. In this work, 20 nm JLTFET is proposed with Silicon in the drain/channel region whereas source uses different materials, Silicon Germanium (SiGe), Gallium Nitride (GaN), Gallium Arsenide (GaAs), Indium Arsenide (InAs). The device performance is examined by subjecting it to heavy ion radiation at a lower and higher dose of linear energy transfer (LET) values. It can be seen that the most sensitive location is the source/channel (S/C) interface for SiGe, GaN and GaAs whereas the drain/channel (D/C) interface for InAs. Further analysis is carried out at these vulnerable regions by matching ION of all materials. The parameters, transient peak current (Ipeak), collected charge (QC), threshold voltage shift (ΔVth) and bipolar gain (β) are extracted using transient simulations. It is observed that for a lower dose of LET, Ipeak of SiGe is 27% lesser than InAs and for higher dose of LET, SiGe shows 56% lesser Ipeak than InAs. SiGe is less sensitive at lower and higher dose of LET due to reduced ΔVth, tunneling and electron density.

Steering Electron-Induced Surface Reaction via a Molecular Assembly Approach.

Electrons not only serve as a "reactant" in redox reactions but also play a role in "catalyzing" some chemical processes. Despite the significance and ubiquitousness of electron-induced chemistry, many related scientific issues still await further exploration, among which is the impact of molecular assembly. In this work, microscopic insights into the vital role of molecular assembly in tweaking the electron-induced surface chemistry are unfolded by combined scanning tunneling microscopy and density functional theory studies. It is shown that the selective dissociation of a C-Cl bond in 4,4″-dichloro-1,1':3',1''-terphenyl (DCTP) on Cu(111) can be efficiently triggered by an electron injection via the STM tip into the unoccupied molecular orbital. The DCTP molecules are embedded in different assembly structures, including its self-assembly and coassemblies with Br adatoms. The energy threshold for the C-Cl bond cleavage increases as more Br adatoms stay close to the molecule, indicative of the sensitive response of the electron-induced surface reactivity of the C-Cl bond to the subtle change in the molecular assembly. Such a phenomenon is rationalized by the energy shift of the involved unoccupied molecular orbital of DCTP that is embedded in different assemblies. These findings shed new light on the tuning effect of molecular assembly on electron-induced reactions and introduce an efficient approach to precisely steer surface chemistry.

Separation of Halogen Atoms by Sodium from Dehalogenative Reactions on a Au(111) Surface.

On-surface dehalogenative reactions have been promising in the construction of nanostructures with diverse morphologies and intriguing electronic properties, while halogen (X), as the main byproduct, often impedes the formation of extended nanostructures and property characterization, and the reaction usually requires high C-X activation temperatures, especially on relatively inert Au(111). Enormous efforts in precursor design, halogen-to-halide conversion, and the introduction of extrinsic metal atoms have been devoted to either eliminating dissociated halogens or reducing reaction barriers. However, it is still challenging to separate halogens from molecular systems while facilitating C-X activation under mild conditions. Herein, a versatile halogen separation strategy has been developed based on the introduction of extrinsic sodium (Na) into dehalogenative reactions on Au(111) as model systems that both isolates the dissociated halogens and facilitates the C-Br activation under mild conditions. Moreover, the combination of scanning tunneling microscopy imaging and density functional theory calculations reveals the formation of sodium halides (NaX) from halogens in these separation processes as well as the reduction in reaction temperatures and barriers, demonstrating the versatility of extrinsic sodium as an effective "cleaner" and "dehalogenator" of surface halogens. Our study demonstrates a valuable strategy to facilitate the on-surface dehalogenative reactions, which will assist in the precise fabrication of low-dimensional carbon nanostructures.

Genesis and evolution mechanism of loess tunnels in the Loess Plateau, China

Loess tunnels are very common in the Loess Plateau, and they pose unique geological threats. Loess tunnels are often difficult to detect and control due to their concealment and sudden appearance. Thus far, research on the genesis and evolution of loess tunnels remains scarce. In this paper, the genesis and evolution mechanism of the loess tunnels in the Loess Plateau is studied in depth, and the location, shape, and size information are obtained via field investigations. The potential correlations between the loess sediment, the basic physical properties (depth, water content, particle size composition, collapsibility coefficient, and self-weight collapsibility coefficient), and the tunnel density are inferred based on the Pearson’s correlation coefficients and tests on the physical and mechanical properties of the loess sediments. In addition, spatial statistical modelling is employed to justify and predict the observed spatial distribution of the loess tunnels assuming Gaussian Markov random fields. The formation of loess tunnels is due to a combination of factors, including the formation thickness, soil properties, joints and fissures, topography, hydrogeology, and climatic conditions. The thickness of the loess, loess sediment properties, and their spatial relationship jointly determine the material basis of the formation of the loess tunnels. The loess tunnels at different depths have different main controlling factors that are hierarchical by depth. The evolution process of loess tunnels can be divided into five stages: the incubation stage, formation stage, development stage, failure stage, and withered stage. The characteristics of each stage are discussed in detail. Our work provides novel insights into subsurface erosion from the aspect of soil tunnels. It improves our understanding of hill slope geomorphological evolution and also provides effective techniques for tunnel erosion control.