用HREELS研究氢在GaAs和InP的(111),(111)表面上的吸附

氢在GaAs和InP表面上的吸附可以用高分辨率电子能量损失谱(HREELS)来探测。Ga—H,As—H,In—H和P—H键的伸缩振动各自对应于不同的能量损失。但是As—H振动极容易和Ga—H振动追加声子损失相混淆,只有从损失峰的相对强度比较上来区别。实验得到吸附的氢与表面原子的成键情况取决于表面的原子结构及电子分布。对于GaAs(111)面,低暴露量时只形成Ga—H键,而高暴露量时还可以形成As—H键。而InP(111)表面由于是经过磷气氛退火处理的,在低暴露量下In—H与P—H键均可形成。InP(Ⅲ)面上只看到P—H损失峰,说明这个表面是完全以P原子结尾的。在(Ⅲ)面上出现小面的情形,则表面Ⅲ族和Ⅴ族原子均可同氢成键。 关键词：     

用HREELS研究氢在GaAs和InP的（111），（III）表面上的吸附

氢在GaAs, 和InP 表面上的吸附可以用高分辨率电子能量损失谱(HREELS) 来探测.Ga-H侧, As-H , In-H 和P-H 键的伸缩振动各自对应于不同的能量损失. 但是A-H 振动极容易和Ga-H 振动追加声子损失相混淆, 只有从损失峰的相对强度比较上来区别。实验得到吸附的氢与表面原子的成键情况取决于表面的原子结构及电子分布. 对于GaAs (1 1 1)面, 低暴露量时只形成Ga-H 键, 而高暴露量时还可以形成As-H 键.而InP(1 1 1 ) 表面由于是经过磷气氛退火处理的, 在低暴露量下In 一H 与P一H 键均可形成. InP (III) 面上只看到P-H 损失峰, 说明这个表面是完全以P 原子结尾的. 在(1 1 1 ) 面上出现小面的情形, 则表面III族和V族原子均可同氢成键. 关键词：     

HREELS of H/GaN(0001): evidence for Ga termination

Two issues relevant to the growth and processing of GaN are the termination of the GaN(0001) surface and its reaction with hydrogen. We have used high-resolution electron energy loss spectroscopy (HREELS), low-energy electron diffraction (LEED), and Auger electron spectroscopy (AES) to study the adsorption of hydrogen on MOCVD-grown GaN(0001). LEED of the sputtered and annealed surface shows evidence of facetting. No adsorbate vibrations are observed on the clean surface by HREELS, only Fuchs–Kliewer phonons at intervals of 700 cm⁻¹. Following exposure of the clean GaN surface to hydrogen atoms, HREEL spectra show adsorbate loss peaks at 2580, 3280, and 3980 cm⁻¹. The Ga–H stretching vibration at 1880 cm⁻¹ becomes evident when the HREEL spectrum is deconvoluted to remove the phonon multiple-loss peaks. We assign the 2580, 3280, and 3980 cm⁻¹ peaks to combination modes of the Ga–H stretch and phonon(s). Upon dosing with deuterium, the Ga–D bending mode is observed at 400 cm⁻¹. No vibrational peaks due to N–H (N–D) species are observed after H (D) exposure. We conclude that sputtered and annealed GaN(0001) is Ga-terminated.     

B2-和B19'-NiTi表面原子弛豫、表面能、电子结构及性能的理论研究

采用基于密度泛函理论的第一性原理系统研究了B2-和B19'-NiTi合金所有低指数表面的表面能、表面结构稳定性、表面电子结构等性质.计算结果表明两种NiTi合金所有低指数表面的原子弛豫主要集中在表面2-3个原子层,且以Ti原子为终止原子表面构型的原子振荡最为剧烈,Ni和Ti原子共同终止表面构型的原子振荡最小;价电荷密度沿着表面构型向真空层方向快速衰减;表面能计算结果显示其与配位数成反相关.B2-和B19'-NiTi合金的非密排且非化学计量比表面的表面能取决于Ti的化学势,表面能数值较高;而密排面的表面构型符合化学计量比,其表面能较低,表现出卓越的化学稳定性;其中以B2-NiTi(101)密排面的表面稳定性最优.     

