Curvature as a Guiding Field for Patterns in Thin Block Copolymer Films.

Experimental data on thin films of cylinder-forming block copolymers (BC)-free-standing BC membranes as well as supported BC films-strongly suggest that the local orientation of the BC patterns is coupled to the geometry in which the patterns are embedded. We analyze this phenomenon using general symmetry considerations and numerical self-consistent field studies of curved BC films in cylindrical geometry. The stability of the films against curvature-induced dewetting is also analyzed. In good agreement with experiments, we find that the BC cylinders tend to align along the direction of curvature at high curvatures. At low curvatures, we identify a transition from perpendicular to parallel alignment in supported films, which is absent in free-standing membranes. Hence both experiments and theory show that curvature can be used to manipulate and align BC patterns.

Wrinkles and splay conspire to give positive disclinations negative curvature.

Recently, there has been renewed interest in the coupling between geometry and topological defects in crystalline and striped systems. Standard lore dictates that positive disclinations are associated with positive Gaussian curvature, whereas negative disclinations give rise to negative curvature. Here, we present a diblock copolymer system exhibiting a striped columnar phase that preferentially forms wrinkles perpendicular to the underlying stripes. In free-standing films this wrinkling behavior induces negative Gaussian curvature to form in the vicinity of positive disclinations.

Smectic block copolymer thin films on corrugated substrates.

In this work we study equilibrium and non-equilibrium structures of smectic block copolymer thin films deposited on a topographically patterned substrate. A Brazovskii free energy model is employed to analyze the coupling between the smectic texture and the local mean curvature of the substrate. The substrate's curvature produces out-of-plane deformations of the block copolymer such that equilibrium textures are modified and dictated by the underlying geometry. For weak curvatures it is shown that the free energy of the block copolymer film follows a Helfrich form, scaling with the square of the mean curvature, with a bending constant dependent on the local pattern orientation. On substrates of varying mean curvature simulations show that topological defects are rapidly expelled from regions with large curvature. These results compare well with available experimental data of poly(styrene)-co-poly(ethylene-alt-propylene) smectic thin films.

Defect formation and coarsening in hexagonal 2D curved crystals.

In this work we study the processes of defect formation and coarsening of two-dimensional (2D) curved crystal structures. These processes are found to strongly deviate from their counterparts in flat systems. In curved backgrounds the process of defect formation is deeply affected by the curvature, and at the onset of a phase transition the early density of defects becomes highly inhomogeneous. We observe that even a single growing crystal can produce varying densities of defects depending on its initial position and local orientation with regard to the substrate. This process is completely different from flat space, where grain boundaries are formed due to the impingement of different propagating crystals. Quenching the liquid into the crystal phase leads to the formation of a curved polycrystalline structure, characterized by complex arrays of defects. During annealing, mechanisms of geodesic curvature-driven grain boundary motion and defect annihilation lead to increasing crystalline order. Linear arrays of defects diffuse to regions of high curvature, where they are absorbed by disclinations. At the early stage of coarsening the density of dislocations is insensitive to the geometry while the population of isolated disclinations is deeply affected by curvature. The regions with high curvature act as traps for the diffusion of different structures of defects, including disclinations and domain walls.

Defect dynamics in crystalline buckled membranes.

We study the dynamics of defect annihilation in flexible crystalline membranes suffering a symmetry-breaking phase transition. The kinetic process leading the system toward equilibrium is described through a Brazovskii-Helfrich-Canham Hamiltonian. In membranes, a negative disclination has a larger energy than a positive disclination. Here we show that this energetic asymmetry does not only affect equilibrium properties, like the Kosterlitz-Thouless transition temperature, but also plays a fundamental role in the dynamic of defects. Both unbinding of dislocations and Carraro-Nelson "antiferromagnetic" interactions between disclinations slow down the dynamics below the Lifshitz-Safran regime observed in flat hexagonal systems.

Dynamics of dislocations in a two-dimensional block copolymer system with hexagonal symmetry.

Block copolymer thin films have attracted considerable attention for their ability to self-assemble into nanometre-scale architectures. Recent advances in the use of block copolymer thin films as nano-lithographic masks have driven research efforts in order to have better control of long-range ordering in the plane of the film. Irrespective of the method of sample preparation, different quasi-two-dimensional systems with hexagonal symmetry unavoidably contain translational defects, called dislocations. Dislocations control the process of coarsening in the nano/meso-scales and provide one of the most important mechanisms of length-scale selection in hexagonal patterns. Although in the last decade the nonlinear dynamics of topological defects in quasi-two-dimensional systems has witnessed significant progress, still little is known about the role of external fields on the creation and annihilation mechanisms involved in the relaxation process towards equilibrium states. In this paper, the dynamics of dislocations in non-optimal hexagonal patterns is studied in the framework of the Ohta-Kawasaki model for a diblock copolymer. Measurements of the climb and glide velocities as a function of the wave vector deformation reveal the main mechanisms of relaxation associated with the motion of dislocations.