Journal
CHEMISTRY OF MATERIALS
Volume 14, Issue 12, Pages 5173-5178Publisher
AMER CHEMICAL SOC
DOI: 10.1021/cm0207503
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Hydrophobic organosilicates with controlled morphologies at the nanometer length scale have many potential applications in microelectronics and photonics. Here we report the use of block copolymers of poly(butadiene-b-ethylene oxide) (PB-b-PEO) as templates to create 10-20-nm periodic hexagonal arrays of cylinders in hydrophobic organosilicates. The self-assembly process of the block copolymers is monitored and studied by solid-state NMR, transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). It is found that the microstructure and phase behavior of the nanocomposites are very sensitive to the polymer-matrix interface and the intrinsic properties of the block copolymers. When methyltriethoxysilane (MTES) is solely used as sol precursor to swell polymer domains, a disordered structure is always obtained, presumably because MTES changes its nature from hydrophilic to increasingly hydrophobic during curing, and block copolymers are repelled from the matrix. A hydrophilic silicate precursor, (3-glycidyoxypropyl)-trimethoxysilane (GPTS), is introduced as an amphiphilic organosilicate precursor and to preserve the polymer-silicate interface. A layered core-shell structure is formed with PEO and GPTS located at the interface, while PEO and GPTS are microphase separated. Understanding of the templating mechanism may provide a new route for nonlithographic nanopatterning and incorporating functionalities for photonic applications.
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