Observations of defect propagation in [100]-oriented opal-type photonic crystals

Charged colloidal suspensions have been used as experimental models for the study of crystal nucleation. Here we propose that the technique of template-assisted colloidal self-assembly can be used to visualize the effects of defect propagation in atomic crystal films produced using epitaxial growth. Templates with periodic line defects were used to grow [100]-oriented three-dimensional photonic crystals by means of the template-assisted colloidal self-assembly method, aided by capillary and gravitational forces. The defect propagation in the [100]-oriented photonic crystal was observed using scanning electron microscopy, both at the surface of the crystal and on cleaved facets. This method is useful in the understanding of defect propagation in the growth of colloidal films on templates - and the same approach may also prove useful for the understanding of atomic crystal growth on substrates with defects. Additionally, the deliberate incorporation of line defects may prove valuable as a way of introducing waveguide channels into three-dimensional photonic crystals.     

Bragg rods and multiple X-ray scattering in random-stacking colloidal crystals

Synchrotron small-angle x-ray diffraction images of random-stacking-induced Bragg scattering rods are obtained in a wide range of wave vectors from a single colloidal crystal. The results reveal a strong multiple scattering effect, which leads to new features in the diffraction pattern-secondary Bragg rods. We argue that dynamic x-ray diffraction is rather common for high-quality colloidal photonic crystals and should be taken into account.     

Determination of the colloidal crystal nucleation rate density

Colloidal suspensions of charged latex microspheres in water exhibit liquid-like or crystalline ordering depending on particle interaction and concentration. By virtue of large particle spacing and slow dynamics, colloidal systems offer a unique opportunity to study interfacial structure and dynamics. This paper presents the first reported experimental study of the nucleation rate density, c, of an nonequilibrium (supercooled) colloidal liquid to colloidal crystal first order phase transition. Local and global observations of colloidal crystals growing from a metastable colloidal liquid were used to determine c. Microscopic local observations revealed homogeneous nucleation and constant interface velocity growth of quasispherical crystallites in the bulk and heterogeneous nucleation of a crystalline sheet with lower growth velocity at the cell wall. Complementary global observations of the recrystallization transition made by measuring the time dependence of the suspension transparency (the fraction of transmitted laser light) determined c by fitting this curve to a model based on an extension of Avrami's theory of crystallization.     

Colloidal crystal growth at externally imposed nucleation clusters

We study the conditions under which and how an imposed cluster of fixed colloidal particles at prescribed positions triggers crystal nucleation from a metastable colloidal fluid. Dynamical density functional theory of freezing and Brownian dynamics simulations are applied to a two-dimensional colloidal system with dipolar interactions. The externally imposed nucleation clusters involve colloidal particles either on a rhombic lattice or along two linear arrays separated by a gap. Crystal growth occurs after the peaks of the nucleation cluster have first relaxed to a cutout of the stable bulk crystal.     

Polymer-mediated and ultrasound-assisted crystallization of ropivacaine: Crystal growth and morphology modulation

The objective of this research was to modify the crystal shape and size of poorly water-soluble drug ropivacaine, and to reveal the effects of polymeric additive and ultrasound on crystal nucleation and growth. Ropivacaine often grow as needle-like crystals extended along the a-axis and the shape was hardly controllable by altering solvent types and operating conditions for the crystallization process. We found that ropivacaine crystallized as block-like crystals when polyvinylpyrrolidone (PVP) was used. The control over crystal morphology by the additive was related to crystallization temperature, solute concentration, additive concentration, and molecular weight. SEM and AFM analyses were performed providing insights into crystal growth pattern and cavities on the surface induced by the polymeric additive. In ultrasound-assisted crystallization, the impacts of ultrasonic time, ultrasonic power, and additive concentration were investigated. The particles precipitated at extended ultrasonic time exhibited plate-like crystals with shorter aspect ratio. Combined use of polymeric additive and ultrasound led to rice-shaped crystals, which the average particle size was further decreased. The induction time measurement and single crystal growth experiments were carried out. The results suggested that PVP worked as strong nucleation and growth inhibitor. Molecular dynamics simulation was performed to explore the action mechanism of the polymer. The interaction energies between PVP and crystal faces were calculated, and mobility of the additive with different chain length in crystal-solution system was evaluated by mean square displacement. Based on the study, a possible mechanism for the morphological evolution of ropivacaine crystals assisted by PVP and ultrasound was proposed.     

