表面物理讲座第七讲 表面缺陷和表面扩散

表面缺陷和表面扩散在真空镀膜、薄膜半导体器件工艺、粉末冶金、多孔载体上催化剂颗粒的稳定性等实际问题中有重要的作用,得到了广泛的重视.本讲主要介绍晶体表面的原子结构、表面缺陷、表面扩散和有关的一些实验研究方法. 一、晶体表面的原子结构 理想的具有平移对称性的晶体     

表面熔化

对近年来人们十分关注的表面熔化问题，从理论和实验上进行了综述性讨论。综述了一些金属晶体、冰及石墨吸附Ａｒ膜表面熔化的特征及其热力学理论解释。评述了半导体Ｇｅ（１１１）表面熔化的独特性质。     

表面电磁波

一、引 言 近几年来,表面物理的研究引起人们的很大重视.与此同时,对表面电磁波的兴趣也随之增加起来.我们这里所说的表面电磁波,是指表面极性元激发与电磁波(光子)的耦合模即表面极化激元波(surface polaritons),它沿着两种介质之间的界面以准波的形式传播。其振幅随着远离界面指数式迅速衰减.也就是说,波被“束缚”在界面上.以铜一空气界面为例,当入射激光波长是10.6um时,表面电磁波沿界面的传播长度为1.9cm,而它在金属内的穿透深度仅为250A,即传播长度是穿透深度的7.6×105倍.依照不同的界面条件,极性元激发可以是光学声子、激子、等离…     

表面物理与表面物理国家重点实验室

 日常生活中人们无时无刻不在与表面打交道,人类对物质的认识也总是从表面开始才能够逐渐深入的。我们生活在地球表面,在板块运动以及空气和水的侵蚀作用下,地表形成复杂的山川河流,由此我们欣赏到迷人的自然风光。在较小的尺度下,各种植物的枝叶、果实在表面应力作用下呈现不同的形状,为我们识别、利用丰富的自然资源提供了特征依据。人们甚至通过对材料表面进行修饰,从而实现对其功能的设计和调控,比如在钢铁表面电镀惰性金属,可以大大提高钢铁结构的抗腐蚀能力和美观性;而通过对镜头表面镀膜厚度的控制,能够实现滤光或增透的目的。在肉眼不能直接观察的微观尺度上,表面上发生的众多物理、化学现象和过程,也在我们的生产生活中扮演着重要的角色,比如金属纳米颗粒对一些重要化学反应的催化作用,半导体界面对电子传输的调制作用等。正是表面科学帮助人们理解这些行为产生的微观机理,并帮助人们探索控制、优化材料相应功能的方法,从而推动人类文明社会的发展。     

表面物理讲座第五讲 半导体表面

在半导体器件发展的初期,人们就已经知道半导体器件的稳定性在很大程度上依赖于半导体表面的状况.由于在工艺过程中难以严格控制表面的条件,为了保证器件的稳定性,只得对表面尽量采取有效的钝化措施.近十余年来由于超高真空技术的发展,不仅可以制备清洁的表面,而且可以在超高真     

表面谱学

十五年来表面分析取得了很大的进展,其中表面谱学的发展及其应用起了重要作用。本文试图介绍表面光谱分析中的一些基本概念以及它们在表面科学中能够解决的一些重要问题。实际上,我们是想给读者提供一些表面分析中的基本技术。文中所涉及的例子都取自国际商用机器公司ThomasJ·Watson 实验室。     

表面缺陷对一氧化碳和甲基基团在金红石TiO2(110)表面吸附的影响

本文利用程序升温脱附技术研究了氧空位浓度对甲基基团和CO在R-TiO₂(110)表面吸附的影响. 结果表明,随着氧空位浓度的变化,吸附在桥氧位的甲基基团和吸附在五配位Ti⁴⁺位点上的CO分子的脱附温度呈现了不同的趋势,揭示了表面缺陷可能对R-TiO₂(110)不同位点上的物质吸附具有重要影响.     

