Spectroscopic Imaging Scanning Tunneling Research Articles

Design and performance of an ultrahigh vacuum spectroscopic-imaging scanning tunneling microscope with a hybrid vibration isolation system.

A spectroscopic imaging-scanning tunneling microscope (SI-STM) allows for the atomic scale visualization of the surface electronic and magnetic structure of novel quantum materials with a high energy resolution. To achieve the optimal performance, a low vibration facility is required. Here, we describe the design and performance of an ultrahigh vacuum STM system supported by a hybrid vibration isolation system that consists of a pneumatic passive and a piezoelectric active vibration isolation stage. We present the detailed vibrational noise analysis of the hybrid vibration isolation system, which shows that the vibration level can be suppressed below 10-8 m/sec/√Hz for most frequencies up to 100Hz. Combined with a rigid STM design, vibrational noise can be successfully removed from the tunneling current. We demonstrate the performance of our STM system by taking high resolution spectroscopic maps and topographic images on several quantum materials. Our results establish a new strategy to achieve an effective vibration isolation system for high-resolution STM and other scanning probe microscopies to investigate the nanoscale quantum phenomena.

Nanoscale visualization and spectral fingerprints of the charge order in ScV6Sn6 distinct from other kagome metals

Charge density waves (CDWs) in kagome metals have been tied to many exotic phenomena. Here, using spectroscopic-imaging scanning tunneling microscopy and angle-resolved photoemission spectroscopy, we study the charge order in kagome metal ScV6Sn6. The similarity of electronic band structures of ScV6Sn6 and TbV6Sn6 (where charge ordering is absent) suggests that charge ordering in ScV6Sn6 is unlikely to be primarily driven by Fermi surface nesting of the Van Hove singularities. In contrast to the CDW state of cousin kagome metals, we find no evidence supporting rotation symmetry breaking. Differential conductance dI/dV spectra show a partial gap Δ1CO ≈ 20 meV at the Fermi level. Interestingly, dI/dV maps reveal that charge modulations exhibit an abrupt phase shift as a function of energy at energy much higher than Δ1CO, which we attribute to another spectral gap. Our experiments reveal a distinctive nature of the charge order in ScV6Sn6 with fundamental differences compared to other kagome metals.

A unique van Hove singularity in kagome superconductor CsV3-xTaxSb5 with enhanced superconductivity

Van Hove singularity (VHS) has been considered as a driving source for unconventional superconductivity. A VHS in two-dimensional (2D) materials consists of a saddle point connecting electron-like and hole-like bands. In a rare case, when a VHS appears at Fermi level, both electron-like and hole-like conduction can coexist, giving rise to an enhanced density of states as well as an attractive component of Coulomb interaction for unconventional electronic pairing. However, this van Hove scenario is often destroyed by an incorrect chemical potential or competing instabilities. Here, by using angle-resolved photoemission measurements, we report the observation of a VHS perfectly aligned with the Fermi level in a kagome superconductor CsV3-xTaxSb5 (x ~ 0.4), in which a record-high superconducting transition temperature is achieved among all the current variants of AV3Sb5 (A = Cs, Rb, K) at ambient pressure. Doping dependent measurements reveal the important role of van Hove scenario in boosting superconductivity, and spectroscopic-imaging scanning tunneling microscopy measurements indicate a distinct superconducting state in this system.

Cryogenic spectroscopic imaging scanning tunnelling microscope in a water-cooled magnet down to 1.7 K

Spectroscopic-imaging scanning tunnelling microscope (SI-STM) in a water-cooled magnet (WM) at low temperature has long been desirable in the condensed matter physics area since it is crucial for addressing various scientific problems, such as the behaviour of Cooper electrons crossing Hc2 in a high-temperature superconductor. Here we report on the construction and performance of the first atomically resolved cryogenic SI-STM in a WM. It operates at low temperatures of down to 1.7 K and in magnetic fields of up to 22 T (the WM's upper safety limit). The WM-SI-STM unit features a high-stiffness sapphire-based frame with the lowest eigenfrequency being 16 kHz. A slender piezoelectric scan tube (PST) is coaxially embedded in and glued to the frame. A well-polished zirconia shaft is spring-clamped onto the gold-coated inner wall of the PST to serve both the stepper and the scanner. The microscope unit as a whole is elastically suspended in a tubular sample space inside a 1K-cryostat by a two-stage internal passive vibrational reduction system, achieving a base temperature below 2 K in a static exchange gas. We demonstrate the SI-STM by imaging TaS2 at 50 K and FeSe at 1.7 K. Detecting the well-defined superconducting gap of FeSe, an iron-based superconductor, at variable magnetic fields demonstrates the device's spectroscopic imaging capability. The maximum noise intensity at the typical frequency is 3 pA per square root Hz at 22 T, which is only slightly worse than at 0 T, indicating the insensitivity of the STM to harsh conditions. In addition, our work shows the potential of SI-STMs for use in a WM and hybrid magnet with a 50 mm-bore size where high fields can be generated.

