Synthesis, self-assembly and applications of amorphous polyferrocenylsilane block copolymers.

摘要

A series of well-defined polystyrene-block-poly(ferrocenylethylmethylsilane) (PS-b-PFEMS) diblock copolymers was synthesized. Both PFEMS and PS- b-PFEMS were shown to be amorphous due to the atactic nature of the PFEMS. As a result, PS- b-PFEMS readily undergo solid-state self-assembly in the bulk producing a spectrum of ordered nanometer sized iron-rich morphologies. When cylinder-forming PS-b-PFEMSs were studied in thin films, well-ordered arrays of hexagonally packed iron-rich cylindrical microdomains oriented either parallel to or normal to the substrate were produced. The orientation was found to depend strongly on the film thickness and/or the conditions of annealing. The etching of these films using (i) reactive plasmas, and (ii) an oxidative chemical wet etch technique were investigated. Using (i), surface-patterned magnetic ceramics were produced as well as a nanotextured silver metal film. The latter was found to dramatically enhance the Raman spectroscopy of an adsorbed analyte molecule. Using (ii), nanoporous polystyrene films were generated by the quantitative elimination of PFEMS domains by exposure to a nucleophilic non-solvent under oxidizing conditions.;The influence of strong 3D confinement on the self-assembly of PS-b-PFEMS was studied. Both silica colloidal crystals and silica inverse colloidal crystals were used for directing the self-assembly. Unusual morphologies, such as concentric shells and branched lamellae, resulted from the interaction of the lamellar-forming PS-b-PFEMS with the high surface area templates. In addition, the control of the 3D confined morphology of cylinder-forming PS-b-PFEMS was demonstrated through mediation of the interfacial interactions within the colloidal crystal.;For solution state self-assembly, PS-b -PFEMSs and polystyrene-block-poly(ferrocenylmethylphenylsilanes) (PS-b-PFEMSs) were stoichiometrically oxidized in solution. Due to a redox-induced polarity change for the PFEMS and PFMPS blocks, self-assembly into well-defined spherical micelles occurred. The micelles, composed of a core of partially oxidized PFS segments and a corona of PS, disassembled when treated with a reducing agent and regenerated unassociated free chains.;Lastly, the photochemical treatment of metal-containing ferrocenophane monomers with low energy Pyrex-filtered light from a mercury lamp (lambda > 310 nm) or bright sunlight in the presence of an anionic initiator led to living polymerizations in which the conversion and molecular weight of the resulting polymer was controlled by irradiation time. The polymerization proceeded via attack of the initiator or propagating anion on the iron atom of the photoexcited monomer. The formation of functional block copolymer architectures was possible when the light is alternately switched on and off in between the sequential addition of different monomers.;Thin films of PS-b-PFEMS generated efficient iron nanoparticle catalysts for single-walled carbon nanotube (SWNT) growth via a chemical vapor deposition growth process. The kinetics of the formation of iron catalysts from PS- b-PFEMS and PFEMS were compared. Despite the lower iron content for PS-b -PFEMS films, more active iron sites were produced. Additionally, the tube diameter and density were tunable by adjusting the chain lengths of polyferrocenylsilane- block-polysiloxanes in thin films. Lastly, high-throughput field-effect SWNT transistors have been fabricated with more than 160 individually addressable devices on a chip.