The atomic force microscope (AFM) has a unique capability of allowing the high-resolution imaging of biological samples on substratum surfaces in physiological solutions. Recent technological progress of AFM in biological research has resulted in remarkable improvements in both the imaging rate and the tip force acting on the sample. These improvements have enabled the direct visualization of dynamic structural changes and dynamic interactions Occurring in individual biological macromolecules, which is currently not possible with other techniques. Therefore, high-speed AFM is expected to have a revolutionary impact on biological sciences. In addition, the recently achieved atomic-resolution in liquids will further expand the usefulness of AFM in biological research. In this article, we first describe the various capabilities required of AFM in biological sciences, which is followed by a detailed description of various devices and techniques developed for high-speed AFM and atomic-resolution in-liquid AFM. We then describe various imaging Studies performed using our cutting-edge microscopes and their current capabilities as well as their limitations, and conclude by discussing the future prospects of AFM as an imaging tool in biological research. (C) 2008 Elsevier Ltd. All rights reserved.
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(110) and Ag(111), 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(111), ZrB2(0001) and Au(110) 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. (C) 2014 Elsevier Ltd. All rights reserved.
The technological importance of TiO2 has led to a broad effort aimed at understanding the elementary steps that underlie catalytic and photocatalytic reactions. The most stable surface, rutile TiO2(1 1 0), in particular, has became a prototypical model for fundamental studies of TiO2. In this critical review we have selected oxygen, water, and alcohols to evaluate recent progress relevant for applications in the areas of water splitting and oxidation of organic contaminants. We first focus on the characterization of defects and the distribution of excess charge that results from their formation. The subsequent section concentrates on the role of individual surface sites and the effect of available charge in the adsorption processes. The discussion of adsorbate dynamics follows, providing models for intrinsic and extrinsic diffusion processes as well as rotational dynamics of anchored alkoxy species. The final section summarizes our current understanding of TiO2(1 1 0) catalyzed reactions between water, oxygen, and their dissociation products. (C) 2010 Elsevier Ltd. All rights reserved.
The study of tin oxide is motivated by its applications as a solid state gas sensor material, oxidation catalyst, and transparent conductor. This review describes the physical and chemical properties that make tin oxide a suitable material for these purposes. The emphasis is on surface science studies of single crystal surfaces, but selected studies on powder and polycrystalline films are also incorporated in order to provide connecting points between surface science studies with the broader field of materials science of tin oxide. The key for understanding many aspects of SnO2 surface properties is the dual valency of Sn. The dual valency facilitates a reversible transformation of the surface composition from stoichiometric surfaces with Sn4+ surface cations into a reduced surface with Sn2+ surface cations depending on the oxygen chemical potential of the system. Reduction of the surface modifies the surface electronic structure by formation of Sn 5s derived surface states that lie deep within the band gap and also cause a lowering of the work function. The gas sensing mechanism appears, however, only to be indirectly influenced by the surface composition of SnO2, Critical for triggering a gas response are not the lattice oxygen concentration but chemisorbed (or ionosorbed) oxygen and other molecules with a net electric charge. Band bending induced by charged molecules cause the increase or decrease in surface conductivity responsible for the gas response signal. In most applications tin oxide is modified by additives to either increase the charge carrier concentration by donor atoms, or to increase the gas sensitivity or the catalytic activity by metal additives. Some of the basic concepts by which additives modify the gas sensing and catalytic properties of SnO2 are discussed and the few surface science studies of doped SnO2 are reviewed. Epitaxial SnO2 films may facilitate the surface science studies of doped films in the future. To this end film growth on titania, alumina, and Pt(111) is reviewed. Thin films on alumina also make promising test systems for probing gas sensing behavior. Molecular adsorption and reaction studies on SnO2 surfaces have been hampered by the challenges of preparing well-characterized surfaces. Nevertheless some experimental and theoretical studies have been performed and are reviewed. Of particular interest in these studies was the influence of the surface composition on its chemical properties. Finally, the variety of recently synthesized tin oxide nanoscopic materials is summarized. (c) 2005 Elsevier Ltd. All rights reserved.
