Nonspherical colloidal crystals fabricated by the thermal pressing of colloidal crystal chips

Nonspherical colloids and their ordered arrays may be more attractive in applications such as photonic crystals than their spherical counterparts because of their lower symmetries, although such structures are difficult to achieve. In this letter, we describe the fabrication and characterization of colloidal crystals constructed from nonspherical polyhedrons. We fabricated such nonspherical colloidal crystals by pressing spherical polymer colloidal crystal chips at a temperature slightly lower than the glass-transition temperature (T(g)) of these polymer colloids. During this process, the polymer microspheres were distinctively transformed into polyhedrons according to their crystal structures, whereas the long-range order of the 3D lattice was essentially preserved. Because a working temperature lower than T(g) effectively prevented the colloidal crystals from fusing into films, the spherical colloidal crystals were transformed greatly under pressure, which lead to obvious change in the optical properties of colloidal crystals. Besides their special symmetry and optical properties, these nonspherical colloidal crystals can be used as templates for 2D or 3D structures of special symmetry, such as 2D nano-networks. We anticipate that this fabrication technique for nonspherical colloidal crystals can also be extended to nonspherical porous materials.     

Chemical bath deposition synthesis of sub-micron ZnS-coated polystyrene

The synthesis of ZnS-coated polystyrene composite colloids by the decomposition of thioacetamide in the presence of polystyrene seed particles and metal salt is presented. The chemical bath deposition technique incorporates poly(vinyl pyrrolidone) to inhibit particle aggregation during the synthesis so that core-shell particles with sizes in the low sub-micron range were achieved. The shell thickness was well controlled through the reaction time and core size. ZnS shells were composed of primary crystallites, approximately 5 nm in diameter, which had the zinc blend crystal structure. The porosity of the shells was between 12 and 19%. Accordingly, the effective refractive index of the particles varied between 1.73 and 1.98 at wavelengths above the optical absorption edge of ZnS. Ordered colloidal crystals were produced by convective assembly of the poly(sodium 4-styrenesulfonate) stabilized core-shell particles. Assemblies of ZnS shell-polystyrene core particles are photonic crystal materials which may have applications in optical computing and communications environments.     

Colloidal lithographic nanopatterning via reactive ion etching

We report here a novel colloidal lithographic approach to the fabrication of nonspherical colloidal particle arrays with a long-range order by selective reactive ion etching (RIE) of multilayered spherical colloidal particles. First, layered colloidal crystals with different crystal structures (or orientations) were self-organized onto substrates. Then, during the RIE, the upper layer in the colloidal multilayer acted as a mask for the lower layer and the resulting anisotropic etching created nonspherical particle arrays and new patterns. The new patterns have shapes that are different from the original as a result of the relative shadowing of the RIE process by the top layer and the lower layers. The shape and size of the particles and patterns were dependent on the crystal orientation relative to the etchant flow, the number of colloidal layers, and the RIE conditions. The various colloidal patterns can be used as masks for two-dimensional (2-D) nanopatterns. In addition, the resulting nonspherical particles can be used as novel building blocks for colloidal photonic crystals.     

Polystyrene@TiO2 core-shell microsphere colloidal crystals and nonspherical macro-porous materials

High-quality and stable PS@TiO(2) core-shell microsphere colloidal crystals were prepared by electrostatic colloid stabilization combined with two-substrate vertical deposition method. The polyelectrolyte stabilized colloids self-assembled into face-centered cubic arrays with the (111) face perpendicular to the substrate. These colloidal crystals are gifted with high mechanical stability toward the flow of solution. Structure-property correlations were made using scanning electron microscopy and UV-vis-NIR spectroscopy. Optical spectra showed the presence of an L-stopband peak in the photonic band structure. Besides, these PS@TiO(2) colloidal crystals can be used as templates to fabricate the nonspherical macro-porous materials, and complete band gaps can be more easily obtained from such structure than from their spherical counterparts due to their lower symmetries. This work will hold the promise of enhanced photonic band gap materials.     

