Microscopic structure of the wetting film at the surface of liquid Ga-Bi alloys

X-ray reflectivity measurements of the binary liquid Ga-Bi alloy reveal a dramatically different surface structure above and below the monotectic temperature T(mono) = 222 degrees C. A Gibbs-adsorbed Bi monolayer resides at the surface in both regimes. However, a 30 A thick, Bi-rich wetting film intrudes between the Bi monolayer and the Ga-rich bulk for T>T(mono). The wetting film's internal structure, not hitherto measured, is determined with A resolution, showing a concentration gradient not predicted by theory and a highly diffuse interface with the bulk phase.     

Influence of surface ordering on the wetting of structured liquids

The substrate is shown to induce substantial ordering in diblock copolymer thin films above the bulk order-disorder transition (ODT) where, thermodynamically, a phase mixed state is favored. Initially, uniform films reorganize to form a hierarchy of transient surface patterns and stable film thicknesses that depend on the initial film thickness and on the substrate. Self-consistent field calculations of the free energy of the system for different situations, depending on the relative tendency for the different block components to be attracted to the substrate and/or free surface, provide an explanation of the formation of the stable film thicknesses. A continuum picture proposed earlier by Brochard et al.rovides an explanation of the wetting characteristics of this system. In some cases the ordering destabilizes the film so that dewetting occurs (wetting autophobicity), whereas in other cases the surface ordering results in a kinetic stabilization of a film that would otherwise dewet. Received 3 August 2001 and Received in final form 1 November 2001     

多晶铁电薄膜的相变——应力和晶粒尺寸效应

用掠入射X射线衍射法观察到钛酸铅多晶铁电薄膜表面层与体内的相变温度不同,表面层的结构参数也有异于体内;唯象地把多晶铁电薄膜抽象为一个表面层为细晶粒、低应变层,体内为粗晶粒、高应变层的两层结构,根据应力和晶粒尺寸效应对铁电相变的影响,解释了钛酸铅多晶铁电薄膜的相变特征 关键词：     

面心立方(001)方向AB合金薄膜表面层的有序无序相变

采用平均场近似方法对两组元面心立方合金薄膜的有序无序相转变过程进行模拟计算，结果表明，合金薄膜的有序无序相变受薄膜层数奇偶性的影响.薄膜层数奇偶性不同，会导致薄膜具有不同的相结构和热力学性质.在弱表面偏析作用下，对于偶数层薄膜，由于薄膜边界对称性破缺，对应体组分x=0.5的化学势区间，偶数层薄膜有序无序相变过程中出现了中间温度相和浸润现象.而奇数层薄膜的有序无序相变类似体材料的相变.在强表面偏析作用下，由于受表面偏析作用和有限尺寸效应影响，对应体组分x=0.5的化学势区间，奇数层薄膜中出现AB(AB)关键词： 合金薄膜 有序无序相变 浸润现象 准热力学相变     

Reversible sphere-to-lamellar wetting transition at the interface of a diblock copolymer system

We use ellipsometry to investigate a transition in the morphology of a sphere-forming diblock copolymer thin-film system. At an interface the diblock morphology may differ from the bulk when the interfacial tension favours wetting of the minority domain, thereby inducing a sphere-to-lamella transition. In a small, favourable window in energetics, one may observe this transition simply by adjusting the temperature. Ellipsometry is ideally suited to the study of the transition because the additional interface created by the wetting layer affects the polarisation of light reflected from the sample. Here we study thin films of poly(butadiene-ethylene oxide) (PB-PEO), which order to form PEO minority spheres in a PB matrix. As temperature is varied, the reversible transition from a partially wetting layer of PEO spheres to a full wetting layer at the substrate is investigated.     

Phase behavior in thin films of cylinder-forming block copolymers

We have experimentally determined a phase diagram for cylinder-forming polystyrene-block-polybutadien-block-polystyrene triblock copolymer in thin films. The phase behavior can be modeled in great detail by dynamic density functional theory. Deviations from the bulk structure, such as wetting layer, perforated lamella, and lamella, are identified as surface reconstructions. Their stability regions are determined by an interplay between surface fields and confinement effects.     

