Chemisorption-Induced Formation of Biphenylene Dimer on Ag(111).

We report an example that demonstrates the clear interdependence between surface-supported reactions and molecular-adsorption configurations. Two biphenyl-based molecules with two and four bromine substituents, i.e., 2,2'-dibromobiphenyl (DBBP) and 2,2',6,6'-tetrabromo-1,1'-biphenyl (TBBP), show completely different reaction pathways on a Ag(111) surface, leading to the selective formation of dibenzo[e,l]pyrene and biphenylene dimer, respectively. By combining low-temperature scanning tunneling microscopy, synchrotron radiation photoemission spectroscopy, and density functional theory calculations, we unravel the underlying reaction mechanism. After debromination, a biradical biphenyl can be stabilized by surface Ag adatoms, while a four-radical biphenyl undergoes spontaneous intramolecular annulation due to its extreme instability on Ag(111). Such different chemisorption-induced precursor states between DBBP and TBBP consequently lead to different reaction pathways after further annealing. In addition, using bond-resolving scanning tunneling microscopy and scanning tunneling spectroscopy, we determine with atomic precision the bond-length alternation of the biphenylene dimer product, which contains 4-, 6-, and 8-membered rings. The 4-membered ring units turn out to be radialene structures.

Realization of Electron Antidoping by Modulating the Breathing Distortion in BaBiO3.

The recent proposal of antidoping scheme breaks new ground in conceiving conversely functional materials and devices; yet, the few available examples belong to the correlated electron systems. Here, we demonstrate both theoretically and experimentally that the main group oxide BaBiO3 is a model system for antidoping using oxygen vacancies. The first-principles calculations show that the band gap systematically increases due to the strongly enhanced Bi-O breathing distortions away from the vacancies and the annihilation of Bi 6s/O 2p hybridized conduction bands near the vacancies. Our further spectroscopic experiments confirm that the band gap increases systematically with electron doping, with a maximal gap enhancement of ∼75% when the film's stoichiometry is reduced to BaBiO2.75. These results unambiguously demonstrate the remarkable antidoping effect in a material without strong electron correlations and underscores the importance of bond disproportionation in realizing such an effect.

Interfacial Polarons in van der Waals Heterojunction of Monolayer SnSe2 on SrTiO3 (001).

Interfacial polarons have been demonstrated to play important roles in heterostructures containing polar substrates. However, most of polarons found so far are diffusive large polarons; the discovery and investigation of small polarons at interfaces are scarce. Herein, we report the emergence of interfacial polarons in monolayer SnSe2 epitaxially grown on Nb-doped SrTiO3 (STO) surface using angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling microscopy (STM). ARPES spectra taken on this heterointerface reveal a nearly flat in-gap band correlated with a significant charge modulation in real space as observed with STM. An interfacial polaronic model is proposed to ascribe this in-gap band to the formation of self-trapped small polarons induced by charge accumulation and electron-phonon coupling at the van der Waals interface of SnSe2 and STO. Such a mechanism to form interfacial polaron is expected to generally exist in similar van der Waals heterojunctions consisting of layered 2D materials and polar substrates.

Creation of the Dirac Nodal Line by Extrinsic Symmetry Engineering.

The formation of the Dirac nodal line (DNL) requires intrinsic symmetry that can protect the degeneracy of continuous Dirac points in momentum space. Here, as an alternative approach, we propose an extrinsic symmetry protected DNL. On the basis of symmetry analysis and numerical calculations, we establish a general principle to design the nonsymmorphic symmetry protected 4-fold degenerate DNL against spin-orbit coupling in the nanopatterned 2D electron gas. Furthermore, on the basis of experimental measurements, we demonstrate the approximate realization of our proposal in the Bi/Cu(111) system, in which a highly dispersive DNL is observed at the boundary of the Brillouin zone. We envision that the extrinsic symmetry engineering will greatly enhance the ability for artificially constructing the exotic topological bands in the future.

Epitaxial growth of ultraflat stanene with topological band inversion.

