Influence of Substrate Properties on the Dewetting Dynamics of Viscoelastic Polymer Films

We studied the dewetting process of thin polystyrene (PS) films on silicon substrates, coated with a thin, irreversibly adsorbed polydimethylsiloxane (PDMS) layer, by optical microscopy and atomic force microscopy. Besides demonstrating the exceptional potential of dewetting for a sensitive characterization of rheological properties of PS thin films, characterized by a stress-relaxation time, τ₁, we focused on the influence of the frictional behaviour (energy dissipation mechanism) at the interface between the PDMS-coated silicon wafer and the PS film on the dewetting process. Our results show that the initial stages of dewetting depend sensitively on the thickness and the way the PDMS layer was adsorbed. The maximum width of the dewetting rim at τ₁ increased with increasing PDMS layer thickness, which can be interpreted as an increase of the effective, velocity-dependent slippage length. Interestingly, τ₁ was found to be almost independent of the substrate properties. Our results demonstrate that dewetting is a really powerful approach for rheological and frictional studies of thin polymer films.     

Morphology of poly(styrene‐block‐dimethylsiloxane) copolymer films

The morphologies of poly(styrene‐block‐di‐methylsiloxane) (PS‐b‐PDMS) copolymer thin films were analyzed via atomic force microscopy and transition electron microscopy (TEM). The asymmetric copolymer thin films spin‐cast from toluene onto mica presented meshlike structures, which were different from the spherical structures from TEM measurements. The annealing temperature affected the surface morphology of the PS‐b‐PDMS copolymer thin films; the polydimethylsiloxane (PDMS) phases at the surface were increased when the annealing temperature was higher than the PDMS glass‐transition temperature. The morphologies of the PS‐b‐PDMS copolymer thin films were different from solvent to solvent; for thin films spin‐cast from toluene, the polystyrene (PS) phase appeared as pits in the PDMS matrix, whereas the thin films spin‐cast from cyclohexane solutions exhibited an islandlike structure and small, separated PS phases as protrusions over the macroscopically flat surface. The microphase structure of the PS‐b‐PDMS copolymer thin films was also strongly influenced by the different substrates; for an asymmetric block copolymer thin film, the PDMS and PS phases on a silicon substrate presented a lamellar structure parallel to the surface at intervals. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1010–1018, 2007     

Particle nucleation for dewetting initiation of thin polymer films

A quantitative comparison between spontaneous dewetting and particle nucleation for thin (thickness = 17nm) polystyrene (PS) films on nonwettable silicon (Si) surfaces is presented both experimentally and theoretically. Performing experiments in a class 100 clean room, we found that ～ 23% of the observed dry patches formed because of dust particles, while the majority of the holes formed via the well known spontaneous dewetting process. The result was verified qualitatively by diffusion theory, which, however, predicted a diminished role for the airborne particles, leading to the conclusion that pre‐existing particles on the Si surfaces and/or the polymer solutions contribute substantially to the dewetting process. The driving force of particle motion into the polymer film is examined by placing aluminum oxide (Al₂O₃) particles on PS films. Finally, the effect of particle geometry is studied by placing gold (Au) disks on the free surface of PS films. An optically continuous PS film is found to be present around the periphery of the disk particles, even after the completion of the dewetting process in the rest of the sample. An attempt to explain dewetting inhibition at the vicinity of the micro‐disks, on the basis of molecular interactions developed in the system Au/PS/Si, is finally presented. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 138–145, 2005     

Combinatorial investigation of dewetting: polystyrene thin films on gradient hydrophilic surfaces

Film stability and dewetting is important to control for applications in coatings such as photoresists, paints, adhesives, lubricants, and biomaterials. We demonstrate the use of 2D combinatorial libraries to investigate thin film dewetting. Substrate libraries with gradients in contact angle (θ) were prepared by immersing Si-H passivated Si in a Piranha solution (H₂SO₄/H₂O₂/H₂O) at a controlled rate. Libraries of thin films of polystyrene on gradient etched silicon substrates containing orthogonal continuous variation of thickness were screened for dewetting behavior using automated optical microscopy. After comparing the high-throughput screening method to conventional studies of thickness effect on dewetting, a detailed morphological phase-map of the effects of contact angle on dewetting of polystyrene film was generated. Dewetting trends were visibly apparent. The number of polygons of dewetted polymer is sensitive to surface hydrophilicity as characterized by contact angle studies.     

