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We report that the aqueous dispersions of negatively charged submicron-sized colloidal Au particles formed non-close-packed colloidal crystals by the addition of a like-charged linear polyelectrolyte, sodium polyacrylate (NaPAA). Au particles often form irregular aggregates in dispersions because of a strong van der Waals force acting between them. To prevent aggregation, we introduced negative electric charges on particle surfaces. By the addition of NaPAA, colloidal crystals were formed on the bottom of a sample cell because of the supply of Au particles by sedimentation and 2D diffusion even under very dilute conditions. Interparticle potential calculations demonstrated that the addition of NaPAA caused depletion attraction between the particles as well as a significant reduction in the interparticle repulsion because of the electrostatic screening effect. However, the electrostatic repulsion was strong enough to prevent the direct contact of particles in the excluded region between Au particles. Large-area crystals could be obtained by tilting the sample cell. By drying the sample, the Au particles came into contact and the non-space-filling crystals changed into closest packed crystals. These closest packed crystals exhibited a significant enhancement of Raman scattering intensity because of high hot-spot density.
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For the versatile potential applications of colloidal crystals, precisely controlling their growth is required to achieve properties such as high crystallinity and large-area crystals. Because colloidal crystallization is a self-assembly process of dispersed particles in a solution, solution flow directly and markedly changes the behavior of particles. Thus, the effects of solution flow on the growth of colloidal crystals were investigated in the present study. We found three different effects of solution flow on the growth of colloidal crystals: enlarging the first layer, facilitating the growth of superlattice structures, and forming a new circular packing structure. Specifically, in the single-component system, because the flow speed is lower closer to the bottom of the cell, the second and further layers dissolve owing to the large flow speed, whereas the first layer remains undissolved at the appropriate flow speed. The dissolved particles (particles that are detached from the crystals and returned back into the aqueous medium) are transported near the first layer, where they facilitate the growth of the first layer. In a binary system, when colloidal crystals with different particles are neighboring each other, the flow dissolves the surface of each crystal, which forms a dense, melt-like phase between crystals, from which a superlattice structure such as AB2 grows. The flow often moves the second layer more than the first layer because the flow speed varies with the distance from the bottom. This causes the second layer to slide above the first layer of the neighboring crystals composed of different particle sizes, which transform from the initial face-centered cubic structure of the first layer into a circular pattern with strain. These findings contribute to establishing a sophisticated control method for growing colloidal crystals.
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The heterogeneous nucleation of colloidal crystals with attractive interactions has been investigated via in situ observations. We have found two types of nucleation processes: a cluster that overcomes the critical size for nucleation with a monolayer, and a method that occurs with two layers. The Gibbs free energy changes (ΔG) for these two types of nucleation processes are evaluated by taking into account the effect of various interfacial energies. In contrast to homogeneous nucleation, the change in interfacial free energy, Δσ, is generated for colloidal nucleation on a foreign substrate such as a cover glass in the present study. The Δσ and step free energy of the first layer, γ1, are obtained experimentally based on the equation deduced from classical nucleation theory (CNT). It is concluded that the ΔG of q-2D nuclei is smaller than of monolayer nuclei, provided that the same number of particles are used, which explains the experimental result that the critical size in q-2D nuclei is smaller than that in monolayer nuclei.
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Understanding nucleation dynamics is important both fundamentally and technologically in materials science and other scientific fields. Two-dimensional (2D) nucleation is the predominant growth mechanism in colloidal crystallization, in which the particle interaction is attractive, and has recently been regarded as a promising method to fabricate varieties of complex nanostructures possessing innovative functionality. Here, polymers are added to a colloidal suspension to generate a depletion attractive force, and the detailed 2D nucleation process on the terrace of the colloidal crystals is investigated. In the system, we first measured the nucleation rate at various area fractions of particles on the terrace, Ïarea. In situ observations at single-particle resolution revealed that nucleation behavior follows the framework of classical nucleation theory (CNT), such as single-step nucleation pathway and existence of critical size. Characteristic nucleation behavior is observed in that the nucleation and growth stage are clearly differentiated. When many nuclei form in a small area of the terrace, a high density of kink sites of once formed islands makes growth more likely to occur than further nucleation because nucleation has a higher energy barrier than growth. The steady-state homogeneous 2D nucleation rate, J, and the critical size of nuclei, r*, are measured by in situ observations based on the CNT, which enable us to obtain the step free energy, γ, which is an important parameter for characterizing the nucleation process. The γ value is found to change according to the strength of attraction, which is tuned by the concentration of the polymer as a depletant.
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Epitaxial growth is one of the most important techniques for the control of crystal growth, especially for growing thin-film semiconductor crystals. Similarly, colloidal epitaxy, a template-assisted self-assembly method, is a powerful technique for controlling the structure of colloidal crystals. In this study, heteroepitaxial growth, which differs from homoepitaxial growth of conventional colloidal epitaxy, using foreign colloidal crystals as a substrate, was used to grow single-component colloidal crystal films. The Frank-van der Merwe (FM), Stranski-Krastanov (SK), and Volmer-Weber (VW) modes were observed, and the mode varied with the lattice-misfit ratio and interparticle interactions between the substrate and epitaxial phase. The transition of the growth mode (from SK to VW) and the coexistence of different growth modes (FM and VW) were observed, and their processes were revealed by in situ observation. Colloidal heteroepitaxy was confirmed to be useful for controlling structure, which will enable exploration of novel colloidal self-assembly structures.
