Surface Science Reports最新文献

This review covers the surface chemistry of porphyrins, phthalocyanines, their metal complexes, and related compounds, with particular focus on chemical reactions at solid/vacuum interfaces. Porphyrins are not only important biomolecules, they also find, together with the artificial phthalocyanines, numerous technological and scientific applications, which often involve surface and interface related aspects. After a brief summary of fundamental properties of these molecules in the context of surface science, the following topics will be discussed: (1) Aspects of geometric structure, including self-assembly, conformation, mobility and manipulation of the adsorbed molecules. (2) Surface-related changes of the electronic structure and the magnetic properties. (3) The role of the metal center in the surface chemical bond. (4) On-surface coordination reactions, such as direct metalation and coordination of axial ligands. (5) The influence of axial ligands on the surface chemical bond and the magnetic properties.

The oxidation and corrosion of metals are fundamental problems in materials science and technology that have been studied using a large variety of experimental and computational techniques. Here we review some of the recent studies that have led to significant advances in our atomic-level understanding of copper oxide, one of the most studied and best understood metal oxides. We show that a good atomistic understanding of the physical characteristics of cuprous (Cu₂O) and cupric (CuO) oxide and of some key processes of their formation has been obtained. Indeed, the growth of the oxide has been shown to be epitaxial with the surface and to proceed, in most cases, through the formation of oxide nano-islands which, with continuous oxygen exposure, grow and eventually coalesce. We also show how electronic structure calculations have become increasingly useful in helping to characterise the structures and energetics of various Cu oxide surfaces. However a number of challenges remain. For example, it is not clear under which conditions the oxidation of copper in air at room temperature (known as native oxidation) leads to the formation of a cuprous oxide film only, or also of a cupric overlayer. Moreover, the atomistic details of the nucleation of the oxide islands are still unknown. We close our review with a brief perspective on future work and discuss how recent advances in experimental techniques, bringing greater temporal and spatial resolution, along with improvements in the accuracy, realism and timescales achievable with computational approaches make it possible for these questions to be answered in the near future.

Recently, pulsed laser deposition (PLD) technology makes viable the epitaxial growth of group III-nitrides on thermally active substrates at low temperature. The precursors generated from the pulsed laser ablating the target has enough kinetic energy when arriving at substrates, thereby effectively suppressing the interfacial reactions between the epitaxial films and the substrates, and eventually makes the film growth at low temperature possible. So far, high-quality group III-nitride epitaxial films have been successfully grown on a variety of thermally active substrates by PLD. By combining PLD with other technologies such as laser rastering technique, molecular beam epitaxy (MBE), and metal-organic chemical vapor deposition (MOCVD), III-nitride-based light-emitting diode (LED) structures have been realized on different thermally active substrates, with high-performance LED devices being demonstrated. This review focuses on the epitaxial growth of group III-nitrides on thermally active substrates by PLD and their use in the development of LED devices. The surface morphology, interfacial property between film and substrate, and crystalline quality of as-grown group III-nitride films by PLD, are systematically reviewed. The corresponding solutions for film homogeneity on large size substrates, defect control, and InGaN films growth by PLD are also discussed in depth, together with introductions to some newly developed technologies for PLD in order to realize LED structures, which provides great opportunities for commercialization of LEDs on thermally active substrates.

Among nanoalloys, Co–Pt type (CoPt or FePt) supported nanostructures are very interesting systems due to the direct link between atom arrangement and magnetic behavior. In addition, these alloys become model systems in the field of nanoalloys, due to the diversity of atom arrangements either present in the bulk state or specific to the nanoscale (chemically ordered L1₀, L1₂, or disordered fcc structures, core–shell, five-fold structures – icosahedral or decahedral, etc.). The synergy between experimental and modeling efforts has allowed the emergence of an overview of the structural, morphological and chemical behaviors of CoPt-based supported nanoparticles in terms of phase diagrams (temperature, composition, size effect), kinetic behavior (growth, annealing, ordering), and also in terms of environment effects (substrate, capping, matrix, gas) and of magnetic properties. All aspects of this complexity are reviewed: synthesis strategies (physical deposition, cluster beam deposition and wet chemical methods), magnetic behavior (atomic magnetic moment, magnetic anisotropy energy), structural transitions (non-crystalline/crystalline structures, order/disorder, surface/interface segregation), etc. In this field, the investigation techniques, such as electron microscopy and X-ray scattering or absorption techniques, are generally used at their ultimate limit due the small size of the studied objects. Finally, several aspects of the annealing process, which is a key phenomenon to achieve the chemical order, have been discussed in both thermodynamic and kinetic points of view (size effect, critical temperature, annealing time, twinning, coalescence, etc.).