Inhibition of thin polystyrene film dewetting via phase separation

By addition of a small amount of poly(methyl methacrylate) (PMMA) into polystyrene (PS), we present a novel approach to inhibit the dewetting process of thin PS film through phase separation of the off-critical polymer mixture (PS/PMMA). Owing to the preferential segregation of PMMA to the solid SiO_x substrate, a nanometer thick layer, rich in PMMA phase, is formed. It is this diffusive PMMA-rich phase layer near the substrate that alters the dewetting behavior of the PS film. The degree of inhibition of dewetting depends on the concentration and molecular weight of PMMA component. PMMA with low (15.9k) and intermediate (102.7k) molecular weight stabilizes the films more effectively than that with a higher molecular weight (387k).     

Dewetting kinetics of thin polymer bilayers: Role of under layer

A combined experimental and computational study is presented to uncover the dewetting kinetics of the PS/PMMA system by changing the film thickness of the PMMA under layer. On the low M_w PMMA (M_w = 15 kg/mol) layer, the dewetting velocity of PS film firstly rapidly decreases (regime I), and then becomes almost invariant (regime II) with the increase of the film thickness of the liquid lower layer. Experiments suggest that the transition from regime I to regime II is correlative with the property of the solid substrates. The linear stability analysis of thin bilayers uncovers a bimodal behaviour of the instability under the experimental conditions and changeover of dominant mode of instability from one interface to the other is the major reason behind the switching of regimes. The nonlinear simulations closely mimic the experimental interfacial morphologies and suggest two different pathways of hole growth for regimes I and II under experimental condition. The simulations also indicate that the rapid reduction in the dewetting velocity is because of the increased excursion or penetration of the upper layer into the lower layer near the three phase contact line as the viscous resistance at the more viscous PMMA layer reduces with its increasing thickness. A qualitative match is thus found between the experimental and theoretical trends of the dewetting velocities. In addition, the experiments show that on a high M_w PMMA (M_w = 365 kg/mol) layer, the kinetics of hole growth of the PS layer is not affected by the PMMA layer thickness.     

Metalizable Polymer Thin Films in Supercritical Carbon Dioxide

We report an environmentally “green” method to improve adhesion at a polymer/metal interface by using supercritical carbon dioxide (scCO₂). Spun-cast polystyrene (PS) and poly(methyl methacrylate) (PMMA) thin films on cleaned Si wafers were used for this study. Film thicknesses of both polymer films were prepared in the range of 100 Å to 1600 Å. We exposed the films to scCO₂ in the pressure-temperature (P–T) range corresponding to the density-fluctuation ridge, where the excess swelling of both polymer films occurred, and then froze the swollen structures by quick evaporation of CO₂. A chromium (Cr) layer with film thickness of 300–400 Å was deposited onto the exposed film by using an E-beam evaporator. X-ray reflectivity (XR) measurements showed that the interfacial width between the Cr and exposed polymer layers increased by a factor of about two compared with that without exposure to scCO₂. In addition, the large interfacial broadening was found to occur irrespective of the thickness of both polymer films. After the XR measurements, the dewetting structures of the PS/Cr films induced by additional annealing were characterized by using atomic force microscopy, showing improved surface morphology in the exposed films. Contact angle measurements showed that a decrease in interfacial tension with exposure to scCO₂ accompanied the increase in interfacial width.     

Ferroelectric and structural instability of (Pb,Ca)TiO3 thin films prepared in an oxygen atmosphere and deposited on LSCO thin films which act as a buffer layer

