Guillaume Vignaud

Densification and Depression in Glass Transition Temperature in Polystyrene Thin Films

Ellipsometry and X-ray reflectivity were used to characterize the mass density and the glass transition temperature of supported polystyrene (PS) thin films as a function of their thickness. By measuring the critical wave vector (qc) on the plateau of total external reflection, we evidence that PS films get denser in a confined state when the film thickness is below 50 nm. Refractive indices (n) and electron density profiles measurements confirm this statement. The density of a 6 nm (0.4 gyration radius, Rg) thick film is 30% greater than that of a 150 nm (10Rg) film. A depression of 25 °C in glass transition temperature (Tg) was revealed as the film thickness is reduced. In the context of the free volume theory, this result seems to be in apparent contradiction with the fact that thinner films are denser. However, as the thermal expansion of thinner films is found to be greater than the one of thicker films, the increase in free volume is larger for thin films when temperature is raised. Therefore, the free volume reaches a critical value at a lower Tg for thinner films. This critical value corresponds to the onset of large cooperative movements of polymer chains. The link between the densification of ultrathin films and the drop in their Tg is thus reconciled. We finally show that at their respective Tg(h) all films exhibit a critical mass density of about 1.05 g/cm(3) whatever their thickness. The thickness dependent thermal expansion related to the free volume is consequently a key factor to understand the drop in the Tg of ultrathin films.

Stability of Polymer Ultrathin Films (<7 nm) Made by a Top-Down Approach

In polymer physics, the dewetting of spin-coated polystyrene ultrathin films on silicon remains mysterious. By adopting a simple top-down method based on good solvent rinsing, we are able to prepare flat polystyrene films with a controlled thickness ranging from 1.3 to 7.0 nm. Their stability was scrutinized after a classical annealing procedure above the glass transition temperature. Films were found to be stable on oxide-free silicon irrespective of film thickness, while they were unstable (<2.9 nm) and metastable (>2.9 nm) on 2 nm oxide-covered silicon substrates. The Lifshitz-van der Waals intermolecular theory that predicts the domains of stability as a function of the film thickness and of the substrate nature is now fully reconciled with our experimental observations. We surmise that this reconciliation is due to the good solvent rinsing procedure that removes the residual stress and/or the density variation of the polystyrene films inhibiting thermodynamically the dewetting on oxide-free silicon.

Swelling of Poly(n-butyl methacrylate) Films Exposed to Supercritical Carbon Dioxide: A Comparative Study with Polystyrene

We report here the swelling and relaxation properties of confined poly(n-butyl methacrylate) (PBMA) films having thicknesses of less than 70 nm under supercritical carbon dioxide (scCO2) using the X-ray reflectivity technique. Swellability is found to be dominant in thinner films compared to thicker ones as a consequence of the confinement-induced densification of the former. Swellability is proportionately increased with the density of the film. PBMA films exhibit a more significant swelling than do PS films, and their differences become more prominent with the increase in film thickness. A comparison between the results obtained for polystyrene (PS) and PBMA ultrathin films reveals that the swellability is dependent upon the specific intermolecular interaction between CO2 and the chemical groups available in the polymers. Owing to strong Lewis acid-base interactions with scCO2 and the lower glass-transition temperature (bulk Tg ≈ 29 °C), PBMA films exhibit a greater amount of swelling than do PS films (bulk Tg ≈ 100 °C). Though they reach to the different swollen state upon exposition, identical relaxation behavior as a function of aging time is evidenced. This unprecedented behavior can be ascribed to the strong bonding between trapped CO2 and PBMA that probably impedes the release of CO2 molecules from the swollen PBMA films manifested in suppressed relaxation.

Experimental evidence of ultrathin polymer film stratification by AFM force spectroscopy

By performing Atomic Force Microscopy measurements of pull-off force as a function of the temperature, we were able to probe the dynamic of supported thin polystyrene (PS) films. Thermal transitions induce modifications in the surface energy, roughness and surface modulus that are clearly detected by AFM and related to PS chain relaxation mechanisms. We demonstrated the existence of three transition temperatures that can be associated to the relaxation of polymer chains located at different depth regions within the polymer film. Independently of the film thickness, we have confirmed the presence of a region of high mobility for the polymer chains at the free interface. The thickness of this region is estimated to be above 7nm. The detection of a transition only present for film thicker than the gyration radius Rg is linked to the dynamics of polymer chains in a bulk conformation (i.e. not in contact with the free interface). We claim here that our results demonstrate, in agreement with other techniques, the stratification of thin polymer film depth profile in terms of relaxation behavior.Graphical abstract

An x-ray scattering study of laterally modulated structures: the example of diblock copolymers

A study of the specular and off-specular (diffuse) x-ray scattering of a diblock copolymer is presented. In the ordered state the surface of the diblock copolymer is covered with islands. It is shown that the periodicity in the ordered state in the direction normal to the surface in a specular scan differs from the periodicity in the same direction observed in an off-specular scan. This result is explained by an analytical calculation of the differential cross section. The introduction of the statistical properties of the island distribution allows a complete analytical calculation of the transverse scans yielding the determination of the mean distance between the islands and the average size of an island.

Analysis of X-ray reflectivity curves of non-Gaussian surfaces

Surfaces of symmetric diblock copolymers thin films exhibiting non-Gaussian distribution of height are studied by X-ray reflectivity and atomic force microscopy (AFM). When deposited on a silicon substrate, the surface is essentially flat and its roughness may be described by a Gaussian distribution of height. Upon annealing, films operate a two-dimensional phase transformation and form islands at the free surface having height and size that evolve as a function of annealing time. The height probability function cannot be represented by a Gaussian distribution anymore, and the question that arises is how to take into account the morphology of such surfaces in the reflectivity calculations. In a first approach, we show that the height distribution function derived from AFM measurements is directly transferable to analyze X-ray reflectivity curves according to a formalism that we present. In a second part, we determine the height distribution function from a fit to the observed reflectivity.

Resonant soft X-ray reflectivity of ultrathin polymer films at the C-edge: A direct approach

The use of resonant soft X-ray reflectivity (RSXRR) in s-polarization is presented with the aim to show how far it is possible to go in the understanding the evolution of the refractive index n(E)=1−δ(E)−iβ(E) of a ultrathin polystyrene film when the RSXRR is measured through the C-edge. We evidence that a direct fit to the data provides a very good estimation of δ(E) and β(E) in a large range of energies. Nevertheless, at some specific energy close to C-edge we observe that it is not possible to obtain a satisfactory fit to the data though the same formalism is applied to calculate the reflectivity. We show that even though we take into account the energy resolution of the incident beam, we still end up with a poor fit at these energies. Incorporating the strong contribution of 2nd order photons appeared near C-edge we could not eliminate the discrepancy. Probably the data normalisations have some impacts on such discrepancies at some specific energies.