A Study on the Morphology and Mechanical Properties of PVC/nano‐SiO2 Composites

Three methods were used to modify nano‐SiO₂ particles with various interfaces and interfacial interactions between the particles and Poly(vinyl chloride) (PVC) matrix. The experimental results show that direct surface treatment of nano‐SiO₂ particles with a silane coupling agent (KH‐550) is not effective for improving the mechanical properties of PVC/SiO₂ composites. Both ultrasonic oscillations and high energy vibromilling improve the interfacial interactions between SiO₂ particles and PVC matrix. With these methods, the aggregation of SiO₂ particles was inhibited and a good dispersion of SiO₂ particles in PVC matrix was obtained, which improved the mechanical properties of the PVC/SiO₂ composite. The mechanical properties of the PVC/SiO₂ composite with high energy vibromilling modified SiO₂ particles were remarkably improved. Scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), dynamic mechanical analysis (DMA), and theoretical calculations demonstrate these improvements.     

The electronic structure of the interface between thin conjugated oligomer films and inorganic substrates with different work function

In this work, a comparison of the interfacial electronic properties between a semiconducting oligomer and a variety of substrates with different properties—metal, semiconductor and oxide layers—is reported. The interface formation was studied by X-ray and Ultraviolet photoelectron spectroscopies (XPS, UPS). High purity oligomer films with thickness up to 10 nm were prepared by stepwise evaporation on the clean substrates under ultrahigh vacuum (UHV) conditions. Analysis of the oligomer and substrate related XPS spectra clarified the interfacial chemistry and band bending in the semiconducting materials. The valence band structure and the interfacial dipoles were determined by UPS. The barriers for hole injection were measured at the interfaces of the organic film with all substrates. The interfacial energy band diagrams were deduced in all cases from the combination of XPS and UPS results. Emphasis was given on the influence of the substrate work function (eΦ) on the electronic properties of these interfaces.     

Photoemission studies of H2S,H2 and S adsorbed on Ru(110): Evidence for an adsorbed SH species

H₂S, H₂ and S adsorbed on Ru(110) have been studied by angle-integrated ultraviolet photoemission (UPS) as part of a study of the effect of adsorbed sulfur, a common catalytic poison, on this Ru surface. For low exposures of H₂S at 80 K, the work function rises to a value 0.16 eV above that of clean Ru(110) while the associated UPS spectra (hν = 21.2 eV) exhibit features similar to those of H(ads) and S(ads) and different from those of molecular H₂S. We conclude that H₂S dissociates completely at low coverages on Ru(110) at 80 K. At intermediate exposures the work function drops and the UPS spectra show new features which are attributed to the presence of an adsorbed SH species. This appears to be the first direct observation of this surface complex. At higher exposures the work function saturates at a value 0.36 eV below the clean value; the UPS spectra change markedly and indicate the adsorption of molecular H₂S. Heating adsorbed H₂S leaves a stable layer of S(ads) on Ru(110). The surface with adsorbed sulfur strongly modifies the adsorption at 80 K of a number of molecules relative to the clean Ru(110) surface.     

SiO2 and Al2O3 valence band density of states from self-deconvolution of L23VV Auger spectrum

The self-deconvolution of L₂₃VV Auger spectra of SiO₂ and Al₂O₃ has been carried out. The transition density functions obtained are compared with the local density of states (LDOS) of the valence band near the surface, as given by other techniques (XPS, UPS, XES) and also by theory. A fair agreement in the number and peak positions of valence band is produced. These compounds with MgO constitute an oxide series of increasing ionicity and the effects of initial hole localization in the transition density function are discussed.     

Photoemission study of interfacial reactions during annealing of ultrathin yttrium on SiO2/Si(1 0 0)

X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and work-function measurements have been used to investigate the Y/SiO₂/Si(1 0 0) interfaces in situ as a function of annealing temperature. The results show that yttrium is very reactive with SiO₂ and can react with SiO₂ to form Y silicate and Y₂O₃ even at room temperature. Annealing leads to the continual growth of the Y silicate. Two distinctive reaction mechanisms are suggested for the annealing processes below and above 600 K. The reaction between metallic yttrium and SiO₂ dominates the annealing processes below 600 K, while at annealing temperatures above 600 K, a reaction between the new-formed Y₂O₃ and SiO₂ becomes dominant. No Y silicide is formed during Y deposition and subsequent annealing processes. UPS valence-band spectra indicate the silicate layer is formed at the top surface. After 1050 K annealing, a Y-silicate/SiO₂/Si structure free of Y₂O₃ is finally formed.     

