Growth of Mesoscale Ordered Two-Dimensional Hydrogen-Bond Organic Framework with the Observation of Flat Band.

Flat bands (FBs), presenting a strongly interacting quantum system, have drawn increasing interest recently. However, experimental growth and synthesis of FB materials have been challenging and have remained elusive for the ideal form of monolayer materials where the FB arises from destructive quantum interference as predicted in 2D lattice models. Here, we report surface growth of a self-assembled monolayer of 2D hydrogen-bond (H-bond) organic frameworks (HOFs) of 1,3,5-tris(4-hydroxyphenyl)benzene (THPB) on Au(111) substrate and the observation of FB. High-resolution scanning tunneling microscopy or spectroscopy shows mesoscale, highly ordered, and uniform THPB HOF domains, while angle-resolved photoemission spectroscopy highlights a FB over the whole Brillouin zone. Density-functional-theory calculations and analyses reveal that the observed topological FB arises from a hidden electronic breathing-kagome lattice without atomically breathing bonds. Our findings demonstrate that self-assembly of HOFs provides a viable approach for synthesis of 2D organic topological materials, paving the way to explore many-body quantum states of topological FBs.

Semiconductor-Metal Phase Transition and Emergent Charge Density Waves in 1T-ZrX2 (X = Se, Te) at the Two-Dimensional Limit.

A charge density wave (CDW) is a collective quantum phenomenon in metals and features a wavelike modulation of the conduction electron density. A microscopic understanding and experimental control of this many-body electronic state in atomically thin materials remain hot topics in materials physics. By means of material engineering, we realized a dimensionality and Zr intercalation induced semiconductor-metal phase transition in 1T-ZrX2 (X = Se, Te) ultrathin films, accompanied by a commensurate 2 × 2 CDW order. Furthermore, we observed a CDW energy gap of up to 22 meV around the Fermi level. Fourier-transformed scanning tunneling microscopy and angle-resolved photoemission spectroscopy reveal that 1T-ZrX2 films exhibit the simplest Fermi surface among the known CDW materials in TMDCs, consisting only of a Zr 4d derived elliptical electron conduction band at the corners of the Brillouin zone.

Direct Observation of Global Elastic Intervalley Scattering Induced by Impurities on Graphene.

The scattering process induced by impurities in graphene plays a key role in transport properties. Especially, the disorder impurities can drive the ordered state with a hexagonal superlattice on graphene by electron-mediated interaction at a transition temperature. Using angle-resolved photoemission spectroscopy (ARPES), we reveal that the epitaxial monolayer and bilayer graphene with various impurities display global elastic intervalley scattering and quantum interference below the critical temperature (34 K), which leads to a set of new folded Dirac cones at the Brillouin-zone center by mixing two inequivalent Dirac cones. The Dirac electrons generated from intervalley scattering without chirality can be due to the breaking of the sublattice symmetry. In addition, the temperature-dependent ARPES measurements indicate the thermal damping of quantum interference patterns from Dirac electron scattering on impurities. Our results demonstrate that the electron scattering and interference induced by impurities can completely modulate the Dirac bands of graphene.

Bridge-bonded methylthiolate on Au(111) observed with the scanning tunneling microscope.

We report the discovery of bridge-bonded methylthiolate, SCH3, along the step edges of the Au(111) surface. Real-space imaging with a scanning tunnelling microscope reveals the presence of bridge-bonded SCH3 along both the [11[combining macron]0] and the [112[combining macron]] oriented step edges. The nearest neighbour distances of SCH3 along these steps are 2a and , respectively. The Au(111) terrace is covered with the usual CH3SAuSCH3 staples. The bridge-bonded alkanethiolate is expected to play a rather significant role in the formation of thiol-passivated Au nanoclusters because of the high fraction of atoms in similar low-coordination sites.

Topological edge states in a high-temperature superconductor FeSe/SrTiO3(001) film.