Molecular and atomic oxygen adsorption on the kinked Pt(321) surface

Oxygen adsorption and desorption were characterized on the kinked Pt(321) surface using high resolution electron energy loss spectroscopy, thermal desorption spectroscopy and Auger electron spectroscopy. Some dissociation of molecular oxygen occurs even at 100 K on the (321) surface indicating that the activation barrier for dissociation is smaller on the Pt(321) surface than on the Pt(111) surface. Molecular oxygen can be adsorbed at 100 K but only in the presence of some adsorbed atomic oxygen. The dominance of the v(OO) molecular oxygen stretching mode in the 810 to 880 cm^?1 range indicates that the molecular oxygen adsorbs as a peroxo-like species with the OO axis parallel or nearly parallel to the surface, as observed previously on the Pt(111) surface [Gland et al., Surface Sci. 95 (1980) 587]. The existence of at least two types of peroxo-like molecular oxygen is suggested by both the unusual breadth of the v(OO) stretching mode and breadth of the molecular oxygen desorption peak. Atomic oxygen is adsorbed more strongly on the rough step sites than on the smooth (111) terraces, as indicated by the increased thermal stability of atomic oxygen adsorbed along the rough step sites. The two forms of adsorbed atomic oxygen can be easily distinguished by vibrational spectroscopy since oxygen adsorbed along the rough step sites causes a v(PtO) stretching mode at 560 cm^?1, while the v(PtO) stretching mode for atomic oxygen adsorbed on the (111) terraces appears at 490 cm^?1, a value typical of the (111) surface. Two desorption peaks are observed during atomic oxygen recombination and desorption from the Pt(321) surface. These desorption peaks do not correlate with the presence of the two types of adsorbed atomic oxygen. Rather, the first order low temperature peak is a result of the fact that about three times more atomic oxygen can be adsorbed on the Pt(321) surface than on the Pt(111) surface (where only a second order peak is observed). The heat of desorption for atomic oxygen decreases from about 290kJ/mol (70 kcal/mol) to about 196 kJ/mol (47 kcal/mol) with increasing coverage. Preliminary results concerning adsorption of molecular oxygen from the gas phase in an excited state are also briefly discussed.     

Evidence for preferential reactivity of the atomic oxygen with hydrogenated diamond (111) facets

Chemical bonding configuration of the adsorbed oxygen on diamond polycrystalline hydrogenated surface was investigated by high resolution electron energy loss spectroscopy (HR-EELS). Hot filament chemical vapor deposited diamond films with sub-micron grain size have been exposed in-situ to thermally activated atomic oxygen (AO) and annealed in ultra-high vacuum in the range of 600–900 °C. HR-EELS features comparison of as-deposited and AO exposed diamond surface as a function of thermal annealing suggests that AO preferentially adsorbs on hydrogenated (111) facets keeping hydrogenated (100) ones intact.     

无序碳单层的电子结构及氢原子吸附的第一性原理

本研究运用第一性原理计算方法,系统地研究了无序碳单层材料不同位点的电子结构及其析氢性能.计算结果显示无序结构中的C-C键相比于石墨烯中的C-C键在26.7%的范围内有不同程度的拉伸或压缩,使得C原子电荷在-0.17～+0.16个电子范围内变化,导致部分C原子电子局域化.电子的局域化增强了C原子的化学活性,从而表现出了较强的吸附性能.我们发现H原子与C原子的键合及析氢性能与C原子间的键角相关.对于三配位的碳原子,其中三个价电子通过sp~2杂化轨道与最邻近的碳原子结合形成较强的共价键,而余下的一个p_z轨道电子可以与H原子在垂直于原子层的方向形成较弱的化学键.无序结构可以打破三个sp~2杂化轨道的对称性,进而影响p_z轨道与氢的成键.本研究在一定程度上揭示了单层无序碳材料结构-性能的构效关系,为实验上设计特定性能的无序碳功能材料提供理论指导.     

