Low-temperature Scanning Tunneling Microscopy Study Research Articles

Ubiquitous stripe phase and enhanced electron pairing in the interfacial high- Tc superconductor FeSe/BaTiO3

Monolayer FeSe grown on SrTiO$_3$ provides a new playground for high-Tc superconductivity. A recent study shows the importance of stripy instability for superconductivity enhancement in FeSe/SrTiO3. However, it is still under debate whether such a stripe phase is ubiquitously bound to the interfacial superconductivity. Here, we report on molecular beam epitaxy growth and low-temperature scanning tunneling microscopy study of FeSe films on BaTiO$_3$(001). We find that the stripe phase is more prominent in FeSe/BaTiO$_3$. Long-range stripes exist in bilayer and triple-layer FeSe films at 4 K and even persist up to 77 K in the case of bilayer FeSe, with enlarged superconducting gaps upon alkali-metal deposition. The results point out an intimate correlation between the interfacial superconductivity and the stripe phase.

Strain-Relief Patterns and Kagome Lattice in Self-Assembled C60 Thin Films Grown on Cd(0001).

We report an ultra-high vacuum low-temperature scanning tunneling microscopy (STM) study of the C60 monolayer grown on Cd(0001). Individual C60 molecules adsorbed on Cd(0001) may exhibit a bright or dim contrast in STM images. When deposited at low temperatures close to 100 K, C60 thin films present a curved structure to release strain due to dominant molecule–substrate interactions. Moreover, edge dislocation appears when two different wavy structures encounter each other, which has seldomly been observed in molecular self-assembly. When growth temperature rose, we found two forms of symmetric kagome lattice superstructures, 2 × 2 and 4 × 4, at room temperature (RT) and 310 K, respectively. The results provide new insight into the growth behavior of C60 films.

Electronic Characterization of a Charge-Transfer Complex Monolayer on Graphene.

Organic charge-transfer complexes (CTCs) formed by strong electron acceptor and strong electron donor molecules are known to exhibit exotic effects such as superconductivity and charge density waves. We present a low-temperature scanning tunneling microscopy and spectroscopy (LT-STM/STS) study of a two-dimensional (2D) monolayer CTC of tetrathiafulvalene (TTF) and fluorinated tetracyanoquinodimethane (F4TCNQ), self-assembled on the surface of oxygen-intercalated epitaxial graphene on Ir(111) (G/O/Ir(111)). We confirm the formation of the charge-transfer complex by dI/dV spectroscopy and direct imaging of the singly occupied molecular orbitals. High-resolution spectroscopy reveals a gap at zero bias, suggesting the formation of a correlated ground state at low temperatures. These results point to the possibility to realize and study correlated ground states in charge-transfer complex monolayers on weakly interacting surfaces.

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.

Carbon Monoxide Stripe Motion Driven by Correlated Lateral Hopping in a 1.4 × 1.4 Monolayer Phase on Cu(111).

We report an ultra-high-vacuum low-temperature (4.6 K) scanning tunneling microscopy study of the molecular structure and dynamics of a carbon monoxide (CO) monolayer adsorbed at 20 K on Cu(111). We observe the well-known 1.4 × 1.4 phase of CO/Cu(111) for the first time in real-space imaging. At 4.6 K, the hexagonal symmetry of the monolayer is locally broken by the formation of stripes made of single and double CO rows of different apparent heights. Using density functional theory calculations, we assign the high rows to CO molecules adsorbed mostly at off-center top sites and the low rows to bridge sites. Groups of three or four very high molecules appear randomly and are assigned to nearest-neighbor, titled top site molecules. We observe simultaneous hopping of a few CO molecules between adjacent top and bridge sites, which produces the apparent motion of the stripe pattern.

