Slippery or sticky boundary conditions: control of wrinkling in metal-capped thin polymer films by selective adhesion to substrates

Wrinkling patterns at the metallized surface of thin polymer films are shown to be sensitive to the sticky or slippery character of the polymer-substrate interface. Existing theoretical models were expanded to specific boundary conditions (adhesive versus slippery) in order to rationalize these observations. Based on this concept, we were able to propose a new and simple method to orient the wrinkles by chemically patterning the substrate with regions of high and low adhesion.     

A continuum model for the flow of thin liquid films over intermittently chemically patterned surfaces

It is known from both experiments and molecular dynamics simulations that chemically patterning a solid surface has an effect on the flow of an adjacent liquid. This fact is in stark contrast with predictions of classical fluid mechanics where the no-slip boundary condition is insensitive to the chemistry of the solid substrate. It has been shown that the influence on the flow caused by a steep change in the wettability of the solid substrate can be described in the framework of continuum mechanics using the interface formation theory. The present work extends this study to the case of intermittent patterning. Results show that variations in wettability of the substrate can significantly affect the flow, especially of thin films, which may have applications to the design of microfluidic devices.     

Ion beam induced surface and interface engineering

The injection of material into a target specimen in the form of an accelerated ion beam offers a most valuable tool for altering its physical, chemical, structural, surface and interface properties in a controlled manner and tailoring new materials for basic and applied research for science and technology. The present review describes experimental, theoretical and recent aspects of ion beam modifications at various solids, thin films, and multilayered systems covering wider energy ranges including the older basic concepts which are now of interest. These results reveal that the ion–solid interaction physics provides a unique way for controlling the produced defects of the desired type at a desired location. These interests have been stimulated by the possibilities of synthesizing novel materials with potential applications in the field of thin films, surfaces and interface science. Many applications of ion induced engineering are being developed for various sciences of high technological interest for future aspects.     

Breakup of Thin Liquid Filaments on Partially Wetting Substrates: from Micrometric to Nanometric Scales

We present theoretical and experimental results regarding the instability of a thin liquid film in the form a long filament sitted on a solid substrate. We consider this problem in two different scenarios, namely, at submillimetric and nanometric scales, and we study their free surface instability. In the first scale, we take into account the effects due to surface tension and gravity, while in the smaller scale, we add intermolecular interaction and neglect gravity. The flows are modeled within the long wave approximation, which leads to a nonlinear fourth-order differential equation for the fluid thickness. This model equation also includes the partial wetting condition between the liquid and the solid. In the theoretical models, we analyze the linear stability of the equilibrium configurations. The linear stability analyses lead to eigenvalue problems that are solved using pseudo spectral methods in the submillimetric case, and finite differences in the nanoscale. Whenever possible, the theoretical results are compared with experiments performed on a submillimetric scale (silicon oils on glass), as well as on nanometric scale (nickel films melted by laser irradiation on SiO2 substrates).     

Precursor films in wetting phenomena

The spontaneous spreading of non-volatile liquid droplets on solid substrates poses a classic problem in the context of wetting phenomena. It is well known that the spreading of a macroscopic droplet is in many cases accompanied by a thin film of macroscopic lateral extent, the so-called precursor film, which emanates from the three-phase contact line region and spreads ahead of the latter with a much higher speed. Such films have been usually associated with liquid-on-solid systems, but in the last decade similar films have been reported to occur in solid-on-solid systems. While the situations in which the thickness of such films is of mesoscopic size are fairly well understood, an intriguing and yet to be fully understood aspect is the spreading of microscopic, i.e. molecularly thin, films. Here we review the available experimental observations of such films in various liquid-on-solid and solid-on-solid systems, as well as the corresponding theoretical models and studies aimed at understanding their formation and spreading dynamics. Recent developments and perspectives for future research are discussed.     

A mesoscopic model for (de)wetting

We present a mesoscopic model for simulating the dynamics of a non-volatile liquid on a solid substrate. The wetting properties of the solid can be tuned from complete wetting to total non-wetting. This model opens the way to study the dynamics of drops and liquid thin films at mesoscopic length scales of the order of the nanometer. As particular applications, we analyze the kinetics of spreading of a liquid drop wetting a solid substrate and the dewetting of a liquid film on a hydrophobic substrate. In all these cases, very good agreement is found between simulations and theoretical predictions.     

