STM Experiments Research Articles

Cooling rate dependence of charge density wave phases in 1T-TaS2 studied by scanning tunneling microscopy and x-ray diffraction

The role of dynamics in the charge density wave (CDW) phases of 1T-TaS2, especially in accessing metastable phases, is still under scrutiny. We investigated cooling rate dependence on low-temperature CDW phases in this material by scanning tunneling microscopy and x-ray diffraction. In the majority of cases, we found the typical low temperature commensurate CDW and identified no other differences between samples that were fast cooled vs slow cooled from room temperature. In rare cases (1/18 STM experiments and 1/30 XRD experiments), we found a multi-domain structure in the low temperature CDW. The domain structure and metallic behavior revealed by STM and STS measurements of this phase are in excellent agreement with the previously reported metallic mosaic CDW phase.

Aggregation of Size-Selected Oxide Clusters Deposited onto Au(111).

Kinetic Monte Carlo (kMC) simulations along with density functional theory (DFT) calculations were used to investigate the aggregation of size-selected Nb3Oy (y = 5, 6, 7) clusters deposited onto the Au(111) surface. Recent STM experiments showed that the cluster binding sites and sizes of the cluster assemblies on the Nb3Oy/Au(111) surfaces strongly depend on the stoichiometry of the clusters, i.e., the oxygen-to-niobium ratio. To better understand the origins of these differences, kMC simulations of the nucleation and growth of cluster assemblies were performed using energy barriers for diffusion and intercluster interactions estimated from DFT calculations of cluster binding and dimerization energies, respectively. Comparisons of the kMC simulations with STM images of the as-deposited Nb3Oy/Au(111) surfaces at RT and after high temperature annealing were used to further optimize the energetics and gauge the importance of nearest neighbor interactions. The kMC simulations demonstrate that the assembly of Nb3Oy clusters on Au(111) are largely controlled by the magnitude of the barriers for diffusion and interparticle-bond formation, while changes at higher temperatures are sensitive to the binding energies between nearest neighbors. Simulations for the Nb3O5 and Nb3O6 clusters, which exhibit smaller cluster assembly sizes in STM, required larger diffusion barriers as well as different barriers for interparticle binding, which reflected differences in DFT calculated dimerization energies. The results demonstrate the effectiveness of combined DFT and kMC calculations for understanding how the stoichiometry affects the aggregation of small oxide clusters on a metal surface.

Distribution of Electron Density in Self-Assembled One-Dimensional Chains of Si Atoms.

Scanning tunneling microscopy measurements of height profiles, along the chains of Si atoms on the terrace edges of a perfectly ordered Si(553)-Au surface, reveal an STM bias-dependent mixed periodicity with periods of one, two and one and a half lattice constants. The simple linear chain model usually observed with STM cannot explain the unexpected fractional periodicity in the height profile. It was found that the edge Si chain stands for, in fact, a zigzag structure, which is composed of two neighboring rows of Si atoms and was detected in the STM experiments. Tight-binding calculations of the local density of states and charge occupancy along the chain explain the voltage-dependent modulations of the STM profiles and show that oscillation periods are determined mainly by the surface and STM tip Fermi energies.

Unconventional specular optical rotation in the charge ordered state of Kagome metal CsV3Sb5

Kagome metals AV3Sb5 (A = K, Cs, Rb) provide a rich platform for intertwined orders, where evidence for time-reversal symmetry breaking, likely due to the long-sought loop currents, has emerged in STM and muon spin relaxation experiments. An isotropic component in the spontaneous optical rotation has also been reported and was interpreted as the magneto-optic Kerr effect. Intriguingly, the observed rotations differ by five orders of magnitude between different wavelengths and samples, suggesting more intricate physics. Here we report optical rotation and polar Kerr measurements in CsV3Sb5 crystals at the same wavelength. We observe large isotropic components of 1 milliradian in the optical rotation that do not respond to applied magnetic fields, while the spontaneous Kerr signal is less than 20 nanoradians. Our results prove unambiguously that the reported isotropic rotation is not from time-reversal symmetry breaking but represents the long-sought specular optical rotation and indicates a new intertwined order.