Green's function approach to the Kondo effect in nanosized quantum corrals

We present a theoretical study of the Kondo effect for a magnetic atom placed inside nanocorrals using Green's function calculations. Based on the standard mapping of the Anderson impurity model to a one-dimensional chain model, we formulate a weak-coupling theory to study the Anderson impurities in a hosting bath with a surface state. With further taking into account the multiple scattering effect of the surrounding atoms, our calculations show that the Kondo resonance width of the atom placed at the center of the nanocorral can be significantly tuned by the corral size, in good agreement with recent experiments [Q. L. Li et al., Phys. Rev. B 97, 035417 (2018)]. The method can also be applied to the atom placed at an arbitrary position inside the corral where our calculation shows that the Kondo resonance width also oscillates as the function of its separation from the corral center. The prediction is further confirmed by the low-temperature scanning tunneling microscopy studies where a one-to-one correspondence is found. The good agreement with the experiments validates the generality of the method to the system where multiadatoms are involved.

Molecular Self-Assembly Driven by On-Surface Reduction: Anthracene and Tetracene on Au(111)

Epoxyacenes adsorbed on metal surfaces form acenes during thermally induced reduction in ultrahigh vacuum conditions. The incorporation of oxygen bridges into a hydrocarbon backbone leads to an enhanced stability of these molecular precursors under ambient condition; however, it has also a distinct influence on their adsorption and self-assembly on metal surfaces. Here, a low-temperature scanning tunneling microscopy (LT-STM) study of two different epoxyacenes on the Au(111) surface at submonolayer coverage is presented. Both molecules show self-assembly based on hydrogen bonding. While for the molecules with a single epoxy moiety nanostructures of three molecules are formed, extended molecular networks are achieved with two epoxy moieties and a slightly higher surface coverage. Upon annealing at 390 K, the molecules are reduced to the respective acene; however, both systems keep a similar assembled structure. The experimental STM images supported by theoretical calculations show that the self-assembly of...

On-Surface Synthesis of Porous Carbon Nanoribbons from Polymer Chains.

We demonstrate the on-surface synthesis of porous carbon nanoribbons on Ag(111) via a preprogrammed isomerization of conformationally flexible polymer chains followed by dehydrogenation reactions using thermal annealing. The carbon chains are fabricated by polymerization of prochiral 1,3,5-tris(3-bromophenyl)benzene (mTBPB) directly on the surface using an Ullmann-type reaction. At room temperature, mTBPB partially self-assembles in halogen-bonded 2D networks, which transform into organometallic chains and rings after debromination. The chain and ring formation is facilitated by conformational switching from a C3h to Cs symmetry of mTBPB via rotation of m-phenylene units. The high conformational selectivity toward Cs-conformers is templated by the twofold coordination to Ag adatoms. After thermally induced covalent-linking through aryl-aryl coupling, well-ordered nanoporous chains are created. Finally, the rotation of single phenylene units in combination with dehydrogenation cross-linking reactions within the polymer chains leads to the unexpected formation of porous carbon nanoribbons. We unveil the reaction mechanism in a low-temperature scanning tunneling microscopy study and demonstrate that the rotation of m-phenylene units is a powerful design tool to promote structural control in the synthesis of cyclic covalent organic nanostructures on metal surfaces.

Influence of Domain Walls in the Incommensurate Charge Density Wave State of Cu Intercalated 1T-TiSe_{2}.

We report a low-temperature scanning tunneling microscopy study of the charge density wave (CDW) order in 1T-TiSe_{2} and Cu_{0.08}TiSe_{2}. In pristine 1T-TiSe_{2} we observe a long-range coherent commensurate CDW (CCDW) order. In contrast, Cu_{0.08}TiSe_{2} displays an incommensurate CDW (ICDW) phase with localized CCDW domains separated by domain walls. Density of states measurements indicate that the domain walls host an extra population of fermions near the Fermi level which may play a role in the emergence of superconductivity in this system. Fourier transform scanning tunneling spectroscopy studies suggest that the dominant mechanism for CDW formation in the ICDW phase may be electron-phonon coupling.

Covalent Functionalization by Cycloaddition Reactions of Pristine Defect-Free Graphene.