The phase coexistence method to obtain surface free energies and nucleation barriers: a brief review

ABSTRACT

A recently developed method where one analyses the finite size effects associated with liquid–solid phase equilibria including vapour–crystal coexistence is briefly reviewed. It is shown that the estimation of the chemical potential of the vapour surrounding the crystal as function of the crystal volume yields information on the bulk coexistence conditions, when an extrapolation to the thermodynamic limit is performed. Estimating the pressure of the fluid surrounding the crystal nucleus in the finite simulation box and the volume of this nucleus that coexists with the fluid in thermal equilibrium, an estimate for the total surface excess free energy can be obtained, which to a very good approximation is independent of the size of the simulation box. The free energy barrier against homogeneous nucleation of crystals thus can be estimated as a function of the nucleus volume. Monte Carlo simulations for the soft effective Asakura–Oosawa model of colloid-polymer mixtures which form face-centered cubic colloidal crystals are used to exemplify this method, computing the surface excess free energy of these crystals over a wide range of crystal volumes, without the need to characterise the non-spherical crystal shape. A possible extension of these concepts to heterogeneous nucleation is also briefly discussed.     

冷却速率对温敏聚N-异丙基丙烯酰胺胶体结晶过程的影响

冷却速率对结晶过程具有重要的影响. 本文采用温敏poly-N-isopropylacrylamide (PNIPAM) 胶体晶体体系实时观察了冷却速率对结晶晶粒尺寸的影响. 通过高倍透射明场观察和Bragg衍射观察研究连续冷却下的晶粒形核和生长实时演化过程, 发现随着冷却速率的增加, PNIPAM胶体晶体晶粒尺寸不断减少. 晶粒尺寸与冷却速率符合幂指数关系, 与金属体系具有相似的演化规律.     

Research of band gap properties based on two-dimensional photonic crystal with mixed shapes of rods

Two new structures of photonic crystals were designed. The band gap properties of photonic crystals with square and circular dielectric rods mixed arrangement are researched. The band gap properties of mixed shapes rods photonic crystal are calculated and compared with the crystals with square rods or round rods by using plane wave expansion method. Simulation results show that for the square lattice, mixed shapes of rods make the higher-order bands of TM modes moving toward the low frequency range. The gap bands’ widths and locations are between the parameters of square and round rods photonic crystal. In triangle lattice, a significant band gap is presented in photonic crystal with mixed shapes of rods in TE mode, while it is almost not presented in square and round rods crystals. The phenomenon of bands moving toward the low frequency range is also found in the triangle lattice mixed shapes rods photonic crystal. The reasons of the results in the vision were analyzed.     

A phase-field/Monte-Carlo model describing organic crystal growth from solution

In this paper work we present a phase-field/Monte-Carlo hybrid algorithm for the simulation of solutal growth of organic crystals. The algorithm is subsequently used for an investigation of diffusion effects on the growth mechanisms. This method combines a two-scale phase-field model of the liquid phase epitaxial growth and a Monte-Carlo algorithm of the 2D nucleation and thus is faster than previous purely Monte Carlo simulations of crystal growth. The inclusion of supersaturation and diffusion in the method allows the study of crystal growth under various growth conditions. Parameters used in the hybrid algorithm are bound to the energetic parameters of crystal faces, which can be estimated from a detailed study of the actual crystal structure based on a connected nets analysis, which allows the prediction of the shape and morphology of real crystals. The study of the diffusion effect is carried out based on an example of a hydroquinone crystal, which grows from the water solution at various supersaturations. The dependencies of the growth rate and the nucleation rate on the supersaturation indicate the change of the growth mechanism from spiral growth to 2D nucleation. The difference in the growth rate for various faces is in agreement with the crystal morphologies derived from the attachment energy method and observed experimentally. The main result of the simulation is the evaluation of engineering limits for choosing appropriate external process conditions.     

