Electron structure and electron dynamics at InSb(111)2×2 semiconductor surface

The conduction band electronic structure and the electron dynamics of the clean InSb(111)2×2 surface have been studied by laser based pump-and-probe photoemission. The results are compared to earlier studies of the InSb(110) surface. It is found that both the energy location and the time dependence of the photoexcited structures are very similar for the two surfaces. This indicates that the dominant part of the photoemission signal in the conduction band region is due to excitations of electrons in the bulk region and that the surface electronic states play a minor role. The fast decay of the excited state, τ∼12 ps, indicates that diffusion of hot electrons into the bulk is an important mechanism. Received: 9 May 2001 / Accepted: 9 July 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +46-0824/913-1, E-mail: gm@matphys.kth.se     

Local probing of the surface chemical bond using X-ray emission spectroscopy

2 and CO on Ni(100), benzene on Ni(100) and Cu(110), and glycine adsorbed on Cu(110). New types of molecular states are observed which are directly related to the surface chemical bond. The long-accepted Blyholder model which is based on a frontier orbital concept cannot explain our results for N₂ and CO chemisorption. We find it necessary to offer a new picture where changes in the whole molecular orbital framework have to be considered. We show that both π and σ type interactions are important in describing the bonding in benzene to metal surfaces. The future prospect is illustrated by the adsorption of the simplest amino acid, glycine, on Cu(110). The adsorbate has four different atomic centers where X-ray emission spectra are obtained, providing a unique view of the local electronic structure. Accepted: 6 March 1997     

Supramolecular architectures and nanostructures at metal surfaces

The controlled formation of non-covalent bonds (H-bonding, metal–ligand interactions) is the key ingredient for the fabrication of supramolecular architectures and nanostructures. Upon deposition of molecular building blocks at well-defined surfaces, this issue can be directly addressed. Scanning tunneling microscopy observations are presented, which provide insight into the interaction of functional groups on metal substrates at the molecular level. In particular, carboxylic acids were employed: (4-[(pyrid-4-yl-ethynyl)]-benzoic acid (PEBA), 4-[trans-2-(pyrid-4-yl-vinyl)]-benzoic acid (PVBA) and trimesic acid (1,3,5-benzenetricarboxylic acid, TMA), which could be stabilized in a flat geometry at the surface. By choosing the appropriate substrate material and symmetry, the sensitive balance of intermolecular and molecule–substrate interactions can be tuned to obtain well-defined supramolecular architectures and nanostructures. The head-to-tail hydrogen bonding of the related rod-like species PEBA and PVBA stabilizes molecular rows on Ag(111). The subtle difference in the molecular geometries is reflected in the lateral ordering: While 2-D islanding is encountered with PEBA, 1-D nanogratings of supramolecular chiral H-bonded twin chains evolve for PVBA. The threefold symmetry of TMA in conjunction with the self-complementarity of its exodentate groups accounts for the formation of H-bonded honeycomb networks on Cu(100) at low temperatures. Metal–ligand interactions were probed with PVBA and TMA at Cu surfaces at ambient temperature. Deprotonation of the carboxyl moiety takes place, which readily interacts with Cu adatoms evaporated from step edges. This leads to a head-to-head pairing of PVBA on Cu(111) and cloverleaf-shaped Cu–TMA coordination compounds on Cu(001). Received: 4 June 2002 / Accepted: 2 October 2002 / Published online: 5 February 2003 RID="*" ID="*"Corresponding author. Fax: +41-21/693-3604, E-mail: johannes.barth@epfl.ch     

On the initiation of chemical reactions by electronic excitations in molecular solids

In this article we briefly review the results of theoretical simulations for the initiation of chemistry processes in high-explosive crystals from a solid-state-physics viewpoint. We analyze the possibility of initiation of chemical reactions from excited electronic states. In other words, we look for conditions that facilitate electronic excitations in the crystal. Specifically, we describe modifications to the electronic structure of RDX (cyclotrimethylene trinitramine) induced by lattice defects and by a shock wave traversing the solid. Our approach is based on ab initio Hartree–Fock band-structure calculations with electronic correlation corrections. An excitonic mechanism and a hole model, suggested earlier, are discussed in connection with the most recent experimental and theoretical advances in ultrafast optical techniques. We also consider here possible new avenues in the development of detonation theory. Received: 3 December 2001 / Accepted: 9 July 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +1-301/744-4451, E-mail: KuklaMM@ih.navy.mil     