Metal oxides are virtually everywhere - only gold has the property not to form an oxide on its surface when exposed to the ambient. As a result, understanding the physics and chemistry of oxide surfaces is a topic of pronounced general interest and, of course, also a necessary prerequisite for many technical applications. The most important of these is certainly heterogeneous catalysis, but one has to realize that - under ambient conditions - virtually all phenomena occurring at liquid/metal and gas/metal interfaces are determined by the corresponding oxide. This applies in particular to friction phenomena, adhesion and corrosion. A necessary - but not necessarily sufficient - condition for unravelling the fundamentals governing this complex field is to analyze in some detail elementary chemical and physical processes at oxide surfaces. Although the Surface Science of metal surfaces has seen a major progress in the past decades, for oxides detailed experimental investigations for well-defined single crystal surfaces still represent a formidable challenge - mostly because of technical difficulties (charging), but to some extent also due to fundamental problems related to the stabilization of polar surfaces. As a result, the amount of information available for this class of materials is - compared to that at hand for metals - clearly not satisfactory. A particular disturbing lack of information is that about the presence of hydrogen at oxide surfaces - either as hydroxy-species or in form of metal hydrides. In the present review we will summarize recent experimental and theoretical information which has become available from single crystal studies on ZnO surfaces. While the number of papers dealing with another oxide, rutile TiO2, is significantly larger (although titania does not exhibit a polar surface), also for zinc oxide a basis of experimental and theoretical knowledge as been accumulated, which - at least for the non-polar surfaces - allows to understand physico-chemical processes on an atomic level for an increasing number of cases. hi particular with regards to the interaction with hydrogen a number of - often surprising - observations have been reported recently. Some of them carry implications for the behaviour of hydrogen on oxide surfaces in general. We will present the currently available information for both, experiment and theory, and demonstrate the rather large variety of this material's surface properties. (c) 2006 Elsevier Ltd. All rights reserved.
Chemisorption of organosulfur molecules, such as alkanethiols, arenethiols and disulfide compounds on gold surfaces and their subsequent self-organization is the archetypal process for molecular self-assembly on surfaces. Owing to their ease of preparation and high versatility, alkanethiol self-assembled monolayers (SAMs) have been widely studied for potential applications including surface functionalization, molecular motors, molecular electronics, and immobilization of biological molecules. Despite fundamental advances, the dissociative chemistry of the sulfur headgroup on gold leading to the formation of the sulfur-gold anchor bond has remained controversial. This review summarizes the recent progress in the understanding of the geometrical and electronic structure of the anchor bond. Particular attention is drawn to the involvement of gold adatoms at all stages of alkanethiol self-assembly, including the dissociation of the disulfide (S-S) and hydrogen-sulfide (S-H) bonds and subsequent formation of the self-assembled structure. Gold adatom chemistry is proposed here to be a unifying theme that explains various aspects of the alkanethiol self-assembly and reconciles experimental evidence provided by scanning probe microscopy and spectroscopic methods of surface science. While several features of alkanethiol self-assembly have yet to be revisited in light of the new adatom-based models, the successes of alkanethiol SAMs suggest that adatom-mediated surface chemistry may be a viable future approach for the construction of self-assembled monolayers involving molecules which do not contain sulfur. (C) 2010 Elsevier Ltd. All rights reserved.
Graphene, hexagonal boron nitride, molybdenum disulphide, and layered transition metal dichalcogenides (TMDCs) represent a class of two-dimensional (20) 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. (C) 2014 Elsevier Ltd. All rights reserved.