Two-dimensional (2D) topological materials, including quantum spin/anomalous Hall insulators, have attracted intense research efforts owing to their promise for applications ranging from low-power electronics and high-performance thermoelectrics to fault-tolerant quantum computation. One key challenge is to fabricate topological materials with a large energy gap for room-temperature use. Stanene-the tin counterpart of graphene-is a promising material candidate distinguished by its tunable topological states and sizeable bandgap. Recent experiments have successfully fabricated stanene, but none of them have yet observed topological states. Here we demonstrate the growth of high-quality stanene on Cu(111) by low-temperature molecular beam epitaxy. Importantly, we discovered an unusually ultraflat stanene showing an in-plane s-p band inversion together with a spin-orbit-coupling-induced topological gap (~0.3 eV) at the Γ point, which represents a foremost group-IV ultraflat graphene-like material displaying topological features in experiment. The finding of ultraflat stanene opens opportunities for exploring two-dimensional topological physics and device applications.

Landau Quantization of a Narrow Doubly-Folded Wrinkle in Monolayer Graphene.

Folding can be an effective way to tailor the electronic properties of graphene and has attracted wide study interest in finding its novel properties. Here we present the experimental characterizations of the structural and electronic properties of a narrow graphene wrinkle on a SiO2/Si substrate using scanning tunneling microscopy/spectroscopy. Pronounced and nearly equally separated conductance peaks are observed in the d I/d V spectra of the wrinkle. We attribute these peaks to pseudo-Landau levels (PLLs) that are caused by a gradient-strain-induced pseudomagnetic field up to about 42 T in the narrow wrinkle. The introduction of the gradient strain and thus the pseudomagnetic field can be ascribed to the lattice deformation. A doubly-folded structure of the wrinkle is suggested. Our density functional theory calculations show that the band structure of the doubly folded graphene wrinkle has a parabolic dispersion, which can well explain the equally separated PLLs. The effective mass of carriers is obtained to be about 0.02 me ( me: the rest mass of electron), and interestingly, it is revealed that there exists valley polarization in the wrinkle. Such properties of the strained doubly folded wrinkle may provide a platform to explore some exciting phenomena in graphene, like zero-field quantum valley Hall effect.

Tuning the Doping Types in Graphene Sheets by N Monoelement.

The doping types of graphene sheets are generally tuned by different dopants with either three or five valence electrons. As a five-valence-electrons element, however, nitrogen dopants in graphene sheets have several substitutional geometries. So far, their distinct effects on electronic properties predicted by theoretical calculations have not been well identified. Here, we demonstrate that the doping types of graphene can be tuned by N monoelement under proper growth conditions using chemical vapor deposition (CVD), characterized by combining scanning tunneling microscopy/spectroscopy, X-ray/ultraviolet photoelectron spectroscopy, Hall effect measurement, Raman spectroscopy, and density functional theory calculations. We find that a relatively low partial pressure of CH4 (mixing with NH3) can lead to the growth of dominant pyridinic N substitutions in graphene, in contrast with the growth of dominant graphitic N substitutions under a higher partial pressure of CH4. Our results unambiguously confirm that the pyridinic N leads to the p-type doping, and the graphitic N leads to the n-type doping. Interestingly, we also find that the pyridinic N and the graphitic N are preferentially separated in different domains. Our findings shed light on continuously tuning the doping level of graphene monolayers by using N monoelement, which can be very convenient for growth of functional structures in graphene sheets.

Molecule-Confined Engineering toward Superconductivity and Ferromagnetism in Two-Dimensional Superlattice.

Superconductivity is mutually exclusive with ferromagnetism, because the ferromagnetic exchange field is often destructive to superconducting pairing correlation. Well-designed chemical and physical methods have been devoted to realize their coexistence only by structural integrity of inherent superconducting and ferromagnetic ingredients. However, such coexistence in freestanding structure with nonsuperconducting and nonferromagnetic components still remains a great challenge up to now. Here, we demonstrate a molecule-confined engineering in two-dimensional organic-inorganic superlattice using a chemical building-block approach, successfully realizing first freestanding coexistence of superconductivity and ferromagnetism originated from electronic interactions of nonsuperconducting and nonferromagnetic building blocks. We unravel totally different electronic behavior of molecules depending on spatial confinement: flatly lying Co(Cp)2 molecules in strongly confined SnSe2 interlayers weaken the coordination field, leading to spin transition to form ferromagnetism; meanwhile, electron transfer from cyclopentadienyls to the Se-Sn-Se lattice induces superconducting state. This entirely new class of coexisting superconductivity and ferromagnetism generates a unique correlated state of Kondo effect between the molecular ferromagnetic layers and inorganic superconducting layers. We anticipate that confined molecular chemistry provides a newly powerful tool to trigger exotic chemical and physical properties in two-dimensional matrixes.