Based on a low-temperature scanning tunneling microscopy study, we present a direct visualization of a cycloaddition reaction performed for some specific fluorinated maleimide molecules deposited on graphene. Up to now, it was widely admitted that such a cycloaddition reaction can not happen without pre-existing defects. However, our study shows that the cycloaddition reaction can be carried out on a defect-free basal graphene plane at room temperature. In the course of covalently grafting the molecules to graphene, the sp2 conjugation of carbon atoms was broken, and local sp3 bonds were created. The grafted molecules perturbed the graphene lattice, generating a standing-wave pattern with an anisotropy which was attributed to a (1,2) cycloaddition, as revealed by T-matrix approximation calculations. DFT calculations showed that while both (1,4) and (1,2) cycloadditions were possible on free-standing graphene, only the (1,2) cycloaddition could be obtained for graphene on SiC(0001). Globally averaging spectroscopic techniques, XPS and ARPES, were used to determine the modification in the elemental composition of the samples induced by the reaction, indicating an opening of an electronic gap in graphene.

Water and CO (co-)adsorption on pseudomorphic Pt films on Ru(0001) - a low-temperature scanning tunneling microscopy study.

Coadsorption of CO and water under ultrahigh vacuum (UHV) conditions can be considered as a model system for the interaction of metal surfaces with CO in an aqueous electrochemical environment. Nevertheless, this has rarely been investigated, and in particular for catalytically relevant bimetallic systems, there is hardly any information available. Here we report results of a low-temperature scanning tunneling microscopy (STM) study on the adsorption and coadsorption of CO and water on a Ru(0001) surface covered with a pseudomorphic Pt film of 2 or 3 monolayers thickness. The role of kinetic effects introduced by the sequence of adsorption, either pre-adsorption of CO followed by water adsorption or pre-adsorption of water followed by CO adsorption, on the adlayer structure formation will be demonstrated and discussed. Furthermore, the data show a distinct influence of the thickness of the Pt film, reflecting changes in the chemistry of the Pt surface due to electronic interactions with the underlying Ru(0001) substrate ('vertical ligand effects'). Implications of the present findings on the interaction of CO with these bimetallic PtRu surfaces under electrochemical conditions will be discussed.

Bilayer of Terbium Double-Decker Single-Molecule Magnets.

We report a low-temperature scanning tunneling microscopy and spectroscopy study of the structural and electronic properties of a bilayer of terbium double-decker (bis(phthalocyaninato)terbium(III), TbPc2) molecules on Au(111) at 5 K. The TbPc2 molecules are found to adsorb flat on top of a first compact TbPc2 monolayer on Au(111), forming a square-like packing similar to the underlying first layer. Their frontier-orbital electronic structure, measured by tunneling conductance spectroscopy, clearly differs from that of the underlying first monolayer. Our results of second-layer molecules indicate the absence of, both, hybrid molecule–substrate electronic states close to the Fermi level and a zero-bias Kondo resonance. We attribute these findings to a decreased electronic coupling with the Au(111) substrate.

Sticking with the Pointy End? Molecular Configuration of Chloro Boron-Subphthalocyanine on Cu(111).

In this combined low-temperature scanning tunneling microscopy (STM) and density functional theory (DFT) study, we investigate self-assembly of the dipolar nonplanar organic semiconductor chloro boron-subphthalocyanine (ClB-SubPc) on Cu(111). We observe multiple distinct adsorption configurations and demonstrate that these can only be understood by taking surface-catalyzed dechlorination into account. A detailed investigation of possible adsorption configurations and the comparison of experimental and computational STM images demonstrates that the configurations correspond to “Cl-up” molecules with the B–Cl moiety pointing toward the vacuum side of the interface, and dechlorinated molecules. In contrast to the standard interpretation of adsorption of nonplanar molecules in the phthalocyanine family, we find no evidence for “Cl-down” molecules where the B–Cl moiety would be pointing toward the Cu surface. We show computationally that such a configuration is unstable and thus is highly unlikely to occur for ClB-SubPc on Cu(111). Using these assignments, we discuss the different self-assembly motifs in the submonolayer coverage regime. The combination of DFT and STM is essential to gain a full atomistic understanding of the surface–molecule interactions, and our findings imply that phthalocyanines may undergo surface-catalyzed reactions hitherto not considered. Our results also indicate that care has to be taken when analyzing possible adsorption configurations of polar members of the phthalocyanine family, especially when they are adsorbed on comparably reactive surfaces like Cu(111).

