Low-temperature Scanning Tunneling Microscopy Research Articles

Melting of charge density wave and Mott gap collapse on 1T−TaS2 induced by interfacial water

Microscopically revealing the interactions between interfacial water and the quantum states of matter is an important task from both the materials science and the physics points of view. Here we report a low-temperature scanning tunneling microscopy (STM) and spectroscopy study of water adsorption on the charge density wave compound $1T\text{\ensuremath{-}}{\mathrm{TaS}}_{2}$, which has a Mott-insulating ground state. Interfacial water forms monolayer islands with $6\ifmmode\times\else\texttimes\fi{}6$ superstructures on the surface of $1T\text{\ensuremath{-}}{\mathrm{TaS}}_{2}$, and the charge order under water islands can be directly imaged in STM topographies taken with negative bias voltages. Compared with the original $\sqrt{13}\ifmmode\times\else\texttimes\fi{}\sqrt{13}$ charge order in $1T\text{\ensuremath{-}}{\mathrm{TaS}}_{2}$, the charge order under water islands becomes significantly disordered and denser. A $\mathsf{V}$-shaped gaplike feature emerges in water-covered $1T\text{\ensuremath{-}}{\mathrm{TaS}}_{2}$, which may be due to the enhanced dielectric constant of interfacial water, which reduces short-range Coulomb repulsion and induces Mott gap collapse. Our observations open the way to microscopically understanding the interactions between interfacial water and the correlated quantum states of matter.

Experimental Realization of One-Dimensional Metal-Inorganic Chain: Gold–Phosphorus Chain

Porous metal-organic frameworks have attracted tremendous research interest, because of the presence of tunable porous structures and site-isolated catalytic units. However, bottom-up on-surface synthesis of their inorganic counterparts, metal-inorganic frameworks (MIFs), is rarely demonstrated. Here, we report a facile epitaxial growth of one-dimensional (1D) porous metal-inorganic chains, gold–phosphorus chains (AuP chains), in which phosphorus magic clusters P4 are interconnected by Au atoms extracted from the underlying Au(110) surface. The atomic structure has been precisely revealed through the combination of low-temperature scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory calculations. The growth process involves the formation of phosphorus dimers sitting at the bridge sites of the top rows of Au(110) (2 × 1) reconstructed surface at low coverage, followed by the etching of the phosphorus dimers and the transformation to 1D AuP chains with prolonged phosphorus deposition. Our findings provide a facile method for on-surface synthesis of 1D MIFs and pave the way for their potential applications in the future.

Single-molecule imaging of dinitrogen molecule adsorption on individual iron phthalocyanine

Nitrogen fixation is a vital process for both nature and industry. Whereas the nitrogenase can reduce nitrogen in ambient environment in nature, the industrialized Haber-Bosch process is a high temperature and high-pressure process. Since the discovery of the first dinitrogen complex in 1965, many dinitrogen complexes are prepared in a homogeneous solution to mimic the nitrogenase enzyme in nature. However, studies of the heterogeneous process on surface are rarely addressed. Moreover, molecular scale characterization for such dinitrogen complex is lacking. Here, we present a simple model system to investigate, at the single-molecule level, the binding of dinitrogen on a surface confined iron phthalocyanine (FePc) monolayer through the combination of in-situ low-temperature scanning tunneling microscopy (LT-STM) and X-ray photoelectron spectroscopy (XPS) measurements. The iron center in FePc molecule deposited on Au(111) and highly oriented pyrolytic graphite (HOPG) surface can adsorb dinitrogen molecule at room temperature and low pressure. A comparative study reveals that the adsorption behaviors of FePc on these two different substrates are identical. Chemical bond is formed between the dinitrogen and the Fe atom in the FePc molecule, which greatly modifies the electronic structure of FePc. The bonding is reversible and can be manipulated by applying bias using a STM tip or by thermal annealing.

Probing the intermolecular coupled vibrations in a water cluster with inelastic electron tunneling spectroscopy.