Tuning Multiple Landau Quantization in Transition-Metal Dichalcogenide with Strain.

Landau quantization associated with the quantized cyclotron motion of electrons under magnetic field provides the effective way to investigate topologically protected quantum states with entangled degrees of freedom and multiple quantum numbers. Here we report the cascade of Landau quantization in a strained type-II Dirac semimetal NiTe2 with spectroscopic-imaging scanning tunneling microscopy. The uniform-height surfaces exhibit single-sequence Landau levels (LLs) at a magnetic field originating from the quantization of topological surface state (TSS) across the Fermi level. Strikingly, we reveal the multiple sequence of LLs in the strained surface regions where the rotation symmetry is broken. First-principles calculations demonstrate that the multiple LLs attest to the remarkable lifting of the valley degeneracy of TSS by the in-plane uniaxial or shear strains. Our findings pave a pathway to tune multiple degrees of freedom and quantum numbers of TMDs via strain engineering for practical applications such as high-frequency rectifiers, Josephson diode and valleytronics.

A spectroscopic-imaging scanning tunneling microscope in vector magnetic field.

Cryogenic scanning tunneling microscopy and spectroscopy (STM/STS) performed in a high vector magnetic field provide unique possibilities for imaging surface magnetic structures and anisotropic superconductivity and exploring spin physics in quantum materials with atomic precision. Here, we describe the design, construction, and performance of a low-temperature, ultra-high-vacuum (UHV) spectroscopic-imaging STM equipped with a vector magnet capable of applying a field of up to 3T in any direction with respect to the sample surface. The STM head is housed in a fully bakeable UHV compatible cryogenic insert and is operational over variable temperatures ranging from ∼300 down to 1.5K. The insert can be easily upgraded using our home-designed 3He refrigerator. In addition to layered compounds, which can be cleaved at a temperature of either ∼300, ∼77, or ∼4.2 K to expose an atomically flat surface, thin films can also be studied by directly transferring using a UHV suitcase from our oxide thin-film laboratory. Samples can be treated further with a heater and a liquid helium/nitrogen cooling stage on a three-axis manipulator. The STM tips can be treated in vacuo by e-beam bombardment and ion sputtering. We demonstrate the successful operation of the STM with varying the magnetic field direction. Our facility provides a way to study materials in which magnetic anisotropy is a key factor in determining the electronic properties such as in topological semimetals and superconductors.

Unidirectional coherent quasiparticles in the high-temperature rotational symmetry broken phase of AV3Sb5 kagome superconductors

Kagome metals AV3Sb51 (where the A can stand for K, Cs or Rb) display a rich phase diagram of correlated electron states, including superconductivity2–4 and density waves5–7. Within this landscape, recent experiments have revealed signs of a transition below approximately 35 K attributed to an electronic nematic phase that spontaneously breaks the rotational symmetry of the lattice8. Here we show that the rotational symmetry breaking initiates universally at a high temperature in these materials, towards the 2 × 2 charge density wave transition temperature. We do this via spectroscopic-imaging scanning tunnelling microscopy and study the atomic-scale signatures of the electronic symmetry breaking across several materials in the AV3Sb5 family: CsV3Sb5, KV3Sb5 and Sn-doped CsV3Sb5. Below a substantially lower temperature of about 30 K, we measure the quantum interference of quasiparticles, a key signature for the formation of a coherent electronic state. These quasiparticles display a pronounced unidirectional feature in reciprocal space that strengthens as the superconducting state is approached. Our experiments reveal that high-temperature rotation symmetry breaking and the charge ordering states are separated from the superconducting ground state by an intermediate-temperature regime with coherent unidirectional quasiparticles. This picture is phenomenologically different compared to that in high-temperature superconductors, shedding light on the complex nature of rotation symmetry breaking in AV3Sb5 kagome superconductors. The charge density wave state in kagome superconductors is not fully understood. Now, evidence suggests that the rotational symmetry of the lattice is broken before coherence of unidirectional quasiparticles is established at a lower temperature.

