{"title":"Local structure determination in strained-layer semiconductors","authors":"Joseph C. Woicik","doi":"10.1016/j.surfrep.2013.12.002","DOIUrl":"https://doi.org/10.1016/j.surfrep.2013.12.002","url":null,"abstract":"<div><p><span>The theory of elasticity accurately describes the deformations of macroscopic bodies under the action of applied stress </span><span>[1]</span>. In this review, we examine the <em>internal</em><span> mechanisms of elasticity for strained-layer semiconductor heterostructures<span>. In particular, we present extended x-ray-absorption fine structure (EXAFS) and x-ray diffraction (XRD) measurements to show how the bond lengths and bond angles<span> in semiconductor thin-alloy films change with strain when they are grown coherently on substrates with different lattice constants. The structural distortions measured by experiment are compared to valence-force field (VFF) calculations and other theoretical models. Atomic switching and interfacial strain at buried interfaces are also discussed.</span></span></span></p></div>","PeriodicalId":434,"journal":{"name":"Surface Science Reports","volume":"69 1","pages":"Pages 38-53"},"PeriodicalIF":9.8,"publicationDate":"2014-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.surfrep.2013.12.002","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2326770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"The contribution of surfaces and interfaces to the crystal thermal conductivity","authors":"M. Kazan , P. Masri","doi":"10.1016/j.surfrep.2013.11.001","DOIUrl":"https://doi.org/10.1016/j.surfrep.2013.11.001","url":null,"abstract":"<div><p><span>This review provides theoretical understanding of the role of the surface and interface in the thermal conductivity of solids. An attempt is made to collect the various methods used in the analysis of experiments. The adequacy and range of validity of these methods are evaluated, and suggestions are made concerning possible theoretical and experimental investigations which seem desirable. A major part of the paper is devoted to the description of the surface vibrational modes, the surface thermal conductivity, the interaction of defects with </span>crystal surfaces<span>, and the phonon scattering from crystal surfaces.</span></p><p><span>First, a review is made of the general form of the interatomic potential energy and </span>lattice vibrations<span><span>. Certain aspects related to the three- and four-phonon processes are discussed. Then, the heat current is calculated in the presence of scattering processes described by a relaxation time, and a general formalism for the lattice thermal conductivity is derived. A special consideration is given to the effect of boundary scattering and boundary thermal conductance. In the first sections, despite the consideration of boundary scattering, the calculation of the thermal conductivity is carried out with adopting of the cyclic boundary conditions. Such a treatment, while mathematically convenient, eliminates the possibility of studying the dynamical properties of atoms in the neighborhood of a free surface of a real crystal because the crystal structure in the surface layers may differ from the structures in the bulk of the crystal. The forces acting on atoms in the surface layers will be different from the forces acting on atoms in the bulk since an atom in the surface layers has fewer nearest neighbors, next-nearest neighbors, etc., than an atom in the interior of a crystal. Therefore, one would expect that the dynamical properties and the resultant thermal conductivity are different for atoms in the surface layers of a crystal than for atoms in the bulk of the crystal. Moreover, when crystal size becomes small enough that the ratio of surface to volume is not negligible, the modification of the frequency distribution function of the crystal by the presence of free surfaces, which is the addition of a contribution from an essentially two-dimensional crystal, will alter the temperature dependence of thermal conductivity and give rise to distinct size effects on the thermal conductivity. Furthermore, selection rules governing physical properties in crystals, which have their origins in symmetry properties, translational and rotational, of an infinitely extended crystal, can be relaxed for finite crystals or for atoms in the surface layers of crystals for which these symmetry properties no longer hold. Thus, one would expect to find that the thermal conductivity of a </span>thin film or small particle will show specific features that do not appear for the case of bulk material. In order","PeriodicalId":434,"journal":{"name":"Surface Science Reports","volume":"69 1","pages":"Pages 1-37"},"PeriodicalIF":9.8,"publicationDate":"2014-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.surfrep.2013.11.001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2326772","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A. Politano , G. Chiarello , G. Benedek , E.V. Chulkov , P.M. Echenique