Superconducting and topological states are two most intriguing quantum phenomena in solid materials. The entanglement of these two states, the topological superconducting state, will give rise to even more exotic quantum phenomena. While many materials are found to be either a superconductor or a topological insulator, it is very rare that both states exist in one material. Here, we demonstrate by first-principles theory as well as scanning tunnelling spectroscopy and angle-resolved photoemission spectroscopy experiments that the recently discovered 'two-dimensional (2D) superconductor' of single-layer FeSe also exhibits 1D topological edge states within an energy gap of ∼40 meV at the M point below the Fermi level. It is the first 2D material that supports both superconducting and topological states, offering an exciting opportunity to study 2D topological superconductors through the proximity effect.

Electronic evidence of an insulator-superconductor crossover in single-layer FeSe/SrTiO3 films.

In high-temperature cuprate superconductors, it is now generally agreed that superconductivity is realized by doping an antiferromagnetic Mott (charge transfer) insulator. The doping-induced insulator-to-superconductor transition has been widely observed in cuprates, which provides important information for understanding the superconductivity mechanism. In the iron-based superconductors, however, the parent compound is mostly antiferromagnetic bad metal, raising a debate on whether an appropriate starting point should go with an itinerant picture or a localized picture. No evidence of doping-induced insulator-superconductor transition (or crossover) has been reported in the iron-based compounds so far. Here, we report an electronic evidence of an insulator-superconductor crossover observed in the single-layer FeSe film grown on a SrTiO3 substrate. By taking angle-resolved photoemission measurements on the electronic structure and energy gap, we have identified a clear evolution of an insulator to a superconductor with increasing carrier concentration. In particular, the insulator-superconductor crossover in FeSe/SrTiO3 film exhibits similar behaviors to that observed in the cuprate superconductors. Our results suggest that the observed insulator-superconductor crossover may be associated with the two-dimensionality that enhances electron localization or correlation. The reduced dimensionality and the interfacial effect provide a new pathway in searching for new phenomena and novel superconductors with a high transition temperature.

Self-assembled alkanethiol monolayers on gold surfaces: resolving the complex structure at the interface by STM.

The surface properties of metals and metal oxides can be modified by adding a single layer of organic molecules. A most popular route for depositing such a molecular layer is via the formation of self-assembled monolayers (SAMs). The molecules that form SAMs have a functionality which binds to the surface and the adsorption is self-regulated to terminate at exactly one single molecular layer. The very first example, which has become the most widely studied system, of SAMs on metal surfaces consists of chemisorbed alkylthiolate on gold. Despite the simplicity in the preparation of alkanethiol SAMs and the seemingly straightforward structure of such SAMs, the detailed bonding between the sulfur head group and gold is still subject to debate. Experimental and theoretical effort in the last six years has led to a much improved understanding of this classical system of SAMs. In this review, we will highlight the most recent progress in the study of the interfacial structure of alkanethiol SAMs on gold. We focus on the important phenomenon of phase transition that occurs from n-propanethiol to n-butanethiol, and propose a unified structural model to explain how the (3 × 4) phase for short chain alkanethiol monolayers (methyl-, ethyl- and propylthiolate monolayers) changes into the (3 × 2√3)-rect./c(4 × 2) phase for long chain molecular monolayers.

Quantum spin driven Yu-Shiba-Rusinov multiplets and fermion-parity-preserving phase transition in K3C60.

Magnetic impurities in superconductors are of increasing interest due to emergent Yu-Shiba-Rusinov (YSR) states and Majorana zero modes for fault-tolerant quantum computation. However, a direct relationship between the YSR multiple states and magnetic anisotropy splitting of quantum impurity spins remains poorly characterized. By using scanning tunneling microscopy, we systematically resolve individual transition-metal (Fe, Cr, and Ni) impurities induced YSR multiplets as well as their Zeeman effects in the K3C60 superconductor. The YSR multiplets show identical d orbital-like wave functions that are symmetry-mismatched to the threefold K3C60(1 1 1) host surface, breaking point-group symmetries of the spatial distribution of YSR bound states in real space. Remarkably, we identify an unprecedented fermion-parity-preserving quantum phase transition between ground states with opposite signs of the uniaxial magnetic anisotropy that can be manipulated by an external magnetic field. These findings can be readily understood in terms of anisotropy splitting of quantum impurity spins, and thus elucidate the intricate interplay between the magnetic anisotropy and YSR multiplets.