The hydrogen-bonding networks of water have strong intra- and intermolecular vibrational coupling which influences the energy dissipation and proton transfer in water. Disentangling and quantitative characterization of different coupling effects in water at a single-molecular level still remains a great challenge. Using tip-enhanced inelastic electron tunneling spectroscopy (IETS) based on low-temperature scanning tunneling microscopy, we report the direct quantitative assessment of the intermolecular coupling constants of the OH-stretch vibrational bands of an isolated water tetramer adsorbed on a Au(111)-supported NaCl(001) bilayer film. This is achieved by distinguishing various coupled modes of the H-bonded O-H stretching vibrations through tip-height dependent IET spectra. In contrast, such vibrational coupling is negligible in the half-deuterated water tetramer owing to the large energy mismatch between the OH and OD stretching modes. Not only do these findings advance our understanding on the effects of local environment on the intermolecular vibrational coupling in water, but also open up a new route for vibrational spectroscopic studies of extended H-bonded network at the single-molecular level.

Stable π-radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) adsorbed at the elbows of [formula omitted] reconstructed Au(111)

Stable organic radicals serve as model systems for investigating metal-free magnetic phenomena at (sub)nanometer length scales. We have investigated at the single-molecule level the stable π-radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) adsorbed at the elbow sites of the 22×3 reconstructed Au(111) surface. Low-temperature scanning tunneling microscopy (STM) and -spectroscopy under ultrahigh vacuum conditions at 8 K reveal structural as well as frontier-orbital related electronic details of DPPH/Au(111). A Kondo-like spectroscopic signature indicates preservation of the unpaired electron spin state.

Dissimilar Decoupling Behavior of Two-Dimensional Materials on Metal Surfaces.

The efficiency of hexagonal boron nitride and graphene to separate the hydrocarbon molecule C64H36 from Ru(0001) and Pt(111) surfaces is explored in low-temperature scanning tunneling microscopy and spectroscopy experiments. Both 2D materials enable the observation of the Franck-Condon effect in both frontier orbitals. On hexagonal boron nitride, vibronic progression with two vibrational energies gives rise to sharp orbital sidebands that are clearly visible up to the second order of the vibrational quantum number with different Huang-Rhys factors. In contrast, on graphene, orbital and vibronic spectroscopic signatures exhibit broad line shapes, with the second-order progression being hardly discriminable. Only a single vibrational quantum energy leaves its fingerprint in the Franck-Condon spectrum.

Scanned Single-Electron Probe inside a Silicon Electronic Device.

Solid-state devices can be fabricated at the atomic scale, with applications ranging from classical logic to current standards and quantum technologies. Although it is very desirable to probe these devices and the quantum states they host at the atomic scale, typical methods rely on long-ranged capacitive interactions, making this difficult. Here, we probe a silicon electronic device at the atomic scale using a localized electronic quantum dot induced directly within the device at a desired location, using the biased tip of a low-temperature scanning tunneling microscope. We demonstrate control over short-ranged tunnel coupling interactions of the quantum dot with the device's source reservoir using sub-nanometer position control of the tip and the quantum dot energy level using a voltage applied to the device's gate reservoir. Despite the ∼1 nm proximity of the quantum dot to the metallic tip, we find that the gate provides sufficient capacitance to enable a high degree of electric control. Combined with atomic-scale imaging, we use the quantum dot to probe applied electric fields and charge in individual defects in the device. This capability is expected to aid in the understanding of atomic-scale devices and the quantum states realized in them.

Mott phase in a van der Waals transition-metal halide at single-layer limit

Two-dimensional materials offer opportunities for unravelling unprecedented ordered states at single layer limit. Among such ordered states, Mott phase is rarely explored. Here, we report the Mott phase in van der Waals chromium (II) iodide (CrI2) films. High quality CrI2 films with atomically flat surface and macro size are grown on graphitized 6H-SiC(0001) substrate by molecular beam epitaxy. By in situ low temperature scanning tunneling microscopy and spectroscopy (STM/STS), we reveal that the film has a band gap as large as ~3.2 eV, which is nearly thickness independent. Density functional plus dynamic mean field theory calculations suggest that CrI2 films may be a strong Mott insulator with a ferromagnetically ordered ground state. The Mott phase is corroborated by the spectral band splitting, that is consistent with the extended Hubbard model, and gap reduction at charge dopants. Our study provides a platform for studying correlated electron states at single layer limit.

