Dataset Information

Self-Assembled Copolymer Adsorption Layer-Induced Block Copolymer Nanostructures in Thin Films.

ABSTRACT: In polymer thin films, the bottom polymer chains are irreversibly adsorbed onto the substrates creating an ultrathin layer. Although this thin layer (only a few nanometers thick) governs all film properties, an understanding of this adsorbed layer remains elusive, and thus, its effective control has yet to be achieved, particularly in block copolymer (BCP) thin films. Herein, we employ self-assembled copolymer adsorption layers (SCALs), transferred from the air/water interfacial self-assembly of BCPs, as an effective control of the adsorbed layer in BCP thin films. SCALs replace the natural adsorbed layer, irreversibly adsorbing onto the substrates when other BCP is additionally coated on the SCALs. We further show that SCALs guide the thin film nanostructures because they provide topological restrictions and enthalpic/entropic preferences for a BCP self-assembly. The SCAL-induced self-assembly enables unprecedented control of nanostructures, creating novel nanopatterns such as spacing-controlled hole/dot patterns, dotted-line patterns, dash-line patterns, and anisotropic cluster patterns with exceptional controllability.

SUBMITTER: Kim DH

PROVIDER: S-EPMC6764160 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature

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Self-Assembled Copolymer Adsorption Layer-Induced Block Copolymer Nanostructures in Thin Films.

Kim Dong Hyup DH Kim So Youn SY

ACS central science 20190910 9

In polymer thin films, the bottom polymer chains are irreversibly adsorbed onto the substrates creating an ultrathin layer. Although this thin layer (only a few nanometers thick) governs all film properties, an understanding of this adsorbed layer remains elusive, and thus, its effective control has yet to be achieved, particularly in block copolymer (BCP) thin films. Herein, we employ self-assembled copolymer adsorption layers (SCALs), transferred from the air/water interfacial self-assembly of ...[more]

PMID: 31572783

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Project description:Cationic and anionic block copolymer worms are prepared by polymerization-induced self-assembly via reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion copolymerization of 2-hydroxypropyl methacrylate and glycidyl methacrylate (GlyMA), using a binary mixture of a nonionic poly(ethylene oxide) macromolecular RAFT agent and either a cationic poly([2-(methacryloyloxy)ethyl]trimethylammonium chloride) or an anionic poly(potassium 3-sulfopropyl methacrylate) macromolecular RAFT agent. In each case, covalent stabilization of the worm cores was achieved via reaction of the epoxide groups on the GlyMA repeat units with 3-mercaptopropyltriethoxysilane. Aqueous electrophoresis studies indicated a pH-independent mean zeta potential of +40 mV and -39 mV for the cationic and anionic copolymer worms, respectively. These worms are expected to mimic the rigid rod behavior of water-soluble polyelectrolyte chains in the absence of added salt. The kinetics of adsorption of the cationic worms onto a planar anionic silicon wafer was examined at pH 5 and was found to be extremely fast at 1.0 w/w % copolymer concentration in the absence of added salt. Scanning electron microscopy (SEM) analysis indicated that a relatively constant worm surface coverage of 16% was achieved at 20 °C for adsorption times ranging from just 2 s up to 2 min. Furthermore, the successive layer-by-layer deposition of cationic and anionic copolymer worms onto planar surfaces was investigated using SEM, ellipsometry, and surface zeta potential measurements. These techniques confirmed that the deposition of oppositely charged worms resulted in a monotonic increase in the mean layer thickness, with a concomitant surface charge reversal occurring on addition of each new worm layer. Unexpectedly, two distinct linear regimes were observed when plotting the mean layer thickness against the total number of adsorbed worm layers, with a steeper gradient (corresponding to thicker layers) being observed after the deposition of six worm layers.

Dataset Information

Self-Assembled Copolymer Adsorption Layer-Induced Block Copolymer Nanostructures in Thin Films.

Publications

Self-Assembled Copolymer Adsorption Layer-Induced Block Copolymer Nanostructures in Thin Films.

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