On-Surface Synthesis of Self-Assembled Covalently Linked Wavy Chains with Site-Selective Conformational Switching.

Conformational arrangements in polymers on surfaces determine the overall shape as well as the potential properties. It is generally believed that conformational diversity leads to uncontrollable or disordered structures in on-surface synthesis. However, in this study, we obtain two well-ordered self-assembled covalently linked wavy chains with site-selective conformational switching via the Ullmann reaction of 1,2-bis(3-bromophenyl)ethane with multiple conformations on Ag(111). Two kinds of wavy chains exhibit distinct conformational arrangements, where chain I contains one repeating unit conformation of -cis-trans1-cis-trans1-cis-cis-trans1-, while the adjacent parallel parts in wavy chain II have two different conformational arrangements of -cis-cis-trans1- and -cis-cis-trans2-. Wavy chains coassemble with dissociated bromine atoms, suggesting that the Br···H-C interactions between Br atoms and molecular chains are crucial for the construction of ordered wavy chains. High-resolution scanning tunneling microscopy is employed to reveal the surface reaction process at the molecular scale. In depth growth mechanism analysis combined with density functional theory calculations unveils that the substrate also plays an important role in the fabrication of well-ordered wavy chains. The present work extends the surface reaction of conformational flexible precursors.

Effect of Post-Annealing on Magnetotransport and Magnetic Properties of TaCo2Te2 Single Crystals.

The extreme magnetoresistance (XMR) of some compounds, challenging our understanding of magnetoresistance, is an interesting topic in condensed-matter and materials physics and future device applications. Here, we reported magnetotransport and magnetic properties of the as-grown and post-annealed TaCo2Te2 single crystals. The resistivity evolution with temperature in the two TaCo2Te2 single crystals shows a metallic behavior. Below 50 K, the XMR effect for the two crystals is found, and MR values at 3 K under 9 T are about 3.72 × 103% for the as-grown TaCo2Te2 and 5.71 × 102% for the annealed samples, larger than that of the previous report. The studies on the Hall effect of the two TaCo2Te2 single crystals indicate the multiband feature with high carrier mobilities from a two-band model. Electron and hole concentrations and mobilities of as-grown samples are comparable, while for the annealed sample, the hole concentration and mobility are larger than the electron concentration and mobility. The carrier mobilities for the two TaCo2Te2 single crystals have the same order of magnitude, ∼103 cm2 V-1 s-1. The XMR effect may be from high carrier mobilities. Magnetization of the as-grown TaCo2Te2 decreases with increasing temperature, and a weaker magnetic transition at ∼150 K is observed. The annealed TaCo2Te2 shows no magnetic transition and just a paramagnetic behavior with rising temperature. These results indicate that defects/deficiencies may play an important role in magnetotransport and magnetic properties of the two TaCo2Te2 single crystals. These results are helpful in deeply understanding the XMR mechanism and magnetic properties in TaCo2Te2 and offer a way to study the magnetic properties of the XMR Co-Te system.

Canonical Spin Glass and the Anomalous Hall Effect in a Centrosymmetric Ferrimagnet.

Centrosymmetric ferro/ferrimagnets provide an ideal arena for fundamental research due to their fascinating magnetic and structural characters. In this work, the Co0.8MnSn compound with a single hexagonal phase was successfully synthesized, and the magnetic phase transition and magnetic and electronic properties have been systematically investigated. Interestingly, Arrott plots and normalized magnetic entropy changes derived from the isothermal magnetizing curves may imply the first-order nature of the magnetic ordering transition around TC ∼ 121 K. The AC susceptibility analysis and detailed nonequilibrium dynamical studies (including magnetic aging, rejuvenation, and memory effects) reveal the canonical spin-glass state of Co0.8MnSn at lower temperature. Further, negative magnetoresistance and the anomalous Hall effect dominated by a commonly intrinsic term are obtained. Moreover, the field-dependent AC susceptibility data indicated that complicated and nontrivial magnetic spin textures should exist in the compound. These studies may open up further research opportunities in exploring emergent physical phenomena and potential applications in centrosymmetric magnets.

Magnetic Moment Preservation and Emergent Kondo Resonance of Co-Phthalocyanine on Semimetallic Sb(111).

Magnetic molecules on surfaces have been widely investigated to reveal delicate interfacial couplings and for potential technological applications. In these endeavors, one prevailing challenge is how to preserve or recover the molecular spins, especially on highly metallic substrates that can readily quench the magnetic moments of the admolecules. Here, we use scanning tunneling microscopy and spectroscopy to exploit the semimetallic nature of antimony and observe, surprisingly yet pleasantly, that the spin of Co-phthalocyanine is well preserved on Sb(111), as unambiguously evidenced by the emergent strong Kondo resonance across the molecule. Our first-principles calculations further confirm that the optimal density of states near the Fermi level of the semimetal is a decisive factor, weakening the overall interfacial coupling, while still ensuring sufficiently effective electron-spin scattering in the many-body system. Beyond isolated admolecules, we discover that each of the magnetic moments in a molecular dimer or a densely packed island is distinctly preserved as well, rendering such molecular magnets immense potentials for ultrahigh density memory devices.

Quaterrylene molecules on Ag(111): self-assembly behavior and voltage pulse induced trimer formation.