Rotation symmetry breaking in the normal state of a kagome superconductor KV3Sb5

Recently discovered kagome superconductors AV3Sb5 (A=K, Rb, Cs) provide a fresh opportunity to realize and study correlation-driven electronic phenomena on a kagome lattice. The observation of a 2a0 by 2a0 charge density wave (CDW) in the normal state of all members of AV3Sb5 kagome family has generated an enormous amount of interest, in an effort to uncover the nature of this CDW state, and identify any "hidden" broken symmetries. We use spectroscopic-imaging scanning tunneling microscopy to reveal a pronounced intensity anisotropy between different 2a0 CDW directions in KV3Sb5. In particular, by examining the strength of ordering wave vectors as a function of energy in Fourier transforms of differential conductance maps, we find that one of the CDW directions is distinctly different compared to the other two. This observation points towards an intrinsic rotation symmetry broken electronic ground state, where the symmetry is reduced from C6 to C2. Furthermore, in contrast to previous reports, we find that the CDW phase is insensitive to magnetic field direction, regardless of the presence or absence of atomic defects. Our experiments, combined with earlier observations of a stripe 4a0 charge ordering in CsV3Sb5, establish correlation-driven rotation symmetry breaking as a unifying feature of AV3Sb5 kagome superconductors.

Quasiparticle Nodal Plane in the Fulde-Ferrell-Larkin-Ovchinnikov State of FeSe.

The Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) state, characterized by Cooper pairs condensed at finite momentum, has been a long-sought state that remains unresolved in many classes of fermionic systems, including superconductors and ultracold atoms. A fascinating aspect of the FFLO state is the emergence of periodic nodal planes in real space, but its observation is still lacking. Here we investigate the superconducting order parameter at high magnetic fields H applied perpendicular to the ab plane in a high-purity single crystal of FeSe. The heat capacity and magnetic torque provide thermodynamic evidence for a distinct superconducting phase at the low-temperature/high-field corner of the phase diagram. Despite the bulk superconductivity, spectroscopic-imaging scanning tunneling microscopy performed on the same crystal demonstrates that the order parameter vanishes at the surface upon entering the high-field phase. These results provide the first demonstration of a pinned planar node perpendicular to H, which is consistent with a putative FFLO state.

Substitutional Doping of MoS2 for Superior Gas-Sensing Applications: A Proof of Concept.

Two-dimensional layered materials (like MoS2 and WS2) those are being used as sensing layers in chemoresistive gas sensors suffer from poor sensitivity and selectivity. Mere surface functionalization (decorating of material surface) with metal nanoparticles (NPs) might not improve the sensor performance significantly. In this respect, doping of the layered material can play a significant role. Here, we report a simple yet effective substitutional doping technique to dope MoS2 with noble metals. Through various material characterization techniques like X-ray diffraction, scanning tunneling spectroscopy images, and selected area electron diffraction pattern, we were able to put forward the difference between surface decoration and substitutional doping by Au at S-vacancy sites of MoS2. Lattice strain was found to exist in the Au-doped MoS2 samples, while being absent in the Au NP-decorated samples. Surface chemistry studies performed using X-ray photoelectron spectroscopy showed a shift of Mo 3d peaks to lower binding energies, thus realizing p-type doping due to Au. The blue shift of the peaks as observed in Raman spectroscopy further confirmed the p-type doping. We found that gold-doped MoS2 was more sensitive and selective toward ammonia (with a response of 150% for 500 ppm of ammonia at 90 °C) as compared to gold NP-decorated MoS2. The advantages of substitutional doping and the gas-sensing mechanism were also explained by the density functional theory study. From the first principles study, it was found that the adsorption of Au atoms on the S-vacancy site of a monolayer of the MoS2 sheet was thermodynamically favorable with the adsorption energy of 2.39 eV. We also successfully doped MoS2 with Pt using the same technique. It was found that Pt-doped MoS2 gives huge response toward humidity (60,000% at 80% relative humidity). Thus, various noble metal doping of MoS2 selectively improved the sensing response toward specific analytes. From this work, we believe that this method could also be useful to dope other layered nanomaterials to design gas sensors with improved selectivity.