Influence of nano-SiO2 on dilational viscoelasticity of liquid/air interface of cetyltrimethyl ammonium bromide

An investigation was reported on the interfacial rheology of nano-SiO₂ dispersions in the presence of cetyltrimethyl ammonium bromide (CTAB). The interfacial dilational viscoelasticity had been measured as a function of the nano-particle concentration. The properties of the interface were affected by different processes such as the surfactants adsorption at the liquid or at the particle interfaces. It was found that the influence of nano-SiO₂ particles on the interfacial properties was evident and complex. The property of SiO₂ particles would change from hydrophilic to hydrophobic when CTAB molecules absorbed at their surface. The reorganization of surfactants and the participation of hydrophobic SiO₂ at the surface were offered to explain the process. In particular, the interaction between surfactants and particles, and the transfer of particles from bulk to the surface played an important role in changing the properties of the interface.     

Effect of O-vacancy defects on the Schottky barrier heights in Ni/SiO2 and Ni/HfO2 interfaces

We perform first-principles density functional calculations to study the electronic structure of Ni/HfO₂ and Ni/SiO₂ interfaces and the effect of O-vacancy (V_O) defects on the Schottky barrier height and the effective work function. We generate two interface models in which Ni is placed on O-terminated HfO₂ (1 0 0) and α-quartz (1 0 0) surfaces. As the concentration of V_O defects at the interface increases, the p-type Schottky barrier height tends to increase in the Ni/HfO₂ interface, due to the reduction of interface dipoles, whereas it is less affected in the Ni/SiO₂ interface.     

Oxygen adsorption on the LaB6(100), (110) and (111) surfaces

Oxygen adsorption on the LaB₆(100), (110) and (111) clean surfaces has been studied by means of UPS, XPS and LEED. The results on oxygen adsorption will be discussed on the basis of the structurs and the electronic states on the LaB₆(100), (110) and (111) clean surfaces. The surface states on LaB₆(110) disappear at the oxygen exposure of 0.4 L where a c(2 × 2) LEED pattern disappears and a (1 × 1) LEED pattern appears. The work function on LaB₆(110) is increased to ～3.8 eV by an oxygen exposure of ～2 L. The surface states on LaB₆(111) disappear at an oxygen exposure of ～2 L where the work function has a maximum value of ～4.4 eV. Oxygen is adsorbed on the surface boron atoms of LaB₆(111) until an exposure of ～2 L. Above this exposure, oxygen is adsorbed on another site to lower the work function from ～4.4 to ～3.8 eV until an oxygen exposure of ～100L. The initial sticking coefficient on LaB₆(110) has the highest value of ～1 among the (100), (110) and (111) surfaces. The (100) surface is most stable to oxygen among these surfaces. It is suggested that the dangling bonds of boron atoms play an important role in oxygen adsorption on the LaB₆ surfaces.     

The interfacial properties of MgCl2 films grown on a flat SiO2/Si substrate. An XPS and ISS study

The interaction between MgCl₂ and SiO₂ was investigated by X-ray photoelectron spectroscopy (XPS), ion scattering spectroscopy (ISS) and contact potential difference (CPD) measurements. A thin SiO₂ layer was grown for this purpose on a Si(1 0 0) wafer and MgCl₂ was applied on this support at room temperature by evaporation under UHV conditions. It was found that magnesium chloride is deposited molecularly on the SiO₂ substrate, growing in layers and covering uniformly the oxide surface. The interaction with the substrate is initially very weak and limited to the interfacial layer. Above 623 K, most of the molecular MgCl₂ is re-evaporated and the interfacial interaction becomes stronger, as Mg-Cl bonds in the remaining sub-monolayer chloride break and Cl atoms desorb. This leaves on the surface sub-stoichiometric MgCl_x, which interacts with oxygen atoms from the substrate to form a complex surface species. At 973 K all Cl atoms desorb and Mg remains on the surface in the form of an oxide.     

