Dewetting of polymethyl methacrylate on the patterned elastomer substrate by solvent vapor treatment

The dewetting evolution process of polymethyl methacrylate (PMMA) film on the flat and prepatterned polydimethylsiloxane (PDMS) substrates (with square microwells) by the saturated solvent of methyl ethyl ketone (MEK) treatment has been investigated at room temperature by the optical microscope (OM) and atomic force microscope (AFM). The final dewetting on the flat PDMS substrate led to polygonal liquid droplets, similar to that by temperature annealing. However, on the patterned PDMS substrate, depending on the microwells' structure of PDMS substrate and defect positions that initiated the rupture and dewetting of PMMA, two different kinds of dewetting phenomena, one initiated around the edge of the microwells and another initiated outside the microwells, were observed. The forming mechanism of these two different dewetting phenomena has been discussed. The microwells were filled with liquid droplets of PMMA after dewetting due to the formation of fingers caused by the pinning of the three-phase-line at the edge of the microwells and their rupture.     

Formation of nano-patterned protein layers on poly (lactic acid) surface: Induced by dewetting process and self-assembly

A simple method was developed to fabricate nano-patterned protein layers on poly (lactic acid) (PLA) surface by dewetting method. It was found that nano-patterned protein layers were formed on PLA surface by slow drying in high humidity. The influence of wettability and viscoelastic properties of substrates were also investigated. As a result, typical spinodal dewetting patterns formed for BSA. However, network structures were obtained for collagen at acidic condition and well-oriented fibrils at neutral pH. It was attributed to dewetting on hydrophobic substrate as well as the plasticity and variety of collagen self-assemblies.     

Film instability induced evolution of hierarchical structures in annealed ultrathin films of an asymmetric block copolymer on polar substrates

With an atomic-force microscope and a grazing-incidence small-angle X-ray scattering we studied ex situ the evolution of hierarchical structures in isothermally annealed ultrathin films of asymmetric polystyrene-block-poly(methyl methacrylate) P(S-b-MMA) that dewetted on polar substrates via a mechanism involving nucleation and growth. Film instability causes the surface to acquire an undulating thickness through incommensurability, producing not only the relief structures on a micrometer scale but also mesophase-separated domains on a nanometer scale. The dewetted morphologies strongly influence the ordering behavior of the nanoscale domains. The noncylindrical nanostructures become stable at the curved edges of the relief microstructures in the destabilized P(S-b-MMA) films, for which a preferential wetting of the PS block with the free surface is prohibited. Additionally, the shape of relief structures as result of film instability correlates with the formation of mesophase-separated nanodomains. At early stages of film instability, the formation of parallel-oriented PMMA cylindrical nanodomains increases the deformation energy and it further persists to force the shape of relief structures between irregular holes to have a facet-wedge shape. However, those relief structures are expected to be not at equilibrium. At high temperatures, the relief structures between irregular holes progressively developed to form hemispherical-cap drops accompanied by a transformation of cylindrical into noncylindrical nanodomains at curved surfaces.     

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.     

Microstructure of thin film platinum electrodes on yttrium stabilized zirconia prepared by sputter deposition

(111) oriented thin film Pt electrodes were prepared on single crystals of yttrium-stabilized zirconia (YSZ) by sputter deposition of platinum. The electrodes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDX), atomic force microscopy (AFM) and by profilometry. SEM images of the as-sputtered platinum film show a compact amorphous Pt film covering uniformly the substrate. Upon annealing at 1123 K, gaps and pores at the interface develop leading to a partial dewetting of the Pt film. Increasing the annealing temperature to 1373 K transforms the polycrystalline Pt film into single crystalline grains exhibiting a (111) orientation towards the substrate.     

Novel photoactive aggregates of rhodamine 6G: dequenched and quasi-stable aggregates induced by a dewetting process

Self-organized rhodamine 6G particles prepared by wetting/dewetting process of an ethanol solution on a hydrophilic glass surface exhibits fluorescence without quenching, showing a sharp linewidth of 2nm with a large redshift, which indicates an existence of dye aggregates, similar to J-aggregates, inside the particle. Polarized evanescent field excitation showed that the dye molecule's transition moment along the pi-conjugation was oriented unidirectionally within particles and parallel to the substrate surface. This deduced dye orientation showed correlation between adjacent, but separated, particles and pointed roughly 45 degrees off the dewetting direction. In contrast, the particles of another pi-conjugated NK1420 dye, J-aggregates of which grows easily from an oversaturated solution, showed dye orientation along the dewetting direction preferably, still indicating the effect of self-organization, however based on a different mechanism. An annealing procedure revealed that both aggregates are in quasi-stable states, which is consistent with the rapidness of the dewetting process that may lead to crystallization in nonequilibrium.     

Thermal stability of silver thin films on zirconia substrates

The thermal stability of silver thin films between 100 nm and 820 nm thick deposited onto single crystal yttria-stabilised zirconia (YSZ) substrates by evaporation was investigated by annealing the films between 250 °C and 550 °C for different durations. Films approximately 100 nm thick were thermally unstable at temperatures as low as 250 °C. A dewetting process occurred in which grain boundaries ruptured, to uncover the substrate and reduce the overall energy of the system, by a combination of grain boundary grooving at the outer surface and void growth at the Ag-YSZ interface. The surface self diffusion coefficient of Ag was determined from the kinetics of the process to be 2.6 ± 0.3 × 10^− 5 cm²s^− 1 at 500 °C. The resulting silver morphology ranged from ‘self-organised’ interconnected silver network structures to completely isolated silver islands. A structure predominance map of the rearrangement process is presented.     

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.