Ultrathin films of metallosupramolecular coordination polyelectrolytes (MEPEs) on planar solid substrates assembled by electrostatic layer-by-layer self-assembly (ELSA) are characterized with UV-vis spectroscopy, optical ellipsometry, and X-ray reflectometry. MEPEs based on different ditopic ligands and transition metal ions are employed and shown to form regular ELSA multilayers. A quantitative analysis is in agreement with a surface coverage of approximately two MEPE monolayers per deposition step. In addition, we demonstrate that multilayers of MEPEs with different transition metal ions can be assembled. Even with kinetically labile metal ions, there is no metal ion exchange in these multilayers. Absorption spectra of multilayers on silicon show a band inversion of the MLCT band, which is rationalized in terms of optical effects. 相似文献
Summary: Stable thin films of a hyperbranched aromatic-aliphatic OH-terminated polyester (POH) were prepared on silicon substrates. We report on grafting-to processes using macromolecular (PGMA) and bifunctional low-molecular weight coupling agents (BOX). An appropriate annealing procedure was developed for the covalent immobilization. The HBP films were characterized with spectroscopic ellipsometry, drop shape analysis (DSA), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and electrokinetic measurements. The immobilized films have an uniform surface morphology and are slightly hydrophilic (θa = 79°). The grafting process did not influence the chemical composition and the surface properties, which is important for the further application as functional layers in aqueous media. 相似文献
Summary: We report the first Monte Carlo simulations on the thin‐film morphology of symmetric diblock copolymers confined between either symmetrically or antisymmetrically stripe‐patterned surfaces. Under suitable surface configurations (where the lamellae can comply with the surface patterns and can have a period close to the bulk lamellar period L0), tilted lamellae are observed for film thicknesses D ≥ 2L0; the checkerboard morphology is obtained for smaller film thicknesses. The A‐B interfaces in the tilted lamellae are basically perpendicular to the surfaces in their immediate vicinity, and exhibit undulations away from them. In some cases, the severe frustration imposed by the two patterned surfaces leads to irregular or unexpected morphologies, which represent locally stable states. The efficient sampling of our expanded grand‐canonical Monte Carlo technique enables us to observe more than one locally stable morphologies and the flipping between them during a single simulation run.
Tilted lamellae between symmetrically patterned surfaces (perpendicular to z) with a surface pattern period of 1.5L0 and a film thickness of 2.67L0. L0 is the bulk lamellar period and the black curves mark the A‐B interfaces. 相似文献
Herein, we describe the synthesis of a low‐symmetry monodendron, 3,4‐bis(dodecyloxy)‐5‐[3,4,5‐tris(dodecyloxy)benzyloxy]benzoic acid, following a simple route which starts from gallic acid ethyl ester and does not require any protecting groups. The self‐assembled structures formed by the compound in 3D and 2D were investigated by synchrotron X‐ray scattering and scanning force microscopy (SFM). In 3D, the compound forms a stable crystalline phase with an orthorhombic lattice in which the alkyl chains connected to different benzene rings form crystalline and amorphous domains. Upon cooling from the isotropic melt the compound exhibits a monotropic smectic mesophase. In 100‐nm‐thick films on a neutral substrate the structure loses its biaxiality, adopting a hexagonal columnar structure with the columns oriented parallel to the substrate. By contrast, in ultrathin films on graphite the SFM likely reveals two crystal orientations, which can develop due to the epitaxial adsorption on the substrate of the alkyl chains pertinent to different benzene rings. 相似文献
Electrochemical properties of Fc‐PEM films have been studied by changing the chemical structure of the polymer chains and the content of Fc moiety in the film systematically. We have prepared a series of PEM films by a layer‐by‐layer deposition of polycations, Fc‐modified poly(allylamine) (Fc‐PAA) and poly(ethyleneimine) (Fc‐PEI), and polyanionic poly(vinyl sulfate) (PVS) on the surface of a gold electrode. The redox properties of the Fc‐PAA/PVS and Fc‐PEI/PVS films depended significantly on the content of Fc moiety in the polymer chains and on the polymer type. Fc‐ PAA and Fc‐PEI polymer chains can penetrate 3 or 4 PAA/PVS bilayers inserted between the redox polymers and electrode. The Fc‐PAA film‐modified electrode can be used for electrocatalytic oxidation of ascorbic acid. 相似文献
An order–order transition (OOT) in the sequence of a hexagonally arranged core–shell cylinder to a double‐hexagonally arranged dot in polystyrene‐block‐poly(butadiene)‐block‐poly(2‐vinylpyridine) (SBV) triblock copolymer thin films is reported to be induced upon exposure to a solvent vapor that is strongly selective for the two end blocks. These two kinds of hexagonally arranged structures could form when the film thickness is 44, 123, and 223 nm. When the film thickness is decreased to 13 nm, the ordered structure is absent. The sizes of the core–shell cylinder structures formed with the same annealing time in films of different thickness are compared to address the effects of film thickness on the phase structure. The mechanism is analyzed from the total surface area of the blocks and the effective interaction parameter in the solvent vapor.