Metal-organic coordination structures are materials comprising reticular metal centers and organic linkers in which the two constituents bind with each other via metal-ligand coordination interaction. The underlying chemistry is more than a century old but has attracted tremendous attention in the last two decades owing to the rapidly development of metal-organic (or porous coordination) frameworks. These metal-coordination materials exhibit extraordinarily versatile topologies and many potential applications. Since 2002, this traditionally three-dimensional chemistry has been extended to two-dimensional space, that is, to synthesize metal-organic coordination structures directly on solid surfaces. This endeavor has made possible a wide range of so-called surface confined metal-organic networks (SMONs) whose topology, composition, property and function can be tailored by applying the principle of rational design. The coordination chemistry manifests unique characteristics at the surfaces, and in turn the surfaces provide additional control for design structures and properties that are inaccessible in three-dimensional space. In this review, our goal is to comprehensively cover the progress made in the last 15 years in this rapidly developing field. The review summarizes (1) the experimental and theoretical techniques used in this field including scanning tunneling microscopy and spectroscopy, low-energy electron diffraction, X-ray photoelectron spectroscopy, Xray absorption spectroscopy, density functional theory, and Monte Carlo and kinetic Monte Carlo simulation; (2) molecular ligands, metal atoms, substrates, and coordination motifs utilized for synthesizing SMON; (3) representative SMON structures with different topologies ranging from finite-size discrete clusters to one-dimensional chains, two-dimensional periodical frameworks and random networks; and (4) the properties and potential applications of SMONs. We conclude the review with some perspectives. (C) 2016 Elsevier Ltd. All rights reserved.
The extremely high carrier mobility and the unique band structure, make graphene very useful for field-effect transistor applications. According to several works, the primary limitation to graphene based transistor performance is not related to the material quality, but to extrinsic factors that affect the electronic transport properties. One of the most important parasitic element is the contact resistance appearing between graphene and the metal electrodes functioning as the source and the drain. Ohmic contacts to graphene, with low contact resistances, are necessary for injection and extraction of majority charge carriers to prevent transistor parameter fluctuations caused by variations of the contact resistance. The International Technology Roadmap for Semiconductors, toward integration and down-scaling of graphene electronic devices, identifies as a challenge the development of a CMOS compatible process that enables reproducible formation of low contact resistance. However, the contact resistance is still not well understood despite it is a crucial barrier towards further improvements. In this paper, we review the experimental and theoretical activity that in the last decade has been focusing on the reduction of the contact resistance in graphene transistors. We will summarize the specific properties of graphene-metal contacts with particular attention to the nature of metals, impact of fabrication process, Fermi level pinning, interface modifications induced through surface processes, charge transport mechanism, and edge contact formation. (C) 2017 Elsevier Ltd. All rights reserved.
Graphene, a single atomic layer of sp(2)-hybridized carbon atoms arranged in a hexagonal structure and the Nobel winning material in 2010, has attracted extensive research attention in the last few years due to its outstanding physical, chemical, electrical, optical and mechanical properties. To further extend its potential applications, intensive research efforts have been devoted to the functionalization of graphene. Examples include improving graphene solubility by attaching different chemical functional groups to its basal plane, modulating the charge carrier type and concentration via surface transfer doping by coating it with various metals films or organic molecules, improving the bio-selectivity by decorating it with different n-conjugated organic molecules, and so on. Different methods have been developed to functionalize graphene. Among them, non-covalent molecular functionalization represents one of the most effective and promising methods. The extended pi-conjugation is largely preserved without creating extensive structural defects on the graphene sheet, thereby retaining the high charge carrier mobility. In this review, a brief summary about different functionalization methods of graphene and its derivatives by covalent and non-covalent interactions will be presented, with particular focus on the non-covalent molecular functionalization. A broad review of the applications of non-covalently functionalized graphene and its derivatives will be presented in detail, including field-effect-transistors, organic optoelectronics, and molecular sensing. (C) 2013 Elsevier Ltd. All rights reserved.
Adsorption geometry and stability of organic molecules on surfaces are key parameters that determine the observable properties and functions of hybrid inorganic/organic systems (HIOSs). Despite many recent advances in precise experimental characterization and improvements in first-principles electronic structure methods, reliable databases of structures and energetics for large adsorbed molecules are largely amiss. In this review, we present such a database for a range of molecules adsorbed on metal single-crystal surfaces. The systems we analyze include noble-gas atoms, conjugated aromatic molecules, carbon nanostructures, and heteroaromatic compounds adsorbed on five different metal surfaces. The overall objective is to establish a diverse benchmark dataset that enables an assessment of current and future electronic structure methods, and motivates further experimental studies that provide ever more reliable data. Specifically, the benchmark structures and energetics from experiment are here compared with the recently developed van der Waals (vdW) inclusive density-functional theory (DFT) method, DFT + vdW(surf). In comparison to 23 adsorption heights and 17 adsorption energies from experiment we find a mean average deviation of 0.06 A and 0.16 eV, respectively. This confirms the DFT + vdW(surf) method as an accurate and efficient approach to treat HIOSs. A detailed discussion identifies remaining challenges to be addressed in future development of electronic structure methods, for which the here presented benchmark database may serve as an important reference. (C) 2016 Elsevier Ltd. All rights reserved.