Ageing in granular aluminium insulating thin films

We present a new set of electrical field effect measurements on granular aluminium insulating thin films. We have explored how the conductance relaxations induced by gate voltage changes depend on the age of the system, namely the time elapsed since its quench at low temperature. A clear age dependence of the relaxations is seen, qualitatively similar to ageing effects seen in other well studied glassy systems such as spin glasses or polymers. We explain how our results differ from the previous ones obtained with different protocols in indium oxide and granular aluminium thin films. Our experimental findings bring new information on the dynamics of the system and put new constraints on the theoretical models that may explain slow conductance relaxations in disordered insulators.     

Dynamics and instability of solid-state dewetting

Spontaneous dewetting of solid thin films proceeds by edge retraction of film edges and/or by heterogeneous void growth. Classical 1D and 2D continuous models of the evolution of a dewetting film, based on surface diffusion mechanisms, predict that in the long-time limit dewetting obeys universal scaling laws. In this paper, we review 1D and 2D predictions and recent experimental results. For this purpose, using Si(001)/SiO₂ and Ge(001)/SiO₂ single-crystalline thin films in different geometries, we have been able to compare theoretical predictions to experimental results obtained by combining in situ LEEM and ex situ AFM measurements. For dewetting from film edges, experimental results partially differ from continuous models predictions. More precisely, because of the crystallographic anisotropy: (i) the facetted edges remain stable during dewetting (they simply recede at constant shape) while poorly or un-facetted edges are unstable (they recede by finger formation); (ii) rim formation, induced by mass-conservation condition, proceeds in a layer-by-layer mode and is limited by 2D nucleation properties on the top of the rim; (iii) the island generation mechanism differs from the mass shedding behaviour predicted by 1D models. For dewetting mechanisms involving void growth, different behaviours are reported and discussed. For thin Si(001)/SiO₂ films, the corners of the opening square-shaped voids lead to a local destabilisation of the growing voids. For thin Ge(001)/SiO₂ films, the side of the voids invariably turns instable and forms tip dendrites whose branch density depends on the temperature and the initial film thickness. Finally, ultra-thin films, more sensitive to local fluctuations, dewet in a fractal geometry.     

Development of a scanning microscopy by total internal reflection coupled with thermal lens spectroscopy

Non-destructive measurement of a small region on a solid/liquid interface is of great importance in physical chemistry and biochemistry, especially in the research of thin films and cell membranes. Optical methods for surface analysis with high lateral resolution are suitable methods for monitoring them. We now report a new scanning optical microscopic method to which total internal reflection coupled with a thermal lens technique was introduced. Its lateral resolution was estimated both experimentally and theoretically. To experimentally estimate the resolution, the grid patterns of thin photoresist films with well-defined lateral structures were measured. The experimental resolution was about 45 microm, which was almost same as the diameter of the excitation beam at a glass/sample interface. From this result, it was verified that this new scanning microscopy ideally worked.     