Doped colloidal photonic crystal structure with refractive index chirping to the [111] crystallographic axis

A three-dimensionally ordered array of close-packed colloidal spheres, a photonic crystal structure in which the refractive index of the medium interstitial lattice in a colloidal crystal spatially changes in the [111] crystallographic axis, is demonstrated. The colloidal photonic crystal structure with refractive index chirping was produced by infiltration of a monomer and organic dopants with a high refractive index into a silica opal, followed by interfacial gel polymerization. The resulting photonic crystal structure has a gradually varying stop band at each different (111) plane in the face-centered cubic (fcc) crystal structure at a normal incidence. This novel structure exhibited optical characteristics that have band-gap broadening by the superposition of stop bands at each plane of the crystal with different dielectric functions. Moreover, the refractive index perturbation in the [111] fcc opal also showed a defect state within a pseudo-photonic band gap. This new type of photonic crystal structure should be useful for the band-gap engineering of photonic-band-gap materials.     

种子聚合法制备非球形聚合物颗粒的研究进展

十年前,光子晶体的需求促进了非球形颗粒的研究热潮。非球形颗粒由于其对称性下降,带来了新的性能和应用前景,成为当前材料领域研究的热点,得到了较广泛研究,目前其制备方法包括种子聚合法、自组装法、粒子聚集法、微流体法和机械拉伸法等。本文简述了种子聚合法的发展历程,介绍了种子聚合法制备非球形聚合物颗粒的相关机理,以种子微球材质分类综述了种子聚合法制备非球形聚合物颗粒的形貌和结构控制技术进展,概述了其潜在的应用领域,展望了可能的发展趋势。     

Surfactant-assisted alignment of ZnO nanocrystals to superstructures

Self-organization of ZnO nanoparticles into various superstructures (sheet, platelet, ring) has been achieved with the assistance of micelles formed by surfactant cetyltrimethylammonium bromide (CTAB) under one-pot condition. The CTAB-modified zinc hydroxy double salt (Zn-HDS) mesocrystals act as intermediates to form ZnO hexagonal superstructures at temperatures as low as 50 degrees C. The decomposition temperature of Zn-HDS mesocrystals is much lower than that of the corresponding bulk crystals because the organic additive CTAB effectively decreases the degree of crystallinity. Taking advantage of temperature-induced phase transformation of micelles, two-stage self-organization can form ZnO platelets and ring mesocrystals, that is, ZnO ellipsoidal superstructures formed through vertical attachment on (0001) facets of basic units can further assemble to form ZnO platelets and rings through vertical attachment on (0001) facets of ZnO ellipsoidal superstructures. The structural transformation of micelles as shape templates can offer a new route for self-assembly of nonspherical colloids into three-dimensional photonic crystals. ZnO sheet, ring, and platelet mesocrystals with a high population of polar Zn-(0001) plane are expected to have high photocatalytic activity.     

The molecular structure of different species of cuprous chloride from gas-phase electron diffraction and quantum chemical calculations

The molecular geometry of gaseous cuprous chloride oligomers was determined by gas-phase electron diffraction at two different temperatures. Quantum chemical calculations were also performed for Cu(n)Cl(n) (n=1-4) molecules. A complex vapor composition was found in both experiments. Molecules of Cu(3)Cl(3) and Cu(4)Cl(4) were present at the lower temperature (689 K), while dimeric molecules (Cu(2)Cl(2)) were found in addition to the trimers and tetramers at the higher temperature (1333 K). All Cu(n)Cl(n) species were found to have planar rings by both experiment and computation. The bond lengths from electron diffraction (r(g)) at 689 K are 2.166+/-0.008 A and 2.141+/-0.008 A and the Cu-Cl-Cu bond angles are 73.9+/-0.6 degrees and 88.0+/-0.6 degrees for the trimer and the tetramer, respectively. At 1333 K the bond lengths are 2.254+/-0.011 A, 2.180+/-0.011 A, and 2.155+/-0.011 A, and the Cu-Cl-Cu bond angles 67.3+/-1.1 degrees, 74.4+/-1.1 degrees, and 83.6+/-1.1 degrees for the dimer, trimer, and tetramer, respectively.     