The Kondo tip decorated by the Co atom.

The Kondo effect of single Co adatoms on Ru(0001) is detected with two different kinds of co-decorated tip (Kondo tip) by using low temperature scanning tunneling microscopy and scanning tunneling spectroscopy. We call the relatively separated two magnetic impurities in the tunneling region 'two Kondo system' to distinguish it from the 'two-impurity Kondo system'. We find that the artificially constructed Kondo tips can be generally categorized into two types of Kondo resonances, which have distinct Fano line shapes with quantum interference factor |q| â‰« 1 and |q| âˆ¼ 1, respectively. The tunneling spectra of six constructed two Kondo systems can be well fitted by summing the two Fano resonances of the two subsystems and a linear background. More interestingly, by extracting the amplitudes of the two Fano resonances in the spectra, we find that the electron transmission of such a two Kondo system in the tunneling region is dominated by the quantum interference of the Kondo tip, which is directly related to the geometric configuration of the adsorbed Kondo atom on the tip.

Identifying site-dependent effects of an extra Co atom on electronic states of single Co-phthalocyanine molecule.

We investigate the modification of electronic properties of single cobalt phthalocyanine (CoPc) molecule by an extra Co atom co-adsorbed on Au (111) surface using scanning tunneling microscopy (STM), joint with density functional theory (DFT) calculations. By manipulating CoPc molecules using the STM tip to contact individually adsorbed Co atom, two types of relatively stable complexes can be formed, denoted as CoPc-Co(I) and CoPc-Co(II). In CoPc-Co(I), the Co atom is at an intramolecular site close to aza-N atom of CoPc, which induces significant modifications of the electronic states of CoPc, such as energy shifts and splitting of nonlocal molecular orbitals. However, in CoPc-Co(II) where the Co atom is underneath a benzene lobe of CoPc, it only slightly modifies the electronic states of CoPc, and mainly local characteristics of specific molecular orbitals are affected, even though CoPc-Co(II) is more stable than CoPc-Co(I). Our DFT calculations give consistent results with the experiments, and related analyses based on the molecular orbital theory reveal mechanism behind the experimental observations.

Evidence of van Hove singularities in ordered grain boundaries of graphene.

It has long been under debate whether the electron transport performance of graphene could be enhanced by the possible occurrence of van Hove singularities in grain boundaries. Here, we provide direct experimental evidence to confirm the existence of van Hove singularity states close to the Fermi energy in certain ordered grain boundaries using scanning tunneling microscopy. The intrinsic atomic and electronic structures of two ordered grain boundaries, one with alternative pentagon and heptagon rings and the other with alternative pentagon pair and octagon rings, are determined. It is firmly verified that the carrier concentration and, thus, the conductance around ordered grain boundaries can be significantly enhanced by the van Hove singularity states. This finding strongly suggests that a graphene nanoribbon with a properly embedded ordered grain boundary can be a promising structure to improve the performance of graphene-based electronic devices.

STM tip-assisted single molecule chemistry.

Scanning tunnelling microscopy (STM) has been a unique and powerful tool in the study of molecular systems among various microscopic and spectroscopic techniques. This benefits from the local probing ability for the atomically resolved structural and electronic characterization by the STM tip. Moreover, by using the STM tip one can modify a given structure and thus control the physical and chemical properties of molecules at a single-molecule level. The rapid developments in the past 30 years have extended the functions of STM far beyond characterization. It has shown the flexibility to combine STM with other techniques by making use of the advantages of the STM tip, demonstrating important applications in the growing nanotechnology. Here we review some recent progresses in our laboratory on single molecule chemistry by taking advantage of tip-assisted local approaches, such as the identification of specific orbitals or states of molecules on surfaces, tip-induced single-molecule manipulation, atomically resolved chemical reactions in photochemistry and tip-induced electroluminescence. We expect more joint techniques to emerge in the near future by using the unique advantages of STM tip, providing more powerful tools for the growing requirements of new materials design and the mechanism of chemical reactions at the molecular scale.

Joint optic disc and cup segmentation based on elliptical-like morphological feature and spatial geometry constraint.