Investigation of cadmium-hydrogen complexes in silicon

Formation, stability and electric properties of (In-H) and (Cd-H) complexes in Si are studied by the perturbed angular correlation spectroscopy (PAC). The trapping of hydrogen at the acceptors results in three different defect specific electric field gradients (EFGs), which are studied as function of temperature, doping concentration and annealing time. Two of the three observed hydrogen-related EFGs are identified as different charge states of one (Cd-H) acceptor. Within the framework of a model, which takes into account the dynamics of charge fluctuations and Shockley, Read and Hall statistics, the energy level of this (Cd-H) acceptor at E = E_V + 60 meV is deduced. Furthermore, the dynamical behavior of the hydrogen atom within the (Cd-H) complexes is studied. From the relaxation of the PAC signal the hopping rate of the hydrogen atom is extracted. This rate is thermally activated with an activation energy of E = 0.20 eV.     

A vibrational study of ammonia chemisorbed on Ni(110) and Ni(111): whither goest the metal-nitrogen stretching mode on FCC (111) surfaces?

The adsorption of ammonia on the Ni(110) and Ni(111) surfaces has been studied with high resolution (≤ 65 cm_?1) electron energy loss spectroscopy (EELS) combined with thermal desorption spectroscopy. The EELS spectra of the initial chemisorbed layer or α state on each surface are very different. Ammonia chemisorbed on the Ni(110) surface exhibits a strong Ni-N stretching mode at 570 cm^?1 which is absent on the Ni(111) surface. The Ammonia adsorption site appears to be different on the Ni(110) and Ni(111) surfaces. We suggest that the absence of the M-N stretching mode on the Ni(111) surface is a general characteristic of the ammonia adsorption site on the (111) surfaces of fcc Group VIII metals.     

Electronic modifications and surface reactivity of an ion bombarded graphite surface

The first steps of structural and electronic modifications of a graphite surface bombarded with argon, hydrogen and deuterium ions were investigated using high resolution electron energy loss spectroscopy (HREELS). The energy and the damping of the low energy plasmon mode of graphite (E//C mode) were studied with respect to the bombardment settings. We show that argon bombardment affects the energy of the plasmon mode, while no similar change is observed after hydrogen (deuterium) bombardments. This can be related to the variation of inter-planar distance between two graphene layers. Moreover, the damping of the plasmon mode can be correlated with the interstitial defect concentration. Concerning the reactivity of the bombarded surfaces, we demonstrate that deuterium bombardment produce a non-deuterated surface. This last is very reactive to a further atomic deuterium exposure, as it is shown by the formation of C-D bondings. The deuterated sites can be removed after thermal annealings between 473 and 783 K. The occurrence of a chemical erosion mechanism accompanying this deuteration is discussed.     

Single-molecule reaction and characterization by vibrational excitation

Controlled chemical reaction of single trans-2-butene molecules on the Pd(110) surface was realized by dosing tunneling electrons from the tip of a scanning tunneling microscope at 4.7 K. The reaction product was identified as a 1,3-butadiene molecule by inelastic electron tunneling spectroscopy. Threshold voltage for the reaction is approximately 365 mV, which coincides with the vibrational excitation of the C-H stretching mode. The reaction was ascertained to be caused by C-H bond dissociation by multiple vibrational excitations of the C-H stretching mode via inelastic electron tunneling process.     

