Stability of ultrathin nanocomposite polymer films controlled by the embedding of gold nanoparticles.

Thin and ultrathin polymer films combined with nanoparticles (NPs) are of significant interest as they are used in a host of industrial applications. In this paper we describe the stability of such films (hpoly ≤ 30 nm) to dewetting, specifically, how the development of a spinodal instability in a composite NP-polymer layer is controlled by the embedding of Au NPs. At working temperatures (T = 170 °C) above the polymer glass transition temperature (Tg ≈ 100 °C) the absence of Au NPs leads to film rupture by nucleation dewetting, while their presence over a large surface area enhances the development of a spinodal instability without destroying the film continuity. When the NPs embed, the surface undulations are suppressed. The dynamics change from an unstable to a stable state, and the thin composite NP-polymer layer returns to a flat configuration, while the wavelength of the pattern remains constant. Moreover, we demonstrate from a thermodynamic perspective that NPs will remain on the surface or embed in the polymer film depending on their free energy, which is determined by the NP interactions with the underlying polymer, the native SiOx layer, and the Si substrate.

Fractal patterning of nanoparticles on polymer films and their SERS capabilities.

We demonstrate control, via electro-hydrodynamic (EHD) induced polymer instabilities and nanoparticle mobility, of hierarchical fractal arrangements of gold nanoparticles on patterned thin polymer films. The induced changes in the film curvature enhance fractal formation for high and not for low mobility nanoparticles. The high mobility nanoparticles cluster in circular fractal networks on the rims of a hexagonally ordered array of EHD-induced polymer peaks. These arrangements exhibit plasmonic properties for surface-enhanced Raman scattering (SERS) spectroscopy.

Effect of Au nanoparticle spatial distribution on the stability of thin polymer films.

The stability of thin poly(methyl-methacrylate) (PMMA) films of low molecular weight on a solid substrate is controlled by the areal coverage of gold nanoparticles (NPs) present at the air-polymer interface. As the polymer becomes liquid the Au NPs are free to diffuse, coalesce, and aggregate while the polymer film can change its morphology through viscous flow. These processes lead at the same time to the formation of a fractal network of Au NPs and to the development of spinodal instabilities of the free surface of the polymer films. For thinner films a single wavelength is observed, while for thicker films two wavelengths compete. With continued heating the aggregation process results in a decrease in coverage, the networks evolve into disordered particle assemblies, while the polymer films flatten again. The disordering occurs first on the smallest scales and coincides (in thicker films) with the disappearance of the smaller wavelength. The subsequent disordering on larger scales causes the films to flatten.

On-off intermittency and criticality in early stage electromigration.

We have studied here using high resolution resistance measurements the time and statistical behavior of abrupt resistance changes in a thin metal aluminum film undergoing electromigration. We reveal for the first time that early stage electromigration exhibits on-off intermittency. The intermittent resistance fluctuations are also shown to be scale invariant, an effect seen in the fluctuations of several physical systems including earthquakes, superconductor dynamics and stock markets. Finite size scaling of the resistance fluctuations demonstrates that they originate near a critical point.

State Key Laboratory of Nonlinear Mechanics (LNM), Institute of Mechanics, Chinese Academy of Sciences, Beijing 100080, China.

This paper reviews current state-of-the-art methods of measuring pH levels that are based on polymer materials. These include polymer-coated fibre optic sensors, devices with electrodes modified with pH-sensitive polymers, fluorescent pH indicators, potentiometric pH sensors as well as sensors that use combinatory approach for ion concentration monitoring.

pH Sensitivity of Novel PANI/PVB/PS3 Composite Films.

This paper reports on the results from the investigation into the pH sensitivity ofnovel PANI/PVB/PS3 composite films. The conductimetric sensing mode was chosen as itis one of the most promising alternatives to the mainstream pH-sensing methods and it is theleast investigated due to the popularity of other approaches. The films were deposited usingboth screen-printing and a drop-coating method. It was found that the best response to pHwas obtained from the screen-printed thick films, which demonstrated a change inconductance by as much as three orders of magnitude over the pH range pH2-pH11. Thedevices exhibited a stable response over 96 hours of operation. Several films were immersedin buffer solutions of different pH values for 96 hours and these were then investigated usingXPS. The resulting N 1s spectra for the various films confirmed that the change inconductance was due to deprotonation of the PANI polymer backbone. SEM andProfilometry were also undertaken and showed that no considerable changes in themorphology of the films took place and that the films did not swell or contract due toexposure to test solutions.