Evidence for On-Site Carboxylation in the Self-Assembly of 4,4′-Biphenyl Dicarboxylic Acid on Cu(111)

Molecular self-assembly at surfaces is controlled by a complex balance between molecule–substrate and intermolecular interactions. The occurrence of chemical reactions at the surface will alter the governing hierarchy of interaction energies substantially. An important aspect in this respect is whether the chemical reaction happens independently from the self-assembly process, such that reacted species form ordered structures, or whether the reaction is an integral part of the self-assembly process and is triggered during the formation of ordered structures. We report on a low-temperature scanning tunneling microscopy study of ordered phases of 4,4′-biphenyl dicarboxylic acid on Cu(111) at submonolayer coverage in ultrahigh vacuum. For this system the thermally activated carboxylation reaction influences the formation of molecular structures significantly. We find evidence that near room temperature the deprotonation of a molecule is triggered by the specific configuration of neighboring molecules allowin...

Real-Space Imaging of the Atomic Structure of Organic-Inorganic Perovskite.

Organic-inorganic perovskite is a promising class of materials for photovoltaic applications and light emitting diodes. However, so far commercialization is still impeded by several drawbacks. Atomic-scale effects have been suggested to be possible causes, but an unequivocal experimental view at the atomic level is missing. Here, we present a low-temperature scanning tunneling microscopy study of single crystal methylammonium lead bromide CH3NH3PbBr3. Topographic images of the in situ cleaved perovskite surface reveal the real-space atomic structure. Compared to the bulk we observe modified arrangements of atoms and molecules on the surface. With the support of density functional theory we explain these by surface reconstruction and a substantial interplay of the orientation of the polar organic cations (CH3NH3)(+) with the position of the hosting anions. This leads to structurally and electronically distinct domains with ferroelectric and antiferroelectric character. We further demonstrate local probing of defects, which may also impact device performance.

Scanning tunneling microscopy study of the possible topological surface states in BiTeCl

Recently, the non-centrosymmetric bismuth tellurohalides such as BiTeCl are being studied as possible candidates for topological insulators. While some photoemission studies showed that BiTeCl is an inversion asymmetric topological insulator, others showed that it is a normal semiconductor with Rashba splitting. Meanwhile, first-principle calculations have failed to confirm the existence of topological surface states in BiTeCl so far. Therefore, the topological nature of BiTeCl requires further investigation. Here we report a low-temperature scanning tunneling microscopy study on the surface states of BiTeCl single crystals. On the tellurium (Te) -terminated surfaces with relatively low defect density, evidence for topological surface states is observed in the quasi-particle interference patterns, both in the anisotropy of the scattering vectors and the fast decay of the interference near the step edges. Meanwhile, on the samples with much higher defect densities, we observed surface states that behave differently. Our results may help to resolve the current controversy on the topological nature of BiTeCl.

Temperature-dependent self-assembly of NC-Ph5-CN molecules on Cu(111).

We present the results of temperature-dependent self-assembly of dicarbonitrile-pentaphenyl molecules (NC-Ph5-CN) on Cu(111). Our low-temperature scanning tunneling microscopy study reveals the formation of metal-organic and purely organic structures, depending on the substrate temperature during deposition (160-300 K), which determines the availability of Cu adatoms at the surface. We use tip functionalization with CO to obtain submolecular resolution and image the coordination atoms, enabling unequivocal identification of metal-coordinated nodes and purely organic ones. Moreover, we discuss the somewhat surprising structure obtained for deposition and measurement at 300 K.

