Submicrometer Pattern Fabrication by Intensification of Instability in Ultrathin Polymer Films under a Water-Solvent Mix

Dewetting of ultrathin (< 100 nm) polymer films, by heating above the glass transition, produces droplets of sizes of the order of microns and mean separations between droplets of the order of tens of microns. These relatively large length scales are because of the weak destabilizing van der Waals forces and the high surface energy penalty required for deformations on small scales. We show a simple, one-step versatile method to fabricate sub-micron (>~100 nm) droplets and their ordered arrays by room temperature dewetting of ultrathin polystyrene (PS) films by minimizing these limitations. This is achieved by controlled room temperature dewetting under an optimal mixture of water, acetone and methyl-ethyl ketone (MEK). Diffusion of organic solvents in the film greatly reduces its glass transition temperature and the interfacial tension, but enhances the destabilizing field by introduction of electrostatic force. The latter is reflected in a change in the exponent, n of the instability length scale, {\lambda} ~h^n, where h is the film thickness and n = 1.51 \pm 0.06 in the case of water-solvent mix, as opposed to its value of 2.19 \pm 0.07 for dewetting in air. The net outcome is more than one order of magnitude reduction in the droplet size as well as their mean separation and also a much faster dynamics of dewetting. We also demonstrate the use of this technique for controlled dewetting on topographically patterned substrates with submicrometer features where dewetting in air is either arrested, incomplete or unable to produce ordered patterns

Exchange Reactions between Alkanethiolates and Alkaneselenols on Au{111}

When alkanethiolate self-assembled monolayers on Au{111} are exchanged with alkaneselenols from solution, replacement of thiolates by selenols is rapid and complete, and is well described by perimeter-dependent island growth kinetics. The monolayer structures change as selenolate coverage increases, from being epitaxial and consistent with the initial thiolate structure to being characteristic of selenolate monolayer structures. At room temperature and at positive sample bias in scanning tunneling microscopy, the selenolate-gold attachment is labile, and molecules exchange positions with neighboring thiolates. The scanning tunneling microscope probe can be used to induce these place-exchange reactions

Nanopatterned self-assembled monolayers

We report on the fabrication of chemically nanopatterned gold surfaces by combining electron-beam lithography with gas and liquid phase thiolization. The line-edge roughness of the patterns is similar to 4 nm, corresponding to a limiting feature size in the range of 15 nm. Indications for a lower packing density of the self-assembled monolayers grown in the nanofeatures are given, and evidences for the bleeding of thiols along the grain boundaries of the gold substrate are displayed. A comparison is provided between nanopatterned thiol and silane monolayers on gold and on silicon wafers, respectively. The line-edge roughnesses are shown to be close to each other for these two systems, indicating that the limiting step is currently the lithography step, suggesting possible improvement of the resolution. The advantages and drawbacks of thiol versus silane monolayers are finally discussed with respect to the formation of chemically nanopatterned surfaces

Melting and van der Waals Stabilization of PE Single Crystals Grown from Ultrathin Films

We have obtained a series of single- and multilayered extended chain polyethylene (PE) crystals resting on a silicon dioxide substrate by crystallizing a low molar mass oligomer fraction of low polydispersity from an ultrathin film. Crystal thicknesses were determined from the height histograms of atomic force microscopy (AFM) images. For crystallization temperatures above 108 °C, the thickness of each layer was 16.9 ± 1.4 nm, close to the computed average extended length of the oligomer chain. The crystal melting was followed by a hot-stage optical microscopy (OM) in reflection. Different layers melt at different temperatures, due to differences in interfacial free energy depending on whether they are in contact with the substrate or another layer or have a free interface. The interfacial free energies of the different interfaces were obtained by the Gibbs–Thompson equation, and the difference between them was quantitatively related to the van der Waals stabilization energy resulting from placing a layer in contact with the substrate or with another layer. Our study demonstrates the importance of interfaces when considering the thermal behavior of ultrathin films of crystalline polymers and illustrates that a simple energetic concept can be used to explain the stabilization of crystals resting on a surface

Kinetics of Exchange of Alkanethiol Monolayers Self-Assembled on Polycrystalline Gold

We report on the exchange between a hydrophilic thiol (11-mercapto-1-undecanol) in a liquid or gas phase and a hydrophobic thiol (dodecanethiol) of similar length self-assembled on a polycrystalline gold surface for a wide range of temperatures and times. The molecular composition of the mixed monolayers is determined by the static water contact angle and X-ray photoelectron spectroscopy measurements. Atomic force microscopy in lateral forcemodeis used to characterize the molecular domains at the nanometer level. The exchange first occurs rapidly at the gold grain boundaries, with an activation energy of about 66 ( 4 kJ/mol. Then, boundaries of ordered thiol domains are progressively replaced, and the exchange is slowed because only regions of increasing perfection are left untouched. Higher temperatures lead to faster kinetics of replacement and the removal of larger amounts of the original thiol. No significant difference could be detected between exchange occurring in an ethanol solution or in the gas phase, and the initial rate of exchange was found to be similar for the displacement of dodecanethiol by 11-mercapto- 1-undecanol molecules and for the converse displacemen

Nanodecoding by dewetting

Films of a block copolymer fluid are deposited on surfaces bearing nano-stripes of different wettability (see figure). The dewetting process of the fluid decodes the underlying pattern, opening trenches as narrow as 70 nm in the film, and creating fluid nanoribbons as narrow as 300 nm. The fluid ribbons are stabilized by the internal organization of the copolymer in the confined space of the ribbon

Partial dewetting of polyethylene thin films on rough silicon dioxide surfaces.

The effect of roughness on the dewetting behavior of polyethylene thin films on silicon dioxide substrates is presented. Smooth and rough silicon dioxide substrates of 0.3 and 3.2-3.9 nm root-mean-square roughness were prepared by thermal oxidation of silicon wafers and plasma-enhanced chemical vapor deposition on silicon wafers, respectively. Polymer thin films of approximately 80 nm thickness were deposited by spin-coating on these substrates. Subsequent dewetting and crystallization of the polyethylene were observed by hot-stage optical microscopy in reflection mode. During heating, the polymer films melt and dewet on both substrates. Further observations after cooling indicate that, whereas complete dewetting occurs on the smooth substrate surface, partial dewetting occurs for the polymer film on the rough surface. The average thickness of the residual film on the rough surface was determined by ellipsometry to be a few nanometers, and the spatial distribution of the polymer in the cavities of the rough surface could be obtained by X-ray reflectometry. The residual film originates from the impregnation of the porous surface by the polymer fluid, leading to the observed partial dewetting behavior. This new type of partial dewetting should have important practical consequences, as most real surfaces exhibit significant roughness