Block copolymer strands with internal microphase separation structure via self-assembly at the air-water interface.
ABSTRACT Block copolymer microphase separation in the bulk is coupled to amphiphilic block copolymer self-assembly at the air-water interface to yield hierarchical Langmuir-Blodgett (LB) structures combining organization at the meso- and nanoscales. A blend of polystyrene-b-poly(ethylene oxide) (PS-b-PEO) (Mn=141K, 11.4 wt % PEO) and polystyrene-b-poly(butadiene) (PS-b-PB) (Mn=31.9K, 28.5 wt % PB) containing a PS-b-PB weight fraction of f=0.75 was deposited at the air-water interface, resulting in the spontaneous generation of aggregates with multiscale organization, including nanoscale cylinders in mesoscale strands, via evaporation of the spreading solvent. The resulting features were characterized in LB films via AFM and TEM and at the air-water interface via Langmuir compression isotherms. Blends containing lower PS-b-PB contents formed mesoscale aggregate morphologies of continents and strands (f=0.50) or mesoscale continents with holes (f=0.25), but without the internal nanoscale organization found in the f=0.75 blend. The interfacial self-assembly of pure PS-b-PB at the air-water interface (f=1) yielded taller and more irregularly shaped aggregates than blends containing PS-b-PEO, indicating the integral role of the amphiphilic copolymer in regulating the mesoscale organization of the hierarchically structured features.
- SourceAvailable from: Sundaramurthy Jayaraman[Show abstract] [Hide abstract]
ABSTRACT: In this work, we demonstrate a simple method of synthesizing nanoscale polythiophene-gold nanoparticle (AuNP) hybrid systems assembled by the Langmuir-Blodgett (LB) method. Regio-regular poly(3-(2-methoxyethoxy)ethoxymethyl)thiophene-2,5-diyl (PMEEMT) and poly(3-dodecylthiophene) (PDDT) were employed as the polymeric constituents. The presence of PDDT improved the amphiphilicity of PMEEMT by addressing the phase separation that occurred due to convective hydrodynamic instability on the substrate. 4 layer stacks of 90% and 99% PMEEMT films exhibited uniform film structure with a significant reduction in phase separation. A detailed mechanism for minimization of the surface effect has been proposed based on the interaction of polythiophenes with the substrate. For the first time, an ex situ approach has been adopted to incorporate AuNPs into LB films without affecting the film morphology and uniformity. The incorporation of AuNPs into the polythiophene matrix, aided by the affinity of sulphur for gold, was strongly dependent on the molecular arrangement of the matrix, which in turn depended on the composition of the matrix. The hybrid polythiophene films exhibited enhanced conductivity and can be applied in sensors, photovoltaics and memory devices.Nanoscale 03/2013; · 6.74 Impact Factor
- [Show abstract] [Hide abstract]
ABSTRACT: Many technological applications require templates with nanoscale patterns. Block copolymer self-assembly is a method of choice for obtaining a large variety of such patterns, with greatest flexibility achieved when combined with a supramolecular approach. One of the ways to fabricate block copolymer templates is the Langmuir-Blodgett (LB) technique. Here, we briefly summarize recent work with LB films of polystyrene-poly(4-vinyl pyridine) (PS-P4VP) mixed with 3-n-pentade cylphenol (PDP), illustrating the different types of patterns possible and the principles governing them. One interesting pattern that can be easily achieved with this system is the so-called “nanostrand network”, which, when used as a template for gold deposition, can produce double striped lines of gold. Here, we show how this pattern can be modified by acetone swelling to give rise to gold monolayer ribbons with internal structure. The results also suggest new insights into the early stages of morphology formation at the air/water interface.Science China-Chemistry 56(1). · 1.52 Impact Factor
- [Show abstract] [Hide abstract]
ABSTRACT: Langmuir-Blodgett monolayers consisting of a network of nanostrands have occasionally been reported in the literature, but are often coexistent with other morphologies, which is not useful for potential applications. With the use of PS-P4VP/PDP, a polystyrene-poly(4-vinyl pyridine) diblock copolymer of 12 mol % VP content mixed with 3-pentadecylphenol, it is shown that the disordered nanostrand network morphology can be obtained reproducibly and uniformly over large surface areas by spreading chloroform solutions of relatively high copolymer concentration. Use of a more slowly evaporating spreading solvent, 1,1,2,2-tetrachloroethane, and a low subphase temperature, 8-9 °C, results in much more densely aligned nanostrands. Poorly spreading solvents such as nitrobenzene produce the well-known fingerprint pattern often observed in spin- or dip-coated thin films of block copolymers. A mechanism for nanostrand network formation is proposed that involves the momentary formation of a fingerprint morphology in spreading drops followed by its breakup at the level of the mobile P4VP/PDP stripes as spreading continues, leaving P4VP-anchored PS nanostrands floating on the water surface.ACS Nano 10/2010; 4(11):6825-35. · 12.03 Impact Factor