Hydrogen induced structure changes of GaAs(1 0 0) surfaces

The interaction of hydrogen with GaAs(1 0 0) surfaces has been studied at room temperature by means of high-resolution electron energy-loss spectroscopy (HREELS), low-energy electron-diffraction (LEED), and Auger electron spectroscopy (AES). Sample cleaning by Ne⁺ ion bombardment (500 eV) and annealing resulted (with increasing temperatures) in “1 × 1”, 1 × 6, 4 × 1, 4 × 6 and c(8 × 2) LEED structures. As a function of hydrogen exposure, the intensity ratio of the stretching vibrations (As-H/Ga-H) is shown to be characteristic for the specific reconstructed surface. In particular the arsenic hydride concentration gradually decreased in all cases. In addition, an initial weakening of the fractional order LEED spots occurred with increasing hydrogen exposures. Finally, a strong 1 × 2 structure was observed independent of the reconstruction we started with. Simultaneously, a shift of the energetic position of the Ga-H stretching vibration occurred.     

The bonding of water molecules to platinum surfaces

Using high resolution electron energy loss spectroscopy in ultra-high vacuum we have studied the vibrational spectrum of submonolayer and multilayer quantities of water adsorbed on platinum (100) surfaces. For adsorbed multilayers the spectrum resembles the spectrum of ice I. For submonolayer quantities of H₂O we find three different OH stretching vibrations, 2850, 3380, and 3670 cm^?1. The highest frequency is attributed to free OH groups. The vibration around 3380 cm^?1 indicates H bonding between oxygen atoms. It is therefore concluded that the water molecules cluster even at low coverage. The lowest OH stretching frequency is attributed to H bonding to platinum. We find also evidence for additional oxygen lone pair orbital bonding to the surface which disappears however when the first monolayer is completed. The relation to currently considered models in electrochemistry of aqueous solutions is discussed.     

基于芯-电子结合能偏移的碱金属中的表面、尺寸和热效应

密度泛函理论计算结果和X射线光电子能谱测量数据之间的一致性证实了碱金属低配位引起局部键弛豫和芯能级偏移,进而决定了材料的表面、尺寸和热性能. 局域光电子能谱分析方法和键弛豫理论可用于计算有关金属表面键合和电子性质的参数,从而进一步研究碱金属中芯-电子结合能偏移. 同时,结合第一性原理,还可以获得碱金属表面低配位原子的键参数和原子内聚能. 此外,尺寸和温度对表面电子结合能的影响可以从原子键弛豫引起的哈密顿量中导出.     

Infrared spectra of hydrogen impurities in BaTiO3 crystals

The IR spectra in the 2.8 μm region of the OH^? impurities in thick single domain crystals have been measured for different polarization geometries and various temperatures. Simple calculations of the Coulomb interactions between hydrogen and lattice ions show that these interactions are much more important than the hydrogen bonding ones for determining the positions of the hydrogen ions. The appearance of only one strong non-dichroic OH^? stretching line is due to an almost equal population of the proton axial sites. The side bands are interpreted as combinations of the stretching mode with a low-frequency translational mode. The large broadening of the main line just above T_c supports the model which attributes a considerable order—disorder character to the ferroelectric phase transition.     

Surface electronic and chemical structure of (1120)CdSe: Comparison with CdS

Surface photovoltage spectroscopy, Auger electron spectroscopy, LEED, X-ray and ultraviolet photoemission measurements are reported for (112̄0) CdSe under a variety of ultrahigh vacuum conditions. As with CdS, all surface electronic features can be related to chemical contamination, Ar⁺ bombardment-induced lattice defects, or bulk trap states. Oxygen adsorption on CdSe and CdS produce qualitatively different electronic features which are attributed to different bonding at surface vacancy sites. Changes in surface atomic order show no direct effect on measured electronic features. Furthermore, CdSe exhibits no intrinsic surface state features which can account for its Schottky barrier formation with metals.     