Nematic transition and nanoscale suppression of superconductivity in Fe(Te,Se)

The interplay of different electronic phases underlies the physics of unconventional superconductors. One of the most intriguing examples is a high-temperature superconductor, FeTe1 – xSex (refs. 1–11). This superconductor undergoes both a topological transition3,4, linked to the electronic band inversion, and an electronic nematic phase transition, associated with rotation symmetry breaking, around the same Se composition where the superconducting transition temperature peaks12,13. In this regime, nematic fluctuations and symmetry-breaking strain could be important, but this is yet to be fully explored. Using spectroscopic-imaging scanning tunnelling microscopy, we study the electronic nematic transition in FeTe1 – xSex as a function of composition. Near the critical Se composition, we find electronic nematicity in nanoscale regions. The superconducting coherence peaks are suppressed in areas where static nematic order is the strongest. By analysing atomic displacement in scanning tunnelling microscopy topographs, we find that small anisotropic strain can give rise to these strongly nematic localized regions. Our experiments reveal a tendency of FeTe1 – xSex, near x ≈ 0.45, to form puddles hosting static nematic order, suggestive of nematic fluctuations pinned by structural inhomogeneity, and demonstrate the effect of anisotropic strain on superconductivity in this regime. The interplay of superconductivity and nematicity of electrons remains unclear in a wide range of materials. Now, more evidence emerges that nematic fluctuations can be pinned into a static phase by disorder, which hinders the superconductivity.

Imaging the coupling between itinerant electrons and localised moments in the centrosymmetric skyrmion magnet GdRu2Si2

Magnetic skyrmions were thought to be stabilised only in inversion-symmetry breaking structures, but skyrmion lattices were recently discovered in inversion symmetric Gd-based compounds, spurring questions of the stabilisation mechanism. A natural consequence of a recent theoretical proposal, a coupling between itinerant electrons and localised magnetic moments, is that the skyrmions are amenable to detection using even non-magnetic probes such as spectroscopic-imaging scanning tunnelling microscopy (SI-STM). Here SI-STM observations of GdRu2Si2 reveal patterns in the local density of states that indeed vary with the underlying magnetic structures. These patterns are qualitatively reproduced by model calculations which assume exchange coupling between itinerant electrons and localised moments. These findings provide a clue to understand the skyrmion formation mechanism in GdRu2Si2.

Robust pseudogap across the magnetic field driven superconductor to insulator-like transition in strongly disordered NbN films

We investigate the magnetic field evolution of the superconducting state in a strongly disordered NbN thin film which exhibits a magnetic field tuned superconductor to insulator-like transition, employing low temperature scanning tunneling spectroscopy (STS). Transport measurements of the sample reveals a characteristic magnetic field, which separates the low field state where resistance decreases with decreasing temperature, i.e. dR/dT > 0 and a high-field state where dR/dT < 0. However, STS imaging of the superconducting state reveals a smooth evolution across this field and the presence of a robust pseudogap on both sides of this characteristic field. Our results suggest that the superconductor-insulator transition might be a percolative transition driven by the shrinking of superconducting fraction with magnetic field.

Quantum Vortex Core and Missing Pseudogap in the Multiband BCS-BEC Crossover Superconductor FeSe.

FeSe is argued as a superconductor in the Bardeen-Cooper-Schrieffer Bose-Einstein condensation crossover regime where the superconducting gap size and the superconducting transition temperature T_{c} are comparable to the Fermi energy. In this regime, vortex bound states should be well quantized and the preformed pairs above T_{c} may yield a pseudogap in the quasiparticle-excitation spectrum. We performed spectroscopic-imaging scanning tunneling microscopy to search for these features. We found Friedel-like oscillations near the vortex, which manifest the quantized levels, whereas the pseudogap was not detected. These apparently conflicting observations may be related to the multiband nature of FeSe.

Charge-stripe crystal phase in an insulating cuprate.

High-temperature (high-Tc) superconductivity in cuprates arises from carrier doping of an antiferromagnetic Mott insulator. This carrier doping leads to the formation of electronic liquid-crystal phases1. The insulating charge-stripe crystal phase is predicted to form when a small density of holes is doped into the charge-transfer insulator state1-3, but this phase is yet to be observed experimentally. Here, we use surface annealing to extend the accessible doping range in Bi-based cuprates and realize the lightly doped charge-transfer insulating state of the cuprate Bi2Sr2CaCu2O8+x. In this insulating state with a charge transfer gap on the order of ~1 eV, our spectroscopic imaging scanning tunnelling microscopy measurements provide strong evidence for a unidirectional charge-stripe order with a commensurate 4a0 period along the Cu-O-Cu bond. Notably, this insulating charge-stripe crystal phase develops before the onset of the pseudogap and formation of the Fermi surface. Our work provides fresh insight into the microscopic origin of electronic inhomogeneity in high-Tc cuprates.

Definition of design guidelines, construction, and performance of an ultra-stable scanning tunneling microscope for spectroscopic imaging.