Evolution of one-dimensional electronic dynamics in Nb2n+1SinTe4n+2

The electronic dynamics in ${\mathrm{Nb}}_{2n+1}{\mathrm{Si}}_{n}{\mathrm{Te}}_{4n+2}$ with varying component $n$ are systematically investigated by low-temperature scanning tunneling microscopy/spectroscopy (STM/STS). Our quasiparticle interferences reveal a nondecay standing wave at the Fermi level, proving the one-dimensional (1D) nature of the charge carriers (holes) in the materials. The energy and component dependence of phase relaxation length ${l}_{\ensuremath{\phi}}$ and lifetime $\phantom{\rule{4pt}{0ex}}\ensuremath{\tau}$ of 1D holes are unveiled and found to be consistent with the Tomonaga-Luttinger liquid theory. Our work demonstrates ${\mathrm{Nb}}_{2n+1}{\mathrm{Si}}_{n}{\mathrm{Te}}_{4n+2}$ as a platform to manipulate 1D physics and offers an alternative perspective for studying electronic dynamics of non-Fermi liquids through STM experiments.

Zero temperature superconductor–edge metal–insulator transition in two-dimensional bosonic systems

Motivated by the recent experimental observation of an intermediate bosonic metallic state in the two-dimensional superconductor-insulator transition at $T=0$, we study an extended Bose Hubbard model in the limit of large number of particles per site. Using a representation of this in terms of two coupled $XY$ models, we find, in addition to an insulating phase and a $(2+1)D$ superfluid phase, two other phases. One phase is a $2D$ superfluid phase where a crossover from $(2+1)D$ to $2D$ has taken place as a result of incipient charge ordering, signaled by $\theta$ disordering, and which is closely related to a supersolid phase. The other new phase is an edge metal state characterized by zero superfluid stiffness, zero charge ordering, and zero bulk compressibility. However, the edge compressibility of the system is nonzero. While we do not find any intermediate state with $2D$ metallic conductivity, we are able to connect these results to STM experiments on $\mathrm{MoS_2}$ showing brims of finite density of states around the entire edge of $2D$ $\mathrm{MoS_2}$ samples.

Magic-Angle Twisted Bilayer Graphene as a Topological Heavy Fermion Problem.

Magic-angle (θ=1.05°) twisted bilayer graphene (MATBG) has shown two seemingly contradictory characters: the localization and quantum-dot-like behavior in STM experiments, and delocalization in transport experiments. We construct a model, which naturally captures the two aspects, from the Bistritzer-MacDonald (BM) model in a first principle spirit. A set of local flat-band orbitals (f) centered at the AA-stacking regions are responsible to the localization. A set of extended topological semimetallic conduction bands (c), which are at small energetic separation from the local orbitals, are responsible to the delocalization and transport. The topological flat bands of the BM model appear as a result of the hybridization of f and c electrons. This model then provides a new perspective for the strong correlation physics, which is now described as strongly correlated f electrons coupled to nearly free c electrons-we hence name our model as the topological heavy fermion model. Using this model, we obtain the U(4) and U(4)×U(4) symmetries of Refs.[1-5] as well as the correlated insulator phases and their energies. Simple rules for the ground states and their Chern numbers are derived. Moreover, features such as the large dispersion of the charge ±1 excitations [2,6,7], and the minima of the charge gap at the Γ_{M} point can now, for the first time, be understood both qualitatively and quantitatively in a simple physical picture. Our mapping opens the prospect of using heavy-fermion physics machinery to the superconducting physics of MATBG.

Two-dimensional ionic liquids with an anomalous stepwise melting process and ultrahigh CO2 adsorption capacity

Ultrathin ionic liquid (IL) films have shown wide applications in the chemistry and materials fields. However, the structure feature and quantitative controlling mechanism of thin IL films have rarely been reported to date. Here, computational simulations combined with scanning tunnel microscope experiments are used to quantify the structure and function of the thinnest possible IL films, two-dimensional (2D) ILs, which consist of 2D ordered mono-ionic IL structures. Interestingly, the 2D ILs exhibit anomalous stepwise melting processes, involving localized rotated, out-of-plane flipped, and fully disordered states, which are different from 3D ILs. Meanwhile, a theoretical model and temperature-surface phase diagram are constructed to evaluate the critical stepwise melting behaviors. Furthermore, the 2D ILs also possess ultrahigh CO 2 adsorption capabilities and structural robustness during the CO 2 adsorption-desorption process. These findings are promising for the rational design of an IL-solid interface for CO 2 -capture-fixation chemistry and related applications. • 2D ionic liquid with ordered mono-ionic structure • The anomalous stepwise melting processes of 2D ionic liquids is revealed • A theoretical model is developed to evaluate the critical melting points • The 2D ionic liquids possess extremely high CO 2 adsorption capabilities Combining STM experiments and molecular dynamics simulations, Wang et al. investigate 2D ionic liquids that exhibit anomalous stepwise melting processes and superhigh CO 2 adsorption capacity. The 2D modification technique may provide a strategy for the precise control and function design of liquids.