{"title":"Vibrational spectroscopy and theory of alkali metal adsorption and co-adsorption on single-crystal surfaces","authors":"A. Politano , G. Chiarello , G. Benedek , E.V. Chulkov , P.M. Echenique","doi":"10.1016/j.surfrep.2013.07.001","DOIUrl":"https://doi.org/10.1016/j.surfrep.2013.07.001","url":null,"abstract":"<div><p>Alkali-metal (AM) atoms adsorbed on single-crystal surfaces are a model system for understanding the properties of adsorption. AM adsorption, besides introducing new overlayer vibrational states, induces significant modifications in the surface vibrational structure of the metal substrate. Several studies of the vibrational properties of AM on metal surfaces have been carried out in last decades. Most of these investigations have been performed for low coverages of AM in order to make the lateral interaction among co-adsorbates negligible. The adsorbed phase is characterized by a stretch (<em>S</em>) vibrational mode, with a polarization normal to the surface, and by other two modes polarized in the surface plane, known as frustrated translation (<em>T</em>) modes. The frequencies and intensities of these modes depend on the coverage, thus providing a spectroscopic signature for the characterization of the adsorbed phases.</p><p>The vibrational spectroscopy joined to an ab-initio theoretical analysis can provide useful information about surface charge re-distribution and the nature of the adatom–surface bond, establishing, e.g., its partial ionicity and polarization. Gaining this information implies a significant advancement in our knowledge on surface chemical bonds and on catalytic reactions occurring in AM co-adsorption with other chemical species. Hence, systematic studies of co-adsorption systems are essential for a more complete understanding of heterogeneous catalysis.</p><p>The two principal experimental techniques for studying the vibrations of AM adsorbed phases are high-resolution electron energy loss spectroscopy (HREELS) and inelastic helium atom scattering (HAS), the former being better suited to the analysis of the higher part of the vibrational spectrum, while the latter exploits its better resolution in the study of slower dynamics, e.g., <em>T</em> modes, surface acoustic phonons and diffusive phenomena. Concerning AM co-adsorption systems, reflection–absorption infrared spectroscopy (RAIRS) has been also used (as well as HREELS) for obtaining information on the influence of AM adsorption on the vibrational properties of co-adsorbates.</p><p>In this review an extended survey is presented over:</p><p></p><ul><li><span>a)</span><span><p>the existing HREELS and HAS vibrational spectroscopic studies for AM adsorbed on single-crystal metal surfaces;</p></span></li><li><span>b)</span><span><p>the theoretical studies based on semi-empirical and ab-initio methods of vibrational structure of AM atoms on metal surfaces;</p></span></li><li><span>c)</span><span><p>the vibrational (HREELS, RAIRS, TRSHG) characterization of the co-adsorption on metal surfaces of AM atoms with reactive species.</p></span></li></ul></div>","PeriodicalId":434,"journal":{"name":"Surface Science Reports","volume":"68 3","pages":"Pages 305-389"},"PeriodicalIF":9.8,"publicationDate":"2013-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.surfrep.2013.07.001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"3264611","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"In situ high-resolution X-ray photoelectron spectroscopy – Fundamental insights in surface reactions","authors":"Christian Papp, Hans-Peter Steinrück","doi":"10.1016/j.surfrep.2013.10.003","DOIUrl":"https://doi.org/10.1016/j.surfrep.2013.10.003","url":null,"abstract":"<div><p><span>Since the advent of third generation synchrotron light sources optimized for providing soft X-rays up to 2</span> <span><span>keV, X-ray photoelectron spectroscopy (XPS) has been developed to be an outstanding tool to study surface properties and surface reactions at an unprecedented level. The high resolution allows identifying various surface species, and for small molecules even the vibrational fine structure can be resolved in the XP spectra. The high photon flux reduces the required measuring time per spectrum to the domain of a few seconds or even less, which enables to follow surface processes in situ. Moreover, it also provides access to very small coverages down to below 0.1% of a monolayer, enabling the investigation of minority species or processes at defect sites. The photon energy can be adjusted according to the requirement of a particular experiment, i.e., to maximize or minimize the surface sensitivity or the photoionization<span> cross-section of the substrate or the adsorbate. For a few instruments worldwide, a next step forward was taken by combining in situ high-resolution spectrometers with supersonic </span></span>molecular beams. These beams allow to control and vary the kinetic and internal energies of the incident molecules and provide a local pressure of up to ~10</span><sup>−5</sup> <!