Adsorption behavior of tin phthalocyanine onto the (110) face of rutile TiO2.

The adsorption behavior of tin phthalocyanine (SnPc) molecules on rutile TiO2(110) was studied by scanning tunneling microscopy (STM). Low-temperature STM measurements of single molecules reveal the coexistence of two conformations of molecules on the TiO2 surface. Density functional theory-based simulations (DFT) indicate that the difference originates from the position of the tin atom protruding from the molecule plane. The irreversible switching of Sn-up molecules into the Sn-down conformation was observed either after sample annealing at 200 °C or as a result of tip-induced manipulation. Room-temperature measurements conducted for a coverage of close to a monolayer showed no tendency for molecular arrangement.

Structural and local electronic properties of clean and Li-intercalated graphene on SiC(0001)

A low-temperature scanning tunnelling microscope (STM) has been used to study the graphene-SiC(0001) interface before and after Li intercalation. For clean graphene, spectroscopy of the differential conductance corroborates previous theoretical findings for the interfacial electronic structure (M. Kajihara et al., Surf. Sci. 647, 39 (2016)). An unambiguous relation between the spectroscopic onset of the interface states with changes in STM images is presented. Li intercalation leads to the disappearance of the 6 × 6 superstructure of clean graphene on SiC(0001) and efficiently suppresses the interface states. The additional doping of graphene due to the presence of Li is reflected by the shift of the Dirac point further below the Fermi energy.

Atomistic Positioning of Defects in Helium Ion Treated Single-Layer MoS2.

Structuring materials with atomic precision is the ultimate goal of nanotechnology and is becoming increasingly relevant as an enabling technology for quantum electronics/spintronics and quantum photonics. Here, we create atomic defects in monolayer MoS2 by helium ion (He-ion) beam lithography with a spatial fidelity approaching the single-atom limit in all three dimensions. Using low-temperature scanning tunneling microscopy (STM), we confirm the formation of individual point defects in MoS2 upon He-ion bombardment and show that defects are generated within 9 nm of the incident helium ions. Atom-specific sputtering yields are determined by analyzing the type and occurrence of defects observed in high-resolution STM images and compared with Monte Carlo simulations. Both theory and experiment indicate that the He-ion bombardment predominantly generates sulfur vacancies.

Self-Assembly of Metallo-Supramolecules under Kinetic or Thermodynamic Control: Characterization of Positional Isomers Using Scanning Tunneling Spectroscopy.

Coordination-driven self-assembly has been extensively employed to construct a variety of discrete structures as a bottom-up strategy. However, mechanistic understanding regarding whether self-assembly is under kinetic or thermodynamic control is less explored. To date, such mechanistic investigation has been limited to distinct, assembled structures. It still remains a formidable challenge to study the kinetic and thermodynamic behavior of self-assembly systems with multiple assembled isomers due to the lack of characterization methods. Herein, we use a stepwise strategy which combined self-recognition and self-assembly processes to construct giant metallo-supramolecules with 8 positional isomers in solution. With the help of ultrahigh-vacuum, low-temperature scanning tunneling microscopy and scanning tunneling spectroscopy, we were able to unambiguously differentiate 14 isomers on the substrate which correspond to 8 isomers in solution. Through measurement of 162 structures, the experimental probability of each isomer was obtained and compared with the theoretical probability. Such a comparison along with density functional theory (DFT) calculation suggested that although both kinetic and thermodynamic control existed in this self-assembly, the increased experimental probabilities of isomers compared to theoretical probabilities should be attributed to thermodynamic control.

