Scanning Tunneling Spectroscopy Measurements Research Articles

Competing Interactions in the Self-Assembly of NC-Ph3-CN Molecules on Cu(111)

We report on low-temperature scanning tunneling microscopy and spectroscopy measurements on NC-Ph3-CN molecules adsorbed at 300 K on a Cu(111) surface. Upon cooling, the molecules form chain and honeycomb structures, incorporating Cu adatoms supplied by the substrate as metal linkers. In these assemblies, the molecules align along two main directions, with a relative abundance that depends on the coordination number and on the bond length. We show spectroscopic data about the unoccupied molecular orbitals and investigate the patterns obtained by depositing different amounts of molecules. Comparison of these results with the ones obtained for NC-Ph5-CN molecules on the same substrate enables us to establish a hierarchy of the different interaction forces at work in the system.

Tunneling spectroscopy of close-spaced dangling-bond pairs in Si(001):H.

We present a combined experimental and theoretical study of the electronic properties of close-spaced dangling-bond (DB) pairs in a hydrogen-passivated Si(001):H p-doped surface. Two types of DB pairs are considered, called “cross” and “line” structures. Our scanning tunneling spectroscopy (STS) data show that, although the spectra taken over different DBs in each pair exhibit a remarkable resemblance, they appear shifted by a constant energy that depends on the DB-pair type. This spontaneous asymmetry persists after repeated STS measurements. By comparison with density functional theory (DFT) calculations, we demonstrate that the magnitude of this shift and the relative position of the STS peaks can be explained by distinct charge states for each DB in the pair. We also explain how the charge state is modified by the presence of the scanning tunneling microscopy (STM) tip and the applied bias. Our results indicate that, using the STM tip, it is possible to control the charge state of individual DBs in complex structures, even if they are in close proximity. This observation might have important consequences for the design of electronic circuits and logic gates based on DBs in passivated silicon surfaces.

Local Spectroscopic Characterization of Spin and Layer Polarization in WSe_{2}.

We report scanning tunneling microscopy and scanning tunneling spectroscopy (STS) measurements of monolayer and bilayer WSe_{2}. We measure a band gap of 2.21±0.08 eV in monolayer WSe_{2}, which is much larger than the energy of the photoluminescence peak, indicating a large excitonic binding energy. We additionally observe significant electronic scattering arising from atomic-scale defects. Using Fourier transform STS, we map the energy versus momentum dispersion relations for monolayer and bilayer WSe_{2}. Further, by tracking allowed and forbidden scattering channels as a function of energy we infer the spin texture of both the conduction and valence bands. We observe a large spin-splitting of the valence band due to strong spin-orbit coupling, and additionally observe spin-valley-layer coupling in the conduction band of bilayer WSe_{2}.

Creating nanostructured superconductors on demand by local current annealing

Superconductivity results from a Bose condensate of Cooper-paired electrons with a macroscopic quantum wavefunction. Dramatic effects can occur when the region of the condensate is shaped and confined to the nanometer scale. Recent progress in nanostructured superconductors has revealed a route to topological superconductivity, with possible applications in quantum computing. However, challenges remain in controlling the shape and size of specific superconducting materials. Here, we report a new method to create nanostructured superconductors by partial crystallization of the half-Heusler material, YPtBi. Superconducting islands, with diameters in the range of 100 nm, were reproducibly created by local current annealing of disordered YPtBi in the tunneling junction of a scanning tunneling microscope (STM). We characterize the superconducting island properties by scanning tunneling spectroscopic measurements to determine the gap energy, critical temperature and field, coherence length, and vortex formations. These results show unique properties of a confined superconductor and demonstrate that this new method holds promise to create tailored superconductors for a wide variety of nanometer scale applications.

