As technology continues towards smaller, thinner and lighter devices, more stringent demands are placed on thin polymer films as diffusion barriers, dielectric coatings, electronic packaging and so on. Therefore, there is a growing need for testing platforms to rapidly determine the mechanical properties of thin polymer films and coatings. We introduce here an elegant, efficient measurement method that yields the elastic moduli of nanoscale polymer films in a rapid and quantitative manner without the need for expensive equipment or material-specific modelling. The technique exploits a buckling instability that occurs in bilayers consisting of a stiff, thin film coated onto a relatively soft, thick substrate. Using the spacing of these highly periodic wrinkles, we calculate the film's elastic modulus by applying well-established buckling mechanics. We successfully apply this new measurement platform to several systems displaying a wide range of thicknessess (nanometre to micrometre) and moduli (MPa to GPa).
Charged poly(amidoamine) (PAMAM) dendrimers are used to create organic-inorganic hybrid colloids in aqueous solution. The formation of gold colloids upon reduction of a gold salt precursor serves as a model reaction to study the influence of reaction conditions and dendrimer generation on the resulting nanostructures. Characterization by transmission electron microscopy (TEM), small-angle neutron scattering (SANS), and small-angle X-ray scattering (SAXS) show that the gold particles are formed inside the dendrimer and located offset from the center. Although lower generation dendrimers aggregate when stabilizing the metal particles formed, dendrimers of generation 6-9 can template one gold colloid per dendrimer molecule, the size of which is well-controlled by the number of gold atoms added per dendrimer. For generation 10, multiple smaller gold particles per dendrimer are observed. The effectiveness of PAMAM dendrimers as templates in the host-guest nanoscale synthesis is confirmed for different chemical reactions.
We utilize chemically patterned substrates with arrays of progressively narrower stripes (1-15 µm) to investigate the influence of pattern size on the morphology of ultrathin dewetting polystyrene films. The scale and orientation of the spinodal-like height fluctuations of the dewetting patterns are coupled to the imposed substrate chemical frequency, providing a powerful means of morphological control. Dewetting patterns are correlated to the substrate pattern period leading to the formation of droplet arrays. The measurements confirm recent numerical simulations by Kargupta and Sharma of the existence of upper and lower cutoff scales for pattern recognition of a dewetting fluid. For pattern dimensions less than the characteristic scale on nonpatterned substrates, the droplets become anisotropic as they coarsen to a scale comparable to the stripe width, and then undergo a morphological transition to circular droplets that cross multiple stripes. This leads to quantization of droplet size and contact angles, as indicated by theory.
Combinatorial methods involving data collection in multiparameter space allow a rapid identification of measured property trends as a function of system parameters. The technique has been applied with success to pharmaceutical, inorganic and organic materials synthesis, but not significantly to measurements of polymeric films and coatings. We demonstrate the use of 2-D combinatorial libraries to investigate thin-film dewetting. We have prepared libraries of thin films of polystyrene on silicon substrates containing orthogonal, continuous variations of thickness (h), and temperature (T) that represent about 1200 practical state points per library. The libraries were screened for dewetting behavior using automated optical microscopy. Dewetting trends were visibly apparent on the libraries, and a comprehensive map of the T, h, and time (t) dependence was generated in a few hours. The combinatorial libraries, spanning a large T, h, and t range, not only reproduced known dewetting structures and phenomena but also enabled a novel T, h superposition of the heterogeneous nucleated hole dewetting kinetics. We observed three hole nucleation regimes as a function of thickness: heterogeneously nucleated holes (h > 55 nm), a crossover regime where both heterogeneous and capillary instability nucleation compete (33 nm < h < 55 nm), and a regime of holes nucleated by capillary instability (16 nm < h < 33 nm).
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