TiO2分子在GaN(0001)表面吸附的理论研究

采用基于密度泛函理论的平面波超软赝势法,计算了TiO₂分子在GaN(0001)表面的吸附成键过程、吸附能量和吸附位置. 计算结果表明不同初始位置的TiO₂分子吸附后,Ti在fcc或hcp位置,两个O原子分别与表面两个Ga原子成键,Ga-O化学键表现出共价键特征,化学结合能达到7.932-7.943eV,O-O连线与GaN[1120]方向平行,与实验观测(100)[001] TiO₂//(0001)[1120]GaN一致. 通过动力学过程计算分析,TiO₂分子吸附过程经历了物理吸附、化学吸附与稳定态形成的过程,稳定吸附结构和优化结果一致. 关键词： GaN(0001)表面 2分子')" href="#">TiO₂分子 密度泛函理论 吸附     

阳离子空位和吸附氧的协同作用对Na0.5Bi0.5TiO3(100)表面磁性影响的第一性原理研究

The combination effect of cation vacancies and O₂ adsorption on ferromagnetism of Na_0.5Bi_0.5TiO₃(100) surface is studied by using density functional theory.An ideal Na_0.5Bi_0.5TiO₃(100) surface is non-magnetic and the cation vacancy could induce the magnetism.By comparing the formation energies for Na,Bi and Ti vacancy,the Na vacancy is more stable than the others.Therefore,we focus on the configuration and electric structure for the system of O₂ molecule adsorption on the Na_0.5Bi_0.5TiO₃(100) surface with a Na vacancy.Among the five physisorption configurations we considered,the most likely adsorption position is Na vacancy.The O₂ adsorption enhances the magnetism of the system.The contribution of spin polarization is mainly from the O 2p orbitals.The characteristics of exchange coupling are also calculated,which show that the ferromagnetic coupling is favorable.Compared with the previous calculation results,our calculations could explain the room-temperature ferromagnetism of Na_0.5Bi_0.5TiO₃ nanocrytalline powders more reasonably,because of taking into account adsorbed oxygen and cation vacancies.Moreover,our results also show that adsorption of O₂ molecule as well as introduction of cation vacancies may be a promising approach to improve multiferroic materials.     

Adsorption CO2 on the perfect and oxygen vacancy defect surfaces of anatase TiO2 and its photocatalytic mechanism of conversion to CO

The adsorption energies for physisorption and the most stable chemisorption of CO₂ on the neutral charge of perfect anatase [TiO₂] (0 0 1) are −9.03 and −24.66 kcal/mol on the spin-unpolarized and −12.98 and −26.19 kcal/mol on the spin-polarized surface. The small activation barriers of 1.67 kcal/mol on the spin-unpolarized surface and of 6.66 kcal/mol on the spin-unpolarized surface were obtained. The adsorption mechanism of CO₂ on the oxygen vacancy defect [TiO₂ + V_O] surface of anatase TiO₂ using density functional theory calculations was investigated. The energetically preferred conversion of CO₂ to CO was found either on the spin-unpolarized or spin-polarized surfaces of oxygen vacancy defect surface [TiO₂ + V_O] as photocatalyst.     

Theoretical modeling of photocatalytic active species on illuminated TiO2

A theoretical study of the H₂O and O₂ adsorption on an illuminated TiO₂ anatase surface is presented. The electronic structure and the spin distribution were examined by employing the DFT formalism and the BHandHLYP functional. The adsorbates geometries were fully optimized, including the cluster relaxation. Our results show the dissociative adsorption of the H₂O molecule on the photoactivated TiO₂ (0 0 1) surface. This reaction produces one hydroxyl group with radical character (OH) and an unpaired electron localized in the 5c-Ti atom. In case of the O₂ molecule, the non-dissociative chemisorption was obtained. This molecule shows one unpaired electron and a negative charge. In these sense, the adsorbed O₂ acts as a superoxide species (O₂⁻).     

Effect of surface ethoxy groups on photoactivity of TiO2 nanocrystals

TiO₂ nanocrystals modified by ethoxy groups were prepared by a facile nonhydrolytic solvothermal method and characterized by XRD, TEM, TG-DTA and XPS, which showed an enhanced visible-light photocatalytic activity on the degradation of Rhodamine B compared with TiO₂ modified by benzyloxy groups and the “naked” TiO₂. The adsorption and degradation pathway of Rhodamine B on TiO₂ modified by ethoxy groups were also investigated. The zeta-potential (ζ) results showed that the TiO₂ modified by ethoxy groups had high negative surface charge, which incited the positive -N(Et)₂ group of RhB absorbing on the TiO₂ surface and preferably led the N-dealkylation pathway under visible light irradiation.     