-->mbar, which can be switched on and off in a controllable way, thus offering a well-defined time structure to study adsorption or reaction processes.</p><p><span>Herein, we will review some specific scientific aspects which can be addressed by in situ XPS in order to demonstrate the power and potential of the method: In particular, the following topics will be addressed: (1) The sensitivity of the binding energy to adsorption sites will be analyzed, using CO on metals as example. From measurements at different temperatures, the binding energy difference between different sites can be derived, and exchange processes between different adsorbate species at step edges can be followed. (2) The vibrational fine structure of adsorbed small hydrocarbon species on metal surfaces will be analyzed in detail. We will first introduce the linear coupling model, then discuss the properties of adsorbed methyl and of a number of other small hydrocarbons, and show that the vibrational signature can be used as fingerprint for identifying surface species. (3) It is demonstrated that the binding energy of equivalent atoms in a molecule can be differentially changed by adsorption to a substrate; this sensitivity to the local environment will be discussed for adsorbed ethylene, benzene and graphene. (4) By temperature programmed XPS, the thermal evolution of adsorbed species can be followed in great detail, allowing for the identification of reaction intermediates and the determination of their stabilities. (5) The investigation of reaction kinetics by isothermal XPS measurements will be discussed; here results for the </span>oxidation<span> of s","PeriodicalId":434,"journal":{"name":"Surface Science Reports","volume":"68 3","pages":"Pages 446-487"},"PeriodicalIF":9.8,"publicationDate":"2013-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.surfrep.2013.10.003","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"1945448","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Likun Pan , Shiqing Xu , Xinjuan Liu , Wei Qin , Zhuo Sun , Weitao Zheng , Chang Q. Sun
{"title":"Skin dominance of the dielectric–electronic–phononic–photonic attribute of nanoscaled silicon","authors":"Likun Pan , Shiqing Xu , Xinjuan Liu , Wei Qin , Zhuo Sun , Weitao Zheng , Chang Q. Sun","doi":"10.1016/j.surfrep.2013.10.001","DOIUrl":"https://doi.org/10.1016/j.surfrep.2013.10.001","url":null,"abstract":"<div><p><span>Nanoscaled or porous silicon (</span><em>p-Si</em><span>) with and without surface passivation<span> exhibits unusually tunable properties that its parent bulk does never show. Such property tunability amplifies the applicability of Si in the concurrent and upcoming technologies. However, consistent understanding of the fundamental nature of nanoscaled Si remains a high challenge. This article aims to address the recent progress in this regard with focus on reconciling the tunable dielectric<span>, electronic, phononic, and photonic properties of </span></span></span><em>p-Si</em><span><span><span> in terms of skin dominance. We show that the skin-depth bond contraction, local quantum entrapment, and electron localization is responsible for the size-induced property tunability. The shorter and stronger bonds between undercoordinated skin atoms result in the local </span>densification<span> and quantum entrapment of the binding energy and the bonding electrons, which in turn polarizes the dangling bond electrons. Such local entrapment modifies the Hamiltonian and associated properties such as the band gap, core level shift, Stokes shift (electron–phonon interaction), </span></span>phonon<span> and dielectric relaxation. Therefore, given the known trend of one property change, one is expected to be able to predict the variation of the rest based on the notations of the bond order–length–strength correlation and local bond average approach (BOLS-LBA). Furthermore, skin bond reformation due to Al, Cu, and Ti metallization and O and F passivation adds another freedom to enhance or attenuate the size effect. The developed formulations, spectral analytical methods, and importantly, the established database and knowledge could be of use in engineering </span></span><em>p-Si</em> and beyond for desired functions.</p></div>","PeriodicalId":434,"journal":{"name":"Surface Science Reports","volume":"68 3","pages":"Pages 418-445"},"PeriodicalIF":9.8,"publicationDate":"2013-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.surfrep.2013.10.001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"3264612","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