Majorana fermion arcs and the local density of states of UTe2

$\text{UTe}_2$ is a leading candidate for chiral p-wave superconductivity, and for hosting exotic Majorana fermion quasiparticles. Motivated by recent STM experiments in this system, we study particle-hole symmetry breaking in chiral p-wave superconductors. We compute the local density of states from Majorana fermion surface states in the presence of Rashba surface spin-orbit coupling, which is expected to be sizeable in heavy-fermion materials like UTe$_2$. We show that time-reversal and surface reflection symmetry breaking lead to a natural pairing tendency towards a triplet pair density wave state, which naturally can account for broken particle-hole symmetry.

Charge-density-wave-driven electronic nematicity in a kagome superconductor

Electronic nematicity, in which rotational symmetry is spontaneously broken by electronic degrees of freedom, has been demonstrated as a ubiquitous phenomenon in correlated quantum fluids including high-temperature superconductors and quantum Hall systems1,2. Notably, the electronic nematicity in high-temperature superconductors exhibits an intriguing entanglement with superconductivity, generating complicated superconducting pairing and intertwined electronic orders. Recently, an unusual competition between superconductivity and a charge-density-wave (CDW) order has been found in the AV3Sb5 (A = K, Rb, Cs) family with two-dimensional vanadium kagome nets3-8. Whether these phenomena involve electronic nematicity is still unknown. Here we report evidence for the existence of electronic nematicity in CsV3Sb5, using a combination of elastoresistance measurements, nuclear magnetic resonance (NMR) and scanning tunnelling microscopy/spectroscopy (STM/S). The temperature-dependent elastoresistance coefficient (m11 minus m12) and NMR spectra demonstrate that, besides a C2 structural distortion of the 2a0 × 2a0 supercell owing to out-of-plane modulation, considerable nematic fluctuations emerge immediately below the CDW transition (approximately 94 kelvin) and finally a nematic transition occurs below about 35 kelvin. The STM experiment directly visualizes the C2-structure-pinned long-range nematic order below the nematic transition temperature, suggesting a novel nematicity described by a three-state Potts model. Our findings indicate an intrinsic electronic nematicity in the normal state of CsV3Sb5, which sets a new paradigm for revealing the role of electronic nematicity on pairing mechanism in unconventional superconductors.

In Ukrainian

By the method of density functional theory (B3LYP, 6-31G **) three types of displacements are calculated, namely oscillations as a whole, rotation and diffusion of dimers > Ge = Ge <, > Ge = Si < and > Si = Si <, which are formed on the crystalline surface of Si (001) (4×2) during the deposition of germanium atoms under conditions of molecular beam epitaxy. Calculations of angles of buckling of addimers are carried out. It is shown that when the addimers as a whole oscillate around the equilibrium position, the energy barriers are quite low, the highest of them occurs for a mixed addimer > Si = Ge <. Pure adders > Ge = Ge < and > Si = Si < oscillate between two degenerate states with an energy barrier of 0.042 and 0.014 eV, respectively. The structures of the transition state and the intermediate when the addimer > Ge = Ge < is moved between adjacent cells in the approximation of the constant bond length > Ge = Ge < are obtained. As calculations have shown, all transformations of surface dimers occur with relatively small activation energies, the numerical values of which agree satisfactorily with the results of STM experiments available in the literature.

Reassessing the Adsorption Behavior and on-Surface Reactivity of a Brominated Porphyrin on Cu(111)

On-surface coupling reactions and molecular conformation are essential processes for building tailored functional molecular nanostructures. Here, we study the thermal debromination and reactivity of free-base tetra(4-bromophenyl)porphyrin (H2TBrPP) on Cu(111) as a function of the substrate temperature. It has been previously reported in the literature that C–Br bonds remain intact at room temperature (RT) and that the Br···Cu(111) interaction induces a drastic surface reconstruction around the molecule periphery and a distortion in the adsorbate itself. However, based on a combination of STM and XPS experiments, supported by density functional theory (DFT) calculations, we instead demonstrate that debromination readily occurs at RT, leading to a new interpretation of both the adsorption behavior and the molecular coupling of H2TBrPP on Cu(111). For the molecules deposited on the metallic substrate held above RT, our STM measurements show the growth of ordered 2D metal–organic frameworks (MOFs).