Spectroscopic-imaging scanning tunneling microscopy is a powerful technique to study quantum materials, with the ability to provide information about the local electronic structure with subatomic resolution. However, as most spectroscopic measurements are conducted without feedback to the tip, it is extremely sensitive to vibrations coming from the environment. This requires the use of laboratories with low-vibration facilities combined with a very rigid microscope construction. In this article, we report on the design and fabrication of an ultra-stable scanning tunneling microscope (STM) for spectroscopic-imaging measurements that operates in ultra-high vacuum and at low temperatures (4 K). We start from existing designs with sapphire as the main material and improve the stiffness further by performing finite element analysis calculations for the main components of the microscope to guide design choices on the geometry of the parts. With this strategy, we construct a STM head with measured lowest resonant frequencies above f 0 = 13 kHz for the coarse approach mechanism, a value three times higher than what has been previously reported and in good agreement with the calculations. This allows us to achieve an average vibration level of ∼6 fm , without a dedicated low-vibration lab. We demonstrate the microscope's performance with topographic and spectroscopic measurements on the correlated metal Sr2RhO4, showing the quasiparticle interference pattern in real and reciprocal space with high signal-to-noise ratio.

In-situ angle-resolved photoemission spectroscopy of copper-oxide thin films synthesized by molecular beam epitaxy

Angle-resolved photoemission spectroscopy (ARPES) is the key momentum-resolved technique for direct probing of the electronic structure of a material. However, since it is highly surface-sensitive, it has been applied to a relatively small set of complex oxides that can be easily cleaved in ultra-high vacuum. Here we describe a new multi-module system at Brookhaven National Laboratory (BNL) in which an oxide molecular beam epitaxy (OMBE) is interconnected with an ARPES and a spectroscopic-imaging scanning tunneling microscopy (SI-STM) module. This new capability largely expands the range of complex-oxide materials and artificial heterostructures accessible to these two most powerful and complementary techniques for studies of electronic structure of materials. We also present the first experimental results obtained using this system — the ARPES studies of electronic band structure of a La2-xSrxCuO4 (LSCO) thin film grown by OMBE.

Direct imaging of surface states hidden in the third layer of Si (111)-7 × 7 surface by pz-wave tip

The direct visualization of the surface states of dimers in Si (111)-7 × 7 is still challenging although the DAS model has been proposed 33 years ago. In this letter, based on the partial density of states of the atoms in the reconstructed layers examined by the first principles calculations, scanning tunneling spectroscopy images with a pz-wave tip were carried out, which show a skull pattern at ∼0.7 eV, and 9 bright short lines at ∼1.00 eV in each unit cell, exhibiting obviously the electronic states from the third-layer atoms and dimers. The improved sensitivity (intensity and resolution) of scanning tunneling spectroscopy was ascribed to the enhanced tunneling matrix elements for pz-wave tip compared with s-wave tip. This discovery provides us a platform to explore the quantum states hidden in the deep of the materials surface.

Two distinct superconducting pairing states divided by the nematic end point in FeSe1-x S x.

Unconventional superconductivity often competes or coexists with other electronic orders. In iron-based superconductors, a central issue has been the relationship between superconductivity and electronic nematicity, spontaneous breaking of the lattice rotational symmetry. Using spectroscopic-imaging scanning tunneling microscopy, we simultaneously investigated the electronic structure and the superconducting gap in FeSe1-x S x , where the nematicity diminishes above the nematic end point (NEP) at x = 0.17. The nematic band structure appears as anisotropic quasiparticle-interference patterns that gradually become isotropic with increasing x without anomalies at the NEP. By contrast, the superconducting gap, which is intact in the nematic phase, discontinuously shrinks above the NEP. This implies that the presence or absence of nematicity results in two distinct pairing states, whereas the pairing interaction is insensitive to the strength of nematicity.

Quasiparticle interference of Fermi arc states in the type-II Weyl semimetal candidate WTe2

Weyl semimetals possess linear dispersions through pairs of Weyl nodes in three-dimensional momentum spaces, whose hallmark arclike surface states are connected to Weyl nodes with different chirality. $\mathrm{WT}{\mathrm{e}}_{2}$ was recently predicted to be a new type of Weyl semimetal. Here, we study the quasiparticle interference (QPI) of its Fermi arc surface states by combined spectroscopic-imaging scanning tunneling spectroscopy and density functional theory calculations. We observed the electron scattering on two types of $\mathrm{WT}{\mathrm{e}}_{2}$ surfaces unambiguously. Its scattering signal can be ascribed mainly to trivial surface states. We also address the QPI feature of nontrivial surface states from theoretical calculations. The experimental QPI patterns show some features that are likely related to the nontrivial Fermi arc states, whose existence is, however, not conclusive. Our study provides an indispensable clue for studying the Weyl semimetal phase in $\mathrm{WT}{\mathrm{e}}_{2}$.