The dynamic surface evolution of halide perovskites induced by external energy stimulation.

Tracking the dynamic surface evolution of metal halide perovskite is crucial for understanding the corresponding fundamental principles of photoelectric properties and intrinsic instability. However, due to the volatility elements and soft lattice nature of perovskites, several important dynamic behaviors remain unclear. Here, an ultra-high vacuum (UHV) interconnection system integrated by surface-sensitive probing techniques has been developed to investigate the freshly cleaved surface of CH3NH3PbBr3  in situ under given energy stimulation. On this basis, the detailed three-step chemical decomposition pathway of perovskites has been clarified. Meanwhile, the evolution of crystal structure from cubic phase to tetragonal phase on the perovskite surface has been revealed under energy stimulation. Accompanied by chemical composition and crystal structure evolution, electronic structure changes including energy level position, hole effective mass, and Rashba splitting have also been accurately determined. These findings provide a clear perspective on the physical origin of optoelectronic properties and the decomposition mechanism of perovskites.

Realization of monolayer ZrTe5 topological insulators with wide band gaps.

Two-dimensional topological insulators hosting the quantum spin Hall effect have application potential in dissipationless electronics. To observe the quantum spin Hall effect at elevated temperatures, a wide band gap is indispensable to efficiently suppress bulk conduction. Yet, most candidate materials exhibit narrow or even negative band gaps. Here, via elegant control of van der Waals epitaxy, we have successfully grown monolayer ZrTe5 on a bilayer graphene/SiC substrate. The epitaxial ZrTe5 monolayer crystalizes in two allotrope isomers with different intralayer alignments of ZrTe3 prisms. Our scanning tunneling microscopy/spectroscopy characterization unveils an intrinsic full band gap as large as 254 meV and one-dimensional edge states localized along the periphery of the ZrTe5 monolayer. First-principles calculations further confirm that the large band gap originates from strong spin-orbit coupling, and the edge states are topologically nontrivial. These findings thus provide a highly desirable material platform for the exploration of the high-temperature quantum spin Hall effect.

Mixed methyl- and propyl-thiolate monolayers on a Au(111) surface.

Mixed methyl- and propyl-thiolate self-assembled monolayers (SAMs) are prepared on a Au(111) surface by exposing the gold substrate to methyl-propyl-disulfide vapor at room temperature. Scanning tunneling microscopy imaging of such SAMs reveals a (3 × 4) phase consisting of CH3-S-Au-S-CH3, CH3-S-Au-S-(CH2)2CH3, and CH3-(CH2)2-S-Au-S-(CH2)2CH3. Partial desorption of methyl-thiolate occurs when samples are thermally annealed to 373 K, leading to the formation of a striped phase consisting of primarily CH3-(CH2)2-S-Au-S-(CH2)2CH3.

The striped phases of ethylthiolate monolayers on the Au(111) surface: a scanning tunneling microscopy study.

Striped phases of ethylthiolate monolayers, corresponding to surface coverage in between 0.2 ML and 0.27 ML, were studied using high-resolution scanning tunneling microscopy. Striped phases consist of rows of Au-adatom-diethythiolate (AAD) aligned along the [112] direction. In the perpendicular [110] direction, the AAD rows adjust their spacing according to the surface coverage. A (5√3 × âˆš3)-R30° striped phase with 0.27 ML thiolate and a (6√3 × âˆš3)-R30° striped phase with 0.23 ML thiolate, both with long-range order, are found. A localized (5 × âˆš3)-rect. phase is also found as a minority phase embedded in the 5√3 × âˆš3)-R30° phase. This (5 × âˆš3)-rect. phase can be constructed using di-Au-adatom-tri-thiolate species.