Molecular-Scale Investigation of the Thermal and Chemical Stability of Monolayer PTCDA on Cu(111) and Cu(110).

Perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) has been intensively investigated for decades because of its unique electronic and optical properties and its applications in organic electronics and surface engineering and passivation of 2D materials. Recently, the high demand for achieving selective area deposition in device fabrications drives the research of utilizing organic molecules as a passivation layer on metals in the semiconductor industry. PTCDA molecules show promising potential to be used as a passivation layer on a metal surface because of their ability to form self-assembled compact lying-down layers with the well-exposed inert conjugated molecular π-plane. However, the thermal and chemical stabilities of monolayer PTCDA on metal surfaces have not been thoroughly studied. In this paper, we demonstrate that monolayer PTCDA on Cu(110) and Cu(111) surfaces exhibit good thermal and chemical stabilities, as revealed through the combination of in situ X-ray photoelectron spectroscopy and in situ low-temperature scanning tunneling microscopy measurements. We show that monolayer PTCDA on copper is stable up to 220 °C and decomposes to perylene at higher temperature. Monolayer PTCDA also shows good chemical stability when exposed to O2 and water, demonstrating good potential for its future applications as passivation layers in selective area deposition.

Electronic States and Magnetic Response of MnBi2Te4 by Scanning Tunneling Microscopy and Spectroscopy.

Exotic quantum phenomena have been demonstrated in recently discovered intrinsic magnetic topological insulator MnBi2Te4. At its two-dimensional limit, the quantum anomalous Hall effect and axion insulator state were observed in odd and even layers of MnBi2Te4, respectively. Here, we employ low-temperature scanning tunneling microscopy to study the electronic properties of MnBi2Te4. The quasiparticle interference patterns indicate that the electronic structures on the topmost layer of MnBi2Te4 are different from those of the expected out-of-plane A-type antiferromagnetic phase. The topological surface states may be embedded in deeper layers beneath the topmost surface. Such novel electronic structure is presumably related to the modification of crystalline structure during sample cleaving and reorientation of the magnetic moment of Mn atoms near the surface. Mn dopants substituted at the Bi site on the second atomic layer are observed. The electronic structures fluctuate at atomic scale on the surface, which can affect the magnetism of MnBi2Te4.

Controlling Metal-Organic Structure by Tuning Molecular Size, Supported Substrate, and Type of Metal

Metal-organic structures are controllably prepared by tuning molecular size, supported substrates, and different kinds of metals. They are characterized by ultra-high vacuum low-temperature scanning tunnelling microscopy and Density functional theory calculations. The relatively larger size of all-trans-retinoic acid (ReA) compared to (2E,4E)-3-methyl-5-(2,6,6-trimethylcyclohex-1-enyl)penta-2,4-dienoic acid (DiA) leads to a bigger gap between neighboring ReA in a tetramer and allows for insertion of molecules, forming high density patterns. ReA forms various structures with different ratios (4:0, 3:1, 2:2) of the two chiral enantiomers on the less reactive Au(111) other than Ag(111). Unlike transition metals, electrostatic attraction between molecules and alkali metals is the origin of the formation of large quartet islands.

Inelastic Electron Tunneling in 2H-Ta_{x}Nb_{1-x}Se_{2} Evidenced by Scanning Tunneling Spectroscopy.

We report a detailed study of tunneling spectra measured on 2H-Ta_{x}Nb_{1-x}Se_{2} (x=0∼0.1) single crystals using a low-temperature scanning tunneling microscope. The prominent gaplike feature, which has not been understood for a long time, was found to be accompanied by some "in-gap" fine structures. By investigating the second-derivative spectra and their temperature and magnetic field dependencies, we were able to prove that inelastic electron tunneling is the origin of these features and obtain the Eliashberg function of 2H-Ta_{x}Nb_{1-x}Se_{2} at an atomic scale, providing a potential way to study the local Eliashberg function and the phonon spectra of the related transition-metal dichalcogenides.