Recent efforts to understand the interaction of large aromatic molecules with metal surfaces are discussed. We focus exclusively on work involving the model molecule 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) and the noble metal surfaces of Cu, Ag, and Au. Using this material system as an example, salient features of the (chemical) bond between an extended pi-conjugated electron system and a metallic substrate are illustrated. Interface structures are a valuable indicator of the metal-molecule interaction strength. Consistent with the trend observed for small molecule adsorption, they indicate that the interaction strength of PTCDA with the metal substrate decreases in the order Cu-Ag-Au. The interfaces of PTCDA with the Au(111) and Ag(111) surfaces have been studied in particular detail. The interaction of Au(111) with PTCDA is weak, leading to point-on-line coincidence between the lattices of the substrate and the molecular overlayer. Experimental results on this surface are generally consistent with a predominantly physisorptive bonding of PTCDA. The situation is different on Ag surfaces, and in particular on Ag(111), where clear signs of PTCDA chemisorption are observed in many ensemble averaging and single molecule spectroscopies. Issues of electronic and geometric structure as well as electron-vibron interaction, and their relation to the chemical molecule-substrate interaction, are discussed in detail. (c) 2007 Elsevier Ltd. All rights reserved.
Surface transfer doping relies on charge separation at interfaces, and represents a valuable tool for the controlled and nondestructive doping of nanostructured materials or organic semiconductors at the nanometer-scale. It cannot be easily achieved by the conventional implantation process with energetic ions. Surface transfer doping can effectively dope semiconductors and nanostructures at relatively low cost, thereby facilitating the development of organic and nanoelectronics. The aim of this review is to highlight recent advances of surface transfer doping of semiconductors. Special focus is given to the effective doping of diamond, epitaxial graphene thermally grown on SiC, and organic semiconductors. The doping mechanism of various semiconductors and their possible applications in nanoelectronic devices will be discussed, including the interfacial charge transfer and the energy level alignment mechanisms. (c) 2009 Elsevier Ltd. All rights reserved.
Graphene, a single atomic layer of graphite, has been the focus of recent intensive studies due to its novel electronic and structural properties. Metals grown on graphene also have been of interest because of their potential use as metal contacts in graphene devices, for spintronics applications, and for catalysis. All of these applications require good understanding and control of the metal growth morphology, which in part reflects the strength of the metal graphene bond. Also of importance is whether the interaction between graphene and metal is sufficiently strong to modify the electronic structure of graphene. In this review, we will discuss recent experimental and computational studies related to deposition of metals on graphene supported on various substrates (SiC, SiO2, and hexagonal close-packed metal surfaces). Of specific interest are the metal graphene interactions (adsorption energies and diffusion barriers of metal adatoms), and the crystal structures and thermal stability of the metal nanoclusters. (C) 2015 Elsevier Ltd. All rights reserved.
Organic surfaces play a major role in materials science. Most surfaces that we touch in our daily lives are made from organic materials, e.g., vegetables, fruit, skin, wood, and textiles made from natural fibers. In the context of biology, organic surfaces play a prominent role too, proteins docking onto cell surfaces are a good example. To better understand the characteristics of organic surfaces, including physico-chemical properties like wettability or chemical reactivities and physical properties like friction and lubrication, a structurally well-defined model system that can be investigated with numerous analytical techniques is desirable. In the last two decades, one particular system, self-assembled monolayers or SAMs, have demonstrated their suitability for this purpose. In particular, organothiols consisting of an organic molecule with an attached SH-group are well suited to fabricating structurally well-defined adlayers of monolayer thickness on gold substrates using a simple preparation procedure. These ultrathin monolayers expose an organic surface with properties that can be tailored by varying the type of organothiol employed. After a short introduction into the preparation of SAMs, this article provides an overview of the possibilities and limitations of organic surfaces exposed by Au-thiolate SAMs. Applications are as diverse as the metallization of organic surfaces, a fundamental problem in materials science, and the fabrication of surfaces that resist the adsorption of proteins. In addition to a number of different case studies, we will also discuss the most powerful analytical techniques needed to characterize these important model systems. (C) 2009 Elsevier Ltd. All rights reserved.
