Assembling binary mixtures of nanoparticles into crystals, gives rise to collective properties depending on the crystal structure and the individual properties of both species. However, quantitative 3D real-space analysis of binary colloidal crystals with a thickness of more than 10 layers of particles has rarely been performed. Here we demonstrate that an excess of one species in the binary nanoparticle mixture suppresses the formation of icosahedral order in the self-assembly in droplets, allowing the study of bulk-like binary crystal structures with a spherical morphology also called supraparticles. As example of the approach, we show single-particle level analysis of over 50 layers of Laves phase binary crystals of hard-sphere-like nanoparticles using electron tomography. We observe a crystalline lattice composed of a random mixture of the Laves phases. The number ratio of the binary species in the crystal lattice matches that of a perfect Laves crystal. Our methodology can be applied to study the structure of a broad range of binary crystals, giving insights into the structure formation mechanisms and structure-property relations of nanomaterials.

We investigate the effect of hydrodynamic interactions (HIs) on the crystal nucleation of hard-sphere colloids for varying supersaturations. We use molecular dynamics and stochastic rotation dynamics techniques to account for the HIs. For high supersaturation values, we perform brute force simulations and compute the nucleation rate, obtaining good agreement with previous studies where HIs were neglected. In order to access low supersaturation values, we use a seeding approach method and perform simulations with and without HIs. We compute the nucleation rates for the two cases and surprisingly find good agreement between them. The nucleation rate in both cases follows the trend of the previous numerical results, thereby corroborating the discrepancy between experiments and simulations. Furthermore, we investigate the amount of fivefold symmetric clusters (FSCs) in a supersaturated fluid under different physical conditions, following the idea that FSCs compete against nucleation. To this end, we explore the role of the softness of the pair interactions, different solvent viscosities, and different sedimentation rates in simulations that include HIs. We do not find significant variations in the amount of FSCs, which might reflect the irrelevance of these three features on the nucleation process.

Although the self-alignment of asymmetric macro-sized objects of a few tens of microns in size have been studied extensively in experiments and theory, access to much smaller length scales is still hindered by technical challenges. We combine molecular dynamics and stochastic rotation dynamics techniques to investigate the self-orientation phenomenon at different length scales, ranging from the micron to the nano scale by progressively increasing the relative strength of diffusion over convection. To this end, we model an asymmetric dumbbell particle in Hele-Shaw flow and explore a wide range of Péclet numbers (Pe) and different particle shapes, as characterized by the size ratio of the two dumbbell spheres (R). By independently varying these two parameters we analyse the process of self-orientation and characterize the alignment of the dumbbell with the direction of the fluid flow. We identify three different regimes of strong, weak and no alignment and we map out a state diagram in Pe versus R plane. Based on these results, we estimate dimensional length scales and flow rates for which these findings would be applicable in experiments. Finally, we find that the characteristic reorientation time of the dumbbell is a monotonically decreasing function of the dumbbell anisotropy.

Oriented attachment of PbSe nanocubes can result in the formation of two-dimensional (2D) superstructures with long-range nanoscale and atomic order. This questions the applicability of classic models in which the superlattice grows by first forming a nucleus, followed by sequential irreversible attachment of nanocrystals, as one misaligned attachment would disrupt the 2D order beyond repair. Here, we demonstrate the formation mechanism of 2D PbSe superstructures with square geometry by using in situ grazing-incidence X-ray scattering (small angle and wide angle), ex situ electron microscopy, and Monte Carlo simulations. We observed nanocrystal adsorption at the liquid/gas interface, followed by the formation of a hexagonal nanocrystal monolayer. The hexagonal geometry transforms gradually through a pseudo-hexagonal phase into a phase with square order, driven by attractive interactions between the {100} planes perpendicular to the liquid substrate, which maximize facet-to-facet overlap. The nanocrystals then attach atomically via a necking process, resulting in 2D square superlattices.

We present experimental and theoretical results on suspensions of silica rods in DMSO-water, subjected to an applied electric field. The experimental results indicate that, if the electrode used for generating the electric field is in direct contact with the suspension, a fraction of the rods close to the electrode surface does not stand parallel to the field but instead lies flat on the electrode when the field is switched on. To explain these results theoretically, we modify the coupled dipole method to include “image dipoles”, and find that a rod close to the electrode experiences not only the expected global potential energy minimum at an orientation parallel to the electric field, but also a local minimum several times the thermal energy in depth for orientations parallel to the electrode surface. Additionally, we indicate how the magnitude of the potential energy depends on the electric field strength and include results not only for negatively polarizable (which correspond to the aforementioned experimental system), but also for positively polarizable rods.

We study the sedimentation of an initially inhomogeneous distribution of binary colloidal mixtures confined to a slit using a coarse-grained hybrid molecular dynamics and stochastic rotation dynamics simulation technique. This technique allows us to take into account the Brownian motion and hydrodynamic interactions between colloidal particles in suspensions. The sedimentation of such systems results in the formation of Rayleigh-Taylor-like hydrodynamic instabilities, and here we examine both the process of the formation and the evolution of the instability, as well as the structural organization of the colloids, depending on the properties of the binary mixture. We find that the structural properties of the swirls that form as a consequence of the instability depend greatly on the relative magnitudes of the Peclet numbers, and much less on the composition of the mixture. We also calculate the spatial colloid velocity correlation functions which allow us to follow the time evolution of the instability and the time dependence of the characteristic correlation length. Finally, we calculate the growth rates of the unstable modes both directly from our simulation data, and also using a theoretical approach, finding good agreement.