三氧化钨表面氢吸附机理的第一性原理研究

采用基于密度泛函理论的第一性原理平面波超软赝势方法,在广义梯度近似下,研究了立方WO_3,WO_3(001)表面结构及其氢吸附机理.计算结果表明立方晶体WO_3理论带隙宽度为0.587 eV.WO_3(001)表面有WO终止(001)表面和O终止(001)表面两种结构,表面结构优化后W—O键长和W—O—W键角改变,从而实现表面弛豫;WO终止(001)表面和O终止(001)表面分别呈现n型半导体特征和p型半导体特征.分别计算了H原子吸附在WO终止(001)表面和O终止(001)表面的H—O_(2c)—H,H—O_(2c)…H—O_(2c),H—O_(1c)—H和H—O_(1c)…H—O_(1c)四种吸附构型,其中H—O_(1c)—H吸附构型的吸附能最小,H—O键最短,H失去电子数最多,分别为-3.684 eV,0.0968 nm和0.55e,此吸附构型最稳定.分析其吸附前后的态密度,带隙从吸附前的0.624 eV增加到1.004 eV,价带宽度基本不变.H的1s轨道电子与O的2p,2s轨道电子相互作用,在-8和-20 eV附近各形成了一个较强的孤立电子峰,两个H原子分别与一个O_(1c)原子形成化学键,最终吸附反应生成了一个H_2O分子,同时产生了一个表面氧空位.     

活性质吸附氢修饰金刚石表面的第一性原理研究

采用基于密度泛函理论的第一性原理方法,构建了不同活性质吸附氢修饰和氧修饰金刚石(100)表面,计算了氢修饰和氧修饰金刚石(100)表面吸附体系的平衡态几何构型和态密度.结果表明,氢修饰金刚石表面与H_3O~+离子间具有较强的相互作用,在费米能级附近出现浅受主能级,电荷会发生从氢修饰金刚石表面向吸附H_3O~+离子迁移,从而呈现p型导电性;当吸附物为H_3O~+离子和H_2O分子混合吸附时,能带结构发生改变,但是其导电性并没有发生变化.相比之下,含水分子和H_3O~+离子的吸附物在氧修饰金刚石表面将发生分解,不能稳定存在,吸附体系仍呈现绝缘性质.     

氢吸附金刚石（001）表面的第一性原理研究

采用第一性原理方法研究氢吸附的金刚石（001）表面，计算了氢吸附金刚石表面构型.通过分析吸附前后空间电荷分布的变化，发现吸附H原子的金刚石（001）表面电荷向H原子转移，即表明氢吸附的金刚石表面带负电.分析了这种现象的微观机制，以及它对金刚石表面电学性质的影响. 关键词： 第一性原理计算 金刚石（001）面 表面吸附 电荷密度分布     

W_(20)O_(58)(010)表面氢吸附机理的第一性原理研究

采用基于密度泛函理论的第一性原理平面波超软赝势方法,在广义梯度近似下,研究了W_(20)O_(58)晶胞、W_(20)O_(58)(010)表面结构及其氢吸附机理.计算结果表明:W_(20)O_(58)晶体理论带隙宽度为0.8 eV,为间接带隙,具有金属性.W_(20)O_(58)晶体中W—O共振较强,以共价键居多.W_(20)O_(58)(010)表面有WO终止(010)表面和O终止(010)表面,表面结构优化后使得W—O键长和W—O—W键角改变,从而实现表面弛豫.分别计算了H_2分子吸附在WO终止(001)表面和O终止(001)表面的WO-L-O_(1c),WO-V-O_(1c),WO-L-O_(2c),WO-V-O_(2c),O-L-O_(1c)和O-V-O_(1c)六种吸附构型,其中WO-L-O_(1c),WO-V-O_(1c)和WO-L-O_(2c)这三种吸附构型不稳定;而WO-V-O_(2c),O-L-O_(1c)和O-V-O_(1c)这三种吸附构型都很稳定,H_2分子都解离成两个H原子,吸附能均为负值,分别为-1.164,-1.021和-3.11 eV.WO-V-O_(2c)吸附构型的两个H原子分别吸附在O和W原子上;O-L-O_(1c)吸附构型的两个H原子,一个与O原子成键,另一个远离了表面.其中O-V-O_(1c)吸附构型最稳定,两个H原子失去电子,为O原子提供电子.分析其吸附前后的态密度,H的1s轨道电子与O的2p,2s轨道电子相互作用,均形成了一些较强的成键电子峰,两个H原子分别与O_(1c)形成化学键,最终吸附反应生成了一个H_2O分子,同时产生了一个表面氧空位.     

