Progress in Surface Science最新文献

Considering studies of molecular adsorption we review recent developments in the field of scanning probe microscopy and in particular in scanning tunnelling microscopy, concentrating on the progress that has been achieved by controlled decoration of the microscope tip. A view is presented according to which the tip decoration generally introduces additional degrees of freedom into the scanning junction and thus extends its functionality. In particular tips decorated with atomic point-like particles may attain the additional function of a force sensor which is realized through the degrees of freedom associated with the relative position of the decorating probe-particle with respect to the tip. It is shown how the force sensor function of such tips helps when studying large molecular adsorbates. Further prospects of more complex junctions equipped with numerous internal degrees of freedom are discussed. It is argued that the main problem impeding the utilization of such junctions is related to their control. An approach towards a higher degree of control is presented that is based on the analysis of single molecule manipulation experiments.

The atomic structure and electronic properties of the tip apex can strongly affect the contrast of scanning tunneling microscopy (STM) images. This is a critical issue in STM imaging given the, to date unsolved, experimental limitations in precise control of the tip apex atomic structure. Definition of statistically robust procedures to indirectly obtain information on the tip apex structure is highly desirable as it would open up for more rigorous interpretation and comparison of STM images from different experiments. To this end, here we introduce a statistical correlation analysis method to obtain information on the local geometry and orientation of the tip used in STM experiments based on large scale simulations. The key quantity is the relative brightness correlation of constant-current topographs between experimental and simulated data. This correlation can be analyzed statistically for a large number of modeled tip orientations and geometries. Assuming a stable tip during the STM scans and based on the correlation distribution, it is possible to determine the tip orientations that are most likely present in an STM experiment, and exclude other orientations. This is especially important for substrates such as highly oriented pyrolytic graphite (HOPG) since its STM contrast is strongly tip dependent, which makes interpretation and comparison of STM images very challenging. We illustrate the applicability of our method considering the HOPG surface in combination with tungsten tip models of two different apex geometries and 18,144 different orientations. We calculate constant-current profiles along the $〈1\overline{1}00〉$ direction of the HOPG(0 0 0 1) surface in the $\left|V\right|⩽1\text{V}$ bias voltage range, and compare them with experimental data. We find that a blunt tip model provides better correlation with the experiment for a wider range of tip orientations and bias voltages than a sharp tip model. Such a combination of experiments and large scale simulations opens up the way for obtaining more detailed information on the structure of the tip apex and more reliable interpretation of STM data in the view of local tip geometry effects.

Graphene, hexagonal boron nitride, molybdenum disulphide, and layered transition metal dichalcogenides (TMDCs) represent a class of two-dimensional (2D) atomic crystals with unique properties due to reduced dimensionality. Stacking these materials on top of each other in a controlled fashion can create heterostructures with tailored properties that offers another promising approach to design and fabricate novel electronic devices. In this report, we attempt to review this rapidly developing field of hybrid materials. We summarize the fabrication methods for different 2D materials, the layer-by-layer growth of various vertical heterostructures and their electronic properties. Particular interests are given to in-situ stack aforementioned 2D materials in controlled sequences, and the TMDCs heterostructures.

Silicene is emerging as a two-dimensional material with very attractive electronic properties for a wide range of applications; it is a particularly promising material for nano-electronics in silicon-based technology. Over the last decade, the existence and stability of silicene has been the subject of much debate. Theoretical studies were the first to predict a puckered honeycomb structure with electronic properties resembling those of graphene. Though these studies were for free-standing silicene, experimental fabrication of silicene has been achieved so far only through epitaxial growth on crystalline surfaces. Indeed, it was only in 2010 that researchers presented the first experimental evidence of the formation of silicene on Ag(1 1 0) and Ag(1 1 1), which has launched silicene in a similar way to graphene. This very active field has naturally led to the recent growth of silicene on Ir(1 1 1), ZrB₂(0 0 0 1) and Au(1 1 0) substrates. However, the electronic properties of epitaxially grown silicene on metal surfaces are influenced by the strong silicene–metal interactions. This has prompted experimental studies of the growth of multi-layer silicene, though the nature of its “silicene” structure remains questionable. Of course, like graphene, synthesizing free-standing silicene represents the ultimate challenge. A first step towards this has been reported recently through chemical exfoliation from calcium disilicide (CaSi₂). In this review, we discuss the experimental and theoretical studies of silicene performed to date. Special attention is given to different experimental studies of the electronic properties of silicene on metal substrates. New avenues for the growth of silicene on other substrates with different chemical characteristics are presented along with foreseeable applications such as nano-devices and novel batteries.

