Heteroepitaxial Growth of Colloidal Crystals: Dependence of the Growth Mode on the Interparticle Interactions and Lattice Spacing.

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.

Heteroepitaxial fabrication of binary colloidal crystals by a balance of interparticle interaction and lattice spacing.

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.

Crystallization of charged gold particles mediated by nonadsorbing like-charged polyelectrolyte.

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.

Control of strain in subgrains of protein crystals by the introduction of grown-in dislocations.

It is important to reveal the exact cause of poor diffractivity in protein crystals in order to determine the accurate structure of protein molecules. It is shown that there is a large amount of local strain in subgrains of glucose isomerase crystals even though the overall crystal quality is rather high, as shown by clear equal-thickness fringes in X-ray topography. Thus, a large stress is exerted on the subgrains of protein crystals, which could significantly lower the resistance of the crystals to radiation damage. It is also demonstrated that this local strain can be reduced through the introduction of dislocations in the crystal. This suggests that the introduction of dislocations in protein crystals can be effective in enhancing the crystal quality of subgrains of protein crystals. By exploiting this effect, the radiation damage in subgrains could be decreased, leading to the collection of X-ray diffraction data sets with high diffractivity.

Structural transformations of growing thin colloidal crystals in confined space via convective assembly.

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.

High-Density Liquid Water at a Water-Ice Interface.

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.

Effects of Solution Flow on the Growth of Colloidal Crystals.

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.

Heterogeneous Nucleation of Colloidal Crystals on a Glass Substrate with Depletion Attraction.

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.

Two-Dimensional Nucleation on the Terrace of Colloidal Crystals with Added Polymers.

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, ϕarea. 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.

Developmental changes in the corpus callosum from infancy to early adulthood: a structural magnetic resonance imaging study.

Previous research has reported on the development trajectory of the corpus callosum morphology. However, there have been only a few studies that have included data on infants. The goal of the present study was to examine the morphology of the corpus callosum in healthy participants of both sexes, from infancy to early adulthood. We sought to characterize normal development of the corpus callosum and possible sex differences in development. We performed a morphometric magnetic resonance imaging (MRI) study of 114 healthy individuals, aged 1 month to 25 years old, measuring the size of the corpus callosum. The corpus callosum was segmented into seven subareas of the rostrum, genu, rostral body, anterior midbody, posterior midbody, isthmus and splenium. Locally weighted regression analysis (LOESS) indicated significant non-linear age-related changes regardless of sex, particularly during the first few years of life. After this increase, curve slopes gradually became flat during adolescence and adulthood in both sexes. Age of local maximum for each subarea of the corpus callosum differed across the sexes. Ratios of total corpus callosum and genu, posterior midbody, as well as splenium to the whole brain were significantly higher in females compared with males. The present results demonstrate that the developmental trajectory of the corpus callosum during early life in healthy individuals is non-linear and dynamic. This pattern resembles that found for the cerebral cortex, further suggesting that this period plays a very important role in neural and functional development. In addition, developmental trajectories and changes in growth do show some sex differences.

Normal development of human brain white matter from infancy to early adulthood: a diffusion tensor imaging study.

Diffusion tensor imaging (DTI), which measures the magnitude of anisotropy of water diffusion in white matter, has recently been used to visualize and quantify parameters of neural tracts connecting brain regions. In order to investigate the developmental changes and sex and hemispheric differences of neural fibers in normal white matter, we used DTI to examine 52 healthy humans ranging in age from 2 months to 25 years. We extracted the following tracts of interest (TOIs) using the region of interest method: the corpus callosum (CC), cingulum hippocampus (CGH), inferior longitudinal fasciculus (ILF), and superior longitudinal fasciculus (SLF). We measured fractional anisotropy (FA), apparent diffusion coefficient (ADC), axial diffusivity (AD), and radial diffusivity (RD). Approximate values and changes in growth rates of all DTI parameters at each age were calculated and analyzed using LOESS (locally weighted scatterplot smoothing). We found that for all TOIs, FA increased with age, whereas ADC, AD and RD values decreased with age. The turning point of growth rates was at approximately 6 years. FA in the CC was greater than that in the SLF, ILF and CGH. Moreover, FA, ADC and AD of the splenium of the CC (sCC) were greater than in the genu of the CC (gCC), whereas the RD of the sCC was lower than the RD of the gCC. The FA of right-hemisphere TOIs was significantly greater than that of left-hemisphere TOIs. In infants, growth rates of both FA and RD were larger than those of AD. Our data show that developmental patterns differ by TOIs and myelination along with the development of white matter, which can be mainly expressed as an increase in FA together with a decrease in RD. These findings clarify the long-term normal developmental characteristics of white matter microstructure from infancy to early adulthood.