Completing the picture of initial oxidation on copper

Accurate atomistic models for metal/oxide interfaces play a pivotal role in determining copper-based interfacial processes, ranging from electronic circuitry wirings to chemical catalysis. The “29” and “44” surfaces represent two of the most classical embryonic oxides on Cu(111). Although many attempts have been made to offer detailed atomistic models of these surface oxides, their atomic structures remain elusive. Here, we address this open question via ab initio STM simulations, where the functionalized-metal tips are explicitly included, and they are corroborated by STM experiments. We find that the fine structures of STM images of the “29” and “44” surfaces are correctly captured with STM theories going beyond the Tersoff-Hamann approximation only. Furthermore, we elucidate a complete atomistic model for the larger “44” surface, completing the picture of early oxidation on copper.

Electric-field-tunable electronic nematic order in twisted double-bilayer graphene

Graphene-based moiré systems have attracted considerable interest in recent years as they display a remarkable variety of correlated phenomena. Besides insulating and superconducting phases in the vicinity of integer fillings of the moiré unit cell, there is growing evidence for electronic nematic order both in twisted bilayer graphene and twisted double-bilayer graphene (tDBG), as signaled by the spontaneous breaking of the threefold rotational symmetry of the moiré superlattices. Here, we combine symmetry-based analysis with a microscopic continuum model to investigate the structure of the nematic phase of tDBG and its experimental manifestations. First, we perform a detailed comparison between the theoretically calculated local density of states and recent scanning tunneling microscopy data (arXiv:2009.11645) to resolve the internal structure of the nematic order parameter in terms of the layer, sublattice, spin, and valley degrees of freedom. We find strong evidence that the dominant contribution to the nematic order parameter comes from states at the moiré scale rather than at the microscopic scale of the individual graphene layers, which demonstrates the key role played by the moiré degrees of freedom and confirms the correlated nature of the nematic phase in tDBG. Secondly, our analysis reveals an unprecedented tunability of the orientation of the nematic director in tDBG by an externally applied electric field, allowing the director to rotate away from high-symmetry crystalline directions. We compute the expected fingerprints of this rotation in both STM and transport experiments, providing feasible ways to probe it. Rooted in the strong sensitivity of the flat bands of tDBG to the displacement field, this effect opens an interesting route to the electrostatic control of electronic nematicity in moiré systems.

Spin-spiral state of a Mn monolayer on W(110) studied by soft x-ray absorption spectroscopy at variable temperature

The noncollinear magnetic state of epitaxial Mn monolayers on tungsten (110) crystal surfaces is investigated by means of soft x-ray absorption spectroscopy, to complement earlier spin-polarized STM experiments. X-ray absorption spectra (XAS), x-ray linear dichroism (XLD) and x-ray magnetic circular dichroism (XMCD) Mn L23-edge spectra were measured in the temperature range from 8 to 300 K and compared to results of fully-relativistic ab initio calculations. We show that antiferromagnetic (AFM) helical and cycloidal spirals give rise to significantly different Mn L23-edge XLD signals, enabling thus to distinguish between them. It follows from our results that the magnetic ground state of a Mn monolayer on W(110) is an AFM cycloidal spin spiral. Based on temperature-dependent XAS, XLD and field-induced XMCD spectra we deduce that magnetic properties of the Mn monolayer on W(110) vary with temperature, but this variation lacks a clear indication of a phase transition in the investigated temperature range up to 300 K - even though a crossover exists around 170 K in the temperature dependence of XAS branching ratios and in XLD profiles.

Measurement of electronic structure and surface reconstruction in the superionic Cu2−xTe

Recently, layered copper chalcogenides Cu2X family (X=S, Se, Te) has attracted tremendous research interests due to their high thermoelectric (TE) performance, which is partly due to the superionic behavior of mobile Cu ions, making these compounds phonon liquids. Here, we systematically investigate the electronic structure and its temperature evolution of the less studied single crystal Cu2-xTe by the combination of angle resolved photoemission spectroscopy (ARPES) and scanning tunneling microscope/spectroscopy (STM/STS) experiments. While the band structure of the Cu2-xTe shows agreement with the calculations, we clearly observe a 2 * 2 surface reconstruction from both our low temperature ARPES and STM/STS experiments which survives up to room temperature. Interestingly, our low temperature STM experiments further reveal multiple types of reconstruction patterns, which suggests the origin of the surface reconstruction being the distributed deficiency of liquid-like Cu ions. Our findings reveal the electronic structure and impurity level of Cu2Te, which provides knowledge about its thermoelectric properties from the electronic degree of freedom.