Band splitting and enhanced charge density wave modulation in Mn-implanted CsV3Sb5.

Kagome metal CsV3Sb5 has attracted unprecedented attention due to the charge density wave (CDW), Z2 topological surface states and unconventional superconductivity. However, how the paramagnetic bulk CsV3Sb5 interacts with magnetic doping is rarely explored. Here we report a Mn-doped CsV3Sb5 single crystal successfully achieved by ion implantation, which exhibits obvious band splitting and enhanced CDW modulation via angle-resolved photoemission spectroscopy (ARPES). The band splitting is anisotropic and occurs in the entire Brillouin region. We observed a Dirac cone gap at the K point but it closed at 135 K ± 5 K, much higher than the bulk value of ∼94 K, suggesting enhanced CDW modulation. According to the facts of the transferred spectral weight to the Fermi level and weak antiferromagnetic order at low temperature, we ascribe the enhanced CDW to the polariton excitation and Kondo shielding effect. Our study not only offers a simple method to realize deep doping in bulk materials, but also provides an ideal platform to explore the coupling between exotic quantum states in CsV3Sb5.

Electronic Janus lattice and kagome-like bands in coloring-triangular MoTe2 monolayers.

Polymorphic structures of transition metal dichalcogenides (TMDs) host exotic electronic states, like charge density wave and superconductivity. However, the number of these structures is limited by crystal symmetries, which poses a challenge to achieving tailored lattices and properties both theoretically and experimentally. Here, we report a coloring-triangle (CT) latticed MoTe2 monolayer, termed CT-MoTe2, constructed by controllably introducing uniform and ordered mirror-twin-boundaries into a pristine monolayer via molecular beam epitaxy. Low-temperature scanning tunneling microscopy and spectroscopy (STM/STS) together with theoretical calculations reveal that the monolayer has an electronic Janus lattice, i.e., an energy-dependent atomic-lattice and a Te pseudo-sublattice, and shares the identical geometry with the Mo5Te8 layer. Dirac-like and flat electronic bands inherently existing in the CT lattice are identified by two broad and two prominent peaks in STS spectra, respectively, and verified with density-functional-theory calculations. Two types of intrinsic domain boundaries were observed, one of which maintains the electronic-Janus-lattice feature, implying potential applications as an energy-tunable electron-tunneling barrier in future functional devices.

Observation of a Folded Dirac Cone in Heavily Doped Graphene.

Superlattice potentials imposed on graphene can alter its Dirac states, enabling the realization of various quantum phases. We report the experimental observation of a replica Dirac cone at the Brillouin zone center induced by a superlattice in heavily doped graphene with Gd intercalation using angle-resolved photoemission spectroscopy (ARPES). The replica Dirac cone arises from the (√3× âˆš3)R30° superlattice formed by the intervalley coupling of two nonequivalent valleys (e.g., the Kekulé-like distortion phase), accompanied by a bandgap opening. According to the findings, the replica Dirac band in Gd-intercalated graphene disappears beyond a critical temperature of 30 K and can be suppressed by potassium adsorption. The modulation of the replica Dirac band is primarily attributable to the residual frozen gas, which can act as a source of intervalley scattering at temperatures below 30 K. Our results highlight the persistence of the hidden Kekulé-like phase within the heavily doped graphene, enriching our current understanding of its replica Dirac Fermions.

Charge instability of topological Fermi arcs in chiral crystal CoSi.