Tunneling into thin superconducting films: Interface-induced quasiparticle lifetime reduction

Scanning tunneling spectroscopy measurements of superconducting thin lanthanum films grown on a normal metal tungsten substrate reveal an extraordinarily large broadening of the coherence peaks. The observed broadening corresponds to very short electron-like quasiparticle lifetimes in the tunneling process. A thorough analysis considering the different relaxation processes reveals that the dominant mechanism is an efficient quasiparticle relaxation at the interface between the superconducting film and the underlying substrate. This process is of general relevance to scanning tunneling spectroscopy studies on thin superconducting films and enables measurements of film thicknesses via a spectroscopic method.

Interplay of electron-electron and electron-phonon interactions in the low-temperature phase of1T−TaS2

We investigate the interplay of the electron-electron and electron-phonon interactions in the electronic structure of an exotic insulating state in the layered dichalcogenide 1T-TaS2, where the charge-density-wave (CDW) order coexists with a Mott correlation gap. Scanning tunneling microscopy and spectroscopy measurements with high spatial and energy resolution determine unambiguously the CDW and the Mott gap as 0.20-0.24 eV and 0.32 eV, respectively, through the real space electron phases measured across the multiply formed energy gaps. An unusual local reduction of the Mott gap is observed on the defect site, which indicates the renormalization of the on-site Coulomb interaction by the electron-phonon coupling as predicted by the Hubbard-Holstein model. The Mott-gap renormalization provides new insight into the disorder-induced quasi-metallic phases of 1T-TaS2.

Inverse proximity effect at superconductor-ferromagnet interfaces: Evidence for induced triplet pairing in the superconductor

Considerable evidence for proximity-induced triplet superconductivity on the ferromagnetic side of a superconductor-ferromagnet (S-F) interface now exists; however, the corresponding effect on the superconductor side has hardly been addressed. We have performed scanning tunneling spectroscopy measurements on NbN superconducting thin films proximity coupled to the half-metallic ferromagnet La2/3Ca1/3MnO3 (LCMO) as a function of magnetic field. We have found that at zero and low applied magnetic fields the tunneling spectra on NbN typically show an anomalous gap structure with suppressed coherence peaks and, in some cases, a zero-bias conductance peak. As the field increases to the magnetic saturation of LCMO where the magnetization is homogeneous, the spectra become more BCS-like and the critical temperature of the NbN increases, implying a reduced proximity effect. Our results therefore suggest that triplet-pairing correlations are also induced in the S side of an S-F bilayer.

Fully gapped superconductivity in In-doped topological crystalline insulatorPb0.5Sn0.5Te

Superconductors derived from topological insulators and topological crystalline insulators by doping have long been considered to be candidates as topological superconductors. Pb$_{0.5}$Sn$_{0.5}$Te is a topological crystalline insulator with mirror symmetry protected surface states on (001), (011) and (111) oriented surfaces. The superconductor (Pb$_{0.5}$Sn$_{0.5}$)$_{0.7}$In$_{0.3}$Te is induced by In doping in Pb$_{0.5}$Sn$_{0.5}$Te, and is thought to be a topological superconductor. Here we report the first scanning tunneling spectroscopy measurement of the superconducting state as well as the superconducting energy gap in (Pb$_{0.5}$Sn$_{0.5}$)$_{0.7}$In$_{0.3}$Te on a (001)-oriented surface. The spectrum can be well fitted by an anisotropic $s$-wave gap function of $\Delta=0.72+0.18\cos4\theta$ meV using Dynes model. The results show that the quasi-particle density of states seem to be fully gapped without any in-gap states, in contradiction with the expectation of a topological superconductor.