We summarize both historical and recent challenges on angle-resolved and high-energy resolution ultraviolet photoelectron spectroscopy (UPS) of organic thin films. Topics selected for this article are mainly on electron spectroscopic study of the electronic states in relation to charge mobility of organic molecular thin films, especially of weakly interacting organic molecular solids. We describe intramolecular band dispersion in a quasi-one-dimensional molecular chain and intermolecular band dispersion measured with angle-resolved UPS. The latter offers a spectroscopic estimation of the drift hole mobility in organic semiconductors. Furthermore we describe briefly hole-vibration coupling in organic ultrathin films, which dominates the hopping hole mobility and has been recently measured with high resolution UPS. These experiments are thus considered to be a kind of the first-principle measurement of the mobility of organic thin films, which have not yet been realized with electrical measurements. Conduction band dispersion studied with low-energy electron transmission, which is needed in analyzing angle-resolved UPS, ultrafast phenomena appearing in conventional UPS measurements and other interesting work are also introduced. (c) 2008 Elsevier Ltd. All rights reserved.
In this article, spectroscopic ellipsometry studies of plasmon resonances at metal–dielectric interfaces of thin films are reviewed. We show how ellipsometry provides valuable non-invasive amplitude and phase information from which one can determine the effective dielectric functions, and how these relate to the material nanostructure and define exactly the plasmonic characteristics of the system. There are three related plasmons that are observable using spectroscopic ellipsometry; volume plasmon resonances, surface plasmon polaritons and particle plasmon resonances. We demonstrate that the established method of exploiting surface plasmon polaritons for chemical and biological sensing may be enhanced using the ellipsometric phase information and provide a comprehensive theoretical basis for the technique. We show how the particle and volume plasmon resonances in the ellipsometric spectra of nanoparticle films are directly related to size, surface coverage and constituent dielectric functions of the nanoparticles. The regularly observed splitting of the particle plasmon resonance is theoretically described using modified effective medium theories within the framework of ellipsometry. We demonstrate the wealth of information available from real-time in situ spectroscopic ellipsometry measurements of metal film deposition, including the evolution of the plasmon resonances and percolation events. Finally, we discuss how generalized and Mueller matrix ellipsometry hold great potential for characterizing plasmonic metamaterials and sub-wavelength hole arrays.
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. (C) 2014 Elsevier Ltd. All rights reserved.
This review reports on experimental and theoretical results on the inelastic decay of optically excited volume electrons in different types of metals, including simple metals (Al), noble metals (Au, Ag, Cu), transition metals (Ta, Mo, Rh, Co, Fe, Ni) and rare earth metals (Gd, Tb, Yb, La). The comparison of the different materials and material classes provides particular insight into the relevance of the localization and delocalization of electronic states for inelastic carrier scattering processes. The discussion of the data illustrates furthermore the capabilities and limitations of the time-resolved two-photon photoemission technique as well as current theoretical approaches in analyzing and determining inelastic lifetimes of excited electrons. (C) 2015 Elsevier Ltd. All rights reserved.
Sum-frequency generation vibrational spectroscopy (SFG-VS) was first developed in the 1980s and it has been proven a uniquely sensitive and surface/interface selective spectroscopic probe for characterization of the structure, conformation and dynamics of molecular surfaces and interfaces. In recent years, there have been many progresses in the development of methodology and instrumentation in the SFG-VS toolbox that have significantly broadened the application to complex molecular surfaces and interfaces. In this review, after presenting a unified view on the theory and methodology focusing on the SFG-VS spectral lineshape, as well as the new opportunities in SFG-VS applications with such developments, some of the controversial issues that have been puzzling the community are discussed. The aim of this review is to present to the researchers and students interested in molecular surfaces and interfacial sciences up-to-date perspectives complementary to the existing textbooks and reviews on SFG-VS. (C) 2016 Elsevier Ltd. All rights reserved.