Viscoelastic dynamics of polymer thin films and surfaces

The strain relaxation behavior in a viscoelastic material, such as a polymer melt, may be strongly affected by the proximity of a free surface or mobile interface. In this paper, the viscoelastic surface modes of the material are discussed with respect to their possible influence on the freezing temperature and dewetting morphology of thin polymer films. In particular, the mode spectrum is connected with mode coupling theory assuming memory effects in the melt. Based on the idea that the polymer freezes due to these memory effects, surface melting is predicted. As a consequence, the substantial shift of the glass transition temperature of thin polymer films with respect to the bulk is naturally explanied. The experimental findings of several independent groups can be accounted for quantitatively, with the elastic modulus at the glass transition temperature as the only fitting parameter. Finally, a simple model is put forward which accounts for the occurrence of certain generic dewetting morphologies in thin liquid polymer films. It demonstrates that by taking into account the viscoelastic properties of the film, a morphological phase diagram may be derived which describes the observed structures of dewetting fronts. It is demonstrated that dewetting morphologies may also serve to determine nanoscale rheological properties of liquids.Received: 1 January 2003, Published online: 14 October 2003PACS: 47.50. + d Non-Newtonian fluid flows - 68.47.Mn Polymer surfaces - 68.60.Dv Thermal stability; thermal effects     

Hole formation in thin polymer films: a two-stage process

Thin, supported liquid films are known to rupture, creating holes throughout the film, due to defects or to van der Waals interactions. We show that the hole formation process before rupturing occurs in two stages, each characterized by distinct dynamical and morphological features. The time scale for the formation process is orders of magnitude slower than the translational (reptation) relaxation time of the individual chains. This has implications regarding the transition from the formation regime to subsequent hole growth regime on the underlying substrate.     

Low energy muons as probes of thin films and surfaces

Polarized muons with kinetic energies of a few eV (epithermal μ⁺) can be generated by slowing down energetic muons in appropriate moderators consisting of a thin layer of a van der Waals gas frozen on a substrate. The availability of polarized muons with kinetic energies in the eV to several keV range opens the possibility to extend the μSR technique to the study of thin films and surfaces (low energy μSR, LE-μSR). We summarize the characteristics of the very slow polarized muons and of a low energy beam based on the moderation technique. We discuss the implantation of muons in thin film samples and the potential and limitations of LE-μSR. As an example first results obtained by implanting slow μ⁺ in a sample consisting of a Ni film deposited on Ag are presented.     

Positronium as a probe of sorption states of vapor molecules in polymers

Positron lifetime measurements were performed for two different polymers (low density polyethylene and a polyimide 6FDA-TMPD) during sorption of various vapors (n-hexane, cyclohexane, benzene, acrylic acid, methyl acrylate). The vapor sorption affected the long-lived component (ortho-positronium component) in a systematic way regardless of the kind of vapor, i.e. for the polyethylene both the lifetime and the intensity of the long-lived component were enhanced, while for the polyimide they were decreased significantly. These different effects are interpreted in terms of the different aggregation states, i.e. rubbery for the polyethylene and glassy for the polyimide.     

Polyaniline films with nanostructure used as neural probe coating surfaces

Polyaniline (PANi) films with high conductivity and nanostructure were prepared by a modified dipping method using four acids on a polytetrafluoroethylene (PTFE) substrate. The “doping-dedoping-redoping” process was carried out to investigate whether the electrical and surface properties of PANi coating could be changed. We found that the conductivity decreased with prolonged immersing time in both water and DMEM, until the PANi films were almost non-conductive. The as-prepared PANi films were hydrophilic, and the immersing treatment with DMEM made them hydrophobic. Moreover, they recovered their hydrophilicity following the redoping treatment. The morphologies of the PANi films became heterogeneous after the immersing-redoping treatment. These results provide a good reference for the use of conducting polymers as a neural probe coating.     

Dewetting of thin polymer films

We study the dewetting of thin polymer films deposited on slippery substrate. Recent experiments on these systems have revealed many unexpected features. We develop here a model that takes into account the rheological properties of polymer melts, focussing on two dewetting geometries (the receding of a straight edge, and the opening of a hole). We show that the friction law associated with the slippage between the film and the substrate has a direct influence on the dewetting dynamic. In addition, we demonstrate that residual stresses, which can be stored in the films due to their viscoelasticity, are a source of destabilization for polymer films, and accelerate the dewetting process.     

Self-organized semiconductor surfaces as templates for nanostructured magnetic thin films

Spontaneous pattern formation during epitaxial growth or ion erosion of semiconductor wafers offers an elegant route towards large-area nanostructured surfaces. In homoepitaxy, kinetics may result in rather uniform three-dimensional islands. In the case of semiconductor heteroepitaxy, strain relief leads to the formation of nanofaceted three-dimensional crystallites, which may self-organize into quasiperiodic arrays. By tuning substrate miscut and film thickness, or growing superlattices, a variety of patterns with different symmetries can be obtained, as will be summarized for the model system of SiGe on Si(001). Since these self-organized nanostructure arrays cover the entire wafer on which they are grown, they can serve as large-area nanopatterned substrates for subsequent deposition of magnetic thin films. It will be demonstrated that such templates allow the study of correlations between magnetic and chemical interfacial roughness, as well as the influence of pattern symmetry on the magnetic anisotropy of thin Co films. Furthermore, shadow deposition of magnetic material onto specially faceted nanostructure arrays allows the fabrication of nanomagnet arrays and the study of their magnetic properties. Received: 31 July 2002 / Accepted: 2 October 2002 / Published online: 5 February 2003 RID="*" ID="*"Corresponding author. Fax: +43-3842/402-760, E-mail: teichert@unileoben.ac.at     

Electrical breakdown of thin polymer films

Data are presented on the dielectric strength of thin polymer films. The conclusion is drawn that the electron avalanche concept is inapplicable to the breakdown of thin films. It is proposed to consider electrical breakdown as a consequence of an abrupt local field enhancement induced by evolution of the space charge injected into the polymer from electrodes. It is shown that the lifetime of polymer films depends exponentially on electric field strength.     