Electronic Bandgap and Exciton Binding Energy of Layered Semiconductor TiS3

A study of the electronic and optical bandgap is presented in layered TiS3, an almost unexplored semiconductor that has attracted recent attention because of its large carrier mobility and inplane anisotropic properties, to determine its exciton binding energy. Scanning tunneling spectroscopy and photoelectrochemical measurements are combined with random phase approximation and Bethe–Salpeter equation calculations to obtain the electronic and optical bandgaps and thus the exciton binding energy. Experimental values are found for the electronic bandgap, optical bandgap, and exciton binding energy of 1.2 eV, 1.07 eV, and 130 meV, respectively, and 1.15 eV, 1.05 eV, and 100 meV for the corresponding theoretical results. The exciton binding energy is orders of magnitude larger than that of common semiconductors and comparable to bulk transition metal dichalcogenides, making TiS3 ribbons a highly interesting material for optoelectronic applications and for studying excitonic phenomena even at room temperature.

(Invited) Microscopic Studies of Black Phosphorus and Its Field-Effect Transistors

An increasing number of alternative two-dimensional (2D) materials are being explored in the “post-graphene age”, such as transition metal dichalcogenides (TMDs), silicene, and germanene. These materials are studied with the hope of overcoming graphene’s deficiencies such as its zero bandgap. Among these 2D layered materials, layered black phosphorus (phosphorene) is expected to exhibit superior mechanical, electrical, and optical properties due to an intrinsic and tunable bandgap. It is, besides graphene, the only stable elemental 2D material that can be mechanically exfoliated. Its high hole mobility and direct semiconducting bandgap hold the hope for the development of new electronic devices in the postsilicon era. However, before phosphorene can be integrated in everyday electronics, many aspects of the material still remain to be elucidated. Here we report atomic scale studies of electronic variation related to strain-induced anisotropic deformation of the puckered honeycomb structure of freshly cleaved black phosphorus using a high-resolution scanning tunneling spectroscopy (STS) survey along the light (x) and heavy (y) effective mass directions. Through a combination of STS measurements and first-principles calculations, a model for edge reconstruction and the related edge states are also determined. Besides, we also investigate electrical transport and optoelectronic properties of field effect transistors (FETs) made from few-layer black phosphorus (BP) crystals down to a few nanometers. In particular, we explore the anisotropic nature and photocurrent generation mechanisms in BP FETs through spatial-, polarization-, gate-, and bias-dependent photocurrent measurements. Our results reveal that the photocurrent signals at BP-electrode junctions are mainly attributed to the photovoltaic effect in the off-state and photo-thermoelectric effect in the on-state, and their anisotropic feature primarily results from the directional-dependent absorption of BP crystals. 1. Liangbo Liang, Jun Wang, Bobby G. Sumpter, Vincent Meunier, and Minghu Pan, “Electronic Bandgap and Edge Reconstruction in Phosphorene Materials”, Nano Letters, 2014, 14 (11), 6400–6406 2. Tu Hong, Bhim Chamlagain, Wenzhi Lin, Hsun-Jen Chuang, Minghu Pan, Zhixian Zhou, and Ya-Qiong Xu, “Polarized Photocurrent Response in Black Phosphorus Field-Effect Transistors”, Nanoscale, 6, 8978-8983(2014).

Spin-Dependent Conductance in Co/C60/Co/Ni Single-Molecule Junctions in the Contact Regime

The spin-dependent conductance in Co/C60/Co/Ni single-molecule magnetic tunnel junctions has been measured by combining spin-polarized scanning tunneling spectroscopy and current-displacement measurements using an ultrahigh vacuum low temperature scanning tunneling microscope (STM) at 5 K. With an electrical contact between molecule and electrodes, the measured junction conductance is 0.02–0.13 G0 in the low-conductance state and 0.12–0.76 G0 in the high-conductance state, respectively. The investigated single-molecule junctions exhibit large tunnel magnetoresistance (TMR) ratios higher than −60%. A variation of TMR from −63% to −94% has been observed due to different Co/Ni electrodes.

Closed-loop conductance scanning tunneling spectroscopy: demonstrating the equivalence to the open-loop alternative.