Structural, microstructural and ferroelectric properties of Pb_0.90Ca_0.10TiO₃ (PCT10) thin films deposited using La_0.50Sr_0.50CoO₃ (LSCO) thin films which serve only as a buffer layer were compared with properties of the thin films grown using a platinum-coated silicon substrate. LSCO and PCT10 thin films were grown using the chemical solution deposition method and heat-treated in an oxygen atmosphere at 700 °C and 650 °C in a tube oven, respectively. X-ray diffraction (XRD) and Raman spectroscopy results showed that PCT10 thin films deposited directly on a platinum-coated silicon substrate exhibit a strong tetragonal character while thin films with the LSCO buffer layer displayed a smaller tetragonal character. Surface morphology observations by atomic force microscopy (AFM) revealed that PCT10 thin films with a LSCO buffer layer had a smoother surface and smaller grain size compared with thin films grown on a platinum-coated silicon substrate. Additionally, the capacitance versus voltage curves and hysteresis loop measurement indicated that the degree of polarization decreased for PCT10 thin films on a LSCO buffer layer compared with PCT10 thin films deposited directly on a platinum-coated silicon substrate. This phenomenon can be described as the smaller shift off-center of Ti atoms along the c-direction 〈001〉 inside the TiO₆ octahedron unit due to the reduction of lattice parameters. Remnant polarization (P_r) values are about 30 μC/cm² and 12 μC/cm² for PCT10/Pt and PCT10/LSCO thin films, respectively. Results showed that the LSCO buffer layer strongly influenced the structural, microstructural and ferroelectric properties of PCT10 thin films.     

Preferentially oriented BaTiO3 thin films deposited on silicon with thin intermediate buffer layers

Barium titanate (BaTiO₃) thin films are prepared by conventional 2-methoxy ethanol-based chemical solution deposition. We report highly c-axis-oriented BaTiO₃ thin films grown on silicon substrates, coated with a lanthanum oxynitrate buffer layer of 8.9 nm. The influence of the intermediate buffer layer on the crystallization of BaTiO₃ film is investigated. The annealing temperature and buffer layer sintering conditions are optimized to obtain good crystal growth. X-ray diffraction measurements show the growth of highly oriented BaTiO₃ thin films having a single perovskite phase with tetragonal geometry. The scanning electron microscopy and atomic force microscopy studies indicate the presence of smooth, crack-free, uniform layers, with densely packed crystal grains on the silicon surface. A BaTiO₃ film of 150-nm thickness, deposited on a buffer layer of 7.2 nm, shows a dielectric constant of 270, remnant polarization (2P_r) of 5 μC/cm², and coercive field (E_c) of 60 kV/cm.     

Annealing‐promoted unidirectional migration of organic‐modified nanoparticles embedded two‐dimensionally in polymer thin films

The spatial structures of oleic acid‐modified CeO₂ nanoparticles in polystyrene (PS) thin films spin‐coated on silicon substrates were observed by transmission electron microscopy, when the films underwent thermal annealing above the glass‐transition temperature of PS. Before annealing, the nanoparticles have segregated to the surface of the films, and formed two‐dimensional spatial structures in the PS films. Then, the nanoparticles migrated away from the film surface to the substrate/film interface during thermal annealing, maintaining the two‐dimensional spatial structures. In addition, we demonstrated that such unidirectional migration of nanoparticles across the PS film occurs regardless of the characteristics of the substrate surface, the concentration of nanoparticles, and the thickness of the films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42760.     

Phase separation and dewetting in polystyrene/poly(vinyl methyl ether) blend thin films in a wide thickness range

Phase separation and dewetting processes of blend thin films of polystyrene (PS) and poly(vinyl methyl ether) (PVME) in two phase region have been studied in a wide film thickness range from 65 μm to 42 nm (∼2.5R_g, R_g being radius of gyration of a polymer) using optical microscope (OM), atomic force microscope (AFM) and small-angle light scattering (LS). It was found that both phase separation and dewetting processes depend on the film thickness and were classified into four thickness regions. In the first region above ∼15 μm the spinodal decomposition (SD) type phase separation occurs in a similar manner to bulk and no dewetting is observed. This region can be regarded as bulk. In the second region between ∼15 and ∼1 μm, the SD type phase separation proceeds in the early stage while the characteristic wavelength of the SD decreases with the film thickness. In the late stage dewetting is induced by the phase separation. In the third region between ∼1 μm and ∼200 nm the dewetting is observed even in the early stage. The dewetting morphology is very irregular and no definite characteristic wavelength is observed. It is expected that the irregular morphology is induced by mixing up the characteristic wavelengths of the phase separation and the dewetting. In the fourth region below ∼200 nm the dewetting occurs after a long incubation time with a characteristic wavelength, which decreases with the film thickness. It is considered that the layered structure is formed in the thin film during the incubation period and triggers the dewetting through the capillary fluctuation mechanism or the composition fluctuation one.     