Editorial: Special issue on Properties of Thin Polymer Films

The behavior of polymers in thin films or close to interfaces is far from being understood. Many observations, encompassing both structural and dynamical behavior, indicate that the properties of polymers in thin films deviate from what we know from the bulk. Questions about the density (irreversible and reversible changes after annealing even above the bulk glass transition temperature), film stability and dewetting, glass transition temperature, diffusion coefficient and chain conformation and relaxation are intensively debated. In particular, it is not yet clear how the size of such chain-like molecules (their molecular weight) comes into play, especially if the thickness of the film is less than the radius of gyration of these macromolecules. In addition, due to the high surface-to-volume ratio the influence of surface and interfacial properties becomes important if not dominant. This interfacial sensitivity highlights the importance of the properties of the near surface region in polymer films; a topic whose importance is beginning to be recognized. This special issue presents experimental and theoretical works on a variety of questions related to polymers at interfaces and in thin films, ranging from space-averaged properties like adhesion to surface ordering or dynamic molecular (segmental) motion in confining geometries. Since the first reports of anomalous dynamics in thin polymer films almost a decade ago, the subject of dynamics in thin films has gained considerable momentum. Until very recently, this body of work focused almost solely on measurements of the thermodynamic signature of the kinetic glass transition. Such measurements are, at best, a very indirect probe of the microscopic dynamics and convolute the temperature dependence, time dependence and sometimes even the thermal history into a single measured value. The articles focusing on dynamics in thin films published in this special issue illustrate an important shift in this rapidly evolving field. There is now a strong focus on many different fronts. Measurements of dynamics are more varied, ranging from indirect studies such as adhesion to direct measurement of the segmental relaxation using dielectric spectroscopy. There is a concerted effort now to draw analogies to bulk systems in order to learn about what effects may contribute to the observation made in thin films. There is also a strong effort using numerical simulations to make quite direct comparisons to measured values in thin films. Finally, in a way that signals a new maturity to this field, a significant fraction of literature being currently published concerns ideas as to why the dynamics in thin films behave the way they do. In this special issue we have aimed at capturing a cross-section of problems of high current interest. While all contributions definitely provide highly valuable insight in the behavior of polymers in thin films, many questions are still unanswered and await further in-depth-going studies. We just want to note a few of these questions, also highlighted in several commentaries published in this issue: Can polymers in experimental studies on thin films ever be fully equilibrated? What is the relaxation behavior of macromolecules in confining geometries with interacting boundaries? How does the relaxation behavior depend on the length scale over which it is measured? What are the mechanical properties of thin polymer films? We tried to assemble different approaches and opinions from various viewpoints. We hope that such a complementary presentation is helpful and stimulates further discussions in order to dissolve some of the confusion in this area, leading eventually to a clear understanding of thin-film properties of polymers. The European Physical Journal E - Soft Matter will continue to provide a forum for the discussion of such questions and a place for the publication of future work on properties of polymers in thin films for all colleagues interested in these questions. Günter Reiter (Editor) James Forrest (Guest Editor)     

Dewetting patterns and molecular forces: a reconciliation.

We studied the dewetting of thin liquid polymer films from solid surfaces. Our experimental results lead to a consistent picture demonstrating the interplay between short- and long-range interfacial forces. Observations comprise nucleation and spinodal dewetting, as well as thermal nucleation of holes. The effective interface potential of the system, as reconstructed from the morphology of the dewetting patterns, agrees quantitatively with what is computed from the optical properties of the system. This shows that the assumption of additivity of dispersion potentials in multilayer systems yields good results.     

尺寸效应对微通道内固液界面温度边界的影响

采用非平衡分子动力学方法模拟不同浸润性微通道内液体的传热过程,分析了尺寸效应对固液界面热阻及温度阶跃的影响.研究结果表明,界面热阻随微通道尺寸的变化可分为两个阶段,即小尺寸微通道的单调递增阶段和大尺寸微通道的恒定值阶段.随着微通道尺寸的增加,近壁区液体原子受对侧固体原子的约束程度降低,微通道中央的液体原子自由移动,固液原子振动态密度近似不变,使得尺寸效应的影响忽略不计.上述两种阶段的微通道尺寸过渡阈值受固液作用强度与壁面温度的共同作用:减弱壁面浸润性,过渡阈值向大尺寸区域迁移;相较于低温壁面,高温壁面处的过渡阈值更大.增加微通道尺寸,固液界面温度阶跃呈单调递减趋势,致使壁面温度边界和宏观尺度下逐渐符合.探讨尺寸效应有助于深刻理解固液界面能量输运及传递机制.     

Improved liquid－solid－gas interface deposition of nanoparticle thin films

A liquid－solid－gas interface deposition method to prepare nanoparticle thin films is presented in this paper. The nanoparticles in the part of suspension located close to the solid－liquid－gas interface grow on the substrate under the influence of interface force when the partially immersed substrate moves relatively to the suspension. By using statistical theory of the Brownian motion, growth equations for mono-component and multi-component nanoparticle thin films are obtained and some parameters for deposition process are discussed.     

