ABSTRACT
The unique behavior of colloids at liquid interfaces provides exciting opportunities for engineering the assembly of colloidal particles into functional materials. The deformable nature of fluid-fluid interfaces means that we can use the interfacial curvature, in addition to particle properties, to direct self-assembly. To this end, we use a finite element method (Surface Evolver) to study the self-assembly of rod-shaped particles adsorbed at a simple curved fluid-fluid interface formed by a sessile liquid drop with cylindrical geometry. Specifically, we study the self-assembly of single and multiple rods as a function of drop curvature and particle properties such as shape (ellipsoid, cylinder, and spherocylinder), contact angle, aspect ratio, and chemical heterogeneity (homogeneous and triblock patchy). We find that the curved interface allows us to effectively control the orientation of the rods, allowing us to achieve parallel, perpendicular, or novel obliquely orientations with respect to the cylindrical drop. In addition, by tuning particle properties to achieve parallel alignment of the rods, we show that the cylindrical drop geometry favors tip-to-tip assembly of the rods, not just for cylinders, but also for ellipsoids and triblock patchy rods. Finally, for triblock patchy rods with larger contact line undulations, we can achieve strong spatial confinement of the rods transverse to the cylindrical drop due to the capillary repulsion between the contact line undulations of the particle and the pinned contact lines of the sessile drop. Our capillary assembly method allows us to manipulate the configuration of single and multiple rod-like particles and therefore offers a facile strategy for organizing such particles into useful functional materials.
ABSTRACT
The two-dimensional self-assembly of colloidal particles serves as a model system for fundamental studies of structure formation and as a powerful tool to fabricate functional materials and surfaces. However, the prevalence of hexagonal symmetries in such self-assembling systems limits its structural versatility. More than two decades ago, Jagla demonstrated that core-shell particles with two interaction length scales can form complex, nonhexagonal minimum energy configurations. Based on such Jagla potentials, a wide variety of phases including cluster lattices, chains, and quasicrystals have been theoretically discovered. Despite the elegance of this approach, its experimental realization has remained largely elusive. Here, we capitalize on the distinct interfacial morphology of soft particles to design two-dimensional assemblies with structural complexity. We find that core-shell particles consisting of a silica core surface functionalized with a noncrosslinked polymer shell efficiently spread at a liquid interface to form a two-dimensional polymer corona surrounding the core. We controllably grow such shells by iniferter-type controlled radical polymerization. Upon interfacial compression, the resulting core-shell particles arrange in well-defined dimer, trimer, and tetramer lattices before transitioning into complex chain and cluster phases. The experimental phase behavior is accurately reproduced by Monte Carlo simulations and minimum energy calculations, suggesting that the interfacial assembly interacts via a pairwise-additive Jagla-type potential. By comparing theory, simulation, and experiment, we narrow the Jagla g-parameter of the system to between 0.9 and 2. The possibility to control the interaction potential via the interfacial morphology provides a framework to realize structural features with unprecedented complexity from a simple, one-component system.