Temperature- and thickness-dependent elastic moduli of polymer thin films

The mechanical properties of polymer ultrathin films are usually different from those of their counterparts in bulk. Understanding the effect of thickness on the mechanical properties of these films is crucial for their applications. However, it is a great challenge to measure their elastic modulus experimentally with in situ heating. In this study, a thermodynamic model for temperature- (T) and thickness (h)-dependent elastic moduli of polymer thin films E _f(T,h) is developed with verification by the reported experimental data on polystyrene (PS) thin films. For the PS thin films on a passivated substrate, E _f(T,h) decreases with the decreasing film thickness, when h is less than 60 nm at ambient temperature. However, the onset thickness (h*), at which thickness E _f(T,h) deviates from the bulk value, can be modulated by T. h* becomes larger at higher T because of the depression of the quenching depth, which determines the thickness of the surface layer δ.     

Patterning thin polymer films by surface-directed dewetting and pattern transfer

The pattern evolution processes of thin polystyrene (PS) film on chemically patterned substrates during dewetting have been investigated experimentally. The substrates have patterns of self-assembly monolayers produced by microcontact printing with octadecyltrichlorosilane. Optical microscopy and atomic force microscopy images reveal that ordered micrometer scale pattern can be created by surface direct dewetting. Various pattern sizes and pattern complexities can be achieved by controlling the experimental parameters. The dewetting pattern has been transferred to form PDMS stamp for soft lithography.     

Spectroscopic study of film formation from polystyrene latex/TiO2 nanocomposites prepared by dip‐coating method

In this study, we investigated the influence of TiO₂ content and thickness of polystyrene (PS) template on film‐formation behavior of PS/TiO₂ composites using fluorescence and ultraviolet–visible techniques in conjunction with scanning electron microscopy. Films were prepared by coating PS templates with various layers of TiO₂ using dip‐coating method. The results showed that PS latexes present complete film formation on top surface of composites. After extraction of PS, a well‐defined interconnected porosity were obtained for thin films when TiO₂ content was increased, whereas thick samples did not present any interconnected porous structures above a certain TiO₂ layer. POLYM. ENG. SCI., 54:288–302, 2014. © 2013 Society of Plastics Engineers     

Composition fluctuations before dewetting in polystyrene/poly(vinyl methyl ether) blend thin films

We report structural development in blend thin films of deuterated polystyrene (dPS) and poly(vinyl methyl ether) (PVME) below 200 nm in two phase region during the incubation period before dewetting using neutron reflectivity (NR) and atomic force microscopy (AFM). As was predicted by the former optical microscope (OM) and small-angle light scattering (LS) measurements on blend thin films of protonated PS and PVME [Ogawa H, Kanaya T, Nishida K, Matsuba G. Polymer 2008;40:254–62.], the NR results clearly showed that the tri-layer structure consisting of the surface PVME layer, the middle blend layer and the bottom PVME layer was formed in the one phase region. After the temperature jump into the two phase region, it was found that the phase separation of the middle blend layer proceeded in the depth direction during the incubation period before dewetting, suggesting that the dewetting was induced by the composition fluctuations during the incubation period.     

Spinodal clustering induced dewetting and non-monotonic stabilization of polymer blend films at high nanofiller concentrations

We examine the effects of high fullerene nanoparticle (f-NP) concentrations, ?_f-NP ∼ (10–20) mass% on polystyrene (PS)/polybutadiene (PB) blend thin film stability. Dewetting of the polymer blend around spinodally clustered f-NPs in this high concentration limit leads to a spinodal like dewetting morphology. This is in contrast to our previously observed results on the stabilization effects of f-NPs on PS/PB blend thin films in the intermediate f-NP concentration range of 7–10 mass%, wherein, after saturating the polymer–blend interface, the NPs stabilize the film by segregating to the blend–substrate interface. We determine three regimes of polymer blend film stability as a function of filler concentration: a) ?_f-NP < 7 mass% where preferential segregation of the f-NPs to the polymer–polymer interface leads to macroscopic dewetting, b) ?_f-NP ∼ (7–10) mass% where PS/PB blend films exhibit complete film stability, and c) ?_f-NP ∼ (11–20) mass%, where spinodal clustering of the f-NPs gives rise to polymer–NP phase exclusion and subsequent dewetting.     