Understanding the electronic properties of molecule/metal junctions: The case study of thiols on gold

In this work, I review our recent results on the electronic properties of thiolate/metal interface. Work function change, molecular level alignment and interfacial state formation of the methylthiolate/Au(1 1 1) and dimethyl-disulfide/Au(1 1 1) interfaces are investigated by means of UPS and XPS. A complete picture of the electronic properties of both the dimethyl-disulfide (DMDS) weakly-adsorbed and the methylthiolate (MT) chemisorbed phases is obtained by direct quantitative comparison between the experiment and theory. The modifications of the electronic properties of the DMDS thin film, induced by a MT buffer layer are also discussed.Moreover, the cysteine/Au(1 1 1) system is investigated as an example of interface formed by molecules with large intrinsic dipole moment. Finally, surface inhomogeneity and its influence on the interface electronic properties is briefly discussed, in light of the important concept of local work function.     

Absorption cross-sections and lifetimes as a function of size in Si nanocrystals embedded in SiO2

The photoluminescence (PL) emission yield of Si nanocrystals embedded in SiO₂ depends on their size and on Si–SiO₂ interface passivation. In this work we aim at clarifying the relative importance of both contributions by studying lifetimes and absorption cross-sections as a function of size, for samples with and without passivation in forming gas. We find that while the PL lifetime increases steadily (quasi-linear dependence), the radiative lifetime increases exponentially with the nanocrystal size. Thus, as expected, radiative oscillator strengths are much smaller for large nanocrystals, but this reduction is partially compensated by a less effective quenching at interfacial non-radiative states. The absorption cross-section per nanocrystal rises as the nanocrystal size decreases, for all excitation wavelengths, implying that the variation of oscillator strength dominates over the reduction of the density of states. Passivation processes do not affect the emission mechanism and increase the emission yield while reducing the density of non-radiative recombination centers at the Si–SiO₂ interface (P_b centers).     

Wear-out of Al-Ta2O5/SiO2-Si structures under dynamic stress

Wear-out of Al-Ta₂O₅/SiO₂-Si stacked layers under dynamic current stresses was studied. It was found that a detrapping of negative charges occurs between the pulses, similarly to SiO₂ and SiO_xN_y films. Additional consumption of the SiO₂ interfacial layer results in a decrease of the gate voltage in some stages of the stress, depending upon the stress time and current density.     

Interface modification and trap-type transformation in Al-doped CdO/Si-nanowire arrays/p-type Si devices by nanowire surface passivation

The present work reports the fabrication and detailed electrical properties of Al-doped CdO/Si-nanowire (SiNW) arrays/p-type Si Schottky diodes with and without SiNW surface passivation. It is shown that the interfacial trap states influence the electronic conduction through the device. The experimental results demonstrate that the effects of the dangling bonds at the SiNW surface and Si vacancies at the SiO_x/SiNW interface which can be changed by the Si–O bonding on the energy barrier lowering and the charge transport property. The induced dominance transformation from electron traps to hole traps in the SiNWs by controlling the passivation treatment time is found in this study.     

The structure of monolayer SiO2 on Mo(1 1 2): A 2-D [Si-O-Si] network or isolated [SiO4] units?

In this letter, atomically resolved scanning tunneling microscopic (STM) images obtained from monolayer SiO₂/Mo(1 1 2) are presented. The results are consistent with a previously proposed structural model of isolated [SiO₄] units based on vibrational features observed by high-resolution electron energy loss spectroscopy (HREELS) and infrared reflection-absorption spectroscopy (IRAS), and oxygen species identified by ultra-violet photoemission spectroscopy (UPS). These results are inconsistent with a structural model that assumes a two-dimensional (2-D) [Si-O-Si] network. These data illustrate that a metal substrate, although coated with an oxide thin layer, can be directly imaged at the atomic-scale with STM.     

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     

Probing buried interfaces on Ge-based metal gate/high-k stacks by hard X-ray photoelectron spectroscopy

In this contribution, we present results of a non-destructive in-depth analysis of concentration of chemical components at buried interfaces on Ge-based CMOS by means of hard X-ray photoelectron spectroscopy (HAXPES) and low angle X-ray reflectivity (XRR). Two samples composed of a Ge/Si/SiO₂/HfO₂/TiN stack, with layer and interlayer thicknesses of 2500, 0.9, 0.5, 4.9, 3.4 nm and 2500, 0.7, 1, 5.8, 3 nm have been studied. The use of electrons with kinetic energies from few eV up to 15 keV enables to tune the information depth being able to analyze the desired interface in a non-destructive way. XRR enables the determination of the exact layer thickness and density. The results suggest that the Si interlayer prevents the Ge oxidation. Depth profiles of the electronic structure have been obtained for both samples by following the evolution of the photoemission signal from the Hf 2p_3/2 core level as a function of the photoelectron kinetic energy. The depth profile of the electronic structure reveals the presence of a chemical shift of the Hf 2p_3/2 core level, which is related to an interfacial bonding state. Our results demonstrate the excellent capability of HAXPES to study buried interfaces in a non-destructive way.     