PbTe(001)表面原子几何结构和电子结构的第一性原理计算

用第一性原理的密度泛函理论计算了PbTe（001）表面的几何结构和电子结构.计算结果表明：PbTe（001）表面不发生重构，但表面几层原子表现出明显的振荡弛豫现象，其中第一、第二层间距减小4.5%，第二、第三层间距增加2.0%，并且表面层原子出现褶皱.表面带隙在X 点，带隙变宽，在基本带隙中不引入新的表面态，而导带底和价带顶附近等多处出现新的表 面共振态；弛豫后费米面处态密度很低，所以表面结构很稳定. 关键词： 密度泛函理论 表面几何结构 表面电子结构 PbTe     

BiOCl{001}表面原子与电子结构的第一性原理研究

基于密度泛函理论的第一性原理方法研究了BiOCl{001}的三种不同终端面({001}-1Cl, {001}-BiO 和{001}-2Cl)的表面弛豫、能带结构、电子态密度和表面能. 计算结果表明: {001}-1Cl, {001}-BiO和{001}-2Cl表面均发生明显弛豫, 而在双Cl原子层处的层间距变化较大, 但未出现振荡弛豫现象, 其中{001}-1Cl表面弛豫较小. 与体相BiOCl电子结构相比, BiOCl{001}面具有较窄的带隙宽度, 并呈现较强局域性:对于{001}-BiO表面, 其导带与价带均往低能方向发生较大移动, 并且在导带底部出现表面态; 而{001}-2Cl表面的表面态主要出现在价带顶; {001}-1Cl表面的带隙中则无表面态产生; 表面态的出现导致{001}-BiO面和{001}-2Cl面带隙明显减小. BiOCl{001}三种终端表面的表面能分析结果表明, {001}-1Cl表面的表面能最小(0.09206 J·m^-2), 结构最稳定, 而{001}-BiO表面和{001}-2Cl表面的表面能分别为2.392和2.461 J·m^-2. 理论预测{001}-BiO表面和{001}-2Cl表面具有较高的活性, 但在BiOCl晶体生长过程中不易暴露. 本文计算结果为实验获得BiOCl高活性面{001}给予了基础理论解释, 进一步为BiOCl新型光催化材料的应用研究提供理论指导. 关键词： BiOCl{001}表面 表面弛豫 表面能 第一性原理     

Cu(100) (2×22)R45°-O的表面结构与电子态的密度泛函研究

用第一性原理的总能计算研究了Cu(100))面的表面结构、弛豫以及氧原子的(2×22)吸附状 态.计算给出了Cu(100) (2×22)R45°-O吸附表面的结构参数，并得到了上述结构下氧吸附 的Cu(100)表面氧原子和各层Cu原子的电子态密度.计算得到的吸附表面功函数为4.58 eV ，与清洁Cu(100)表面功函数(～4.53 eV)几乎相同.吸附氧原子与最外层铜原子之间的垂直 距离约为0.02 nm，其能带结构体现出一定的金属性，同时由于Cu-O的杂化作用在费米能以 下约6.4 eV附近出现了局域的表面态.可以认为，在Cu(100) (2×22)R45°的氧吸附表面结 构下，吸附氧原子和衬底之间的结合主要来源于表面最外层铜原子与氧原子的相互作用. 关键词： Cu(100)(2×22)R45°-O表面 缺列再构 表面电子态     

