Residual stress, a pervasive consequence of solid materials processing, is stress that remains in a material after external forces have been removed. In polymeric materials, residual stress results from processes, such as film formation, that force and then trap polymer chains into nonequilibrium stressed conformations. In solvent-cast films, which are central to a wide range of technologies, residual stress can cause detrimental effects, including microscopic defect formation and macroscopic dimensional changes. Since residual stress is difficult to measure accurately, particularly in nanoscale thin polymer films, it remains a challenge to understand and control. We present here a quantitative method of assessing residual stress in polymer thin films by monitoring the onset of strain-induced wrinkling instabilities. Using this approach, we show that thin (>100 nm) polystyrene films prepared via spin-coating possess residual stresses of approximately 30 MPa, close to the crazing and yield stress. In contrast to conventional stress measurement techniques such as wafer curvature, our technique has the resolution to measure residual stress in films as thin as 25 nm. Furthermore, we measure the dissipation of residual stress through two relaxation mechanisms: thermal annealing and plasticizer addition. In quantifying the amount of residual stress in these films, we find that the residual stress gradually decreases with increasing annealing time and plasticizer amounts. Our robust and simple route to measure residual stress adds a key component to the understanding of polymer thin film behavior and will enable identification of more effective processing routes that mitigate the detrimental effects of residual stress.

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Quantifying residual stress in nanoscale thin polymer films via surface wrinkling.

Thermal annealing is one of the most indispensable polymer fabrication processes and plays essential roles in controlling morphologies and properties of polymeric materials. We here report that thermal annealing also facilitates polymer adsorption from the melt on planar silicon (Si) substrates, resulting in the formation of a high-density polymer nanolayer with flattened chain confirmations. Three different homopolymers (polystyrene, poly(2-vinylpyridine), and poly(methyl methacrylate)), which have similar inherent stiffness and bulk glass transition temperature (Tg), but have different affinities with Si substrates, were chosen as models. Spin-cast films (∼50 nm in thickness) with the three polymers were prepared on cleaned Si substrates and then placed in a vacuum oven set at a temperature far above the bulk Tg. In order to monitor the polymer adsorption process at the solid-polymer melt interface during thermal annealing, we used the protocol that combines vitrification of the annealed films (via rapi...

Formation Mechanism of High-Density, Flattened Polymer Nanolayers Adsorbed on Planar Solids

The free surface of a thin soft polymer film is often found to become unstable and self-organizes into various meso-scale structures. In this article we classify the instability of a thin polymer film into three broad categories, which are: category 1: instability of an ultra-thin (<100 nm) viscous film engendered by amplification of thermally excited surface capillary waves due to interfacial dispersive van der Waals forces; category 2: instability arising from the attractive inter-surface interactions between the free surface of a soft film exhibiting room temperature elasticity and another rigid surface in its contact proximity; and category 3: instability caused by an externally applied field such as an electric field or a thermal gradient, observed in both viscous and elastic films. We review the salient features of each instability class and highlight how characteristic length scales, feature morphologies, evolution pathways, etc. depend on initial properties such as film thickness, visco-elasticity (rheology), residual stress, and film preparation conditions. We emphasize various possible strategies for aligning and ordering of the otherwise isotropic structures by combining the essential concepts of bottom-up and top-down approaches. A perspective, including a possible future direction of research, novelty and limitations of the methods, particularly in comparison to the existing patterning techniques, is also presented for each setting.

Instability, self-organization and pattern formation in thin soft films.

This paper reports a simple and flexible method for generating hierarchical patterns from wrinkling instability. Complex features with gradually changing topographies are generated by using the spontaneous wrinkling of a rigid membrane (titanium) on a soft foundation (polystyrene) compressed via the diffusion of a solvent. We show that the morphology of these unreported wrinkled patterns is directly related to the rheological properties of the polymer layer and the geometry of the diffusion front. Based on these ingredients, we rationalize the mechanism for the formation of hierarchical wrinkling patterns and quantify our experimental findings with a simple scaling theory. Finally, we illustrate the relevance of our structuration method by studying the mechanosensitivity of fibroblasts.

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Hierarchical wrinkling patterns

We investigate the influence of gold nanoparticle addition on the stability, dewetting, and pattern formation in ultrathin polymer−nanoparticle (NP) composite films by examining the length and time scales of instability, morphology, and dynamics of dewetting. For these 10−50 nm thick (h) polystyrene (PS) thin films containing uncapped gold nanoparticles (diameter ∼3−4 nm), transitions from complete dewetting to arrested dewetting to absolute stability were observed depending on the concentration of the particles. Experiments show the existence of three distinct stability regimes: regime 1, complete dewetting leading to droplet formation for nanoparticle concentration of 2% (w/w) or below; regime 2, partial dewetting leading to formation of arrested holes for NP concentrations in the range of 3−6%; and regime 3, complete inhibition of dewetting for NP concentrations of 7% and above. Major results are (a) length scale of instability, where λH ∼ hn remains unchanged with NP concentration in regime 1 (n ∼ 2) ...

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Stability and dewetting of metal nanoparticle filled thin polymer films: control of instability length scale and dynamics

Performing detailed studies of viscoelastic dewetting of thin polystyrene films on solid substrates, we demonstrate the existence of residual stress due to strongly out of equilibrium chain conformations and a reduced entanglement density resulting from film preparation by spin coating. The ratio of stress over elastic modulus was found to increase strongly with decreasing film thickness and increasing chain length. Full equilibration of chain conformations required long times comparable to bulk reptation times. However, for chains longer than about 3000 monomers, the residual stress relaxed faster, at a rate independent of chain length.

Giinter Reiter

Papers

Relaxation of residual stress and reentanglement of polymers in spin-coated films.