A colloidal crystal double-heterostructure fabricated with the angle controlled inclined deposition method

A self-assembly method, named the angle controlled inclined deposition method, is developed for fabricating well-ordered silica and polystyrene colloidal crystals. A high-quality colloidal crystal with a flat and uniform surface over a large area can be produced rapidly using a minute quantity of suspension and without any additional equipment. By controlling the inclined angle, we can fabricate colloidal crystals with diverse numbers of layers. A colloidal crystal double-heterostructure (composed of three different colloidal photonic crystals) can be rapidly fabricated with this method. Both experimental and simulation results show that the photonic band gap of the double-heterostructure is not a simple superposition of that of the compositional colloidal crystals along the stacking direction.     

Evidence of many-particle interactions in two-dimensional charge-stabilized colloidal crystals

Electrostatic interaction in two-dimensional colloidal crystals obeying the nonlinear Poisson-Boltzmann equation is studied numerically. The force constants which are the coefficients of the energy quadratic form of the crystal are obtained. Significant discrepancy between the results of computer experiments and predictions of the harmonic crystal theory based on the idea of pairwise interaction has been detected. Two simple parameters are introduced for uniform quantitative estimation of many-particle effects and validity of the approximation of nearest-neighbor interaction. It is shown that the contribution of many-particle interaction into the total electrostatic interaction in colloidal crystals is significant for a broad range of crystal lattice constants and particles' sizes.     

Coherent kinetic control over crystal orientation in macroscopic ensembles of polymer nanorods and nanotubes

We show that the crystal orientation in polymer nanotubes and nanorods inside porous templates is controlled by the kinetics of nucleation and growth under 2D confinement. Two clear limiting cases are identified: In separated nanostructures, any crystal orientation allowing the growth of lamellar crystals along the pores appears statistically. If a bulklike surface film connects the nanostructures, macroscopic arrays with uniform crystal orientation are obtained, in which the dominant growth direction of the crystals is aligned with the long axes of the pores of the template.     

Kinetic pathways for the isotropic-nematic phase transition in a system of colloidal hard rods: a simulation study

We study the kinetic pathways for the isotropic-to-nematic transition in a fluid of colloidal hard rods. In order to follow the formation of the nematic phase, we develop a new cluster criterion that distinguishes nematic clusters from the isotropic phase. Applying this criterion in Monte Carlo simulations, we find spinodal decomposition as well as nucleation and growth depending on the supersaturation. We determine the height of the nucleation barrier and we study the shape and structure of the cluster. More specifically, we find ellipsoidal nematic clusters with an aspect ratio of about 1.7 and a homogeneous nematic director field. Our results are consistent with theoretical predictions on the shape and director field of nematic tactoids. Classical nucleation theory gives reasonable predictions for the height of the nucleation barrier and the critical nucleus size.     

On the nonequilibrium phase transition in protein

Considerations are presented that support the idea that the nonequilibrium phase transition in protein is accompanied by the growth of a colloidal nanocrystal (or the vitrified phase of a liquid crystal). To date, the dynamic transition forms of protein, which are “the source of the catalytic power of enzymes,” have been poorly understood. In our experiments, we observed the dehydration (drying) of the colloid solution of protein in an open (far from thermodynamic equilibrium) one-component protein-water system. The protein in this state is found to acquire properties typical of matter self-organization, including the universal properties of colloidal nanocrystals of different nature, namely, nonequilibrium chaotic dynamics with self-replicability, autocatalysis, coherency, autowave fluctuations, synchronism, fractality, 3D epitaxial growth (stacking) of films, nucleation giving rise to blocks (cells) with shell nuclei, etc. It then follows that our realistic model of the nonequilibrium state of protein during growth of its colloidal nanocrystal provides an opportunity of studying the dynamics of the structural and energy-information features of the transition and solid colloidal nanocrystalline phases of protein. In addition, it allows researchers to gain fundamentally new information about the energy characteristics of protein under abiotic and biotic conditions.     

Fabrication of Two-Dimensional Arrays of Micron-Sized Gold Rings Based on Preferential Nucleation at Reentrant Sites

A templating method for fabricating two-dimensional （2D） arrays of micron-sized goM rings is reported. The microstructures are formed by electroless plating in a through-porous polymer membrane on a silicon substrate obtained from a closed-packed silica colloidal crystal. Our results show that the sizes of gold rings can be altered by varying electroless plating conditions for the porous polystyrene membranes. Moreover, we explain the growth mechanism of gold rings using the classical crystal growth theory that is preferential nucleation at reentrant sites.     

