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We present the synthesis and characterization of a series of photolabile phenacyl derivative polymers and their subsequent thin film preparation. These systems are composed of up to three methacrylate units:  a photolabile component including a p-methoxyphenacyl moiety which after selective irradiation (UV/laser) can provide free carboxylic groups in specific areas for further modification; an anchoring unit, trimethoxysiloxane or glycidyl methacrylate derivative, which allows the covalent attachment of the polymer to the substrate; and a spacer, methyl methacrylate or styrene, which in the appropriate proportion ensures the formation of films with good quality. Structural and thermal properties of these materials have been analyzed by means of NMR, FTIR, elemental analysis, UV, gel permeation chromatography, differental scanning calorimetry, and thermogravimetric analysis. The polymers have been subsequently processed by spin coating to render ultrathin films (<50 nm). Topographic and structural characterization studies of the films have been carried out with atomic force microscopy, contact angle measurements, and X-ray photoelectron spectroscopy. The extent of the substrate attachment of the polymers depending on the nature of the anchoring groups have been studied by ellipsometry and FTIR.

Infrared spectroscopic ellipsometry (IRSE) and visible monochromatic ellipsometry (VISE) approaches were applied to investigate the chemical structure and thickness of ultrathin polymer films. Mixed polystyrene−poly(2-vinylpyridine) and polystyrene−poly(tert-butyl acrylate) polymer grafted films (mixed brushes) with gradually changing composition (1D gradient mixed brush) along the sample were prepared on a temperature gradient stage via two subsequent “grafting to” reactions. The films were characterized by high-precision mapping VISE at a single wavelength (632.8 nm) and IRSE. The set of 1D IRSE spectra of the polymer brush films obtained by mapping the 1D gradient brush were used to estimate the thickness and the local composition of the film and to construct the 1D map of the film in terms of the chemical composition of the brush. The results were compared with the data obtained using monochromatic ellipsometry where the brush composition was estimated from the results of two subsequent measurements followed each grafting step. The measurements of the brush thickness and composition with both methods were found to be in gratifying agreement. The results demonstrate the high potential of IRSE methods for the one-step characterization (by thickness and chemical composition) of ultrathin polymer films of complex composition.

A patterned hydrogel was immobilized on a polymer substrate by low-pressure argon plasma treatment using a masking technique. The polymer sample showed a thermoresponsive aggregation behavior in the region of 35−37 °C. The micropatterned, thermoresponsive hydrogel film has been characterized with imaging ellipsometry. The characterization was carried out on the dry film as well as on a swollen sample in water. The thermoresponsive behavior was studied in deionized water by temperature-dependent measurements in a solid−liquid cell. Through imaging ellipsometry, it was possible to distinguish the different regions of interest on a micrometer scale and to follow the swelling of the hydrogel part as a function of the temperature. It was possible to visualize the swelling as 3D profiles of Δ at various temperatures. Long-term changes of the sample could also be detected, which cannot be picked up by conventional ellipsometry.

Particle track etched polyimide membranes on silicon substrates covered with a native oxide layer are investigated. Preparation steps similar to the common classical particle track etched membrane production, giving rise to free-standing membranes, are successfully applied to the supported membranes. Polyimide films are used as a starting material for a template preparation based on high energy ion irradiation. The film/membrane structure is probed at different length scales by grazing incidence small-angle X-ray scattering at each individual preparation step. In addition, characterization with atomic force microscopy, variable-angle spectroscopic ellipsometry, Fourier transform infrared transmission, and attenuated total reflection spectroscopy is performed. An amount of 6 ± 1 vol % pores inside the polyimide film is detected. The pores are oriented perpendicular to the substrate surface and have a conical shape, yielding a slightly reduced pore size at the substrate/film interface.

The phenomenon of contact angle hysteresis was studied on smooth films of polyimide, a polymer type used in the microelectronic industry, by dynamic cycling contact angle measurements based on axisymmetric drop shape analysis-profile in combination with variable angle spectroscopic ellipsometry (VASE). It was found that both advancing and receding contact angles became smaller with increasing the number of cycles and are, therefore, not a property of the dry solid alone. The changes of the wetting behavior during these dynamic cycling contact angle measurements are attributed mainly to swelling and/or liquid retention. To reveal the water-induced changes of the polymer film, the polyimide surface was studied before and after the contact with a water droplet by VASE. Both the experimental ellipsometric spectrum for Δ and that for Ψ as well as the corresponding simulations show characteristic shifts due to the contact with water. The so-called effective medium approximation was applied to recover information about the thickness and effective optical constants of the polymer layer from the ellipsometrically measured values of Δ and Ψ. On the basis of these results, the swelling and retention behavior of the polyimide films in contact with water droplets were discussed.

We develop the route to fabricate mixed brushlike layers on polyamide substrates (PA-6, PA-6I, PA-66) by the “grafting from” approach. The PA substrates were functionalized by NH3 plasma. The azo initiator of radical polymerization was covalently bound to the functionalized PA surface. A two-step grafting procedure was applied to graft polystyrene in the first step and poly(2-vinylpyridine) in the second step. We found remarkable differences between grafting on Si wafers and on the PA substrates. “Grafting from” the PA surface results in a dramatic increase of the surface roughness of the film which can be explained by grafting in a swollen surface layer of PA. Because of this effect, we found a substantial amount of grafted polymers even on not functionalized PA substrates, which was explained by grafting via chain transfer reaction. The synthesized mixed polymer brushes form responsive coatings which switch their morphology due to the interplay between lateral and vertical phase segregation upon exposure to selective solvent. The switching of morphology affects the change of the surface composition of the brushes and their surface energetic state. We performed the same grafting procedure on the surface of PA fabric. In this case the switching behavior was amplified by the texture of the material:  wettability of the fabric with the mixed brush was switched from complete wetting to highly hydrophobic state (150° water contact angle).

We report a simple method to synthesize binary polymer brushes from two incompatible polymers of different polarity. The synthetic route is based on a subsequent step-by-step grafting of carboxyl-terminated polystyrene and poly(2-vinylpyridine) to the surface of a Si wafer functionalized with 3-glycidoxypropyl-trimethoxysilane. The end-functional polymers were spin-coated on the substrate, and grafting was carried out at a temperature higher than the glass transition temperature of the polymers. The composition of the binary brushes can be regulated based on grafting kinetics of the first polymer by the change of time or/and temperature of grafting. This method reveals a smooth and homogeneous polymer film on the macroscopic scale, while at the nanoscopic scale the system undergoes phase segregation effecting switching/adaptive properties of the film. Upon exposure to different solvents, the film morphology reversibly switches from “ripple” to “dimple” structures as well as the surface energetic state switches from hydrophobic to hydrophilic. The same switching of hydrophilic/hydrophobic properties was obtained for the different ratios between two grafted polymers in the binary brush.

The design of new functional materials and devices substantially relies on self-assembly of hierarchical structures. Formation of 2D platelets is known in the enzymatic synthesis of cellulose-like polymers. Here we demonstrate the feasibility of postsynthesis assembly of novel fluorinated cellodextrins. Highly ordered 2D structures of large lateral dimensions, unattainable in the polymerization process, can be formed because of postsynthesis assembly of the cellodextrins. These cellodextrins were also involved in coassembly with cellulose nanocrystals (CNCs) leading to hybrid systems. The hybrid architectures obtained depend on the content of fluorine atoms in the fluorinated cellodextrins. Monofluorinated cellodextrins coassemble with CNCs into a nanoweb, while multifluorinated cellodextrins assemble around the CNCs.