In recent years, the field of catalysis has experienced an astonishing transformation, driven in part by more demanding environmental standards and critical societal and industrial needs such as the search for alternative energy sources. Thanks to the advent of nanotechnology, major steps have been made towards the rational design of novel catalysts. Striking new catalytic properties, including greatly enhanced reactivities and selectivities, have been reported for nanoparticle (NP) catalysts as compared to their bulk counterparts. However, in order to harness the power of these nanocatalysts, a detailed understanding of the origin of their enhanced performance is needed. The present review focuses on the role of the NP size and shape on chemisorption and catalytic performance. Since homogeneity in NP size and shape is a prerequisite for the understanding of structure–reactivity correlations, we first review different synthesis methods that result in narrow NP size distributions and shape controlled NPs. Next, size-dependent phenomena which influence the chemical reactivity of NPs, including quantum size-effects and the presence of under-coordinated surface atoms are examined. The effect of the NP shape on catalytic performance is discussed and explained based on the existence of different atomic structures on the NP surface with distinct chemisorption properties. The influence of additional factors, such as the oxidation state of the NPs and NP–support interactions, is also considered in the frame of the size- and shape-dependency that these phenomena present. Ultimately, our review highlights the importance of achieving a systematic understanding of the factors that control the activity and selectivity of a catalyst in order to avoid trial and error methods in the rational design of the new generation of nanocatalysts with properties tunable at the atomic level.

Nanostructured materials offer the possibility to tailor light–matter interaction at scales below the wavelength. Metallic nanostructures benefit from the excitation of surface plasmons that permit light concentration at ultrasmall length scales and ultrafast time scales. The local density of states (LDOS) is a central concept that drives basic processes of light–matter interaction such as spontaneous emission, thermal emission and absorption. We introduce theoretically the concept of LDOS, emphasizing the specificities of plasmonics. We connect the LDOS to real observables in nanophotonics, and show how the concept can be generalized to account for spatial coherence. We describe recent methods developed to probe or map the LDOS in complex nanostructures ranging from nanoantennas to disordered metal surfaces, based on dynamic fluorescence measurements or on the detection of thermal radiation.

This review covers a wide range of surface analytical techniques: X-ray photoelectron spectroscopy (XPS), scanning photoelectron microscopy (SPEM), photoemission electron microscopy (PEEM), dynamic and static secondary ion mass spectroscopy (SIMS), electron backscatter diffraction (EBSD), atomic force microscopy (AFM). Others that are relatively less widely used but are also important to the Earth Sciences are also included: Auger electron spectroscopy (AES), low energy electron diffraction (LEED) and scanning tunnelling microscopy (STM). All these techniques probe only the very top sample surface layers (sub-nm to several tens of nm). In addition, we also present several other techniques i.e. Raman microspectroscopy, reflection infrared (IR) microspectroscopy and quantitative evaluation of minerals by scanning electron microscopy (QEMSCAN) that penetrate deeper into the sample, up to several μm, as all of them are fundamental analytical tools for the Earth Sciences. Grazing incidence synchrotron techniques, sensitive to surface measurements, are also briefly introduced at the end of this review. (Scanning) transmission electron microscopy (TEM/STEM) is a special case that can be applied to characterisation of mineralogical and geological sample surfaces. Since TEM/STEM is such an important technique for Earth Scientists, we have also included it to draw attention to the capability of TEM/STEM applied as a surface-equivalent tool.

While this review presents most of the important techniques for the Earth Sciences, it is not an all-inclusive bibliography of those analytical techniques. Instead, for each technique that is discussed, we first give a very brief introduction about its principle and background, followed by a short section on approaches to sample preparation that are important for researchers to appreciate prior to the actual sample analysis. We then use examples from publications (and also some of our known unpublished results) within the Earth Sciences to show how each technique is applied and used to obtain specific information and to resolve real problems, which forms the central theme of this review. Although this review focuses on applications of these techniques to study mineralogical and geological samples, we also anticipate that researchers from other research areas such as Material and Environmental Sciences may benefit from this review.