H_2在Ni,Pd与Cu表面的解离吸附

用EAM方法(embeded-atommethod)研究H_2在Ni,Pd与Cu的(100),(110)与(111)面上的解离吸附.首先通过拟合单个H原子在Ni,Pd与Cu不同表面上的吸附能和吸附键长,得到H与这些金属表面相互作用的EAM势,然后计算H_2在这些表面上以不同方式进行解离吸附时的活化势垒E_a,吸附热q_(ad)与吸附键长R.并给出H_2在(110)面上解离吸附的势能曲线.计算结果表明H_2的解离吸附与衬底种类、衬底表面取向及解离方式有关.H_2在Ni表面上解离时活化势垒很低,而在Cu表面解 关键词：     

Nanoscale domain switching mechanism in Pb(Zr,Ti)O<Subscript>3</Subscript> thin film

Pb(Zr,Ti)O₃ (PZT) ferroelectric thin film was prepared by the sol-gel technique and crystallized with a (111) preferred orientation. The domain structure and polarization reversal behavior were investigated by using scanning force microscopy (SFM) piezoresponse mode at the nanometer scale. A step structure of approximately 30 nm in width was directly observed, which was formed during the polarization reversal process. The presence of the step structure reveals that the forward domain-growth mechanism is the dominant domain-switching process in our PZT thin films. Received: 6 August 2002 / Accepted: 9 August 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +86-21/5241-3122, E-mail: huarongzeng@163.net     

Buried interfaces studied by photoelectron diffraction

Angle- and energy-scanned photoelectron diffraction data can be used to investigate structures below surfaces. The modulations in photoelectron intensity result from diffraction of the emitted electron wave at neighbor atoms. In the past, scanned-energy photoelectron diffraction had been mainly used to determine the adsorption site of molecules at surfaces. Recent data show, however, that the technique can also be employed to obtain information about the upper substrate layer(s). At low kinetic energies, backward scattering is strong and in scanned-angle photoelectron diffraction the recorded patterns result from backward- and multiple-scattering effects. For a structural analysis, the intensity modulations have to be compared with the results for simulations performed for model clusters. As an example, recent angle-scanned photoelectron diffraction patterns recorded for the technologically important silicon oxide/silicon interface were compared with simulations. At the Si(001) surface orientation, the interface is extended over a few layers, whereas at the Si(111) surface orientation the transition is rather abrupt and occurs within one or two layers. Received: 9 September 2002 / Accepted: 2 October 2002 / Published online: 5 February 2003 RID="*" ID="*"Corresponding author. Fax: +49-231/755-3657, E-mail: carsten.westphal@physik.uni-dortmund.de     

Structure and electronic factors in benzene coordination to Cr(CO)3 and to cluster models of Ni,Pt, and Ag (111) surfaces

Bonding of benzene to a chromium tricarbonyl fragment and to cluster models of silver, nickel, and platinum (111) surfaces is found by means of molecular orbital calculations to be dominated by a benzene donation bond involving its π (e_1g) orbitals and metal d orbitals. Three-fold hollow sites on the clusters are calculated to be most stable for benzene coordination, a conclusion reached in a number of experimental studies of benzene on metal surfaces. On the Ag, Ni, and pt clusters, the benzene CH bonds are found to bend away from the surface by ?2°, 8° and 19°, respectively, a result of carbon atom hybridization to maximize overlap with metal orbitals. For benzene chromium tricarbonyl, the CH bonds are calculated to bend 3° toward the metal, compared to a 1.7° bend reported in a diffraction study. The direction and magnitude of the CH bending are shown to depend on the metal d orbital occupancy (an electronic factor) and the proximity of metal atoms in the adsorption site (a structure factor). Small Kekulé distortions are calculated for the chromium complex and for the C_3v sites on Pt(111). Finally, recent experimental studies showing a decrease in benzene adsorption energy when potassium is coadsorbed on Pt(111) may be understood to result from decreased π donation which accompanies the shift up of the metal d band with cathodic charging.     

