Breath figures in polymer and polymer blend films spin-coated in dry and humid ambience

We investigate effects of two spin-coating parameters, relative humidity (5% < or = RH < or = 80%) in ambient atmosphere and water content (3 wt % < or = f(H2O) < or = 20 wt %) in solution (rich in tetrahydrofuran), on the structure of breath figures (BF) formed in spin-cast films of polar poly(methyl methacrylate) (PMMA) and PMMA mixed with nonpolar polystyrene (PS). Film morphologies, examined with atomic and lateral force microscopy, are analyzed with integral geometry analysis to yield morphological BF measures. In PMMA, water added to solution has much stronger impact than that from moisture on formed BFs, which could be ordered (with conformational entropy S approximately 0.9-1.0). In PMMA/PS, BFs decorate exclusively polar PMMA domains, resulting in morphologies with two length scales (sub-micrometer BFs and domains >10 microm). This suggests a novel strategy for herarchic structure formation in multicomponent polymer films. In PS/PMMA, BFs are better developed than in pure PMMA spin-coated in identical conditions. These observations show that the air boundary layer facing the spin-cast polymer film (region) is more important than the ambient atmosphere.     

Assessment and formation mechanism of laser-induced periodic surface structures on polymer spin-coated films in real and reciprocal space

In this work we evaluate the potential of grazing incidence X-ray scattering techniques in the investigation of laser-induced periodic surface structures (LIPSSs) in a series of strongly absorbing model spin-coated polymer films which are amorphous, such as poly(ethylene terephthalate), poly(trimethylene terephthalate), and poly(carbonate bisphenol A), and in a weaker absorbing polymer, such as semicrystalline poly(vinylidene fluoride), over a narrow range of fluences. Irradiation was performed with pulses of 6 ns at 266 nm, and LIPSSs with period lengths similar to the laser wavelength and parallel to the laser polarization direction are formed by devitrification of the film surface at temperatures above the characteristic glass transition temperature of the polymers. No crystallization of the surface is induced by laser irradiation, and crystallinity of the material prevents LIPSS formation. The structural information obtained by both atomic force microscopy and grazing incidence small-angle X-ray scattering (GISAXS) correlates satisfactorily. Comparison of experimental and simulated GISAXS patterns suggests that LIPSSs can be well described considering a quasi-one-dimensional paracrystalline lattice and that irradiation parameters have an influence on the order of such a lattice.     

Planarizing surface topography by polymer adhesion to water-soluble templates with replicated null pattern

Water-soluble polymer templates are replicated from flat master surface patterns by spin-casting a poly(vinyl alcohol) film-forming solution that solidifies at standard ambient conditions in less than 1 min. The fabricated water-soluble templates are coupled to substrates with surface topography by polymer adhesion with an intervening reactive or photocurable liquid layer. After curing, the resulting two-layer solid structure is subjected to water thereby dissolving the soluble template to expose the underlying polymer adhesive layer with flat surface topography. The results demonstrate a reduction of surface topography from several micrometers to less than 100 nm. The chemical interactions involved in bonding the soluble template to the polymer adhesive and then dissolving are measured by Raman spectroscopy to demonstrate that the constituents comprising the water-soluble template are absent from the surface of the planarization material.     

Striped pattern formation in polymer dispersed liquid crystal films

Composite films of polymer and liquid crystal (LC) have been prepared by a simple solution casting technique. The films obtained exhibit a polymer dispersed liquid crystal structure where LC droplets are dispersed in the polymer matrix. Casting the mixture of polymer solution and LC on a tilted substrate results in a specific texture in which arrays of LC droplets align parallel to each other, i.e. a striped pattern can be formed. The size of the droplets and the spacing between the lines are dependent on the substrate tilt angle and the preparation temperature. By using a dip-coating technique, a similar striped texture appears at a fast dipping velocity. From in situ observation of the stripe development, it is seen that the translation of the phase-separating region, accompanying the flow, plays a more important role in the formation of the striped patterns than the flow of the solution itself.     

