We
studied the formation of supraparticles from nanocrystals confined
in slowly evaporating oil droplets in an oil-in-water emulsion. The
nanocrystals consist of an FeO core, a CoFe2O4 shell, and oleate capping ligands, with an overall diameter of 12.5
nm. We performed in situ small- and wide-angle X-ray
scattering experiments during the entire period of solvent evaporation
and colloidal crystallization. We observed a slow increase in the
volume fraction of nanocrystals inside the oil droplets up to 20%,
at which a sudden crystallization occurs. Our computer simulations
show that crystallization at such a low volume fraction is only possible
if attractive interactions between colloidal nanocrystals are taken
into account in the model as well. The spherical supraparticles have
a diameter of about 700 nm and consist of a few crystalline face-centered
cubic domains. Nanocrystal supraparticles bear importance for magnetic
and optoelectronic applications, such as color tunable biolabels,
color tunable phosphors in LEDs, and miniaturized lasers.
Colloidal photonic
crystals display peculiar optical properties
that make them particularly suitable for application in different
fields. However, the low packing fraction of the targeted structures
usually poses a real challenge in the fabrication stage. Here, we
propose a route to colloidal photonic crystals via a binary mixture of hard tetramers and hard spheres. By combining
theory and computer simulations, we calculate the phase diagram as
well as the stacking diagram of the mixture and show that a colloidal
analogue of the MgCu2 Laves phase—which can serve
as a precursor of a photonic band-gap structure—is a thermodynamically
stable phase in a large region of the phase diagram. Our findings
show a relatively large coexistence region between the fluid and the
Laves phase, which is potentially accessible by experiments. Furthermore,
we determine the sedimentation behavior of the suggested mixture,
by identifying several stacking sequences in the sediment. Our work
uncovers a self-assembly path toward a photonic structure with a band
gap in the visible region.
Colloidal crystals with a diamond and pyrochlore structure display wide photonic band gaps at low refractive index contrasts. However, these low-coordinated and open structures are notoriously difficult to self-assemble from colloids interacting with simple pair interactions. To circumvent these problems, arXiv:1906.10680v1 [cond-mat.soft]
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.
Colloidal photonic crystals, which show a complete band gap in the visible region, have numerous applications in fibre optics, energy storage and conversion, and optical wave guides. Intriguingly, two of the best examples of photonic crystals, the diamond and pyrochlore structure, can be self-assembled into the colloidal MgCu2 Laves phase crystal from a simple binary hard-sphere mixture. For these colloidal length scales thermal and gravitational energies are often comparable and therefore it is worthwhile to study the sedimentation phase behavior of these systems. For a multicomponent system this is possible through a theoretical construct known as a stacking diagram, which constitutes a set of all possible stacking sequences of phases in a sedimentation column, and uses as input the bulk phase diagram of the system in the chemical potential plane. We determine the stable phases for binary hard-sphere systems with varying diameter ratios using Monte Carlo simulations and analytical equations of state available in literature and calculate the corresponding stacking diagrams. We also discuss observations from event-driven Brownian dynamics simulations in relation to our theoretical stacking diagrams.
Using event-driven Brownian dynamics simulations, we investigate the epitaxial growth of hardsphere crystals with a face-centered-cubic (fcc) structure on the three densest cross-sectional planes of the fcc: (i) fcc (100), (ii) fcc (111), and (iii) fcc (110). We observe that for high settling velocities, large fcc crystals with very few extended defects grow on the fcc (100) template. Our results show good agreement with the experiments of Jensen et al. [Soft Matter 9, 320 (2013)], who observed such large fcc crystals upon centrifugation on an fcc (100) template. We also compare the quality of the fcc crystal formed on the fcc (111) and fcc (110) templates with that of the fcc (100) template and conclude that the latter yields the best crystal. We also briefly discuss the dynamical behavior of stacking faults that occur in the sediments. Published by AIP Publishing. [http://dx
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.