Glaucoma is a chronic degenerative disease that is the second leading cause of irreversible blindness worldwide. For a precise and automatic screening of glaucoma, detecting the optic disc and cup precisely is significant. In this paper, combining the elliptical-like morphological features of the disc and cup, we reformulate the segmentation task from a perspective of ellipse detection to explicitly segment and directly get the glaucoma screening indicator. We detect the minimum bounding boxes of ellipses firstly, and then learn the ellipse parameters of these regions to achieve optic disc and cup segmentation. Considering the spatial geometry prior knowledge that the cup should be within the disc region, Paired-Box RPN is introduced to simultaneously detect the disc and cup coupled. In addition, boundary attention module is introduced to use edges of the disc and cup as an important guide for context aggregation to improve the accuracy. Comprehensive experiments clearly show that our method outperforms the state-of-the-art methods for optic disc and cup segmentation. Simultaneously, the proposed method also obtains the good glaucoma screening performance with calculated vCDR value. Joint optic disc and cup segmentation, which utilizes the elliptical-like morphological features and spatial geometry constraint, could improve the performance of optic disc and cup segmentation.

Observation of photocatalytic dissociation of water on terminal Ti sites of TiO2(110)-1 × 1 surface.

The water splitting reaction based on the promising TiO(2) photocatalyst is one of the fundamental processes that bears significant implication in hydrogen energy technology and has been extensively studied. However, a long-standing puzzling question in understanding the reaction sequence of the water splitting is whether the initial reaction step is a photocatalytic process and how it happens. Here, using the low temperature scanning tunneling microscopy (STM) performed at 80 K, we observed the dissociation of individually adsorbed water molecules at the 5-fold coordinated Ti (Ti(5c)) sites of the reduced TiO(2) (110)-1 × 1 surface under the irradiation of UV lights with the wavelength shorter than 400 nm, or to say its energy larger than the band gap of 3.1 eV for the rutile TiO(2). This finding thus clearly suggests the involvement of a photocatalytic dissociation process that produces two kinds of hydroxyl species. One is always present at the adjacent bridging oxygen sites, that is, OH(br), and the other either occurs as OH(t) at Ti(5c) sites away from the original ones or even desorbs from the surface. In comparison, the tip-induced dissociation of the water can only produce OH(t) or oxygen adatoms exactly at the original Ti(5c) sites, without the trace of OH(br). Such a difference clearly indicates that the photocatalytic dissociation of the water undergoes a process that differs significantly from the attachment of electrons injected by the tip. Our results imply that the initial step of the water dissociation under the UV light irradiation may not be reduced by the electrons, but most likely oxidized by the holes generated by the photons.

Interactions in different domains of truxenone supramolecular assembly on Au(111).

The two-dimensional assemblies of truxenone, diindeno[1,2-a;1',2'-c]fluorene-5,10,15-trione, on the Au(111) surface have been studied by scanning tunnelling microscopy in ultrahigh vacuum. It is found that the truxenone monolayer on Au(111) exhibits different two-dimensional supramolecular structures. The investigation using scanning tunnelling microscopy combined with the density functional theory calculations can be a helpful approach to understand the complicated supramolecular structures of truxenone self-assembly on Au(111).

Design and control of electron transport properties of single molecules.

We demonstrate in this joint experimental and theoretical study how one can alter electron transport behavior of a single melamine molecule adsorbed on a Cu (100) surface by performing a sequence of elegantly devised and well-controlled single molecular chemical processes. It is found that with a dehydrogenation reaction, the melamine molecule becomes firmly bonded onto the Cu surface and acts as a normal conductor controlled by elastic electron tunneling. A current-induced hydrogen tautomerization process results in an asymmetric melamine tautomer, which in turn leads to a significant rectifying effect. Furthermore, by switching on inelastic multielectron scattering processes, mechanical oscillations of an N-H bond between two configurations of the asymmetric tautomer can be triggered with tuneable frequency. Collectively, this designed molecule exhibits rectifying and switching functions simultaneously over a wide range of external voltage.

Ultrathin Van der Waals Antiferromagnet CrTe3 for Fabrication of In-Plane CrTe3 /CrTe2 Monolayer Magnetic Heterostructures.