甲醇分子在金红石TiO2(110)和锐钛矿TiO2(001)表面吸附和反应的活性位点

通过高分辨的扫描隧道显微术研究并比较了金红石型TiO₂(110)-(1×1)和锐钛矿型TiO₂(001)-(1×4)两种表面的活性位点． 在金红石型TiO₂(110)-(1×1)表面, 观察到氧空位缺陷是O₂和CO₂分子的活性吸附位点,而五配位的Ti原子是水分子和甲醇分子的光催化反应活性位点．在锐钛矿型TiO₂(001)-(1×4)表面,观察到完全氧化的表面,Ti原子更可能是六配位的,H₂O和O₂分子均不易在这些Ti原子上吸附．经还原后表面出现富Ti的缺陷位点, 这些缺陷位点对H₂O和O₂分子表现出明显的活性． 锐钛矿型TiO₂(001)-(1×4)表面的吸附和反应活性并不具有很高的活性,某种程度上其表现出的活性似乎低于金红石型TiO₂(110)-(1×1)表面．     

Visible light sensitization effect of polyaminobenzoate adsorbed on TiO2 nanocrystal surface

Poly-o-aminobenzoate (POA) was prepared by oxidizing o-aminobenzoic acid with (NH₄)₂S₂O₈ in an acidic solution. POA was adsorbed on TiO₂ nanocrystal surface to obtain a POA-TiO₂ nanocomposite. The polymerization reaction, structure, adsorption reaction on TiO₂ surface, and visible light sensitization effect of the polymer adsorbed on TiO₂ surface were studied by FT-IR and UV-visible spectra, cyclic voltammetry, and measurements of visible light photoelectrochemical and photocatalytic activities. Three kinds of POA with different long conjugate structures can be formed. These polymers have large absorbance in wide visible light region. POA molecules can be adsorbed on TiO₂ surface by anchoring their carboxylate groups to the TiO₂ surface with a multi-bridging chelating mode, which causes formation of the POA-TiO₂ nanocomposite with a high stability. POA adsorbed on the TiO₂ nanocrystal showed high visible light sensitization effect in the photocatalytic reaction.     

Adsorption of CO, CO2 and NO molecules on a BaTiO3 (0 0 1) surface

Since the development of Scanning Tunnelling Microscopy (STM) technique, considerable attention has been devoted to various molecules adsorbed on various surfaces. Also, a new concept emerged with molecules on surfaces considered as nano machines by themselves. In this context, a thorough knowledge of surfaces and adsorbed molecules at an atomic scale are thus particularly invaluable. The present work describes the first Density Functional Theory (DFT) study of adsorption of CO, CO₂ and NO molecules on a BaTiO₃ surface following a first preliminary calculation of O and O₂ adsorption on the same surface. In the previously considered work, we found that a (0 0 1) surface with BaO termination is more stable than the one with TiO₂-termination. Consequently, we extended our study to CO, CO₂ and NO molecules adsorbed on a (0 0 1) surface with BaO termination. The present calculation was performed on a (1 × 1) cell with one monolayer of adsorbed molecules. Especially, a series of cases implying CO molecules adsorbed in various geometrical configurations has been examined. The corresponding adsorption energy varies in the range of −0.17 to −0.10 eV. The adsorption energy of a CO₂ molecule directly located above an O surface atom (called O_s) is of the order of −0.18 eV. The O-C distance length is then 1.24 Å and the O-C-O and O-C-O_s angles are 134.0° and 113.0°, respectively. For NO adsorption, the most important induced structural changes are the followings: (i) the N-O bond is broken when a NO molecule is absorbed on a Ba-O_s bridge site. In that case, N and O atoms are located above an O and a Ba surface atom, respectively, whereas the O-Ba-O_s and N-O_s-Ba angles are 106.5° and 63.0°, respectively. The N-O distance is as large as 2.58 Å and the adsorption energy is as much as −2.28 eV. (ii) In the second stable position, the NO molecule has its N atom adsorbed above an O_s atom, the N-O axis being tilted toward the Ba atom. The N-O_s-Ba angle is then 41.1° while the adsorption energy is only −0.10 eV. At last, the local densities of states around C, O as well as N atoms of the considered adsorbed molecules have also been discussed.     

CO oxidation of bare and TiO2-coated NiO-Ni(OH)2 nanoparticles

CO oxidation reactivity of bare and TiO₂-coated nanoparticles consisting of both NiO and Ni(OH)₂ surfaces was studied. For the deposition of TiO₂, atomic layer deposition was used, and formation of three-dimensional domains of TiO₂ on NiO-Ni(OH)₂ could be identified. Based on the data of X-ray Photoelectron Spectroscopy, we suggest that upon TiO₂ deposition only Ni(OH)₂ was remained on the surface, whereas NiO surface disappeared. Both CO adsorption and CO oxidation took place on NiO-Ni(OH)₂ surfaces under our experimental conditions. CO adsorption was almost completely suppressed after TiO₂ deposition, whereas CO oxidation activity was maintained to large extent. It is proposed that bare NiO cannot be active for CO oxidation, and can only uptake CO under our experimental condition, whereas hydroxylated surface of NiO can be active for CO oxidation.