Rb吸附石墨烯纳米带电子性质和光学性质的研究

本文基于密度泛函理论的第一性原理方法了计算了Rb、O和H吸附石墨烯纳米带的差分电荷密度、能带结构、分波态密度和介电函数，调制了石墨烯纳米带的电子性质和光学性质，给出了不同杂质影响材料光学特性的规律.结果表明本征石墨烯纳米带为n型直接带隙半导体且带隙值为0.639 eV；Rb原子吸附石墨烯纳米带之后变为n型简并直接带隙半导体，带隙值为0.494eV；Rb和O吸附石墨烯纳米带变为p型简并直接带隙半导体，带隙值增加为0.996eV；增加H吸附石墨烯纳米带后，半导体类型变为n型直接带隙半导体，且带隙变为0.299eV，带隙值相对减小，更有利于半导体发光器件制备.吸附Rb、O和H原子后，石墨烯纳米带中电荷密度发生转移，导致C、Rb、O和H之间成键作用显著.吸附Rb之后，在费米能级附近由C-2p、Rb-5s贡献；增加O原子吸附之后，O-2p在费米能级附近贡献非常活跃，杂化效应使费米能级分裂出一条能带；再增加H原子吸附之后，Rb-4p贡献发生蓝移，O-2p在费米能级附近贡献非常强，费米能级分裂出两条能带.Rb、O和H的吸附后，明显调制了石墨烯纳米带的光学性质.     

Cu(100)(√2×2√2)R 45°-O的表面结构与电子态的密度泛函研究

用第一性原理的总能计算研究了Cu(100))面的表面结构、弛豫以及氧原子的(√2×2√2)吸附状态.计算给出了Cu(100)(√2×2√2)R45°-O吸附表面的结构参数,并得到了上述结构下氧吸附的Cu(100)表面氧原子和各层Cu原子的电子态密度.计算得到的吸附表面功函数φ为4.58 eV,与清洁Cu(100)表面功函数(～4.53 eV)几乎相同.吸附氧原子与最外层铜原子之间的垂直距离约为0.02 nm,其能带结构体现出一定的金属性,同时由于Cu-O的杂化作用在费米能以下约6.4 eV附近出现了局域的表面态.可以认为,在Cu(100)(√2×2√2)R45°的氧吸附表面结构下,吸附氧原子和衬底之间的结合主要来源于表面最外层铜原子与氧原子的相互作用.     

GaP（001）表面吸附性硫的第一性原理研究

采用基于密度泛函理论（Density Functional Theory）的第一性原理计算了GaP（001）面吸附硫原子后的表面结构和电子结构。计算表明,在Ga和P截止的GaP（001）-（1×2）表面吸附两个硫原子后,会形成（1×1）的重构表面,硫原子吸附在桥位置（HB）。电子结构的计算显示,吸附硫原子后,GaP带隙中的表面态密度（Density of States）明显减少了,这表明在GaP（001）表面吸附硫原子后达到了钝化的效果。     

Si(111)理想、弛豫及2×1重构表面的声子谱研究

本文利用微扰的方法考虑了占据态与空态间的耦合对能带能量的影响,给出延展键轨道近似下半导体力常数的解析表达式.利用这些表达式求出Si(111)的理想、1×1弛豫及2×1Haneman模型重构表面的声子色散曲线及其表面振动的振幅分布.不同表面结果的比较显示弛豫及重构对表面声子性质具有决定性的影响.同时,分析表明Haneman的2×1表面重构模型不足以满意地解释有关实验结果.     

Surface photovoltage spectroscopy of electronic surface states on cleaved germanium(111) surfaces

Surface photovoltage (SPV) measurements on UHV cleaved Ge(111) surfaces at 100 K are reported for photon energies 0.4 < ?ω < 1 eV. The SPV spectra are sensitive to surface treatment. Upon annealing to temperatures above 200°C, which is accompanied by a reconstruction change from the (2 × 1) to an (8) superstructure, the SPV spectrum shows 2 shoulders below band gap energy with threshold energies near 0.4 and 0.45 eV. These structures are interpreted in terms of electronic transitions from the valence band into empty surface state levels which are related to the (8) superstructure. Adsorbed oxygen and water vapor both cause new similar transitions from the valence band into empty surface states at 0.08 eV below the bottom of the conduction band.     