Kinetic hindrance during the initial oxidation of Pd(100) at ambient pressures

The oxidation of the Pd(100) surface at oxygen pressures in the 10(-6) to 10(3) mbar range and temperatures up to 1000 K has been studied in situ by surface x-ray diffraction (SXRD). The results provide direct structural information on the phases present in the surface region and on the kinetics of the oxide formation. Depending on the (T,p) environmental conditions, we observe either a thin (sqrt[5]xsqrt[5])R27 degrees surface oxide or the growth of a rough, poorly ordered bulk oxide film of PdO predominantly with (001) orientation. By either comparison to the surface phase diagram from first-principles atomistic thermodynamics or by explicit time-resolved measurements we identify a strong kinetic hindrance to the bulk oxide formation even at temperatures as high as 675 K.     

Phase coexistence in binary mixtures in thin films with symmetric walls: model calculations for two- and three-dimensional Ising lattices

Binary mixtures (A, B) that undergo phase separation in the bulk are considered in thin film geometry, assuming that one of the components is preferentially attracted to one of the walls. We discuss the average profile of the order parameter {volume fraction φ(z) of one of the components} in the z-direction (perpendicular to the surfaces), paying attention to the lateral inhomogeneity of the thin film when the average volume fraction corresponds to a state inside the coexistence curve. We consider the situation where due to (short range) surface forces a second-order wetting transition would occur in semi-infinite geometry: in the thin film geometry, this transition is rounded off and its only remnant is a smooth increase of the adsorbed mass in the surface-enriched layer in the transition region. Monte Carlo calculations for nearest neighbor Ising square and simple cubic lattices are used to derive typical concentration profiles. In the two-dimensional case, also the kinetics of domain formation after the quench from a disordered state is considered, and it is shown that the typical concentration oscillations perpendicular to the wall (“surface directed spinodal decomposition”) do not occur, due to strong lateral fluctuations of the local position of the interface between the enrichment layer at the surface and the neighboring depleted region. Finally, also phase-separated states in thin films with competing walls (where one surface prefers A and the other prefers B) are briefly treated, and experimental applications are discussed.     

Stability of thermoresponsive methylcellulose thin film: x‐ray reflectivity study

Methylcellulose (MC), a thermoreversible polymer, was fabricated as thin films into silicon substrates and characterized by x‐ray reflectivity (XRR) measurements for its stability with time and heating. XRR data from the as‐is thin films showed good agreement with the single‐layer model on top of a substrate from Parratt's formalism. Data fitting showed that the density of the thin films is slightly higher than the reported value by manufacturers. Interface roughness values indicate good wetting of the polymer onto the substrate. Heating the thin films at the phase transition temperatures and quenching them to room temperature showed no significant changes in the thin film parameters before and after heating. This showed the thermal stability and/or thermoreversibility of the film. Diffuse scattering measurements also showed no significant changes in the lateral structure of the film with heating and quenching. XRR measurements done on fabricated thin films stored for a month showed a slight increase in the film thickness which could be due to the hygroscopic nature of the polymer. Vacuum heating of the stored thin films at 100 °C for 1 h slightly decreased the thickness, but it has been found that other parameters such as density and surface/interface roughness show good thermal stability. Copyright © 2009 John Wiley & Sons, Ltd.     

Theoretical analysis of optical properties of dielectric coatings dependence on substrate subsurface defects

A model for refractive index of stratified dielectric substrate was put forward according to theories of inhomogeneous coatings. The substrate was divided into surface layer, subsurface layer and bulk layer along the normal direction of its surface. Both the surface layer (separated into N₁ sublayers of uniform thickness) and subsurface layer (separated into N₂ sublayers of uniform thickness), whose refractive indices have different statistical distributions, are equivalent to inhomogeneous coatings, respectively. And theoretical deduction was carried out by employing characteristic matrix method of optical coatings. An example of mathematical calculation for optical properties of dielectric coatings had been presented. The computing results indicate that substrate subsurface defects can bring about additional bulk scattering and change propagation characteristic in thin film and substrate. Therefore, reflectance, reflective phase shift and phase difference of an assembly of coatings and substrate deviate from ideal conditions. The model will provide some beneficial theory directions for improving optical properties of dielectric coatings via substrate surface modification.     