We demonstrate the validity of using closed-loop z(V) conductance scanning tunneling spectroscopy (STS) measurements for the determination of the effective tunneling barrier by comparing them to more conventional open-loop I(z) measurements. Through the development of a numerical model, the individual contributions to the effective tunneling barrier present in these experiments, such as the work function and the presence of an image charge, are determined quantitatively. This opens up the possibility of determining tunneling barriers of both vacuum and molecular systems in an alternative and more detailed manner.

Intrinsic disorder in graphene on transition metal dichalcogenide heterostructures.

Semiconducting transition metal dichalchogenides (TMDs) are a family of van der Waals bonded materials that have recently received interest as alternative substrates to hexagonal boron nitride (hBN) for graphene, as well as for components in novel graphene-based device heterostructures. We elucidate the local structural and electronic properties of graphene on TMD heterostructures through scanning tunneling microscopy and spectroscopy measurements. We find that crystalline defects intrinsic to TMDs induce substantial electronic scattering and charge carrier density fluctuations in the graphene. These signatures of local disorder explain the significant degradation of graphene device mobilities using TMD substrates, particularly compared to similar graphene on hBN devices.

Low-temperature scanning tunneling microscopy and spectroscopy measurements of ultrathin Pb films

We have investigated the electronic properties of ultrathin Pb films by low temperature scanning tunneling microscopy and spectroscopy. Our results show that 30 nm thick Pb(111) films grown on atomically flat highly oriented pyrolytic graphite (HOPG) and on amorphous SiO2 are both in the strong-coupling limit with transition temperature and energy gap close to the bulk value. Conductance maps and spectroscopy in the vortex state reveal a bound state at the center of the vortices, which suggest that the films are in the clean limit. Measurements of 3 nm Pb films grown on HOPG show a clear crossover to the weak-coupling regime and dirty limit.

Direct observation of ordered configurations of hydrogen adatoms on graphene.

Ordered configurations of hydrogen adatoms on graphene have long been proposed, calculated, and searched for. Here, we report direct observation of several ordered configurations of H adatoms on graphene by scanning tunneling microscopy. On the top side of the graphene plane, H atoms in the configurations appear to stick to carbon atoms in the same sublattice. Scanning tunneling spectroscopy measurements revealed a substantial gap in the local density of states in H-contained regions as well as in-gap states below the conduction band due to the incompleteness of H ordering. These findings can be well explained by density functional theory calculations based on double-sided H configurations. In addition, factors that may influence H ordering are discussed.

Investigation of surface defect states in CeO2-y nanocrystals by Scanning−tunneling microscopy/spectroscopy and ellipsometry

Synthesis process strongly influences the nanocrystalline CeO2-y defective structure. The presence of surface defects, in the form of oxygen vacancies in different charge states (F centers), can change the electronic properties of ceria nanocrystals. Nanocrystalline CeO2-y samples were synthesized using three different methods (precipitation, self-propagating room temperature, and hydrothermal synthesis). Raman spectroscopy was used to identify the presence of oxygen vacancies which presumably were formed at the nanoparticle surface. The defect concentration depended on the crystallite size of differently prepared CeO2-y samples. Scanning tunneling microscopy/spectroscopy and ellipsometry were employed to investigate the electronic band structure of defective CeO2-y nanocrystals. Scanning tunneling spectroscopy measurements demonstrated that inside the band gap of CeO2-y nanocrystals, besides the filled 4 f states, appeared additional states which were related to occupied and empty F center defect states. From the ellipsometric measurements, using the critical points model, the energy positions of different F centers states and the values of the reduced band gap energies were determined. The analysis of obtained data pointed out that depending on the synthesis method, different types of F centers (F+ and F0) can be formed in the CeO2-y nanocrystals. The formation of different F center defect states inside the ceria gap have a strong impact on the electrical, optical, and magnetic properties of ceria nanocrystals.

