Laser-induced ablation dynamics and flight of thin polymer films

We investigated the ejection dynamics of triazene polymer layers in the thickness range of 40 nm to 600 nm upon nanosecond laser ablation at a wavelength of 532 nm. The ablation is due to laser-induced thermal degradation of a small part of the polymer in contact with the silicon substrate. The subsequent dynamics of the flying polymer layer are measured with sub-nanosecond time resolution. The evaluation of the initial velocity for different film thicknesses gives insight into the energy transfer process during the acceleration of the films.     

Probing slow dynamics in supported thin polymer films

We have used variable cooling rate ellipsometric measurements to probe the slow dynamics in thin supported polystyrene films. For the slowest cooling rates (approximately 1 K/min) the measured Tg values are reduced below the bulk value with the measured Tg of 341 K for a 6 nm film. As the cooling rate is increased the Tg reductions become smaller until at cooling rates >90 K/min there is only slight evidence for a film-thickness-dependent Tg value. By relating the cooling rate to a relaxation time, we show that the relaxation dynamics of the thin films appears to become Arrhenius with an activation energy that decreases with decreasing film thickness. We discuss this in terms of a possible connection to a length scale for cooperative motion. Finally, the results can be used to resolve a number of outstanding contradictory reports in the literature.     

Glass transitions and dynamics in thin polymer films: dielectric relaxation of thin films of polystyrene

The glass transition temperature T(g) and the temperature T(alpha) corresponding to the peak in the dielectric loss due to the alpha process have been simultaneously determined as functions of film thickness d through dielectric measurements for polystyrene thin films supported on glass substrate. The dielectric loss peaks have also been investigated as functions of frequency for a given temperature. A decrease in T(g) was observed with decreasing film thickness, while T(alpha) was found to remain almost constant for d>d(c) and to decrease drastically with decreasing d for d相似文献   

On the dynamics and disentanglement in thin and two-dimensional polymer films

We present results from molecular dynamics simulations of strictly two-dimensional (2D) polymer melts and thin polymer films in a slit geometry of thickness of the order of the radius of gyration. We find that the dynamics of the 2D melt is qualitatively different from that of the films. The 2D monomer mean-square displacement shows a t^8/15 power law at intermediate times instead of the t^1/2 law expected from Rouse theory for nonentangled chains. In films of finite thickness, chain entanglements may occur. The impact of confinement on the entanglement length N_e has been analyzed by a primitive path analysis. The analysis reveals that N_e increases strongly with decreasing film thickness.     

Viscoelastic thin polymer films under transient residual stresses: two-stage dewetting on soft substrates

A nonmonotonic, two-stage dewetting behavior was observed for spin coated thin viscoelastic polymer films on soft elastic substrates. At times shorter than the relaxation time of the polymer (ttau_{rep}), dewetting accelerated, accompanied by an unstable rim. However, holes nucleated at t相似文献   

Heterogeneous nature of the dynamics and glass transition in thin polymer films

Recent experiments have demonstrated that the dynamics in liquids close to and below the glass transition temperature is strongly heterogeneous, on the scale of a few nanometers. We use here a model proposed recently for explaining these features, and show that the heterogeneous nature of the dynamics has important consequences when considering the dynamics of thin films. We show how the dominant relaxation time in a thin film is changed as compared to the bulk, as a function of the thickness, the interaction energy with the substrate, and the temperature. The corresponding time scales cover the so-called VFT (or WLF) regime and vary between 10^-8 s to 10⁴ s typically. In the absence of interaction, our model allows for interpreting suspended films experiments, in the case of small polymers for which the data do not depend on the polymer weight. The interaction leads to an increase of for an interaction per monomer of the order of the thermal energy T. This increase saturates at the value corresponding to strongly interacting films for adsorption energies slightly larger and still of order T. In particular, we predict that the shift can be non-monotonous as a function of the film thickness, in the case of intermediate interaction strength.Received: 1 July 2004, Published online: 26 October 2004PACS: 64.70.Pf Glass transitions - 61.41. + e Polymers, elastomers, and plastics - 68.15. + e Liquid thin films     

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.     

Surface dynamics of polymer films

The dynamics of supported polymer films were studied by probing the surface height fluctuations as a function of lateral length scale using x-ray photon correlation spectroscopy. Measurements were performed on polystyrene (PS) films of thicknesses varying from 84 to 333 nm at temperatures above the PS glass transition temperature. Within a range of wave vectors spanning 10(-3) to 10(-2) nm(-1), good agreement is found between the measured surface dynamics and the theory of overdamped thermal capillary waves on thin films. Quantitatively, the data can be accounted for using the viscosity of bulk PS.     

The origins of fast segmental dynamics in 2 nm thin confined polymer films

Molecular-Dynamics computer simulations were used to study 2 nm wide polystyrene films confined in slit pores, defined by inorganic crystalline surfaces. The simulated systems mimic experimentally studied hybrid materials, where polystyrene is intercalated between mica-type, atomically smooth, crystalline layers. A comparison between the experimental findings and the simulation results aims at revealing the molecular origins of the macroscopically observed behavior, and thus provide insight about polymers in severe/nanoscopic confinements, as well as polymers in the immediate vicinity of solid surfaces. Pronounced dynamic inhomogeneities are found across the 2 nm thin film, with fast relaxing moieties located in low local density regions throughout the film. The origins of this behavior are traced to the confinement-induced density inhomogeneities, which are stabilized over extended time scales by the solid surfaces. Received 9 August 2001 and Received in final form 7 January 2002     

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.     

Surface diffusivity of thin polymer films measured by a curvature driven flow and Rouse dynamics

Nanodefects induced by nanoindentation on thin polystyrene (PS) films spin cast on silicon (Si) relax upon annealing at 110 °C. The relaxation process for low molecular weight PS is interpreted in terms of a curvature driven flow which leads to the measurement of a diffusion coefficient. The latter is compared with the expected Rouse predictions using (i) bulk and (ii) surface glass transition temperature data, found in the literature. Deviations from the Rouse predictions are observed when is used for the analysis of the data. On the contrary, excellent agreement with the Rouse model is reported when is used.     

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     

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.     

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).