R. Bergamaschini , F. Isa , C.V. Falub , P. Niedermann , E. Müller , G. Isella , H. von Känel , L. Miglio
{"title":"Self-aligned Ge and SiGe three-dimensional epitaxy on dense Si pillar arrays","authors":"R. Bergamaschini , F. Isa , C.V. Falub , P. Niedermann , E. Müller , G. Isella , H. von Känel , L. Miglio","doi":"10.1016/j.surfrep.2013.10.002","DOIUrl":"https://doi.org/10.1016/j.surfrep.2013.10.002","url":null,"abstract":"<div><p><span><span>In this report we present a novel strategy in selective epitaxial growth on top of Si pillars, which results in a tessellated Ge film, composed by self-aligned micron-sized crystals in a maskless process. Modelling by </span>rate equations<span><span> the morphology evolution of fully facetted crystal profiles is extensively outlined, showing an excellent prediction of the peculiar role played by flux shielding among microcrystals, in the case of dense array configuration. </span>Crack formation<span> and substrate bending, caused by the mismatch in thermal expansion coefficients, are eliminated by the mechanical decoupling among individual microcrystals, which are also shown to be dislocation- and strain-free. The method has been also tested for Si</span></span></span><sub>1−<em>x</em></sub>Ge<sub><em>x</em></sub><span><span><span> alloys, with compositions<span> ranging from pure </span></span>silicon to pure </span>germanium. There are ample reasons to believe that this approach could be extended to other material combinations and substrate orientations, actually providing a technology platform for several device applications.</span></p></div>","PeriodicalId":434,"journal":{"name":"Surface Science Reports","volume":"68 3","pages":"Pages 390-417"},"PeriodicalIF":9.8,"publicationDate":"2013-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.surfrep.2013.10.002","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2326773","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"The interpretation of XPS spectra: Insights into materials properties","authors":"Paul S. Bagus , Eugene S. Ilton , Connie J. Nelin","doi":"10.1016/j.surfrep.2013.03.001","DOIUrl":"https://doi.org/10.1016/j.surfrep.2013.03.001","url":null,"abstract":"<div><p>We review basic and advanced concepts needed for the correct analysis of XPS features. We place these concepts on rigorous foundations and explore their physical and chemical meanings without stressing the derivation of the mathematical formulations, which can be found in the cited literature. The significance and value of combining theory and experiment is demonstrated by discussions of the physical and chemical origins of the main and satellite XPS features for a variety of molecular and condensed phase materials.</p></div>","PeriodicalId":434,"journal":{"name":"Surface Science Reports","volume":"68 2","pages":"Pages 273-304"},"PeriodicalIF":9.8,"publicationDate":"2013-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.surfrep.2013.03.001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2424400","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Theoretical perspective of alcohol decomposition and synthesis from CO2 hydrogenation","authors":"Ping Liu , Yixiong Yang , Michael G. White","doi":"10.1016/j.surfrep.2013.01.001","DOIUrl":"https://doi.org/10.1016/j.surfrep.2013.01.001","url":null,"abstract":"<div><p>Advances in theoretical methods, in particular density functional theory (DFT), make it possible to describe catalytic reactions at surfaces with the detail and accuracy required for computational results to compare with experiment in a meaningful way. The theoretical studies also describe chemical reaction networks and understand variations in catalytic activity from one catalyst to another. Such understanding allows the theoretical optimization for better catalysts.