Giuseppe Soligno

Self-Assembly of Colloidal Hexagonal Bipyramid- and Bifrustum-Shaped ZnS Nanocrystals into Two-Dimensional Superstructures

We present a combined experimental, theoretical, and simulation study on the self-assembly of colloidal hexagonal bipyramid- and hexagonal bifrustum-shaped ZnS nanocrystals (NCs) into two-dimensional superlattices. The simulated NC superstructures are in good agreement with the experimental ones. This shows that the self-assembly process is primarily driven by minimization of the interfacial free-energies and maximization of the packing density. Our study shows that a small truncation of the hexagonal bipyramids is sufficient to change the symmetry of the resulting superlattice from hexagonal to tetragonal, highlighting the crucial importance of precise shape control in the fabrication of functional metamaterials by self-assembly of colloidal NCs.

Self-Assembly of Cubes into 2D Hexagonal and Honeycomb Lattices by Hexapolar Capillary Interactions

Particles adsorbed at a fluid-fluid interface induce capillary deformations that determine their orientations and generate mutual capillary interactions which drive them to assemble into 2D ordered structures. We numerically calculate, by energy minimization, the capillary deformations induced by adsorbed cubes for various Youngs contact angles. First, we show that capillarity is crucial not only for quantitative, but also for qualitative predictions of equilibrium configurations of a single cube. For a Youngs contact angle close to 90°, we show that a single-adsorbed cube generates a hexapolar interface deformation with three rises and three depressions. Thanks to the threefold symmetry of this hexapole, strongly directional capillary interactions drive the cubes to self-assemble into hexagonal or graphenelike honeycomb lattices. By a simple free-energy model, we predict a density-temperature phase diagram in which both the honeycomb and hexagonal lattice phases are present as stable states.

The equilibrium shape of fluid-fluid interfaces: Derivation and a new numerical method for Young’s and Young-Laplace equations

Many physical problems require explicit knowledge of the equilibrium shape of the interface between two fluid phases. Here, we present a new numerical method which is simply implementable and easily adaptable for a wide range of problems involving capillary deformations of fluid-fluid interfaces. We apply a simulated annealing algorithm to find the interface shape that minimizes the thermodynamic potential of the system. First, for completeness, we provide an analytical proof that minimizing this potential is equivalent to solving the Young-Laplace equation and the Young law. Then, we illustrate our numerical method showing two-dimensional results for fluid-fluid menisci between vertical or inclined walls and curved surfaces, capillary interactions between vertical walls, equilibrium shapes of sessile heavy droplets on a flat horizontal solid surface, and of droplets pending from flat or curved solid surfaces. Finally, we show illustrative three-dimensional results to point out the applicability of the method to micro- or nano-particles adsorbed at a fluid-fluid interface.

Sessile Nanodroplets on Elliptical Patches of Enhanced Lyophilicity

We theoretically investigate the shape of a nanodroplet on a lyophilic elliptical patch in lyophobic surroundings on a flat substrate. To compute the droplet equilibrium shape, we minimize its interfacial free energy using both Surface Evolver and Monte Carlo calculations, finding good agreement between the two methods. We observe different droplet shapes, which are controlled by the droplet volume and the aspect ratio of the ellipse. In particular, we study the behavior of the nanodroplet contact angle along the three-phase contact line, explaining the different droplet shapes. Although the nanodroplet contact angle is constant and fixed by Young’s law inside and outside the elliptical patch, its value varies along the rim of the elliptical patch. We find that because of the pinning of the nanodroplet contact line at the rim of the elliptical patch, which has a nonconstant curvature, there is a regime of aspect ratios of the elliptical patch in which the nanodroplet starts expanding to the lyophobic part of the substrate, although there is still a finite area of the lyophilic patch free to be wetted.

Regiospecific Nucleation and Growth of Silane Coupling Agent Droplets onto Colloidal Particles

Nucleation-and-growth processes are used extensively in the synthesis of spherical colloids, and more recently regiospecific nucleation-and-growth processes have been exploited to prepare more complex colloids such as patchy particles. We demonstrate that surface geometry alone can be made to play the dominant role in determining the final particle geometry in such syntheses, meaning that intricate chemical surface patternings are not required. We present a synthesis method for “lollipop”-shaped colloidal heterodimers (patchy particles), combining a recently published nucleation-and-growth technique with our recent findings that particle geometry influences the locus of droplet adsorption onto anisotropic template particles. Specifically, 3-methacryloxypropyl trimethoxysilane (MPTMS) is nucleated and grown onto bullet-shaped and nail-shaped colloids. The shape of the template particle can be chosen such that the MPTMS adsorbs regiospecifically onto the flat ends. In particular, we find that particles with a wider base increase the range of droplet volumes for which the minimum in the free energy of adsorption is located at the flat end of the particle compared with bullet-shaped particles of the same aspect ratio. We put forward an extensive analysis of the synthesis mechanism and experimentally determine the physical properties of the heterodimers, supported by theoretical simulations. Here we numerically optimize, for the first time, the shape of finite-sized droplets as a function of their position on the rod-like silica particle surface. We expect that our findings will give an impulse to complex particle creation by regiospecific nucleation and growth.