Anomalous oxidation properties of the ZnSe (100) surface

We have observed a unique, pressure-dependent adsorption isotherm of oxygen on the ZnSe (100) surface, which consists of an unmeasurable uptake followed by an irreversible, step-like uptake for pressures exceeding a critical value of ～ 0.08 torr at room temperature. A partial depletion of Se accompanies this adsorption process. For incomplete oxidation, oxygen induced (2 × 1) and (3 × 1) surface reconstructions may be generated, the first such structures to be observed for semiconductors. The electron-energy-loss spectra for these surfaces and for the clean ZnSe (100)c(2 × 2) surface are presented. The clean surface exhibits a dangling-bond-derived empty surface state ～ 1 eV above the conductor band edge, and filled surface states near 3.2, 6.5, and 15 eV below the valence band edge.     

Si(100)表面电子态的总电流谱研究

用自制的总电流谱仪研究了Si(100)2×1清洁表面以及H原子饱和吸附后的Si(100)1×1-2H双氢化相表面的电子态。在清洁表面上测得的空电子态位于价带顶以上0.7eV处,而占有电子态则在价带顶以下0.25,8.4和近12eV处。在双氢化相表面上还观测到处于价带顶以下两个诱导表面态。 关键词：     

Photoemission yield spectroscopy of electronic surface states on germanium (111) surfaces

The electronic surface states of cleaved and annealed Ge(111) surfaces have been investigated by photoemission yield spectroscopy and contact potential measurements on a set of differently doped samples. On the 2 × 1 cleaved surface, a surface state band centered about 0.7 eV below the valence band maximum is found. The variations of the work function with the doping level show that an empty surface state band exists above the Fermi level. After annealing at temperatures of the order of 350°C, this surface exhibits a 2 × 8 superstructure. A new surface state band is then found closer to the valence band maximum. This variation of the surface state distribution is correlated to a change in the surface potential. The variation of the electronic characteristics upon oxygen adsorption are also reported and an evaluation of the sticking coefficient is made for both structures.     

Density Functional Calculation of the 0.5ML-Terminated Allyl Mercaptan/Si（100）-（2 × 1） Surface

The structural and electronic properties of the 0.5 ML-terminated allyl mercaptan （ALM）/Si（IO0）-（2 x 1） surface are studied using the density functional method. The calculated absorption energy of the ALM molecule on the 0.5 ML-terminated ALM/Si（IO0）-（2 x 1） surface is 3.36eV, implying that adsorption is strongly favorable. The electronic structure calculations show that the ALM/Si（IO0）-（2 x 1）, the clean Si（100）-（2 x 1）, and the fully-terminated H/Si（IO0）-（2 ~ 1） surfaces have the nature of an indirect band gap semiconductor. The highest occupied molecular orbital is dominated by the ALM, confirming the mechanism proposed by Hossain for its chain reaction.     

Hydrogen adsorption and surface structures of silicon

The adsorption of atomic hydrogen on silicon (111)2 × 1 cleaved, (111) 7 × 7, and (100) 2 × 1 surfaces has been studied by using electron energy loss spectrscopy (ELS) and Photoemission spectroscopy (UPS). On all surfaces the hydrogen removes the “dangling bond” surface state and a new peak in the density of states at lower energies corresponding to the SiH bond is found. The LEED pattern of the equilibrium surfaces (111) 7 × 7 and (100) 2 × 1 is not altered by hydrogen adsorption, while on the cleaved (111) 2 × 1 surface the fractional order spots are extinguished. The Haneman surface-buckling model therefore provides an explanation for the surface reconstruction of the cleaved (111) 2 × 1 surfaces. For the equilibrium surfaces, (111) 7 × 7 and the (100) 2 × 1, the data are consistent with the Lander-Phillips model.     