Stability of thin polymer films on a corrugated substrate

We study the wetting behaviour of thin polystyrene (PS) films on regularly corrugated silicon substrates. Below a critical film thickness the PS films are unstable and dewet the substrates. The dewetting process leads to the formation of nanoscopic PS channels filling the grooves of the corrugated substrates. Films thicker than the critical thickness appear stable and follow the underlying corrugation pattern. The critical thickness is found to scale with the radius of gyration of the unperturbed polymer chains. Received 6 April 2000 and Received in final form 24 August 2000     

Structural relaxation of spin-cast glassy polymer thin films as a possible factor in dewetting

Reiter [1] has recently reported a situation in which the dewetting of quasi-solid films is linked to plastic deformation - rather than viscous flow - resulting from capillary forces. Herein we propose that, in thin films of some glassy polymers - especially poly(methyl methacrylate) (PMMA) - prepared by spin-casting from solvent, structural relaxation might impart sufficient stress to cause plastic deformation. We find that PMMA films decrease in thickness by several percent, which is sufficient to create significant stress in those cases in which the film is attached to a rigid substrate. The floating technique, which can take tens of minutes, might allow most of the structural relaxation to occur prior to dewetting experiments.Received: 1 August 2003PACS: 65.40.De Thermal expansion; thermomechanical effects - 82.60.Lf Thermodynamics of solutions - 61.41. + e Polymers, elastomers, and plasticsM. Sferrazza: Current address: Département de Physique, Université Libre de Bruxelles, Boulevard du Triomphe, CP223, 1050 Bruxelles, Belgium     

Morphological characterization of ITO thin films surfaces

In this study, indium tin oxide (ITO) thin films were deposited by electron beam evaporation method on glass substrates at room temperature, followed by postannealing at 200 and 300 °C for annealing time up to 1 h. Fractal image processing has been applied to describe the surface morphology of ITO thin films from their atomic force microscopy (AFM) images. These topographical images of the ITO thin films indicate changes in morphological behavior of the film. Also, the results suggest that the fractal dimension D can be used to explain the change of the entire grain morphology along the growth direction.     

Acoustic instabilities in thin polymer films

The spatial confinement of a fluctuation spectrum leads to forces at the confining boundaries. While electromagnetic (EM) fluctuations lead to the well-known dispersion forces, the acoustic analogy has widely been neglected. We show that the strength of the forces resulting from confined acoustic modes may be of the same order of magnitude as van der Waals forces. Additionally, the predicted scaling behavior is identical to the non-retarded case of the EM fluctuations. Our results suggest that dewetting experiments using polymer films are strongly influenced by the acoustic dispersion forces. Received 5 March 2002 and Received in final form 21 May 2002     

Molecular mobility in polymer thin films

Fluorescence recovery after photobleaching was used to measure in-plane dye-probe diffusion coefficients, D, in thin films of monodisperse polystyrene supported on fused quartz substrates. The substrates were prepared with a high density of surface hydroxyl groups which interact favorably with repeat units of the polymer. The effects of temperature and film thickness were investigated, at temperatures above the bulk glass transition of the polymer, T(g), and in the range of film thicknesses from 1-10(2) times the radius of gyration (R(g)) of individual polymer molecules. As the film thickness decreases towards R(g) the value of D increases above the bulk values, with significant effects first appearing in films approximately 20R(g). In the thinnest films studied, about 4R(g), the values of D lie as much as two orders over bulk values. At the same time, the temperature dependence of D becomes much weaker than in bulk. Analysis by free volume theory indicates that apparent values of both T(g) and the thermal expansion coefficient for liquid state, alpha(L), decrease as the film thickness decreases. The possible effects of surface segregation of the dye probe are discussed.     

Reduced viscosity in thin polymer films

The dewetting of thin polystyrene films (20-500 nm) on a liquid substrate is studied at time scales that are long compared to the reptation time. It is shown that the kinetics correspond to those of purely viscous flow and that the viscosity measured by this technique is, for the thickest films, consistent with bulk measurements. Films on the order of the coil size are then studied. The effective viscosity of these films displays a large decrease when the film thickness h is below several radius of gyration, R(g). This viscosity reduction is found to depend only on the ratio h/R(g).     

Glass transitions in thin polymer films

Freely standing polystyrene films show an anomalous drop of the glass temperature when the molecular weight is high and the thickness smaller than the coil size R₀. We present here a tentative explanation for these features, where two types of motions compete: a) standard motions, controlled by the free volume, and independent of chain length, b) collective motions along the chain, which require a weaker free volume (except for the end groups). For bulk systems, the standard motion always wins because of the end group hindrance. But for films thinner than the coil size, the dominant process may be the collective motion of a “loop” which does not involve the chain ends. What matters then is not the overall polymerisation index (N), but the length g of a typical loop starting from the surface (which is a more fluid region) and reaching deep into the film. With these ingredients, some surprising aspects of may possibly be understood. Received 7 December 1999