Tuneable topological domain wall states in engineered atomic chains

Topological modes in one- and two-dimensional systems have been proposed for numerous applications utilizing their exotic electronic responses. The 1D, zero-energy, topologically protected end modes can be realized in structures implementing the Su–Schrieffer–Heeger (SSH) model. While the edge modes in the SSH model are at exactly the mid-gap energy, other paradigmatic 1D models such as trimer and coupled dimer chains have non-zero energy boundary states. However, these structures have not been realized in an atomically tuneable system that would allow explicit control of the edge modes. Here, we demonstrate atomically controlled trimer and coupled dimer chains realized using chlorine vacancies in the c(2 × 2) adsorption layer on Cu(100). This system allows wide tuneability of the domain wall modes that we experimentally demonstrate using low-temperature scanning tunneling microscopy (STM).

30 T scanning tunnelling microscope in a hybrid magnet with essentially non-metallic design

We report on the construction and performance of the first hybrid resistive-superconducting magnet (HM) based scanning tunnelling microscope (STM) above 30 T. This custom-design HM-STM features a novel design of the STM head unit, whose tip-sample approach is implemented using a slender piezoelectric tube (PZT). The scanner shares part of PZT by fixing a sapphire frame onto the front quarter of PZT to construct a compact tip-sample loop, realising an outer diameter of 8.8 mm, which makes it compatible with a narrow sample space. Its main components are made of non-metallic materials of sapphire, which allows it to be immune from eddy currents and to operate under the condition of strong magnetic field fluctuation from a hybrid magnet, as well as cryogen-free cryocooler magnet systems. To analyse the stiffness of the STM head unit, the eigenfrequencies with 11 kHz and 12 kHz in bending modes, 25 kHz in a torsional mode, and 67 kHz in a longitudinal mode were simulated by finite element analysis; also, the drifting rates of the STM in ambient conditions in the X-Y plane and Z direction were measured at 25.5 and 38.2 pm/min, respectively. We present the first atomic images in magnetic fields up to 30.1 T in an HM. The raw data show the stable and distinguished performance while ramping up to maximum fields, indicating the new device's potential capability of operating in the future 45T-hybrid magnet and hundred-field pulsed magnet. Meanwhile, our compact and concentric cylindrical STM insert can operate in the low-temperature tubular sample space housed by the HM bore to develop low-temperature and extreme high-magnetic field STM.

Synthesis of Metallopolymers and Direct Visualization of the Single Polymer Chain.

During the past few decades, the study of the single polymer chain has attracted considerable attention with the goal of exploring the structure-property relationship of polymers. It still, however, remains challenging due to the variability and low atomic resolution of the amorphous single polymer chain. Here, we demonstrated a new strategy to visualize the single metallopolymer chain with a hexameric or trimeric supramolecule as a repeat unit, in which Ru(II) with strong coordination and Fe(II) with weak coordination were combined together in a stepwise manner. With the help of ultrahigh-vacuum, low-temperature scanning tunneling microscopy (UHV-LT-STM) and scanning tunneling spectroscopy (STS), we were able to directly visualize both Ru(II) and Fe(II), which act as staining reagents on the repeat units, thus providing detailed structural information for the single polymer chain. As such, the direct visualization of the single random polymer chain is realized to enhance the characterization of polymers at the single-molecule level.

Nanoclusters and amorphous ice flakes built from water dimers

The water-solid interaction is fundamentally important for understanding and controlling the structures of interfacial water. Here we study the initial stage of water adsorption and nucleation on a Cd(0001) surface, through a combination of low temperature scanning tunnelling microscopy (STM) experiments and first-principles density-functional theory (DFT) calculation. Water is found to aggregate into various clusters with the dominant of water dimers. Particularly, the amorphous ice nanoflakes are built exclusively from water dimers. Driven by the electric field from a STM tip, the water dimers can hop across the surface, detach from a cluster with subsequent attaching to another, or rotate or diffuse within the amorphous ice nanoflakes. DFT calculations demonstrate that the ultrahigh stability of water dimers results from the adsorption-induced enhancement of dipole moment of water.