Use of polystyrene brushes to investigate the role of interface between substrates and thin homogeneous films

The viscoelastic properties of thin polystyrene (PS) films depend on confinement, as it can modify the molecular dynamics affecting the glass transition. In the recent past, the authors have investigated the region next to the free interface by means of an atomic force microscope suitably modified to monitor the indentation of a tip into a film during a given lapse of time while applying a constant load. Herein, to explore the interface with the substrate, the authors report on experiments in which PS brushes grafted to native silicon oxide were used. It was found that the film wettability on brushes and H‐terminated silicon can be highly improved when compared with native silicon oxide. In addition, the glass transition temperature of thin films increases up to the bulk value in the case of film/brush combinations with high molecular weight or films with high molecular weight on H‐terminated silicon. Data are discussed according to hypotheses such as residual solvent presence, interface free volume, and molecular mechanical coupling. These observations can be of great interest for nanotechnological applications, especially in those instances where one needs to tailor the temperature dependence of viscoelastic properties of thin films. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1149–1156     

Aggregation and fractal formation of Au and TiO<Subscript>2</Subscript> nanostructures obtained by fs-pulsed laser deposition: experiment and simulation

In the synthesis of nanostructures by pulsed laser deposition (PLD), a crucial role is played by the environmental deposition pressure and the substrate temperature. Due to the high temperature of nanoparticles (NPs) at landing, other factors may determine the structure of the resulting aggregates. Here, Au and TiO₂ nanostructures are obtained by non-thermal fs-PLD in ambient conditions. On Si(100), only TiO₂ NPs form fractals with areas up to ~ 1 × 10⁶ nm², while on quartz Au NPs also form fractals with areas up to ~ 5 × 10³ nm², a much smaller size with respect to the TiO₂ case. The aggregation is described by a simple diffusive model, taking into account isotropic diffusion of the NPs, allowing quantitative simulations of the NPs and fractal area. The results highlight the key role of substrate thermal conductivity in determining the formation of fractals.

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Influence of a reduced mobility layer on the structural relaxation dynamics of aluminum capped ultrathin films of poly(ethylene terephthalate)

The structural dynamics of ultrathin polymer films of poly(ethylene terephthalate) capped between aluminum electrodes have been investigated by dielectric relaxation spectroscopy. A deviation from bulk behavior, appearing as an increase of the relaxation time at a fixed temperature, is observed for films of thickness below 35 nm. The slowing down acts as a constant shift factor independent from the temperature, and the fragility is constant. The interfacial energy between aluminum and poly(ethylene terephthalate) is calculated to be 3 mJ/m2, confirming a strong interaction between polymer and substrate, which leads to the presence of a layer characterized by a reduced mobility at their interfaces. We proposed a mathematical schematization of a multylayer model that allowed qualitative reproduction of the observed thickness dependences of the static and dynamic properties. In terms of such a model, the upper limit for the thickness of the reduced mobility layer was estimated as 20 nm. The conditions to extend the proposed model to different observables are finally suggested.     

High-resolution poly(ethylene terephthalate) (PET) hot embossing at low temperature: thermal, mechanical, and optical analysis of nanopatterned films

In this work we present controlled, low-damage nanotopographic surface modification of poly(ethylene terephthalate) (PET). High-resolution nanopatterning over macroscopic areas was performed by " low-temperature" hot embossing lithography (HEL). While for standard HEL the temperature is typically raised up to many tens of Celsius degrees above the polymer glass transition temperature (Tg), we demonstrate optimal results at a temperature very close to the bulk Tg of PET (72 degrees C). Nanopits and nanobarcodes were transferred onto the surface of PET commercial sheets, demonstrating reliable sub-100 nm resolution over macroscopic areas. Sample optical, mechanical, and thermal characteristics were systematically analyzed before and after embossing at low (75 degrees C) and high (150 degrees C) temperature by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, tensile tests, and differential scanning calorimetry (DSC). We show that, while conventional high-temperature HEL can lead to dramatic degradation of the polymer in terms of transparency, flexibility, and crystallinity content, our low-temperature process fully maintains original surface and bulk substrate properties.     

Investigation of structural relaxation and surface modification of ultrathin films of poly(ethylene terephthalate)

We studied dynamic properties of ultrathin films of poly(ethylene terephthalate) spincoated on different substrates, by means of dielectric spectroscopy and surface patterning experiments. We did not observe any variations of structural dielectric relaxation dynamics for films spincoated on aluminium substrate having thicknesses down to 40 nm. On the same substrate, 13 nm thick films are instead characterized by a reduction of the chains mobility. Surprisingly the chains dynamics as probed by a surface nanopatterning experiment evidenced a strong dependence on the substrate interaction even for 50 nm thick films, where dielectric relaxation dynamics is unaffected. It can be deduced that different length scales characterise dielectric relaxation dynamics and the processes related to the surface patterning, even if both are related to the chain mobility. Further experiments are wished to better understand this intriguing scenario.     

Engineered Green Fluorescence Proteins for Proteomics and Biomolecular Electronic Applications

The discovery of the photochromic characteristics of engineered green fluorescent proteins (GFPs) allows new proteomics and biomolecular electronic applications. In particular, photoreversibility among two distinct optical states can lead to the realization of a bio-optical high density storage memory. Here we review our recent work on an optically bistable GFP and we report the recent developments of self-assembly methods for spatial immobilization of proteins into well-definite 2D patterns.