Observation of novel liquid-crystalline phase above the bulk-melting temperature

In this paper, we show that a noncrystalline but ordered smectic-like phase exists above the bulk-melting temperature (T(m)) at poly(n-alkyl acrylates)-air interface. The surface ordered phase is one monolayer thick and undergoes a sharp transition from order to disorder 10 degrees C above T(m) for n=22. The presence of a surface phase that does not exist in the bulk has important implications in the design of thermally responsive adhesives.     

对硅片上自组装生长的Pentacene薄膜生长机制及其结晶相态的研究

采用热蒸发的方法在硅片衬底上自组装生长的Pentacene薄膜,薄膜在80℃温度下经2 h恒温真空热处理,通过原子力显微镜(AFM)对Pentacene薄膜表面形貌及其生长机制进行研究.结果得到,在硅片上生长的Pentacene薄膜足以台阶岛状结构生长,其岛状直径约为100 nm.且Pentacene分子以垂直于衬底的方向生长,台阶岛状结构中每个台阶的平均高度约为1.54 nnl·s-1,与Pentacene分子的沿长轴方向的长度相近.从Pentacene薄膜的XRD图谱中可以看出,薄膜在形成的过程中会因条件的不同而形成不同的结晶相,分别为薄膜相和三斜体相,且薄膜的结晶相将随着薄膜厚度的增加向三斜体相转变,其临界厚度为80和150 nm,当薄膜大于150 nm时,薄膜的三斜体相占主导地位,而当Pentacene薄膜的厚度小于80 nm时,Pentacene薄膜呈薄膜相存在.     

Epitaxy surface effect on the first-order phase transition properties in a ferroelectric thin film

By modifying the interchange interactions and the transverse fields on the epitaxy surface layer,this paper studies the phase transition properties of an n-layer ferroelectric thin film by the Fermi-type Green’s function technique based on the transverse Ising model with a four-spin interaction.The special attention is given to the effect of the epitaxy surface layer on the first-order phase transition properties in the parameter space constructed by the ratios of the bulk transverse field and the bulk four-spin interaction to the bulk two-spin interaction with the framework of the higher-order decoupling approximation to the Fermi-type Green’s function.The results show that the first-order phase transition properties will be changed significantly due to the modification of interchange interaction and transverse field parameters on the epitaxy surface layer.The dependence of the first-order phase transition properties on the thickness of ferroelectric thin films is also discussed.     

A model for surface space charge in thin films of AgBr

A model for the surface space charge layer in ionic crystals has been developed for thin films where the film thickness is less than or comparable to the Debye length. A potential difference between the surface and the bulk is present which depends on the film thickness and the impurity concentration. The implications of this model have been examined with respect to thin films of AgBr at room temperature.     

Spin-reorientation phase transition on the surface and in the bulk of α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> single crystals

Direct comparison of the properties of a thin surface layer and the bulk of macroscopic hematite (α-Fe₂O₃) crystals was used to study the magnetic structure of the surface layer and the bulk and the processes attendant on spin-reorientation phase transition (SRT). The investigation tool was simultaneous γ-ray, X-ray, and electronic Mössbauer spectroscopy, which enabled us to study the bulk and surface properties of macroscopic samples simultaneously and to compare them directly. Direct evidence of the existence of a surface “transition layer” on hematite crystals is obtained. The existence of this layer was suggested and described by Krinchik and Zubov [JETP 69, 707 (1975)]. The study in the SRT region showed that (1) the Morin SRT in the crystal bulk occurs in a jump (as a first-order phase transition), whereas in the surface layer of about 200 nm thick, some smoothness appears in the mechanism of magnetic-moment reorientation; (2) SRT in the surface layer, as in the bulk, involves an intermediate state in which low-and high-temperature phases coexist; and (3) SRT in the surface layer occurs at a temperature several degrees higher than in the bulk. Our experimental evidence on the SRT mechanism in the surface layer correlates with the inferences from phenomenological theory developed by Kaganov [JETP 79, 1544 (1980)].     

