TiO2-rich reconstructions of SrTiO3(0 0 1): a theoretical study of structural patterns

We have recently reported structure solutions for the (2 × 1) and c(4 × 2) reconstructions of SrTiO₃(0 0 1) based on high-resolution electron microscopy, direct methods analysis of diffraction data and density functional theory. Both reconstructions were found to be TiO₂-rich and feature a single overlayer of TiO₂ stoichiometry on top of a bulk-like TiO₂ layer. Qualitatively, the two reconstruction geometries differ in the cation sub-lattice of the overlayer only, where Ti atoms occupy half of the fivefold cation sites. In the present work we use density functional theory to generate a number of variations of this structural motif in search of patterns of stability. We find a reliable predictor for the reconstruction energy in the ability of oxygen atoms to relax vertically out of the overlayer plane to minimize non-bonded oxygen-oxygen repulsions. Out-of-plane relaxation of oxygen atoms in turn is modulated by the number and relative position of coordinating Ti atoms, which yields simple empirical rules as to how cations are distributed in low energy reconstructions.     

A combined ab initio and atomistic simulation study of the surface and interfacial structures and energies of hydrated scheelite: introducing a CaWO4 potential model

Density functional theory (DFT) calculations of the calcium tungstate material scheelite CaWO₄ have shown that water introduced into the bulk material remains undissociated and leads to swelling and layering of the structure, a behaviour which may resemble silicate clays more than three-dimensional poly-anionic materials, but which results in a structure that is even more similar to a rare hydrous calcium carbonate phase--a finding which suggests the existence of semi-crystalline hydrous pre-cursor phases to the dehydrated scheelite material. An interatomic potential model was derived for CaWO₄ which adequately reproduces structural and physical properties of the material and is in good agreement with the DFT calculations in respect of the structure and energy of hydration (DFT: 85 kJ mol⁻¹, atomistic: 105 kJ mol⁻¹). Atomistic simulations of a range of scheelite surfaces confirm the dominance of the experimental {1 0 1} and {0 0 1} cleavage planes in the morphology of the dry crystal and the presence of the experimentally found {1 0 3} and {1 0 1} surfaces in the hydrated morphology. Hydration of the surfaces shows non-Langmuir behaviour, where the interactions between surface calciums and oxygen atoms of the water molecules outweigh hydrogen-bonding to the surface oxygen atoms or intermolecularly within the water layer. The hydration energies indicate physisorption of water, ranging from 22 kJ mol⁻¹ on the {0 0 1} surface to 78 kJ mol⁻¹ on the more reactive {1 0 3} surface.     

On the microscopic origin of the kinetic step bunching instability on vicinal Si(0 0 1)

A scanning tunneling microscopy/atomic force microscopy study is presented of a kinetically driven growth instability, which leads to the formation of ripples during Si homoepitaxy on slightly vicinal Si(0 0 1) surfaces miscut in [1 1 0] direction. The instability is identified as step bunching, that occurs under step-flow growth conditions and vanishes both during low-temperature island growth and at high temperatures. We demonstrate, that the growth instability with the same characteristics is observed in two dimensional kinetic Monte Carlo simulation with included Si(0 0 1)-like diffusion anisotropy. The instability is mainly caused by the interplay between diffusion anisotropy and the attachment/detachment kinetics at the different step types on Si(0 0 1) surface. This new instability mechanism does not require any additional step edge barriers to diffusion of adatoms. In addition, the evolution of ripple height and periodicity was analyzed experimentally as a function of layer thickness. A lateral “ripple-zipper” mechanism is proposed for the coarsening of the ripples.     

共路外差表面轮廓仪

本文提出了一种改进的外差共路干涉仪,用于表面粗糙度的测量,它对机械振动、温度变化等极不敏感,纵向分辨率为0.1nm,可用于表面粗糙度的实际检测工作.     

Enhanced surface atomic step motion observed in real time after nanoindentation of NaCl(100)

The nanometer-scale indentation of a crystalline surface produces nanostructures that evolve on a timescale that is inaccessible to existing imaging methods for the vast majority of surfaces. We have been able to observe the dynamic evolution of the freshly cleaved surface of a NaCl(100) crystal after indentation with an atomic force microscope (AFM) in air. Here we present sequential AFM images featuring vertical atomic resolution which show that atomic terrace motion is greatly enhanced by the AFM indentation. Moreover, some of the nanometric features generated by the indentation become reassimilated into the crystalline surface structure of the surroundings of the indentation over a period of time of the order of several minutes.     