</p><p>In the current report we discussed the theoretical studies in the past few years on decomposition and synthesis of methanol and ethanol on various catalyst surfaces. The knowledge of reactions including the intermediates and transition states along different reaction pathways together with kinetic modeling was demonstrated. The theoretical studies on alcohol synthesis help gain better understanding of the complex kinetics and the roles that each component of a catalyst plays. In general, moving from mono-functional catalysts to multi-functional catalysts by increasing the complexity offers new opportunities to tune the behavior of a catalyst. A good multi-functional catalyst is not necessary to compromise the binding strong enough to adsorb and dissociate reactants and weak enough to allow the formation of intermediates and removal of products; instead, it may take advantage of each component, which catalyzes different elementary steps depending on its unique activity. The synergy between the different components can enable the multi-functional catalyst a novel activity in catalysis. This is of great importance for rational design of better catalysts for alcohol renewal synthesis and efficient use.</p></div>","PeriodicalId":434,"journal":{"name":"Surface Science Reports","volume":"68 2","pages":"Pages 233-272"},"PeriodicalIF":9.8,"publicationDate":"2013-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.surfrep.2013.01.001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"2326775","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Unravelling the secrets of Cs controlled secondary ion formation: Evidence of the dominance of site specific surface chemistry, alloying and ionic bonding","authors":"Klaus Wittmaack","doi":"10.1016/j.surfrep.2012.11.001","DOIUrl":"https://doi.org/10.1016/j.surfrep.2012.11.001","url":null,"abstract":"<div><p><span>Exposure of ion bombarded solids to Cs gives rise to a very strong enhancement of the yields of negatively charged secondary ions and, concurrently, to a lowering of </span>positive ion<span> yields. The phenomena have been explored in a large number of experimental and theoretical studies but attempts to clarify the mechanism of ion formation were not as successful as assumed. This review examines the state of the art in Cs controlled secondary ion mass spectrometry (SIMS) in great detail, with due consideration of low-energy alkali-ion scattering.</span></p><p><span><span>In very basic studies on alkali induced secondary ion yield changes, sub-monolayer quantities of Cs or Li were deposited on the sample surface, followed by low-fluence ion bombardment<span>, to avoid significant damage. If SIMS is applied to characterise the composition of solid materials, the simplest approach to achieving sample erosion as well as high negative-ion yields is bombardment with primary ions of Cs. Two other methods of sample loading with Cs provide more flexibility, (i) exposure to a collimated beam of Cs vapour and concurrent bombardment with high-energy non-Cs ions and (ii) the mixed-beam approach involving quasi-simultaneous bombardment with Cs and </span></span>Xe ions<span>. Both concepts have the advantage that undesirable sample overload with Cs can be avoided. High Cs concentrations reduce the formation probability of target specific molecular ions<span> and lower the yields of all types of positive secondary ions, including Cs</span></span></span><sup>+</sup>, M<sup>+</sup>, X<sup>+</sup>, MCs<sup>+</sup> and XCs<sup>+</sup> (M and X denoting matrix and impurity elements). Quantitative SIMS analysis using MCs<sup>+</sup> and XCs<sup>+</sup> ions appears feasible, provided the Cs coverage is kept below about 5%.</p><p><span>The semi-classical model of resonant charge transfer, also known as the tunnelling model, has long been considered a solid framework for the interpretation of Cs and Li based SIMS data. The model predicts ionisation probabilities for cases in which, at shallow distances from the surface, the affinity (ionisation) level of the departing atom is shifted below (above) the Fermi level. Ion yields should be controlled by the work function (WF) of the sample, </span><em>Φ</em><span>, and the normal velocity of the ejected ions. To explore the predicted velocity dependence, the performance characteristics of the employed SIMS instrument need to be known. The Cs induced negative-ion yield enhancement observed with pure metal and alloy targets often exceeded five orders of magnitude, with enhancement factors essentially independent of the emission energy. This absence of a velocity dependence is at variance with the predictions of the tunnelling model.</span></p><p>Previous theoretical attempts to model the <em>Φ</em>-dependence and the apparent velocity effect for the overrated case of O<sup>−</sup><span><span><span>emission fr","PeriodicalId":434,"journal":{"name":"Surface Science Reports","volume":"68 1","pages":"Pages 108-230"},"PeriodicalIF":9.8,"publicationDate":"2013-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.surfrep.2012.11.001","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"1945449","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}