This review covers the structure of, and chemical reactions on, well-defined cerium oxide surfaces. Ceria, or mixed oxides containing ceria, are critical components in automotive three-way catalysts due to their well-known oxygen storage capacity. Ceria is also emerging as an important material in a number of other catalytic processes, particularly those involving organic oxygenates and the water–gas shift reaction. Ceria׳s acid–base properties, and thus its catalytic behavior, are closely related to its surface structure where different oxygen anion and cerium cation environments are present on the low-index structural faces. The actual structure of these various faces has been the focus of a number of theoretical and experimental investigations. Ceria is also easily reducible from CeO₂ to CeO_2−X. The presence of oxygen vacancies on the surface often dramatically alters the adsorption and subsequent reactions of various adsorbates, either on a clean surface or on metal particles supported on the surface. Most surface science studies have been conducted on the surfaces of thin-films rather than on the surfaces of bulk single crystal oxides. The growth, characterization and properties of these thin-films are also examined.

Both density functional theory calculations and numerous experimental studies demonstrate a variety of unique features in metal supported oxide films and transition metal doped simple oxides, which are markedly different from their unmodified counterparts. This review highlights, from the computational perspective, recent literature on the properties of the above mentioned surfaces and how they adsorb and activate different species, support metal aggregates, and even catalyse reactions. The adsorption of Au atoms and clusters on metal-supported MgO films are reviewed together with the cluster׳s theoretically predicted ability to activate and dissociate O₂ at the Au–MgO(100)/Ag(100) interface, as well as the impact of an interface vacancy to the binding of an Au atom. In contrast to a bulk MgO surface, an Au atom binds strongly on a metal-supported ultra-thin MgO film and becomes negatively charged. Similarly, Au clusters bind strongly on a supported MgO(100) film and are negatively charged favouring 2D planar structures. The adsorption of other metal atoms is briefly considered and compared to that of Au. Existing computational literature of adsorption and reactivity of simple molecules including O₂, CO, NO₂, and H₂O on mainly metal-supported MgO(100) films is discussed. Chemical reactions such as CO oxidation and O₂ dissociation are discussed on the bare thin MgO film and on selected Au clusters supported on MgO(100)/metal surfaces. The Au atoms at the perimeter of the cluster are responsible for catalytic activity and calculations predict that they facilitate dissociative adsorption of oxygen even at ambient conditions. The interaction of H₂O with a flat and stepped Ag-supported MgO film is summarized and compared to bulk MgO. The computational results highlight spontaneous dissociation on MgO steps. Furthermore, the impact of water coverage on adsorption and dissociation is addressed. The modifications, such as oxygen vacancies and dopants, at the oxide–metal interface and their effect on the adsorption characteristics of water and Au are summarized. Finally, more limited computational literature on transition metal (TM) doped CaO(100) and MgO(100) surfaces is presented. Again, Au is used as a probe species. Similar to metal-supported MgO films, Au binds more strongly than on undoped CaO(100) and becomes negatively charged. The discussion focuses on rationalization of Au adsorption with the help of Born–Haber cycle, which reveals that the so-called redox energy including the electron transfer from the dopant to the Au atom together with the simultaneous structural relaxation of lattice atoms is responsible for enhanced binding. In addition, adsorption energy dependence on the position and type of the dopant is summarized.

We have summarized recent ultrafast spectroscopic studies on phenomena associated with dye-sensitization of semiconductor metal oxide nanoparticles, especially TiO₂ nanocrystalline film from a surface science perspective with a strong relation to mechanism of electron injection in dye-sensitized solar cells, which are attracting much interest from both viewpoints of pure science and applied science.

A lot of chemical and physical processes are involved in this solar cell, such as light harvesting by molecules and nanostructures, interfacial electron transfer, charge migration in solid and electrolyte, degradation of the materials, and so on. Among them, the very primary process initiated by photoabsorption by sensitizing dye molecules; that is, electron injection from excited adsorbates into the conduction band of semiconductor metal oxides is significantly important, because this process must be 100% efficient with a minimum driving force for high current and voltage generation.

We have first focused on details of experimental methods used in this research area, and then in the following Sections, have organized this review by concentrating on each parameter that influences dynamics of electron injection in dye-sensitized semiconductors. Finally we have emphasized it is important to measure actual DSSCs for the precise comparison between electron injection dynamics and device performance.