Growth and thermal properties of ultrathin cerium oxide layers on Rh(1 1 1)

Ultrathin layers of cerium oxide have been deposited on a Rh(1 1 1) surface and their growth morphology, structure, and thermal stability have been investigated by LEED, STM, XPS, and valence band resonant photoemission. STM and LEED indicate that the ceria grows epitaxially in form of ordered CeO₂ islands at elevated substrate temperature (250–300 °C), with (1 1 1) faces parallel and orientationally aligned to the main azimuthal directions of the substrate. The ultrathin ceria films contain significant amounts of reduced Ce³⁺ species, which appear to be located predominantly at the ceria–Rh interface. For thicker films (>6 equivalent monolayers) stoichiometric CeO₂ is detected in XPS. Vacuum annealing produces morphologically well-defined hexagonal islands, accompanied by partial reduction and the formation of oxygen vacancies at the ceria surface. The thermal stability and the degree of reduction is a function of the oxide layer thickness, with thinner layers being thermally less stable. At temperatures >800 °C, the ceria decomposes and Ce–Rh alloy phases are identified.     

Investigation of the performance of an SPR-based optical fiber sensor using finite-difference time domain

Finite-difference time domain (FDTD) method was used to investigate the performance of surface plasmon resonance (SPR)-based optical fiber sensors. The results show that the performance of the fiber sensor can be optimized by choosing a proper combination of metal layer thickness of 40–60 nm and residual cladding thickness of 400–500 nm. Furthermore, the roughness effect of the gold surface layering the fiber sensor is significant in rough surfaces when sigma rms is greater than 5 nm or correlation length is lower than 100 nm.     

Kinetic six-vertex model as model of bcc crystal growth

The growth of bcc crystals is studied using van Beijeren's mapping onto the six-vertex model. The growth-evaporation processes are described in terms of vertices. The time evolution is given by a master equation for the probability of the six-vertex configurations. The model, studied in the finite-size case by both Monte Carlo and analytic methods, applies to the (001) surface and its vicinal surfaces. Different growth modes (including nucleation) are found, depending on the strength of disequilibrium and on temperature, and the transition between them is investigated.On leave of absence from the Institute of Physics, Czechoslovak Academy of Science, Prague, Czechoslovakia.     

The adsorption of carbon monoxide on TiO2(110) supported palladium

Palladium overlayers deposited on TiO₂(110) by metal vapour deposition have been investigated using LEED, XPS and FT-RAIRS of adsorbed CO. Low coverages of palladium (<3 ML) deposited at 300 K adsorb CO exclusively in a bridged configuration with a band (B₁ at 1990 cm⁻¹) characteristic of CO adsorption on Pd(110) and Pd(100) surfaces. When annealed to 500 K, XPS and LEED indicate the nucleation of Pd particles on which CO adsorbs predominantly as a strongly bound linear species which we associate with edge sites on the Pd particles (L* band at 2085 cm⁻¹). Both bridged and linear CO bands are exhibited as increases in reflectivity at the resonant frequency, indicating the retention of small particle size during the annealing process. Palladium overlayers of intermediate coverages (10–20 ML) deposited at 300 K undergo some nucleation during growth, and adsorbed CO exhibits both absorption and transmission bands in the B₁ (1990 cm⁻¹) and B₂ (1940 cm⁻¹) regions. The latter is associated with the formation of Pd(111) facets. Highly dispersed Pd particles are produced on annealing at 500 K. This is evidenced by the dominance of transmission bands for adsorbed CO and a significant concentration of edge sites, which accommodate the strongly bound linear species at 300 K. Adsorption of CO at low temperature also allows the identification of the constituent faces of Pd and the conversion of Pd(110)/(100) facets to Pd(111) facets during the annealing process. High coverages of palladium (100 ML) produce only absorption bands in FT-RAIRS of adsorbed CO associated with the Pd facets, but annealing these surfaces also shows a conversion to Pd(111) facets. LEED indicates that at coverages above 10 ML, the palladium particles exhibit (111) facets parallel to the substrate and aligned with the TiO₂(110) unit cell, and that this ordering in the particles is enhanced by annealing.     

Radiative Striations and Surface Roughness of Alkoxide-Derived Spin Coating Films

Spin coating silica films were prepared from acid-catalyzed tetraethoxysilane (TEOS) solutions, and the magnitude of radiative striations formed on the surface of the resulting films was quantitatively evaluated by measuring surface roughness using a contact probe profilometer. Wave-like transverse profiles were obtained on the films prepared. Surface roughness parameters, Ra (arithmetical mean deviation), Rz (ten point height of irregularities) and S (mean spacing of local peaks), were determined. When the gel films were heated at higher temperatures (500°C), the film thickness decreased up to 22%, while none of Ra, Rz or S varied with heat-treatment temperature, indicating that the surface of the films is already densified at room temperature. Higher substrate rotation speeds caused decrease in Ra, Rz and S, revealing that the striations decreased both in amplitude and wavelength. Application of viscous sols aged for longer periods of time resulted in increased amplitude (Rz) of striations without change in wavelength (S).