Influence of the thermal power of a Fe atomic flux on the formation of Cu/Fe nanofilms on a Si(001) substrate

The growth of a Fe sublayer 1.5–14.0 monolayers (MLs) thick and a Cu film (about 5 MLs) on this sublayer is studied at a reduced temperature (1240°C) and an elevated temperature (1400°C) of a Fe source and at a reduced temperature (900°C) of a Cu source. The films are examined by Auger electron spectroscopy, low-energy electron diffraction, and atomic force microscopy. As metal sources, thin Fe and Cu strips on a Ta foil are used. It is shown that a nonequilibrium 2D phase forms in the Fe-on-Si(001) film up to a thickness of 4–5 MLs. This phase appears as closely packed atomically smooth nanoislands. When the thickness of the film exceeds 4–5 MLs, the nonequilibrium Fe phase changes to the bulk (3D) phase of Fe and its silicide Fe _x Si. At Fe source temperatures of 1240 and 1400°C, the nonequilibrium phase consists of Fe with Si segregated on the Fe surface, and a Fe-Si mixture. Copper on the nonequilibrium Fe and Fe-Si phases grows, respectively, as a smooth layer Cu with Si segregated on the top and in the form of Cu-Fe and Cu-Si mixtures. Cu islands growing on the bulk Fe and Fe _x Si phases have smaller and larger sizes, respectively.     

Substrate and chain size dependence of near surface dynamics of glassy polymers

We use nanohole relaxation to study the surface relaxation of films of glassy isotactic poly (methyl methacrylate) (i-PMMA) films. These measurements allow us to obtain the time dependent relaxation function at a number of different sample temperatures for the first 2-3 nm of the free surface in a system often used as a model system for the effect of the substrate on thin film dynamics. The surface is observed to relax at temperatures up to 42 K below the bulk Tg value, even on systems where the thin film Tg is known to be greater than the bulk value. We are able to determine the range over which the substrate directly affects the free surface relaxation, and determine a surprisingly large (Mw independent) limiting thickness of approximately 180 nm where the free surface relaxation is not affected by the substrate. For thick films (h>200 nm) we find an unexpected linear Mw dependence of the near surface relaxation time.     

Influence of Surface Transition Layers on Phase Transformation and Pyroelectric Properties of Ferroelectric Thin Film

Taking into account surface transition layers （STLs）, we study the phase transformation and pyroelectric properties of ferroelectric thin films by employing the transverse Ising model （TIM） in the framework of the mean field approximation. The distribution functions representing the intra-layer and inter-layer couplings between the two nearest neighbour pseudo-spins are introduced to characterize STLs. Compared with the results obtained by the traditional treatments for the thin films using only the single surface transition layer （SSL）, it is shown that the STL model reflects a more realistic and comprehensive situation of films. The effects of various parameters on the phase transformation properties have shown that STL can make the Curie temperature of the film higher or lower than that of the corresponding Sulk material, and the thickness of STL is a key factor influencing the film properties. For a film with definite thickness, there exists a critical STL thickness at which ferroelectricity will disappear when the intra-layer and inter-layer interactions are weak.     

Diffusion in thin films on the surface of a porous solid.

A water-wet mono-dispersed glass bead system is saturated with two phases, a wetting phase of water and a non-wetting phase of tetrachloroethylene (no 1H signal). Pulsed field gradient NMR measurements of the one-dimensional probability density distribution P(Delta) (X) for the diffusive displacements of water molecules in times, Delta, are presented for the whole accessible water saturation range. At lower water contents the distributions show a distinctive shape, which is attributed to the distribution of the aqueous phase in thin surface wetting films connecting pendular rings where the beads are in contact. The data are reproduced well by a computer simulation of a random walk model based on diffusion of molecules within such a structure, allowing determination of the surface film thickness.