Silicene, a two-dimensional honeycomb sheet consisting of Si atoms, has attracted much attention as a new low-dimensional material because it gains various fascinating characteristics originating from the combination of Dirac fermion features with spin–orbit coupling. The novel properties such as the quantum spin Hall effect and the compatibility with the current Si device technologies have fueled competition to realize the silicene. This review article focuses on the geometric and electronic structures of silicene grown on Ag(1 1 1) investigated by scanning tunneling microcopy (STM), low energy electron diffraction (LEED) and density functional theory (DFT) calculations. The silicene on Ag(1 1 1) takes locally-buckled structure in which the Si atoms are displaced perpendicularly to the basal plane. As a result, several superstructures such as $4\times 4\text{,}\sqrt{13}\times \sqrt{13}R13.9°\text{,}4/\sqrt{3}\times 4/\sqrt{3}$, and etc. emerge. The atomic arrangement of the 4 × 4 silicene has been determined by STM, DFT calculations and LEED dynamical analysis, while the other superstructures remain to be fully-resolved. In the 4 × 4 silicene, Si atoms are arranged to form a buckled honeycomb structure where six Si atoms of 18 Si atoms in the unit cell are displaced vertically. The displacements lead to the vertical shift of the substrate Ag atoms, indicating the non-negligible coupling at the interface between the silicene layer and the substrate. The interface coupling significantly modifies the electronic structure of the 4 × 4 silicene. No Landau level sequences were observed by scanning tunneling spectroscopy (STS) with magnetic fields applied perpendicularly to the sample surface. The DFT calculations showed that the π and π^∗ bands derived from the Si 3p_z are hybridized with the Ag electronic states, leading to the drastic modification in the band structure and then the absence of Dirac fermion features together with the two-dimensionality in the electronic states. These findings demonstrate that the strong coupling at the interface causes the symmetry breaking for the 4 × 4 silicene and as a result the disappearance of Dirac fermion features. The geometric and electronic structures of other superstructures are also discussed.

Aluminosilicates have traditionally been important materials for applications related to adsorbents, water softeners, catalysis and mechanical and thermal reinforcement due to their high surface area, excellent thermal/hydrothermal stability, high shape-selectivity and superior ion-exchange ability. Recently, their use as polymer fillers has allowed to increasingly extending their application range to innovative areas such as medical and biological fields as well as in sensors, filtration membranes, energy storage and novel catalysis routes. Further, the large versatility and tailoring possibilities of both filler and matrix indicates this area as one of the enabling key technologies of the near future.

This work summarizes the main developments up to date in this increasingly interesting field, focuses on the main applications already developed as well as on the key challenges for the near future.

In this article, we review basic information about the interaction of transition metal atoms with the (0 0 0 1) surface of graphite, especially fundamental phenomena related to growth. Those phenomena involve adatom-surface bonding, diffusion, morphology of metal clusters, interactions with steps and sputter-induced defects, condensation, and desorption. General traits emerge which have not been summarized previously. Some of these features are rather surprising when compared with metal-on-metal adsorption and growth. Opportunities for future work are pointed out.

Carbon dioxide chemistry has attracted significant interest in recent years. Although the field is diverse, a current and more comprehensive review of the surface science literature may be of interest for a variety of communities since environmental chemistry, energy technology, materials science, catalysis, and nanocatalysis are certainly affected by gas–surface properties. The review describes surface phenomena and characterization strategies highlighting similarities and differences, instead of providing only a list of system-specific information. The various systems are roughly distinguished as those that clearly form carbonates and those that merely physisorb CO₂ at ultra-high vacuum conditions. Nevertheless, extended sections about specific systems including rarely studied surfaces and unusual materials are included, making this review also useful as a reference.

We review recent studies of double-decker and triple-decker phthalocyanine (Pc) molecules adsorbed on surfaces in terms of the bonding configuration, electronic structure and spin state.

The Pc molecule has been studied extensively in surface science. A Pc molecule can contain various metal atoms at the center, and the class of the molecule is called as metal phthalocyanine (MPc). If the center metal has a large radius, like as lanthanoid metals, it becomes difficult to incorporate the metal atom inside of the Pc ring. Pc ligands are placed so as to sandwich the metal atom, where the metal atom is placed out of the Pc plane. The molecule in this configuration is called as a multilayer-decker Pc molecule. After the finding that the double-decker Pc lanthanoid complex shows single-molecule magnet (SMM) behavior, it has attracted a large attention. This is partly due to a rising interest for the ‘molecular spintronics’, in which the freedoms of spin and charge of an electron are applied to the quantum process of information. SMMs represent a class of compounds in which a single molecule behaves as a magnet.

The reported blocking temperature, below which a single SMM molecule works as an quantum magnet, has been increasing with the development in the molecular design and synthesis techniques of multiple-decker Pc complex. However, even the bulk properties of these molecules are promising for the use of electronic materials, the films of multi-decker Pc molecules is less studied than those for the MPc molecules.

An intriguing structural property is expected for the multi-decker Pc molecules since the Pc planes are linked by metal atoms. This gives an additional degree of freedom to the rotational angle between the two Pc ligands, and they can make a wheel-like symmetric rotation. Due to a simple and well-defined structure of a multi-decker Pc complex, the molecule can be a model molecule for molecular machine studies.

The multi-decker Pc molecules can provide interesting spin configuration. The center metal atom, including a lanthanoid metal of Tb, tends to be 3+ cation, while the Pc ligand to be 2− anion. This realizes two-spin system, in which spins from 4f electrons and π radical coexist. Though the spins of 4f orbitals of those molecules have been studied, the importance of the π radicals has been highlighted recently from the measurement of electronic conductance properties of these molecules.

In this article, recent researches on multi-decker Pc molecules are reviewed. The manuscript is organized with groups of chapters as follows: (1) Film formation, (2) Spin of TbPc₂ film and Kondo resonance observation, (3) Rotation of double-decker Pc complex and chemical modification for spin control, (4) Device formation using double-decker Pc complex.