Referential framework for transcranial anatomical correspondence for fNIRS based on manually traced sulci and gyri of an infant brain.

Functional near infrared spectroscopy (fNIRS), which is compact, portable, and tolerant of body movement, is suitable for monitoring infant brain functions. Nevertheless, fNIRS also poses a technical problem in that it cannot provide structural information. Supplementation with structural magnetic resonance images (MRI) is not always feasible for infants who undergo fNIRS measurement. Probabilistic registration methods using an MRI database instead of subjects' own MRIs are optimized for adult studies and offer only limited resources for infant studies. To overcome this, we used high-quality infant MRI data for a 12-month-old infant and manually delineated segmented gyri from among the highly visible macroanatomies on the lateral cortical surface. These macroanatomical regions are primarily linked to the spherical coordinate system based on external cranial landmarks, and further to traditional 10-20-based head-surface positioning systems. While macroanatomical structures were generally comparable between adult and infant atlases, differences were found in the parietal lobe, which was positioned posteriorly at the vertex in the infant brain. The present study provides a referential framework for macroanatomical analyses in infant fNIRS studies. With this resource, multichannel fNIRS functional data could be analyzed in reference to macroanatomical structures through virtual and probabilistic registrations without acquiring subject-specific MRIs.

Impurity partitioning during colloidal crystallization.

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.

Electrical conduction mechanism in La3Ta0.5Ga5.3Al0.2O14 single crystals.

The electrical conduction mechanism in La3Ta0.5Ga5.3Al0.2O14 (LTGA) single crystals was studied by nonstoichiometric defect formation during crystal growth. Since stoichiometric LTGA is not congruent, the single crystal grown from the stoichiometric melt was Ta-poor and Al-rich, where Al atoms were substituted not only in Ga sites but also in Ta sites. The population of the substitutional Al in Ta sites increased with increasing oxygen partial pressure during growth (growth-pO2) in the range from 0.01 to 1 atm. Below 600 °C, substitutional Al atoms in Ta sites were ionized to yield holes, and thus the electrical conductivity of the LTGA crystal depended on temperature and the growth-pO2. The dependence of the electrical conductivity on the growth-pO2 decreased as temperature increased. The temperature rise increases ionic conductivity, for which the dominant carriers are oxygen defects formed by the anion Frenkel reaction.

Precipitation phenomena in and electrical resistivity of high-temperature treated langatate (La3Ta0.5Ga5.5O14).

La(3)Ta(0.5)Ga(5.5)O(14) (LTG) single crystals, which have no phase transition up to the melting point, were heat-treated in air at temperatures from 1000°C to 1450°C for 10 h. LaTaO(4) (LT) and LaGaO(3) (LG), which coexist with LTG in the three-phase region on the Ga-poor side, precipitated on the surface of the crystal for heat treatments above 1300°C because of Ga evaporation during the heat treatment. The Ga-poor state near the surface of the 1450°C heat-treated specimen was confirmed by electron probe micro-analysis measurements. The electrical resistivity of LTG single crystals decreased by heat treatment in the range of 1000°C to 1200°C for 10 h in air, where no precipitation was observed, whereas the resistivity increased with heat treatment over 1400°C for 10 h in air. The electrical resistivity of the Ga-poor surface region was higher than that of the interior.