Topological boundary states emerged at the spatial boundary between topological non-trivial and trivial phases, are usually gapless, or commonly referred as metallic states. For example, the surface state of a topological insulator is a gapless Dirac state. These metallic topological boundary states are typically well described by non-interacting fermions. However, the behavior of topological boundary states with significant electron-electron interactions, which could turn the gapless boundary states into gapped ordered states, e.g., density wave states or superconducting states, is of great interest theoretically, but is still lacking evidence experimentally. Here, we report the observation of incommensurable charge density wave (CDW) formed on the topological boundary states driven by the electron-electron interactions on the (001) surface of CoSi. The wavevector of CDW varies as the temperature changes, which coincides with the evolution of topological surface Fermi arcs with temperature. The orientation of the CDW phase is determined by the chirality of the Fermi arcs, which indicates a direct association between CDW and Fermi arcs. Our finding will stimulate the search of more interactions-driven ordered states, such as superconductivity and magnetism, on the boundaries of topological materials.

Inducing itinerant ferromagnetism by manipulating van Hove singularity in epitaxial monolayer 1T-VSe2.

The itinerant ferromagnetism can be induced by a van Hove singularity (VHS) with a divergent density of states at Fermi level. Utilizing the giant magnified dielectric constant εr of SrTiO3(111) substrate with cooling, here we successfully manipulated the VHS in the epitaxial monolayer (ML) 1T-VSe2 film approaching to Fermi level via the large interfacial charge transfer, and thus induced a two-dimensional (2D) itinerant ferromagnetic state below 3.3 K. Combining the direct characterization of the VHS structure via angle-resolved photoemission spectroscopy (ARPES), together with the theoretical analysis, we ascribe the manipulation of VHS to the physical origin of the itinerant ferromagnetic state in ML 1T-VSe2. Therefore, we further demonstrated that the ferromagnetic state in the 2D system can be controlled through manipulating the VHS by engineering the film thickness or replacing the substrate. Our findings clearly evidence that the VHS can serve as an effective manipulating degree of freedom for the itinerant ferromagnetic state, expanding the application potentials of 2D magnets for the next-generation information technology.

Adsorption and electron-induced dissociation of ethanethiol on Au(111).

Dissociation of ethanethiol and the formation of Au-adatom-diethylthiolate rows on the Au(111) surface were investigated using scanning tunneling microscopy (STM) at low temperature. Ethanethiol molecules physisorb on Au(111) at 120 K by sequentially occupation of the elbow site, the fcc domain before covering the whole surface with a semiliquid layer without long-range order. Scanning the physisorbed layer with a sample bias higher than +1.2 V leads to dissociation via cleaving the H-S bond. One of the dissociation products, ethylthiolate, forms a double-row structure with the rows aligned in one of the [112(-)] directions. These double rows arise from the Au-adatom-dithiolate species: CH(3)CH(2)S-Au-SCH(2)CH(3).

Suppression of Intervalley Coupling in Graphene via Potassium Doping.

The quantum interference patterns induced by impurities in graphene can form the (√3 × âˆš3)R30° superlattice with intervalley scattering. This superlattice can lead to the folded Dirac cone at the center of Brillouin zone by coupling two non-equivalent valleys. Using angle-resolved photoemission spectroscopy (ARPES), we report the observation of suppression of the folded Dirac cone in mono- and bilayer graphene upon potassium doping. The intervalley coupling with chiral symmetry broken can persist upon a light potassium-doped level but be ruined at the heavily doped level. Meanwhile, the folded Dirac cone can be suppressed by the renormalization of the Dirac band with potassium doping. Our results demonstrate that the suppression of the intervalley scattering pattern by potassium doping could pave the way toward the realization of novel chiraltronic devices in superlattice graphene.

Relationship between the c(4×2) and the (√3×√3)R30° phases in alkanethiol self-assembled monolayers on Au(111).

Transformation between the two well-known phases of alkanethiol monolayers on Au(111), c(4×2) and (√3×√3)R30°, has been studied using scanning tunneling microscopy in ultra-high vacuum. Among the many versions of the c(4×2) phases observed, one particular structure where a lateral shift of adsorbate by as much as 0.17 nm within the unit cell is found. This lateral shift along the [112[combining macron]] direction corresponds to the movement of one adsorbed unit, towards its nearest neighbour from one hollow site to another (fcc to hcp, or hcp to fcc).