Excitation spectrum of Josephson vortices on surface superconductor

Motivated by recent discovery of superconductivity in monatomic In layer on silicon surfaces and scanning tunneling microscopy and spectroscopy (STM/STS) measurement, we study the excitation spectrum of vortex in a two-dimensional superconductor. According to the STM/STS measurements, the zero bias conductance (ZBC) for the vortices trapped at atomic steps has an anisotropic shape. In order to understand the experimental results, we study the local density of states (LDOS) as a function of strength of hopping integral at atomic steps. Our analysis is based on the self-consistent solution of the Bogoliubov-de Gennes equation coupled with a gap equation. The amplitude of the order parameter is restored at the vortex core and the phase winding becomes anisotropic with decreasing the hopping strength at atomic steps. The zero energy LDOS stretches along the step and the intensity decreases associated with the deformation of the order parameter. By comparing the theoretical results with experiments, we conclude Josephson vortices in 2D superconductivity have been observed.

Rashba splitting of graphene-covered Au(111) revealed by quasiparticle interference mapping

We report on low-temperature scanning tunneling spectroscopy measurements on epitaxial graphene flakes on Au(111). We show that using quasiparticle interference (QPI) mapping, we can discriminate between the electronic systems of graphene and Au(111). Beyond the scattering vectors, which can be ascribed to the elastic scattering within each of the systems, we observe QPI features related to the scattering process between graphene states and the Au(111) surface state. This additional interband scattering process at the graphene/Au(111) interface allows the direct quantitative determination of the Rashba-splitting of the Au(111) surface state, which cannot be evaluated from QPI measurements on pure Au(111). This experiment demonstrates a unique local spectroscopic approach to investigate the Rashba-split bands at weakly interacting epitaxial graphene/substrate interfaces.

Electronic bandgap and edge reconstruction in phosphorene materials.

Single-layer black phosphorus (BP), or phosphorene, is a highly anisotropic two-dimensional elemental material possessing promising semiconductor properties for flexible electronics. However, the direct bandgap of single-layer black phosphorus predicted theoretically has not been directly measured, and the properties of its edges have not been considered in detail. Here we report atomic scale electronic variation related to strain-induced anisotropic deformation of the puckered honeycomb structure of freshly cleaved black phosphorus using a high-resolution scanning tunneling spectroscopy (STS) survey along the light (x) and heavy (y) effective mass directions. Through a combination of STS measurements and first-principles calculations, a model for edge reconstruction is also determined. The reconstruction is shown to self-passivate most dangling bonds by switching the coordination number of phosphorus from 3 to 5 or 3 to 4.

High-stability cryogenic scanning tunneling microscope based on a closed-cycle cryostat.

We report on the design and operation of a cryogenic ultra-high vacuum (UHV) scanning tunneling microscope (STM) coupled to a closed-cycle cryostat (CCC). The STM is thermally linked to the CCC through helium exchange gas confined inside a volume enclosed by highly flexible rubber bellows. The STM is thus mechanically decoupled from the CCC, which results in a significant reduction of the mechanical noise transferred from the CCC to the STM. Noise analysis of the tunneling current shows current fluctuations up to 4% of the total current, which translates into tip-sample distance variations of up to 1.5 picometers. This noise level is sufficiently low for atomic-resolution imaging of a wide variety of surfaces. To demonstrate this, atomic-resolution images of Au(111) and NaCl(100)/Au(111) surfaces, as well as of carbon nanotubes deposited on Au(111), were obtained. Thermal drift analysis showed that under optimized conditions, the lateral stability of the STM scanner can be as low as 0.18 Å/h. Scanning Tunneling Spectroscopy measurements based on the lock-in technique were also carried out, and showed no detectable presence of noise from the closed-cycle cryostat. Using this cooling approach, temperatures as low as 16 K at the STM scanner have been achieved, with the complete cool-down of the system typically taking up to 12 h. These results demonstrate that the constructed CCC-coupled STM is a highly stable instrument capable of highly detailed spectroscopic investigations of materials and surfaces at the atomic scale.