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Title: Bulk, thin film and solution self-assembly of block copolymers containing a polyferrocenysilane metalloblock
Author: Nunns , Adam
ISNI:       0000 0004 5372 6753
Awarding Body: University of Bristol
Current Institution: University of Bristol
Date of Award: 2014
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The research presented in this thesis involves the development of a variety of synthetic routes which have enabled the preparation of a library of novel polymeric materials, primarily block copolymers containing a polyferrocenylsilane metalloblock. A large emphasis has been placed on the subsequent investigations into the self-assembly of these materials, where they have been found to form a variety of interesting nanostructures, making them candidates for use in a number of different scientific fields. An introduction to the principal areas of research of this thesis is given in Chapter 1. Block copolymer (BCP) self-assembly in the bulk is discussed, highlighting the interest in studying BCP systems exhibiting greater complexity. This is followed by a similar discussion concerning block copolymer self-assembly in the solution phase. The synthesis and selfassembly of BCPs containing polyferrocenylsilane is introduced. The final sections of the introduction are dedicated to block copolymer lithography and bit-patterned media. Miktoarm star terpolymers represent a class of BCPs which are comprised of three chemically distinct polymeric blocks joined at a single junction point. Previous studies into their bulk self-assembly have shown them to self-assemble into a large number of complex morphologies, including a range of Archimedean tiling patterns which aren't obtainable through the self-assembly of their linear triblock terpolymer counterparts. These materials could be utilised for block copolymer lithography, facilitating the fabrication of features ~xhibiting greater complexity than simpler diblock copolymer. In Chapter 2, the synthesis of a range of polystyrene-arm-polyisoprene-arm-poly(ferrocenylethylmethylsilane) miktoarm star terpolymers ()..t-SIF) is discussed; two synthetic routes were pursued, a chlorosilane route and a core-first route. In total, 5 j.l-SIFs were prepared. Their bulk self-assembly was investigated by transmission electron microscopy (TEM) and three different morphologies were obtained - two Archimedean tiling patterns ([8.8.4] and [12.6.4]) and a lamellae + cylinder morphology. Additionally, the thin film self-assembly and pattern transfer of one of the [8.8.4] Archimedean-tiling-pattern-forming j.l-SIFs is presented, demonstrating the applicability of these materials for use in block copolymer lithography. In addition to the structures formed by the self-assembly of block copolymers in the bulk and thin film, a wide variety of colloidally stable nanoscale architectures have been shown to be accessible through the solution self-assembly of block copolymers. The solution self-assembly of two j.l-SIF terpolymers is described in Chapter 3, one bearing a crystallisable poly(ferrocenyldimethylsilane) block (j.l-SIFc) and the other bearing an amorphous, non-crystallisable poly(ferrocenylethylmethylsilane) block (j.l-SIFa). The selfassembly of these materials was studied by TEM, atomic force microscopy (AFM) and dynamic light scattering (DLS), whereupon it was shown that the solvent and the 1 crystallisable nature of the PFS block have a profound influence on the micelle architectures formed. Spheres bearing phase-mixed cores and distorted spheres bearing phase-separated cores were obtained for j.l-SIFa in different solvents. For j.l-SIFc, a transition from distorted spherical micelles bearing a phase-separated core to elongated fibres bearing a phaseseparated core was observed. Additionally, cylindrical micelles with a phase-separated corona were obtained for Il-SIFc in another solvent. Finally, successful seeded growth studies with the crystallisable j.l-SIFc terpolymer were demonstrated, yielding B-A-B block co-micelles.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available