Competition of spinon Fermi surface and heavy Fermi liquid states from the periodic Anderson to the Hubbard model

We study a model of correlated electrons coupled by tunnelling to a layer of itinerant metallic electrons, which allows to interpolate from a frustrated limit favorable to spin liquid states to a Kondo-lattice limit favorable to interlayer coherent heavy metallic states. We study the competition of the spinon fermi surface state and the interlayer coherent heavy Kondo metal that appears with increasing tunnelling. Employing a slave rotor mean-field approach, we obtain a phase diagram and describe two regimes where the spin liquid state is destroyed by weak interlayer tunnelling, (i) the Kondo limit in which the correlated electrons can be viewed as localized spin moments and (ii) near the Mott metal-insulator-transition where the spinon Fermi surface transitions continuously into a Fermi liquid. We study the shape of LDOS spectra of the putative spin liquid layer in the heavy Fermi liquid phase and describe the temperature dependence of its width arising from quasiparticle interactions and disorder effects throughout this phase diagram, in an effort to understand recent STM experiments of the candidate spin liquid 1T-TaSe$_2$ residing on metallic 1H-TaSe$_2$. Comparison of the shape and temperature dependence of the theoretical and experimental LDOS suggest that this system is either close to the localized Kondo limit, or in an intermediate coupling regime where the Kondo coupling and the Heisenberg exchange interaction are comparable.

A Large Starphene Comprising Pentacene Branches.

Starphenes are attractive compounds due to their characteristic physicochemical properties that are inherited from acenes, making them interesting compounds for organic electronics and optics. However, the instability and low solubility of larger starphene homologs make their synthesis extremely challenging. Herein, we present a new strategy leading to pristine [16]starphene in preparative scale. Our approach is based on a synthesis of a carbonyl-protected starphene precursor that is thermally converted in a solid-state form to the neat [16]starphene, which is then characterised with a variety of analytical methods, such as 13 C CP-MAS NMR, TGA, MS MALDI, UV/Vis and FTIR spectroscopy. Furthermore, high-resolution STM experiments unambiguously confirm its expected structure and reveal a moderate electronic delocalisation between the pentacene arms. Nucleus-independent chemical shifts NICS(1) are also calculated to survey its aromatic character.

A Large Starphene Comprising Pentacene Branches

AbstractStarphenes are attractive compounds due to their characteristic physicochemical properties that are inherited from acenes, making them interesting compounds for organic electronics and optics. However, the instability and low solubility of larger starphene homologs make their synthesis extremely challenging. Herein, we present a new strategy leading to pristine [16]starphene in preparative scale. Our approach is based on a synthesis of a carbonyl‐protected starphene precursor that is thermally converted in a solid‐state form to the neat [16]starphene, which is then characterised with a variety of analytical methods, such as 13C CP‐MAS NMR, TGA, MS MALDI, UV/Vis and FTIR spectroscopy. Furthermore, high‐resolution STM experiments unambiguously confirm its expected structure and reveal a moderate electronic delocalisation between the pentacene arms. Nucleus‐independent chemical shifts NICS(1) are also calculated to survey its aromatic character.

Bimetallic AuM (M = Ni and Ag) clusters/nanoparticles and their extended (111) surfaces for NO2 adsorption: A computational material study

Various compositions and structural motifs of bimetallic AuM (M = Ni and Ag) nanoalloy particles were investigated systematically in terms of structural, energetic, electronic, and stability properties by using the Density Functional Theory based ab initio approach. This method is used for exploring the properties of nanosized materials at the atomic/nano level. Synergetic effects were found on bimetallic AuNi and AuAg and NO2 adsorbed AuNi structures. The studied bimetallic nanoparticles/clusters may be superior to their monometallic ones and that it may be possible to tune the bimetallic nanoparticles/clusters to obtain better performance. Results indicate that the AuNi clusters support the dissociation of NO2 as NO + O, which provides a possible dissociation mechanism for the NO2 conversion into harmless substances. This may be important for reducing environmental pollution. Furthermore, the STM calculations were made for a comparison of future STM and AFM experiments.