The self-assembly behavior of quaterrylene (QR) molecules on Ag(111) surfaces has been investigated by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. It is found that the QR molecules are highly mobile on the Ag(111) surface at 78 K. No ordered assembled structure is formed on the surface with a sub-monolayer coverage up to 0.8 monolayer due to the intermolecular repulsive interactions, whereas ordered molecular structures are observed at one monolayer coverage. According to our DFT calculations, charge transfer occurs between the substrate and the adsorbed QR molecule. As a result, out-of-plane dipoles appear at the interface, which are ascribed to the repulsive dipole-dipole interactions between the QR molecules. Furthermore, due to the planar geometry, the QR molecules exhibit relatively low diffusion barriers on Ag(111). By applying a voltage pulse between the tunneling gap, immobilization and aggregation of QR molecules take place, resulting in the formation of a triangle-shaped trimer. Our work demonstrates the ability of manipulating intermolecular repulsive and attractive interactions at the single molecular level.

Graphene-like nanoribbons periodically embedded with four- and eight-membered rings.

Embedding non-hexagonal rings into sp2-hybridized carbon networks is considered a promising strategy to enrich the family of low-dimensional graphenic structures. However, non-hexagonal rings are energetically unstable compared to the hexagonal counterparts, making it challenging to embed non-hexagonal rings into carbon-based nanostructures in a controllable manner. Here, we report an on-surface synthesis of graphene-like nanoribbons with periodically embedded four- and eight-membered rings. The scanning tunnelling microscopy and atomic force microscopy study revealed that four- and eight-membered rings are formed between adjacent perylene backbones with a planar configuration. The non-hexagonal rings as a topological modification markedly change the electronic properties of the nanoribbons. The highest occupied and lowest unoccupied ribbon states are mainly distributed around the eight- and four-membered rings, respectively. The realization of graphene-like nanoribbons comprising non-hexagonal rings demonstrates a controllable route to fabricate non-hexagonal rings in nanoribbons and makes it possible to unveil their unique properties induced by non-hexagonal rings.

Fe on Sb(111): Potential Two-Dimensional Ferromagnetic Superstructures.

It is highly desirable to fabricate two-dimensional ferromagnetic membranes based on orthodox magnetic elements because of their inherent magnetic properties. In this work, we report on two superstructures including a honeycomb-like lattice and identical nanocluster arrays formed by depositing Fe on Sb(111). Combined with first-principles calculations, both detailed atomic structures have been clarified. The honeycomb structure consists of a single layered Fe-Sb phase, and the cluster phase is assigned as a (3 × 3) Fe3Sb7 superlattice. Both structural phases exhibit high magnetic moments localized on d bands of Fe. Our results provide a method to fabricate 2D magnetic superstructures possessing great potential in the realization of the Haldane model, spintronics applications, and single atom catalysis.

Atomic Structures of CH3NH3PbI3 (001) Surfaces.

We report on the atomic structures of methylammonium (MA) lead iodide (CH3NH3PbI3) perovskite surfaces, based on a combined scanning tunneling microscopy and density functional theory calculation study. A reconstructed surface phase with iodine dimers, coexisting with the pristine zigzag phase, was found at the MA-iodine-terminated (001) surfaces of the orthorhombic perovskite films grown on Au(111) surfaces. The reorientation of surface MA dipoles, which strengthens the interactions with surface iodine anions, resulting in a slight energy reduction of 34 meV per unit cell, is responsible for the surface iodine dimerization. According to our calculation, the surface MA dipoles weaken the surface polarity and are therefore considered to be stabilizing the surface structures.

Linear alkane C-C bond chemistry mediated by metal surfaces.

Linear alkanes undergo different C-C bond chemistry (coupling or dissociation) thermally activated on anisotropic metal surfaces depending on the choice of the substrate material. Owing to the one-dimensional geometrical constraint, selective dehydrogenation and C-C coupling (polymerization) of linear alkanes take place on Au(110) surfaces with missing-row reconstruction. However, the case is dramatically different on Pt(110) surfaces, which exhibit similar reconstruction as Au(110). Instead of dehydrogenative polymerization, alkanes tend to dehydrogenative pyrolysis, resulting in hydrocarbon fragments. Density functional theory calculations reveal that dehydrogenation of alkanes on Au(110) surfaces is an endothermic process, but further C-C coupling between alkyl intermediates is exothermic. On the contrary, due to the much stronger C-Pt bonds, dehydrogenation on Pt(110) surfaces is energetically favorable, resulting in multiple hydrogen loss followed by C-C bond dissociation.

Kondo effect mediated topological protection: Co on Sb(111).

We report on a Kondo effect on Co/Sb(111) mediating topological protection of the surface states against local magnetic perturbations. A sharp scanning tunneling spectroscopic peak near the Fermi energy is interpreted as a fingerprint of the Kondo resonance with a high Kondo temperature of about 200 K. Density function theory calculations reveal that the protruding Co adatoms are responsible for the Kondo peak, while the Co atoms underneath present as nonmagnetic impurities. By identifying the quasiparticle interference wavevectors, we demonstrate that only scattering channels related to backscattering confinements are observed for surfaces with and without the Co adsorption. It suggests that the Kondo effect suppresses the backscattering of the topological surface states and may help to expand the functionality of magnetically coupled topological materials for spintronics applications.

Structures and orientations of cobalt phthalocyanine adsorbed on Sb(111).

The structures and orientations of cobalt phthalocyanine (CoPc) adsorbed on Sb(111) were investigated by low-temperature scanning tunneling microscope. We found that at the initial coverage molecular domains formed both on the terraces and at the vicinity of step edges that were saturated by molecular chains in advance. With the increasing of molecular coverage, the alternately arranged molecular rows of CoPc adsorbed on the bridge sites of Sb(111) and the orientations of them were rotated by 14° ± 2° with respect to the [-101] direction. At the coverage above one monolayer, the molecules of the second layer were assembled along the directions of the underlying molecular rows and showed similar configurations. Consequently, the second-layer CoPc molecules interacted with neighboring molecules via π orbitals, resulting in the observation of overlapped molecular orbitals.