基底上覆分层薄膜超声Scholte波特性与薄膜定征

分层薄膜-基底结构广泛应用于微电子器件等诸多领域,但薄膜材料参数超声测量尤其是横波速度的定征是一个困难的问题。本文对液固界面Scholte界面波的频散特性和脉冲激励的声压响应进行了理论分析。结果表明,液固界面Scholte波频散与分层膜-基底结构的速度分布密切相关。薄膜材料各层的厚度和横波速度对界面波频散特性有显著影响。基于Scholte界面波的频散特性,提出了一种多层膜的多参数反演定征方法。首先针对理论信号进行薄膜参数反演,验证了该方法的可行性。后续对不同类型的多层膜材料样品进行了液固界面波激发与采集实验,实验信号的薄膜参数反演结果进一步验证了该方法的可行性和有效性。     

Nano- and microstructured polymer LB layers: A combined AFM/SIMS study

Ultra thin structured polymer films have been prepared by horizontal precipitation Langmuir-Blodgett (HP-LB) method of polymer blends. In particular we used mixtures of two incompatible polymers, poly-2-vinylpyridine and polystyrene, the former giving the necessary surface activity for LB film formation. Upon spreading at the air-water interface, the blend forms different surface structures depending on the relative amount of the two components. By adjusting the experimental parameters it is possible to obtain relatively regular structures in the submicron size range, which can be transferred on a solid substrate. These systems have been investigated by means of SIMS and atomic force microscopy.     

Stability of thin nematic films

We discuss the peculiarity of thin nematic films on solid substrates with a free surface, underlining the differences with what is usually seen in dewetting. We review the thermodynamic basis of the coupled phase/thickness separation that has previously been shown experimentally. We give new experimental evidences for the origin of the coupling force chosen in our previous theoretical model. This additional information contributes to the discussion raised by the article of Ziherl and Zumer in this issue [19].Received: 3 December 2003PACS: 68.15. + e Liquid thin films - 64.70.Md Transitions in liquid crystals - 61.30 Surface phenomena in liquid crystals including anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions and wetting transitions     

Molecular dynamics simulation of Ga penetration along grain boundaries in Al: a dislocation climb mechanism

Many systems where a liquid metal is in contact with a polycrystalline solid exhibit deep liquid grooves where the grain boundary meets the solid-liquid interface. For example, liquid Ga quickly penetrates deep into grain boundaries in Al, leading to intergranular fracture under very small stresses. We report on a series of molecular dynamics simulations of liquid Ga in contact with an Al bicrystal. We identify the mechanism for liquid metal embrittlement, develop a new model for it, and show that is in excellent agreement with both simulation and experimental data.     

Partially wetting thin liquid films: structure and dynamics studied with coherent x rays

We studied the surface structure of thin liquid films vapor deposited on solid substrates in a partial wetting situation by means of coherent x-ray scattering. No dynamics has been observed showing the absence of capillary waves on liquid films partially wetting a substrate. Instead an exponential form of the height-height correlation function has been found pointing toward a solidlike behavior of the thin liquid films at large length scales. The exact surface structure and degree of replication with the substrate depend on the deposition rate of the molecules.     

Electrical conductivity of multi-layered metallic thin films

Multi-layered metallic thin films have quite unique properties such as electrical conductivity because of their enhanced interactions at the interfaces between different metals. A theoretical solution has been derived for the distribution functions of the conduction electrons, through Boltzmann's equation and certain interface boundary conditions. The solution of the electrical conductivity for the multi-layered metallic thin films is given.     

Power laws in surface physics: the deep, the shallow and the useful

The growth and dynamics of solid surfaces displays a multitude of power law relationships, which are often associated with geometric self-similarity. In many cases the mechanisms behind these power laws are comparatively trivial, and require little more than dimensional analysis for their derivation. The information of interest to surface physicists then resides in the prefactors. This point will be illustrated by recent experimental and theoretical work on the growth-induced roughening of thin films and step fluctuations on vicinal surfaces. The conventional distinction between trivial and nontrivial power laws will be critically examined in general, and specifically in the context of persistence of step fluctuations.