Low-temperature scanning tunneling microscopy study on the electronic properties of a double-decker DyPc2 molecule at the surface.

To fully achieve potential applications of the double-decker molecules containing rare earth elements as single-molecule magnets in molecular spintronics, it is crucial to understand the 4f states of the rare earth atoms sandwiched in the double-decker molecules by metal electrodes. In this study, low-temperature scanning tunneling microscopy and spectroscopy were employed to investigate the isolated double-decker DyPc2 molecule adsorbed on Au(111) via its differential conductance measurements. The experimental results revealed that the differential conductance maps acquired at a constant height mode simply depicted the authentic molecular orbitals; moreover, the differential conductance maps achieved at a constant current mode could not directly probe the 4f states of the sandwiched Dy atom. This was consistent with the spectra obtained over the molecule center around the Fermi level, indicative of no Kondo feature. Upon decreasing the tip-molecule distance, the CH-mode images presented high-resolution structure but no information of the 4f states. All results indicated that the Dy atom barely contributed to the tunneling current because of the absence of coupling with the microscope tip, echoing the inaccessibility of the Dy 4f states in the double-decker DyPc2 molecule.

Review of magnetic atomic structures and their properties on noble metal surfaces

Ordered arrays of magnetic nanostructures have rich physical properties and potential applications, attracting much theoretical and experimental interest. These structures can now be fabricated and investigated at scales down to the atomic level. Herein, we review recent advances in the study of magnetic atomic structures on the surfaces of noble metals. These structures include one-dimensional strings, two-dimensional hexagonal superlattices, and novel structures stabilized by quantum guiding. We focus on low-temperature scanning tunneling microscopy studies as well as kinetic Monte Carlo simulations and ab initio calculations, to discuss the self- assembly formation conditions. Combining the results of scanning tunneling spectroscopy and tight-binding calculations, we studied the spectra of these well-ordered structures. We also discuss how quantum confinement in nanocorrals significantly influences adatom diffusion and self-assembly, leading to quantum-guided self-assembly and self-regulated atom trapping in open nanocorrals.

Structural analysis of the intermetallic surface compoundCePt5/Pt(111)

We report on a detailed low-energy electron diffraction (LEED) and low-temperature scanning tunneling microscopy (STM) study of the intermetallic surface compound ${\mathrm{CePt}}_{5}$ on Pt(111). Depending on the thickness we observe various diffraction patterns and superstructures. In the low-thickness regime a slightly compressed $(2\ifmmode\times\else\texttimes\fi{}2)$ superstructure is aligned along the $\ensuremath{\langle}1\overline{1}0\ensuremath{\rangle}$ direction of the Pt(111) substrate. STM reveals another, much larger superstructure with a periodicity of ($9.02\ifmmode\pm\else\textpm\fi{}0.45$) nm presumably responsible for the strongly broadened LEED spots. At about 3 unit cells (u.c.) the surface is dominated by a $(3\sqrt{3}\ifmmode\times\else\texttimes\fi{}3\sqrt{3})R{30}^{\ensuremath{\circ}}$ pattern as revealed by LEED satellites and Fourier-transformed high-resolution STM images. It is interpreted as a moir\'e pattern between the film and the substrate. We precisely determine the superstructure of the intermetallic film to $(\frac{10}{9}\sqrt{3}\ifmmode\times\else\texttimes\fi{}\frac{10}{9}\sqrt{3})R{30}^{\ensuremath{\circ}}$ with respect to the Pt(111) substrate. Above 3 u.c. the satellites progressively disappear. A model is developed that consistently describes this thickness-dependent transition. For ${\mathrm{CePt}}_{5}$ films with a thickness between 6 and 11 u.c. the lattice of the compressed $(2\ifmmode\times\else\texttimes\fi{}2)$ superstructure rotates back into the substrate's $\ensuremath{\langle}1\overline{1}0\ensuremath{\rangle}$ directions.