Chemisorption of carbon monoxide on copper-nickel alloy surfaces

The adsorption of CO on Cu-Ni alloy surfaces has been studied at 300 and 120 K using LEED, AES, TDS, and work function measurement. The alloys have been prepared as thin (111) epitaxial films evaporated on mica, and as poly crystalline foils. At 300 K the alloy surfaces show an adsorption behavior similar to that of pure Ni: the work function increases to a saturation value which is higher for Ni-rich surfaces than for Cu-rich. The isosteric heat of adsorption (106 kJ/mole) is nearly as high as with pure Ni. At 120 K the alloys exhibit a more Cu-like adsorption behavior: the work function passes through a minimum which becomes deeper at higher Cu surface concentration. The isosteric heat of adsorption at low temperatures (50 kJ/mole) is nearly as low as for pure Cu. From TDS it can be shown, that the binding energy of the highest (Ni-like) adsorption states increases with increasing Ni surface concentration. At the (111) alloy surfaces no LEED superstructures due to CO adsorption could be observed.     

Exciton dispersion in silicon nanostructures formed by intense,ultra-fast electronic excitation

The intense, ultra-fast electronic excitation of clean silicon (100)–(2×1) surfaces leads to the formation of silicon nanostructures embedded in silicon, which photoluminesce in the yellow-green (∼2-eV band gap). The silicon surfaces were irradiated with slow, highly charged ions (e.g. Xe⁴⁴⁺ and Au⁵³⁺) to produce the ultra-fast electronic excitation. The observation of excitonic features in the luminescence from these nanostructures has recently been reported. In this paper we report the dispersion of the excitonic features with laser excitation energy. A phonon-scattering process is proposed to explain the observed dispersion. Received: 2 October 2001 / Accepted: 18 July 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +1-925/423-7040, E-mail: Hamza1@llnl.gov RID="**" ID="**"Present address: University of California, Lawrence Berkeley National Laboratory, Berkeley, CA 94 720, USA     

Pulsed-laser-deposited epitaxial aluminum nitride films on (111) Si for surface acoustic-wave applications

Epitaxial (001) aluminum nitride (AlN) thin films on (111) Si substrates are prepared using pulsed-laser deposition. The epitaxial structure of the as-prepared thin films is characterized by checking the X-ray-diffraction θ-2 θ scan and pole-figure, using scanning electron microscopy, infrared radiation (IR) spectroscopy and Raman spectroscopy. The surface acoustic-wave resonance at 345 MHz for a 1.5 μm thick AlN film on a (111) Si substrate is observed using an inter-digital electrode. Received: 18 September 2001 / Accepted: 29 January 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +86-25/359-5535, E-mail: liujm@nju.edu.cn     

A comparative first-principles study of the adsorption of a carbon atom on copper and nickel surfaces

The adsorption energies of a carbon atom at the most stable adsorption sites on the Cu and Ni(100), (110) and (111) surfaces have been studied by first-principles calculations. The preference order of the adsorption sites for both Cu and Ni surfaces is the same. The (100) hollow site is the most stable one. The diffusion barriers for a C atom on the three surfaces have also been obtained, with the highest mobility on the (111) surface of both metals. Our investigation shows that the adsorption energies of the C atom on Ni are significantly higher in magnitude than those on Cu for all the three surfaces. This phenomenon is mainly due to the interaction and hybridization between C p-orbits and partially filed d-shell of Ni, which forms a stronger binding.     