Si/SiO2 multilayers: synthesis by reactive magnetron sputtering and photoluminescence emission

This paper relates a complete study of Si/SiO₂ multilayer (ML) structures. First, we suggest an original way of synthesis based on reactive magnetron sputtering of a pure silica target. The photoluminescence spectra of these MLs consist of two Gaussian bands in the visible-near infrared spectral region. The stronger one (I band) is fixed at about 780 nm and probably due to interface states. The weaker one (Q band) is tuneable with the Si sublayer thickness and originates from a radiative recombination within the nanosized Si layers. For this latter band the peak position is a function of the Si sublayer thickness and shows a discontinuity at 30 Å. This corresponds to an Si phase change. For thicknesses above 30 Å, the sublayers are composed of nanocrystalline silicon whereas below 30 Å the sublayers are made of amorphous silicon. We develop a model based on a quantum well to which we have added an interfacial region between Si and SiO₂. It is characterised by an interfacial potential of 0.3 eV. This model depicts the simultaneous behaviour of Q and I bands for an Si sublayer thickness below 30 Å.     

A two-dimensional threshold voltage analytical model for metal-gate/high-k/SiO2/Si stacked MOSFETs

In this paper the influences of the metal-gate and high-k/SiO 2 /Si stacked structure on the metal-oxide-semiconductor field-effect transistor（MOSFET） are investigated.The flat-band voltage is revised by considering the influences of stacked structure and metal-semiconductor work function fluctuation.The two-dimensional Poisson＇s equation of potential distribution is presented.A threshold voltage analytical model for metal-gate/high-k/SiO 2 /Si stacked MOSFETs is developed by solving these Poisson＇s equations using the boundary conditions.The model is verified by a two-dimensional device simulator,which provides the basic design guidance for metal-gate/high-k/SiO 2 /Si stacked MOSFETs.     

Characterization of Si nanocrystals into SiO2 matrix

Silicon nanocrystals (nc-Si) have gained great interest due to their excellent optical and electronic properties and their applications in optoelectronics. The aim of this work is the study of growth mechanism of nc-Si into a-SiO₂ matrix from SiO/SiO₂ multilayer annealing, using non-destructive and destructive techniques. The multilayer were grown by e-beam evaporation from SiO and SiO₂ materials and annealing at temperatures up to 1100 °C in N₂ atmosphere. X-rays reflectivity (XRR) and high resolution transmission electron microscopy (HRTEM) were used for the structural characterization and spectroscopic ellipsometry in IR (FTIRSE) energy region for the study of the bonding structure. The ellipsometric results gave a clear evidence of the formation of an a-SiO₂ matrix after the annealing process. The XRR data showed that the density is being increased in the range from 25 to 1100 °C. Finally, the HRTEM characterization proved the formation of nc-Si. Using the above results, we describe the growth mechanism of nc-Si into SiO₂ matrix under N₂ atmosphere.     

SiO2分子的基态(X1A1)结构与分析势能函数

应用群论及原子分子反应静力学方法推导了SiO₂分子的电子态及其离解极限，采用B3P86方法，在6-311G^**水平上,优化出SiO₂基态分子稳定构型为单重态的C_2V构型，其平衡核间距R_e=R_Si—O=0.1587 nm,∠OSiO＝111.2°,能量为-440.4392 a.u..同时计算出基态的简正振动频率:对称伸缩振动频率ν(B₂)=945.4cm^-1，弯曲振动频率ν(A₁)=273.5 cm^-1和反对称伸缩振动频率ν(A₁)=1362.9cm^-1.在此基础上，使用多体项展式理论方法，导出了基态SiO₂分子的全空间解析势能函数，该势能函数准确再现了SiO₂(C_2V)平衡结构.