Ultrathin van der Waals (vdW) magnets are heavily pursued for potential applications in developing high-density miniaturized electronic/spintronic devices as well as for topological physics in low-dimensional structures. Despite the rapid advances in ultrathin ferromagnetic vdW magnets, the antiferromagnetic counterparts, as well as the antiferromagnetic junctions, are much less studied owing to the difficulties in both material fabrication and magnetism characterization. Ultrathin CrTe3 layers have been theoretically proposed to be a vdW antiferromagnetic semiconductor with intrinsic intralayer antiferromagnetism. Herein, the epitaxial growth of monolayer (ML) and bilayer CrTe3 on graphite surface is demonstrated. The structure, electronic and magnetic properties of the ML CrTe3 are characterized by combining scanning tunneling microscopy/spectroscopy and non-contact atomic force microscopy and confirmed by density functional theory calculations. The CrTe3 MLs can be further utilized for the fabrication of a lateral heterojunction consisting of ML CrTe2 and ML CrTe3 with an atomically sharp and seamless interface. Since ML CrTe2 is a metallic vdW magnet, such a heterostructure presents the first in-plane magnetic metal-semiconductor heterojunction made of two vdW materials. The successful fabrication of ultrathin antiferromagnetic CrTe3 , as well as the magnetic heterojunction, will stimulate the development of miniaturized antiferromagnetic spintronic devices based on vdW materials.

Intra- and Inter-Self-Assembly of Identical Supramolecules on Silver Surfaces.

Self-assembly of identical organometallic supramolecules into ordered superstructures is of great interest in both chemical science and nanotechnology due to its potential to generate neoteric properties through collective effects. In this work, we demonstrate that large-scale self-organization of atomically precise organometallic supramolecules can be achieved through cascaded on-surface chemical reactions, by the combination of intra- and inter-supramolecular interactions. Supramolecules with defined size and shape are first built through intramolecular reaction and intermolecular metal coordination, followed by the formation of well-ordered two-dimensional arrays with the assistance of Br atoms by -C-H···Br interactions. The mechanism of this process has been investigated from the perspectives of thermodynamics and kinetics.

Molecular oxygen adsorption behaviors on the rutile TiO2(110)-1×1 surface: an in situ study with low-temperature scanning tunneling microscopy.

A knowledge of adsorption behaviors of oxygen on the model system of the reduced rutile TiO(2)(110)-1×1 surface is of great importance for an atomistic understanding of many chemical processes. We present a scanning tunneling microcopy (STM) study on the adsorption of molecular oxygen either at the bridge-bonded oxygen vacancies (BBO(V)) or at the hydroxyls (OH) on the TiO(2)(110)-1×1 surface. Using an in situ O(2) dosing method, we are able to directly verify the exact adsorption sites and the dynamic behaviors of molecular O(2). Our experiments provide direct evidence that an O(2) molecule can intrinsically adsorb at both the BBO(V) and the OH sites. It has been identified that, at a low coverage of O(2), the singly adsorbed molecular O(2) at BBO(V) can be dissociated through an intermediate state as driven by the STM tip. However, singly adsorbed molecular O(2) at OH can survive from such a tip-induced effect, which implies that the singly adsorbed O(2) at OH is more stable than that at BBO(V). It is interesting to observe that when the BBO(V)s are fully filled with excess O(2) dosing, the adsorbed O(2) molecules at BBO(V) tend to be nondissociative even under a higher bias voltage of 2.2 V. Such a nondissociative behavior is most likely attributed to the presence of two or more O(2) molecules simultaneously adsorbed at a BBO(V) with a more stable configuration than singly adsorbed molecular O(2) at a BBO(V).

Flexible Alkali-Halogen Bonding in Two Dimensional Alkali-Metal Organic Frameworks.

On-surface fabrication of two-dimensional (2D) metal organic frameworks (MOFs) has been continuously attracting attentions for years. However, the synthesis of 2D MOFs with large-amplitude flexibility was rarely carried out since the bonding configurations in the coordination nodes are typically highly directional. Here we demonstrate that single alkali ions, which are fully isotropic in ionic bonding, can act as pivot joints for constructing tunable 2D MOFs by bonding to dihalogen groups in organic molecules. We take 2,3,6,7,10,11-hexabromotriphenylene, a 3-fold polycyclic molecule with three ortho-dibromo groups, and sodium (Na) atoms as a model system and successfully construct Na-based MOFs on Au(111) surface. The deflection angle of the Na coordination nodes is variable in an unprecedentedly large range between ±36° that allows the construction of multiple 2D MOF architectures. Such a flexible alkali-halogen bonding may provide a unique toolbox for designing and constructing more tunable MOFs by choosing various alkali atoms and halogen moieties.