Vibrational characterization of carbon monoxide adsorption on sulfur modified Ni(100) surfaces

Carbon monoxide adsorption has been studied on a series of presulfided Ni(100) surfaces using vibrational spectroscopy. The sulfided Ni(100) surfaces were characterized using Auger electron spectroscopy and low energy electron diffraction, binding states were isolated by heating CO-dosed surfaces to prescribed temperatures, corresponding to the desorption temperatures of the CO. Adsorption of CO on Ni(100) with a p(2 × 2) array of sulfur lead to CO stretching frequencies of 1740 and 1930 cm^?1 corresponding to desorption temperatures of 370 and 290 K, respectively. Adsorption of CO into the c(2 × 2)S structure resulted in a CO stretching frequency of 2115 cm^?1 and a desorption peak near 140 K. The binding sites on the p(2 × 2)S structure were interpreted as metal four-fold hollows and bridging sites. The high frequency state was interpreted as weak bonding into the four-fold hollow with back donation into the π¹ orbital on CO restricted by stearic hindrance due to adsorbed sulfur. Both the thermal desorption and vibrational results indicated that local CO-sulfur interactions are dominant on the presulfided Ni(100) surface in the coverage range studied.     

The interface structure of nano-SiO2/PA66 composites and its influence on material's mechanical and thermal properties

The PA66-based nanocomposites containing surface-modified nano-SiO₂ were prepared by melt compounding. The interface structure formed in composite system was investigated by thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The influence of interface structure on material's mechanical and thermal properties was also studied. The results indicated that the PA66 chains were attached to the surface of modified-silica nanoparticles by chemical bonding and physical absorption mode, accompanying the formation of the composites network structure. With the addition of modified silica, the strength and stiffness of composites were all reinforced: the observed increase depended on the formation of the interface structure based on hydrogen bonding and covalent bonding. Furthermore, the differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) showed that the presence of modified silica could affect the crystallization behavior of the PA66 matrix and lead to glass transition temperature of composites a shift to higher temperature.     

Thin PTCDA films on Si(0 0 1): 1. Growth mode

We have studied the interface and thin film formation of the organic molecular semiconductor 3,4,9,10 perylene tetracarboxylic dianhydride (PTCDA) on clean and on hydrogen passivated Si(0 0 1) surfaces. The studies were made by means of high resolution X-ray photoelectron spectroscopy (HRXPS), near edge X-ray absorption fine structure (NEXAFS), low energy electron diffraction (LEED), and atomic force microscopy (AFM). On the passivated surface the LEED pattern is somewhat diffuse but reveals that the molecules grow in several ordered domains with equivalent orientations to the substrate. NEXAFS shows that the molecules are lying flat on the substrate. The Si 2p XPS line shape is not affected when the film is deposited so it can be concluded that the interaction at the interface between PTCDA and the substrate is weak. The evolution of the film formation appears to be homogeneous for the first monolayer with a nearly complete coverage of flat lying molecules based on the XPS attenuation. For layer thickness of 0.5-2 monolayers (ML) the molecules start to form islands, attracting the molecules in between, leaving the substrate partly uncovered. For thicker films there is a Stranski-Krastanov growth mode with thick islands and a monolayer thick film in between. For the clean surface the ordering of the film is much lower and angle resolved photoelectron spectroscopy (ARPES) of the molecular orbitals have only a small dependence of the emission angle. NEXAFS shows that the molecules do not lie flat on the surface and also reveal a chemical interaction at the interface.     

Interactions of oxygen and CO with AgAu bimetallic nanoparticles on sputtered highly ordered pyrolytic graphite (HOPG) surfaces

Oxidation of AgAu bimetallic nanoparticles on sputtered HOPG by atomic oxygen and reduction of the oxidized surface by CO at room temperature were studied using X-ray photoelectron spectroscopy (XPS). For 2 nm-sized nanoparticles, prepared by postdeposition of Ag on Au-core, atomic oxygen exposure mostly leads to the formation of chemically inert oxygen species. This result is analogous to that of pure Ag and Au nanoparticles of similar sizes on the same substrate. In contrast, “Au on Ag-core” nanoparticles form chemically active oxygen species, suggesting that depending on detailed structures of bimetallic nanoparticles, diverse chemical properties can be obtained.