Striped pattern formation in polymer dispersed liquid crystal films

Composite films of polymer and liquid crystal (LC) have been prepared by a simple solution casting technique. The films obtained exhibit a polymer dispersed liquid crystal structure where LC droplets are dispersed in the polymer matrix. Casting the mixture of polymer solution and LC on a tilted substrate results in a specific texture in which arrays of LC droplets align parallel to each other, i.e. a striped pattern can be formed. The size of the droplets and the spacing between the lines are dependent on the substrate tilt angle and the preparation temperature. By using a dip-coating technique, a similar striped texture appears at a fast dipping velocity. From in situ observation of the stripe development, it is seen that the translation of the phase-separating region, accompanying the flow, plays a more important role in the formation of the striped patterns than the flow of the solution itself.     

Structure formation in polymer blend solutions

Development of phase-separated morphologies has been studied in polymer blend solutions and forced mixtures of highly immiscible polymers by optical microscopy, DSC and light scattering. Unmixing was induced by different courses of solvent evaporation and by thermal agitation, respectively. Blends comprising different kinds of flexible and rigid chain molecules display various phase patterns in the late stage of phase decomposition which can be characterized roughly as being either regularly bicontinuous or irregularly shaped. Effects of polymer-polymer interaction and the blending ratio are discussed. Generally, evolution of morphologies depends on both internal parameters of the system and externally imposed unmixing conditions. Limits of percolating morphologies in the course of phase separation can be established qualitatively.     

Poly(4-styrenesulfonate) templated polyaniline-carboxymethyl cellulose blend: Morphology and surface resistivity of the spin-coated films

Poly (4-styrenesulfonate) (PSS) templated polyaniline-carboxymethyl cellulose blend forming stable aqueous colloidal suspensions was prepared through simple synthesis. Morphology of the spin-coated films obtained from different concentrations of colloidal suspensions was studied through atomic force microscopy (AFM). The AFM images were found to be drastically altered at lower concentrations showing a regular network-like structure. Room-temperature surface resistivity for the network featured spin-coated film showed semiconducting behavior. This indicates the efficacy of dilution as a new design element for network structures, further exhibiting resistivity.     

Modeling diffusion in miscible polymer blend films

Recent experiments designed to probe polymer transport in the bulk and in the vicinity of surfaces have examined the interdiffusion of multilayer sandwiches of isotopically labeled polymers. The measured time dependent concentration profiles normal to the surface are typically fit to Fick's law, with a single fitting parameter, the mutual binary diffusion coefficient (MBDC). The resulting MBDCs are found to vary over a broad range of film thicknesses and time, with the time dependence being viewed as a unique signature of the reptation mechanism of long chain motion, and the thickness dependence being attributed to the slowing down of chain dynamics near surfaces. Since the experiments are conducted at finite concentration, the MBDC, which is a product of the bare mobility and the concentration derivative of the chemical potential, could be dominated by the time and thickness dependence of this second term (which is ignored in Fick's law). To quantify this conjecture we consider the more rigorous Cahn formulation of the diffusion problem in terms of chemical potential gradients. We use square gradient theory to evaluate chemical potentials, and fit the resulting time dependent concentration profiles to the analytical solution of Fick's law. By thus mimicking the experimental analysis we find that the apparent MBDCs vary with time as t(-1/2) at short times, in good agreement with existing experiments. We show that this time dependence reflects the system's desire to minimize concentration gradients, a fact ignored in Fick's law. Since these arguments make no reference to the mechanism of chain motion, we argue that the time dependence of MBDC derived from interdiffusion experiments does not provide unequivocal support for the reptation mechanism of long chain transport. The MBDC values, which also vary with the degree of confinement, are predicted to increase with decreasing thickness for model parameters corresponding to experimental systems. In contrast, since the experimental fits yield an opposite trend, we suggest that the bare mobility of the chains decreases strongly with decreasing thickness. These findings strongly support the idea that the chains are "pinned" irreversibly to the surfaces, in good agreement with other, independent experiments.     

Surface aggregation structure and surface mechanical properties of binary polymer blend thin films

During preparation of very thin polymer belnd films from a solution of polymers, the phase‐separated structures which are quite different from that observed for the bulk blend film was observed. From atomic force microscopic(AFM) observation, it is concluded that the surface undulation, which reflects the phase separated morphology of the blend system, is present. In the case of (polystyrene(PS)/poly(methyl methacrylate)(PMMA)) blend system, a large influence of end‐group chemistry on the surface morphology was observed. The phase identification of the (rubbery polymer/glassy polymer) binary blend thin films was successfully achieved by scanning vioscoelasticity microsopy(SVM).     