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HYPOTHESIS: The colloidal epitaxy utilizing a patterned substrate is used to fabricate colloidal crystals of the same structure and lattice spacing with the substrate, which is an effective technique for creating desired nanoscale architectures. However, this technique has been mainly limited to a single-component system. The colloidal epitaxy is versatile if multicomponent colloidal crystals can be produced, which is inspired by our previous study regarding binary colloidal crystals (b-CCs) fabricated at the edge of single-component crystals. EXPERIMENTS: We have examined various particle size combinations of binary colloidal mixture and substrates for heteroepitaxial growth of b-CCs. Colloidal crystallization was achieved through depletion attraction induced by added polymers. FINDINGS: We demonstrated heteroepitaxial growth of b-CCs on the foreign colloidal crystals as the substrate. Under depletion attraction, deviation from equilibrium interparticle distance because of lattice mismatch between the substrate and epitaxial layers induces strain energy among the particles, yielding the b-CCs to attain minimum strain energy. Various types of b-CCs are created by adjusting the particle size ratio and polymer concentration. The heteroepitaxial growth technique enables the fabrication of complex multicomponent colloidal crystals that greatly facilitate versatile applications of the colloidal crystals.
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Three-dimensional colloidal crystals made of ferromagnetic particles, such as magnetite (Fe(3)O(4)), cannot be synthesized in principle because of the strong attractive magnetic interaction. However, we discovered colloidal crystals composed of polyhedral magnetite nanocrystallites of uniform size in the range of a few hundred nanometers in the Tagish Lake meteorite. Those colloidal crystals were formed 4.6 billion years ago and thus are much older than natural colloidal crystals on earth, such as opals, which formed about 100 million years ago. We found that the size of each individual magnetite particle determines its morphology, which in turn plays an important role in deciding the packing structure of the colloidal crystals. We also hypothesize that each particle has a flux-closed magnetic domain structure, which reduces the interparticle magnetic force significantly.
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The structural evolution of growing thin colloidal crystals in a confined space via the convective assembly technique has been investigated. The thin colloidal crystals were grown in a wedge-shaped cell, where the height of the cell increased with increased crystal growth. Triangle and square patterns, denoted as [111]- and [100]-oriented grains, respectively, were formed alternately as the height of the cell increased. The structural transformation was associated with an increase in the number of layers when the n-layer [100]-oriented grains changed to n + 1-layer [111]-oriented grains. Between the different grain structures, a stripe pattern was observed, which was a transitional region, where particle configuration gradually changed. The structural transformation occurred through the continuous change of particle configuration rather than through the abrupt formation of a grain boundary. The interval of the strip pattern lengthened as the number of layers increased, which is understood to be the structure with the highest packing density. The findings of the study give a better insight into convective assembly in a confined space, and also contribute to the greater structural control of colloidal crystals, useful for a number of applications.
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Because ice surfaces catalyze various key chemical reactions impacting nature and human life, the structure and dynamics of interfacial layers between water vapor and ice have been extensively debated with attention to the quasi-liquid layer. Other interfaces between liquid water and ice remain relatively underexplored, despite their importance and abundance on the Earth and icy extraterrestrial bodies. By in situ optical microscopy, we found that a high-density liquid layer, distinguishable from bulk water, formed at the interface between water and high-pressure ice III or VI, when they were grown or melted in a sapphire anvil cell. The liquid layer showed a bicontinuous pattern, indicating that immiscible waters with distinct structures were separated on the interfaces in a similar manner to liquid-liquid phase separation through spinodal decomposition. Our observations not only provide a novel opportunity to explore ice surfaces but also give insight into the two kinds of structured water.
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The majority of water has vanished from modern meteorites, yet there remain signatures of water on ancient asteroids. How and when water disappeared from the asteroids is important, because the final fluid-concentrated chemical species played critical roles in the early evolution of organics and in the final minerals in meteorites. Here we show evidence of vestigial traces of water based on a nanometre-scale palaeomagnetic method, applying electron holography to the framboids in the Tagish Lake meteorite. The framboids are colloidal crystals composed of three-dimensionally ordered magnetite nanoparticles and therefore are only able to form against the repulsive force induced by the surface charge of the magnetite as a water droplet parches in microgravity. We demonstrate that the magnetites have a flux closure vortex structure, a unique magnetic configuration in nature that permits the formation of colloidal crystals just before exhaustion of water from a local system within a hydrous asteroid.
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We have found that an impurity partitioning takes place during growth of colloidal crystals, which was recognized by the fact that the impurity concentration in the solid (CS) was different from that in the initial solution (C0). The effective partition coefficient k(eff) (=CS/C0) was investigated for pure polystyrene and polystyrene dyed with fluorescent particles by changing the ratio of particle diameters d(imp)/d(cryst) and growth rate V. At each size ratio for the polystyrene impurity, k(eff) was less than unity and increased to unity with increasing V, whereas at a given growth rate, k(eff) increased to unity as d(imp)/d(cryst) approached unity. These results were consistent with the solute behavior analyzed using the Burton, Prim, and Slichter (BPS) model. The obtained k0, equilibrium partition coefficient, from a BPS plot increased as d(imp)/d(cryst) approached unity. In contrast, while the fluorescent particles also followed the BPS model, they showed higher k0 values than those of the same size of polystyrene particles. A k0 value greater than unity was obtained for impurities that were similar in size to the host particle. This behavior is attributed to the positive free energy of fusion associated with the incorporation of the fluorescent particles into the host matrix. Such positive free energy of fusion implies the presence of the enthalpy associated with interaction between particles.