The influence of hydrogen on the electronic and magnetic structures of TM(0 0 1) (TM=Fe, Co, Ni, and Cu) surfaces and interfaces: Ab-initio calculations

We present ab-initio investigation of the electronic and magnetic structure of TM(0 0 1) surfaces and TM/Cu(0 0 1) systems (TM=Fe, Co, Ni, Cu) with and without hydrogen adsorbed layer. The adsorption energy of hydrogen atom is found to be energetically more stable above the surface layer of Ni(0 0 1) surface than other TM(0 0 1) surfaces. The adsorption energies of hydrogen on TM/Cu(0 0 1) systems are larger than those on TM(0 0 1) surfaces. The relaxed geometries show that hydrogen has a strong influence on the interlayer distance. Furthermore, a marked reduction of Fe, Co, and Ni surface magnetic moments to 2.54, 1.41 and 0.25 μ_B, respectively, is obtained due to the presence of hydrogen.     

Atomic mixing of Ni2O3/SiO2, NiO/SiO2, and Ni/SiO2 interfaces induced by swift heavy ion irradiation

We have investigated the interface mixing of Ni₂O₃/SiO₂, NiO/SiO₂, and Ni/SiO₂ induced by the irradiation with Ar, Kr and Xe ions of energies ranging from 90 MeV to 260 MeV. Since these energies are in the electronic stopping regime, atomic transport processes will not be directly initiated by elastic ion–target collisions, but need to be excited by secondary processes like electron–phonon coupling or Coulomb explosion. Nevertheless, we have observed a strong mixing effect in the ceramic systems if the electronic energy loss exceeds a certain threshold value. Estimation of an effective diffusion constant indicates that diffusion takes place in the molten ion track. In contrast to the ceramics, the metallic Ni layer is still insensitive even for the highest electronic stopping power used (S_e=28 keV/nm) and does not exhibit mixing with its SiO₂ substrate. In addition, NiO/SiO₂ and Ni/SiO₂ were irradiated in the nuclear stopping regime with 600 keV Kr and 900 keV Xe–ions. Here the intermixing effect is in good agreement with the assumption of ballistic atomic transport. Received: 5 February 2002 / Accepted: 11 February 2002 / Published online: 3 May 2002 RID="*" ID="*"Corresponding author. Fax: +49-711/685-3866, E-mail: bolse@ifs.physik.uni-stuttgart.de     

Adhesion and bonding of Pt/Ni and Pt/Co overlayers: Density functional calculations

The electronic and energetic properties of bimetallic surfaces Pt/Ni(111) and Pt/Co(111) are examined using the FP-LAPW (Full-PotentialLinearized Augmented Plane Wave) method by means of spin-polarized and non-polarized calculations. We present both the results of the shifts in the d-band centers when one metal (Pt) is pseudomorfically deposited on another with smaller lattice constant (Ni, Co) and those corresponding to the surface and adhesion energies. The surface is modeled by a seven layer slab separated in z direction by a vacuum region of six substrate layers. The results obtained for pure Ni, Co and Pt surfaces are presented in order to compare with experimental and theoretical data reported in the literature     

The angular distribution of electrons photoemitted from benzene molecules adsorbed on nickel and palladium single crystal surfaces

The polar emission angle dependence of the He I (21.2 eV) excited photoemission bands induced by adsorption of benzene on Ni(111), Pd(111) and Pd(100) single crystal surfaces is described and discussed. The differences between adsorption on nickel and palladium are related to the strength of the adsorbate/substrate interaction.     

NH3在Ni/Pt(111)和Ni/WC(001)表面上分解的第一性原理研究

采用密度泛函理论和slab模型,研究NH₃在Ni单原子层覆盖的Pt（111）和WC（001）表面上的物理与化学行为,计算了Ni单原子覆盖表面的电子结构以及NH₃的吸附与分解.表面覆盖的单原子层中,Ni原子的性质与Ni（111）面上的Ni原子明显不同.与Ni（111）相比,Ni/Pt（111）和Ni/WC（001）表面上Ni原子dz²轨道上的电子更多地转移到了其它位置,该轨道上电荷密度降低有利于NH₃吸附.在Ni/Pt（111）和Ni/WC（001）面上NH₃吸附能均大于Ni（111）,NH₃分子第一个N-H键断裂的活化能则明显比Ni（111）面上低,有利于NH₃的分解,吸附能增大使NH₃在Ni/Pt（111）和Ni/WC（001）面上更倾向于分解,而不是脱附.N₂分子的生成是NH₃分解的速控步骤,该反应能垒较高,说明N₂分子只有在较高温度下才能生成.WC与Pt性质相似,但Ni/Pt（111）和Ni/WC（001）的电子结构还是有差异的,与Ni（111）表面相比,NH₃在Ni/Pt（111）表面上分解速控步骤的能垒降低,而在Ni/WC（001）上却升高.要获得活性好且便宜的催化剂,需要对Ni/WC（001）表面做进一步改进,降低N₂分子生成步骤的活化能.     