Characterization and modification of polymer blend films

Films of immiscible blends of (PS) and poly(methyl methacrylate) (PMMA) were characterized by contact-angle measurements with sessile drop and atomic force microscopy (AFM). These blends showed a linear dependence of the contact angles on the composition, as predicted by Cassie's equation for ideal surfaces. The surface structure investigated by AFM showed low roughness and phase-separation features. The ratio between the drop radius and the roughness amounted to the order of 10⁴–10⁵. This magnitude seemed to be sufficient to put the PS/PMMA films close to ideality. Upon sulfonation, the wettability and the microscopic surface roughness of the PS/PMMA blends increased. The treatment with sulfuric acid yielded sulfonated PS domains on the surface, causing an increase in the surface wettability. The SO₃ ⁻ groups were evidenced by X-ray photoelectron spectroscopy. The sulfonation of the PS/PMMA blends enables the formation of multiphase surfaces with hydrophobic, charged and polar domains. Received: 11 December 2000 Accepted: 6 April 2001     

Electrohydrodynamic effect on phase separation morphology in polymer blend films

We have investigated the effect of electrohydrodynamic (EHD) convection on the domain structure in a polystyrene (PS)/polyvinyl acetate (PVA) blend film to demonstrate the feasibility of using the EHD effect as a means of mixing and morphology control in a polymer blend film prepared by solvent evaporation. Here, polymers-toluene solutions were spread on a glass substrate with patterned electrodes to apply a dc electric field, and well-defined structures of EHD convection were formed in the polymer solutions. As a result, regular patterns were formed in the PS/PVA polymer blend film in which PVA-rich domains were confined within each unit of patterned electrodes, i.e., between positive and negative electrodes, at an appropriate electric voltage. In addition, it was demonstrated that such novel morphology is not due to the wetting/dewetting effect of polymer components to the Pt electrodes deposited on the glass substrate, by experiments with a SiO2-covered substrate.     

Optical order of the polymer phase within polymer/fullerene blend films

This study reports on how the degree of polymer order within a polymer/fullerene blend can be investigated by spectroscopic methods. Non‐annealed blend compositions with 0–80 wt % fullerene content were analyzed using temperature dependent photoluminescence (PL) and room temperature spectroscopic ellipsometry (SE) measurements. To evaluate the SE data with respect to the optical order, an optical model was developed, including a lower and higher ordered polymer phase within a fullerene matrix. This was done using an effective medium approach describing the polymer by combining lower and higher ordered polymer properties (polymer‐EMA). The polymer/fullerene blend was then evaluated using another EMA consisting of the polymer‐EMA and the dielectric function of the disordered fullerene. The degree of optical order obtained by SE, was confirmed using another independent measurement, photoluminescence spectroscopy, according to the method of Francis C. Spano (2005). The volume fraction of the ordered polymer within the polymer‐EMA was found to be between 70 and 60 vol % for fullerene contents lower than 20 wt % in the polymer/fullerene blend. Above 20 wt % fullerene, the optical order of the polymer strongly decreases all the way down to 0 vol %. In contrast to the complementary performed X‐ray diffraction measurements, which address only the long‐range structural order of the blends, we give quantitative information on the optical order, including information on the composition, that is, volume fractions of the higher and lower ordered polymer. The gained information on the tilt of the polymer molecules with respect to the substrate is discussed comparing XRD results from the literature with those obtained by our SE model. Finally, the developed model is used to describe the influence of the P3HT molecular weight on the optical order. Results obtained with our model were compared to the structural data and mobility data in the literature. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Surface structure analysis of thin dewetted polymer blend films

The surface structure of thin polymer blend films of deuterated polystyrene (dPS) and polyparamethylstyrene (PpMS) after annealing above the glass transition temperature was investigated. With scanning force microscopy (SFM) the surface topography originated by a dewetting process is detected. The sample surface is covered with small droplets consisting of several polymer molecules. Utilizing grazing incidence small angle neutron scattering (GISANS) the topographical information as well as the in‐plane composition is probed. For thin confined blend films a substructure of the droplets resulting from an additional phase separation process at different length scales is detected.     