Fabrication of two-dimensional colloidal arrays

We report the effective fabrication of two-dimensional (2D) arrays of submicron colloidal particles. These colloidal arrays are produced in thin layers of monodisperse colloid suspensions on flat surfaces of solids such as clean glass or cleaved mica. The process of colloid assembling includes two steps, nucleation and growth, similar to those found in crystallization in solution but each of the steps in detail progresses with different mechanisms. The nucleation process is initiated by a special kind of capillary force acting parallel to the surface. The growth is guided by a laminar flow of water to the crystals, which is driven by water evaporation from 2D arrays. What is distinguishable in the 2D assembling is its active nature governed by the forces and flows, making a contrast to the diffusive mechanism in ordinary crystallization. With this two-step mechanism, a domain of hexagonally packed colloidal array can grow with time. A large and uniform film of particle monolayer is, thus, formed in a short period, from several seconds up to several minutes depending on the conditions controlled.     

A colloidal crystal microstructure fiber: fabrication and characterization

A method of fabricating colloidal crystal microstructured fiber is presented. The proposed structure relies on partial etching of the cladding layer of a single-mode fiber and growth of colloidal photonic crystals inside eroded area. The photonic crystal cylindrical annulus embedded in fiber is characterized by optical and scanning electron microscopy. The optical characterization was analyzed by optical transmission spectroscopy. The measurement results show a about 1550-nm band gap. The results also reveal the possibility of cladding cylindrical fibers with three-dimensional photonic crystals.     

Sonocrystallization and sonofragmentation

The application of ultrasound to crystallization (i.e., sonocrystallization) can dramatically affect the properties of the crystalline products. Sonocrystallization induces rapid nucleation that generally yields smaller crystals of a more narrow size distribution compared to quiescent crystallizations. The mechanism by which ultrasound induces nucleation remains unclear although reports show the potential contributions of shockwaves and increases in heterogeneous nucleation. In addition, the fragmentation of molecular crystals during ultrasonic irradiation is an emerging aspect of sonocrystallization and nucleation. Decoupling experiments were performed to confirm that interactions between shockwaves and crystals are the main contributors to crystal breakage. In this review, we build upon previous studies and emphasize the effects of ultrasound on the crystallization of organic molecules. Recent work on the applications of sonocrystallized materials in pharmaceutics and materials science are also discussed.     

Crystallographic symmetry effect on the nucleation in non-equilibrium aggregation pattern

Some non-equilibrium patterns formed in different systems are composed by crystallites with correlations in their crystallographic orientation. This reflects the fact that crystallographic symmetry controls the successive nucleation in the crystallite aggregating process. Based on the crystallographic symmetry, a new classification to describe the different kinds of anisotropy for non-equilibrium aggregation pattern has been proposed: parallel aggregation, twin aggregation and radial (random) aggregation. This new classification can clarify the different anisotropy related to the crystal point group, which the previous classifications cannot. The nucleation mechanisms for these three kinds of patterns are also discussed based on the symmetric relationship among the crystallites. It is shown that the crystallographic symmetry plays an important role not only on the crystal polyhedral shape formed by growth, but also on the aggregation pattern formed by nucleation.     

Shape alterations of ZnO nanocrystal arrays fabricated from NH3·H2O solutions

Well-aligned crystalline ZnO nanorod arrays were synthesized via an aqueous solution route with ammonia and zinc nitrate as inorganic precursors. ZnO crystalline seed films were firstly coated on ITO substrates for epitaxial growth of rods through sol-gel processing and heat treatment. SEM, TEM, SAED and XRD were utilized to characterize morphologies and structures of ZnO crystals. Heterogeneous nucleation is crucial for rod growth. A broad scope of pH favorable for heterogeneous nucleation was disclosed at zinc concentration from 0.04 to 0.1 M in the inorganic system due to the complex reaction of ammonia with Zn²⁺. Elevation of initial zinc concentration or pH promoted growth rate of rods and enlarged rod size. ZnO nanorods were transformed to nanotubes, nanosheets and rods with blanket-like shaped surface mainly by secondary pH adjustment. All ZnO nanocrystals are wurtzite structure preferentially oriented in c-axis direction.