Reflectometric study of surface states and oxygen adsorption on clean Si(100) and (110) surfaces

External differential reflection measurements were carried out on clean Si(100) and (110) surfaces in the photon energy range of 1.0 to 3.0 eV at 300 and 80 K. The results for Si(100) at 300 K showed two peaks in the joint density of states curve, which sharpened at 80 K. One peak at 3.0 ± 0.2 eV can be attributed to optical transitions from a filled surface states band near the top of the valence band to empty bulk conduction band levels. The other peak at 1.60 ± 0.05 eV may be attributed to transitions to an empty surface states band in the energy gap. This result favours the asymmetric dimer model for the Si(100) surface. For the (110) surface at 300 K only one peak was found at 3.0 ± 0.2 eV. At 80 K the peak height diminished by a factor of two. Oxygen adsorption in the submonolayer region on the clean Si(100) surface appeared to proceed in a similar way as on the Si(111) 7 × 7 surface. For the Si(110) surface the kinetics of the adsorption process at 80 K deviated clearly. The binding state of oxygen on this surface at 80 K appeared to be different from that on the same surface at 300 K.     

Study of chemisorption on copper low-index and stepped surfaces

Adsorption of CHCl₃, O₂, and hydrocarbons has been studied on Cu(111) and stepped surfaces using LEED, AES, and UPS at room temperature. We find that ordered Cl overlayers form upon Cu(111), Cu[3(111) × (100)], and Cu[5(111) × (100)] surfaces upon exposure to CHCl₃. Exposure to O₂ results in rearrangement of the Cu[5(111) × (100)] surface to hill-and-valley regions with large (111) areas, whereas Cu[2(111) × (100)] is stable for the same exposure. The photoemission spectra show new energy levels due to C1 above and below the Cu d band region and a small splitting of the halogen p orbitals. Effects consistent with interaction with the Cu d band are observed. Similar effects are observed with oxygen adsorption. The initial rate of Cl or O₂ chemisorption as measured by photoemission is proportional to the density of steps on these surfaces. Apparently, structural effects play an important role in chemisorption on metals (such as copper) with low density of states at the Fermi energy.     

Low energy electron diffraction and electron spectroscopy studies of the clean (110) and (100) titanium dioxide (rutile) crystal surfaces

Low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), electron energy loss (ELS) and ultraviolet photoemission spectroscopies (UPS) were used to study the structures, compositions and electron state distributions of clean single crystal faces of titanium dioxide (rutile). LEED showed that both the (110) and (100) surfaces are stable, the latter giving rise to three distinct surface structures, viz. (1 × 3), (1 × 5) and (1 × 7) that were obtained by annealing an argon ion-bombarded (100) surface at ~600,800 and 1200° C respectively. AES showed the decrease of the $\text{O(510 eV)}\text{Ti(380 eV)}$ peak ratio from ~1.7 to ~1.3 in going from the (1 × 3) to the (1 × 7) surface structure. Electron energy loss spectra obtained from the (110) and (100)?(1 × 3) surfaces are similar, with surface-sensitive transitions at 8.2, 5.2 and 2.4 eV. The energy loss spectrum from an argon or oxygen ion bombarded surface is dominated by the transition at 1.6 eV. UPS indicated that the initial state for this ELS transition is peaked at ?0.6 eV (referred to the Fermi level E_F in the photoemission spectrum, and that the 2.4 eV surface-sensitive ELS transition probably arises from the band of occupied states between the bulk valence band maximum to the Fermi level. High energy electron beams (1.6 keV 20 μA) used in AES were found to disorder clean and initially well-ordered TiO₂ surfaces. Argon ion bombardment of clean ordered TiO₂ (110) and (100)?(1 × 3) surfaces caused the work function and surface band bending to decrease by almost 1 eV and such decrease is explained as due to the loss of oxygen from the surface.