Electrical properties of sputtered PZT films on stabilized platinum electrode

PZT (54/46) thin films were deposited by r.f. magnetron sputtering followed by a post-annealing treatment on silicon substrates. The crucial role of a Ti adhesion layer on the Ti/Pt bottom electrode is presented. The deposition conditions and the thickness of Ti have dominant effects on the interactions between Ti and Pt during the annealing treatment. The Pt layer, whatever its thickness, did not act as a barrier against Ti-out diffusion. The stability of the bottom electrode was achieved by using a TiO_x layer instead of a pure metallic Ti adhesion layer. The electrical properties of PZT films in terms of dielectric and ferroelectric performance were evaluated, particularly as a function of the PZT film thickness.     

Formation and characterization of perfluorocyclobutyl polymer thin films

Perfluorocyclobutyl (PFCB) polymers are a new class of materials that show promise as selective layer materials in the development of composite membranes for gas separations, such as carbon dioxide/methane (α_{pure gas} = 38.6) and oxygen/nitrogen (α_{pure gas} = 4.8) separations. In many of the flat sheet applications, a thin film of the selective layer that is free of major defects must be coated onto a support membrane. A focus of this study was to elucidate the impacts of solvents, polymer concentration, and dip‐coating withdrawal speed on PFCB thin film thickness and uniformity. An extension was proposed to the Landau–Levich model to estimate the polymer film thickness. The results show that the extended model fits the thickness‐withdrawal speed data well above about 55 mm/min, but, at lower withdrawal speeds, the data deviated from the model. This deviation could be explained by the phenomenon of polymer surface excess. Static surface excesses of polymer solutions were estimated by applying the Gibbs adsorption equation using measured surface tension data. Prepared films were characterized by ellipsometry. Refractive index was found to increase with decreasing film thickness below about 50 nm, indicating densification of ultrathin films prepared from PFCB solutions below the overlap concentration. Atomic force microscopy was used to characterize surface morphologies. Films prepared from tetrahydrofuran and chloroform yielded uniform nanolayers. However, films prepared using acetone as solvent yielded a partial dewetting pattern, which could be explained by a surface depletion layer of pure solvent between the bulk PFCB/acetone solution and the substrate. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Swelling measurement of polymers in high pressure carbon dioxide using a spectroscopic reflectometer

We developed an in situ thickness monitor using a spectroscopic reflectometer to measure the swelling behaviors of polymer thin films in carbon dioxide up to 30 MPa. Because the change in thickness was measured under high-pressure CO₂, the measurement was performed through a sapphire window with a relatively high refractive index. We found that the window effect on the reflectivity can be successfully eliminated. To confirm the accuracy of the analysis, we measured the swelling behaviors of four polymers (poly(methyl methacrylate) (PMMA), polystyrene (PS), poly(n-butyl methacrylate) (PBMA), and poly(dimethylsiloxane) (PDMS)), and compared the swelling measurements with reported data. The swelling ratios of the polymers were in reasonable agreement with literature data. Notably, anomalous swelling was observed for PBMA and PDMS, although anomalous swelling has been observed in films much thinner than those of our samples, probably due to the low glass transition temperatures and high swelling ratios of PBMA and PDMS.     

Investigation into the effect of substrate material on microstructure and optical properties of thin films deposited via magnetron sputtering technique

This study aims at investigating the effect of the substrate material on growth mechanism and also microstructure of Ta₂O₅ thin films. For this purpose, atomic force microscopy, scanning electron microscopy, and interferometry analyses were implemented to reveal the influence of silicon wafer and amorphous BK7 glass substrates on the nucleation and growth mechanisms of Ta₂O₅ thin films deposited via the radio frequency magnetron sputtering technique. Results indicated that those films with finer morphologies had relatively higher nucleation densities. Compared with BK7 glass substrate, crystals formed on the silicon wafer were shown to be finer and had lower mean areas in more nucleation sites. Moreover, optical properties and morphological characteristics of the films on the silicon substrates had much more endurance after the annealing treatment. It was observed that shift in the transmission spectra of the deposited films after the treatment was insignificant, implying high packing density of the films. However, a 6-nm shift in the transmission spectra indicated low density and high porosity of the films. Finally, atomic force microscopy analysis along with the light scattering measurements confirmed the formation of a low-roughness film on the silicon wafer substrates.