Diblock copolymers in bulk and in thin films: Morphology and kinetics

In this thesis I numerically study the phase diagram and kinetics of a diblock copolymers melt in both bulk and thin films in the strong segregation limit.; I probe various values of the volume fraction, f, of the shorter block of the copolymer chains, spanning the bulk phase diagram for the diblock copolymers from a spherical body-centered cubic (BCC) phase to a hexagonally packed cylindrical (HCP) phase, to a bicontinuous gyroid phase (G), to finally a lamellar phase(L).; Finite size and wetting properties of the substrate modify the film morphology by shifting the effective value of the composition in the film. For neutral substrates, the film morphology is shifted toward a smaller relative composition f, while for substrates which prefer the longer blocks of the copolymers, the film morphology is shifted toward a large value of f. A dramatic change in thin film morphology takes place for a small change in external parameters if one chooses the composition f to be at the borderline between two different bulk phases.; The next question addressed is that of the control over the thin film structure in the case of a symmetric diblock copolymer films with a thickness smaller than the bulk equilibrium period. These films are cast on either flat or corrugated substrates. The results show that the formation of uniformly sized lateral domains that appear randomly on a flat surface can be controlled by using topographically patterned substrates. Control of lateral pattern fails if the distance between steps is smaller than the lamellar wavelength or the lateral size of the corrugation is larger than the bulk lamellar wavelength.; For thin block copolymer (BCP) films on a homogeneous substrate, a fast domain growth exponent has recently been observed in experiments. I have carried out numerical simulations of ordering and domain growth in a two-dimensional system of BCP melts. The model calculations explicitly include viscous, hydrodynamic flow and provide a scaling description of the growth of domains in a quenched BCP system. Our results indicate that the growth kinetics of BCP melts in two dimensions belong to the same dynamical universality class of small molecular liquid mixtures in the viscosity dominated regime.