A single-dipole model of surface relief grating formation on azobenzene polymer films

A new model that keeps track of the dynamics of single dipoles is suggested for the photoinduced formation of a surface relief grating on azobenzene polymer films by two optical fields. Interfering optical fields provide a single dipole of an azobenzene molecule with two dynamical resources: rotation of the molecule caused by the torque, leading to an induced dipole, and its subsequent migration because of the electric force. Explicit development of the induced dipole of the molecule and its real-time migration, which depend on the details of the optical fields such as polarization and wavelength, can be understood self-consistently within the model.     

Structure of spin-coated lipid films and domain formation in supported membranes formed by hydration

An atomic force and fluorescence microscopy investigation of the structure of spin-coated lipid films is presented. In the surface of the dry film, lipids are found to orient in a conformation where acyl chains are pointing outward while laterally the individual layers of the multilamellar film exhibit a dewetting pattern similar to what is found in polymer thin films. Hydration of the film in liquid water promotes detachment of bilayers from the surface while a single membrane remains on the mica substrate. This supported membrane is highly uniform and defect-free as compared to supported membranes prepared by conventional methods. It is further demonstrated that supported membranes of binary lipid mixtures prepared by this method exhibit gel-fluid domain coexistence in accordance with expectations from the phase diagrams.     

Glass transition behavior of spin-coated thin films of a hydrophilic polymer on supported substrates

Using ellipsometry, it is found the glass transition temperature of the spin-coated polyacrylamide(PAL) thin films on the supported silicon(Si) substrates with an oxide layer decreases with decreasing the film thickness. But Tgs of the asprepared thin films are much higher than that of the bulk sample. Such observations can be attributed to the combined result of the "surface effect" and increased hydrogen bonding interaction between PAL chains due to spin coating/thin film confinement.     

Suppression of surface pattern formation in spin‐coated polymer films by the addition of polydimethylsiloxane‐grafted silica nanoparticles

Polydimethylsiloxane (PDMS)‐grafted nanoparticles and PDMS were added, respectively, to inhibit the dewetting of polymer films and the formation of surface patterns in spin coating. Uniform and flat films were successfully achieved with the addition of PDMS‐grafted silica nanoparticles or PDMS. Time‐of‐flight secondary ion mass spectrometry depth profiling indicated that PDMS‐grafted silica nanoparticles and PDMS preferentially segregated to the surface. A high concentration of bromine end groups was observed at the interface. The surface layer of PDMS or PDMS‐grafted silica nanoparticles can decrease the surface tension of the polymer solutions and reduce the evaporation rates of the solvents, providing more time for the bromine end groups to anchor themselves at the silicon substrates. Copyright © 2016 John Wiley & Sons, Ltd.     

Submicron films prepared from aqueous dispersions of nanoscale polymer crystals

Thin and ultrathin films of polyethylene of variable thickness are obtained from aqueous dispersions of prefabricated nanoscale crystals by spin‐coating. Continuous films with a thickness of only 15 nm, up to 220 nm, homogeneous over hundreds of μm, or assembled discontinuous monolayers of flat‐on lamella particles were prepared, depending on the solids content of the dispersion employed, as revealed by AFM and TEM. The morphology of melt‐recrystallized films was not affected by the surfactant present. Homogeneous continuous films without undesirable dewetting were retained upon melting and recrystallization of the films upon cooling, composed of polygonal spherulites for a thicker film (220 nm), randomly grown edge‐on lamella for a 40 nm film, and dominant flat‐on lamella for a 15 nm thick film. Annealing below T_m resulted in lamella thickening, without changes of crystal orientation or structure of the particle assemblies for discontinuous monolayers. Surfactant adsorbed to the nanocrystals in the aqueous dispersion desorbs at least partially during formation of the nascent films, and upon annealing below the melting point surfactant migrates to the film‐air interface to form aggregates, which can be removed by rinsing, during which the film stays intact and structurally unaltered as revealed, amongst others, by water contact angles. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6420–6432, 2009     

Radical ion pair mediated triplet formation in polymer-fullerene blend films

Efficient triplet formation is observed for films of high ionisation potential polythiophenes blended with a fullerene derivative, and assigned to formation via geminate charge recombination of bound radical ion pair states.