Crystal structure, morphology, depth profile of elements and mid-infrared optical constants of ‘mild’ lead telluride film

The characterizations of a so-called ‘mild’ PbTe layer thermal-evaporated from an excess of Te (<1 mol.%) evaporable materials are reported. The results reveal that the film obtained is polycrystalline and has a single-phase NaCl-type PbTe crystal structure. It is also demonstrated that the film has a homogeneous surface morphology and a high degree of homogeneous distribution of Te-rich components along the layer. The study of mid-infrared optical constants of a surface-polished film indicates that the influence of surface scattering on optical properties is very small. Received: 3 July 2002 / Accepted: 7 August 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +86-21/6516-9946, E-mail: lbincome@yahoo.com     

Layer-resolved microscopy of magnetic domains in multi-layered systems

Photoelectron emission microscopy in connection with magnetic circular dichroism in soft X-ray absorption can be used for the microscopic imaging of magnetic domains in layered thin film structures consisting of several magnetic layers. Due to the element-selectivity of the method, the different magnetic layers in such a structure can be imaged separately, provided that they contain different elements. This has been applied for the investigation of Co/Cu/Ni trilayers, epitaxially grown on Cu (001). The magnetic coupling between the Co and Ni layers can be directly visualized from comparing layer-resolved magnetic domain images of both layers. As a consequence of the competition between the anisotropy energies of the two magnetic layers and the magnetic coupling energy, spin-reorientation transitions between collinear and non-collinear magnetic configurations are observed. Apart from this globally observable magnetic interlayer coupling a micromagnetic coupling mechanism is also evident from the layer-resolved domain images. It is caused by magnetostatic interaction of local stray fields from domain walls. Received: 22 August 2002 / Accepted: 2 October 2002 / Published online: 5 February 2003 RID="*" ID="*"Corresponding author. Fax: +49-345/5511-223, E-mail: kuch@mpi-halle.de     

Microstructural properties of bulk nanocrystalline Ag–Ni alloy prepared by hot pressing of mechanically pre-alloyed powders

A bulk nanocrystallined Ag50Ni alloy has been prepared by hot-pressing the mechanically pre-alloyed powders at 620 °C under a normal pressure of 58 MPa in vacuum. The microstructural characteristics of the alloy were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results of the precise determination of the lattice parameters of the phases in the powders and in the alloy by XRD show that, after mechanical alloying for 200 h, the solid solubility of Ag in Ni reaches 4.85±0.21 at %, while that of Ni in Ag reaches 0.84±0.30 at %. After hot pressing, the Ag- and Ni-rich phases in the alloy still show a certain degree of supersaturation, with a solid solubility of 0.45±0.11 at % of Ag in Ni. After further annealing of the alloy at 700 °C for 24 h, the solubility decreases to a value of 0.21±0.11 at % for Ag in Ni and to less than 0.1 at % for Ni in Ag. The grain size of the mechanically alloyed powders was of ca 6 nm. After hot pressing, the grain size of the alloy increased to 40–60 nm and then grew further to 100–110 nm after annealing. The influence of the variation of the grain size and the internal stress on the line breadth of the X-ray diffraction peaks has been evaluated in detail. Finally, the role of the nanocrystalline structure in the fast densification process of the powders is also discussed. Received: 12 September 2001 / Accepted: 18 Febraury 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +86-24/2389-3624, E-mail: wwt@icpm.syb.ac.cn