New low-index liquid refractive index standard: SRM 1922

A new standard for the calibration of refractometers has been developed. Standard Reference Material (SRM) 1922 is a mineral oil with a refractive index nD = 1.46945 at 20 degrees C, which is within the range of the Brix scale (% sucrose). The change in refractive index with temperature (dn/dT) has been characterized for the range 15 degrees C to 35 degrees C to allow for calibrations within that range of temperatures. The refractive indices were measured at 5 wavelengths in the visible spectrum by using the method of minimum deviation with a +/- 2-3 x 10(-5) uncertainty at 20 degrees C. The values of nD and dnD/dT were determined by fits of a two-term Cauchy function to the values at the measured wavelengths with a +/- 6 x 10(-5) uncertainty in nD at 20 degrees C.     

气相沉积技术在制备高折射率光子晶体中的应用

采用激光全息光刻技术或激光直写技术制作微结构具有便捷、灵活、高效等优势,目前已成为研究制备光子晶体的一种有效方法.用全息光刻技术所制备的微结构的特点是单晶面积大(即内部结构缺陷较少)和可根据需要制作研究多种周期或准周期的晶格结构.但是所制备的结构由于感光树脂与空气的折射率比值较低,不能得到完全带隙光子晶体,从而使其应用受到局限性.以此树脂结构为模板,通过各种方法对其进行二次加工,制作高介电常数材料的反结构,近期已成为研究热点.本文介绍了气相沉积技术在制备高折射率光子晶体方面的应用和研究进展.     

Fabrication of bimodal porous silicate with silicalite-1 core/mesoporous shell structures and synthesis of nonspherical carbon and silica nanocases with hollow core/mesoporous shell structures

In this work, an attempt has been made to modify the shape and nanostructure of core-shell materials, which have been usually generated on the basis of amorphous spherical cores. Novel core-shell silicate particles, each of which consists of a silicalite-1 zeolite crystal core and mesoporous shell (ZCMS), were synthesized for the first time. The ZCMS core-shell particles are unique because they are of pseudohexagonal prismatic shape and have hierarchical porosity of both a uniform microporous core and a mesoporous shell coexisting in a particle framework. The nonspherical bimodal porous core-shell particles were then utilized as templates to fabricate a new carbon replica structure. Interestingly, the pore replication process was carried out only through the mesopores in the shell, and not through the micropores due to the narrower micropore size in the core, resulting in nonspherical carbon nanocases with a hollow core and mesoporous shell (HCMS) structure. Nonspherical silica nanocases with HCMS structure were also generated by replication using the carbon nanocases as templates, which are not possible to synthesize through other synthetic methods. Interestingly, the pseudohexagonal prismatic shape of the zeolite crystals was transferred onto the carbon and silica nanocases.     

Synthesis of amorphous silicon colloids by trisilane thermolysis in high temperature supercritical solvents

Colloidal submicrometer-diameter amorphous silicon (a-Si) particles are synthesized with >90% yield by thermal decomposition of trisilane (Si3H8) in supercritical hexane at temperatures ranging from 400 to 500 degrees C and pressures up to 345 bar. A range of synthetic conditions was explored to optimize the quality of the product. Under the appropriate synthetic conditions, the colloids are spherical and unagglomerated. The colloids can be produced with average diameters ranging from 50 to 500 nm by manipulating the precursor concentration, temperature, and pressure. Relatively narrow particle size distributions, as measured by transmission electron microscopy (TEM), with standard deviations about the mean as low as approximately +/-10% could be obtained in some cases. We explored the thermal annealing of the amorphous silicon particles after isolation from the reactor and found that crystallization to diamond structure silicon occurred at temperatures as low as 650 degrees C. The amorphous and crystalline materials were characterized by X-ray diffraction and high resolution scanning and transmission electron microscopy.     

Formation mechanism of nonspherical gold nanoparticles during seeding growth: roles of anion adsorption and reduction rate

A small section of nonspherical particles can be observed in the further growth of spherical gold colloids exposed to a mixture of NH2OH and HAuCl4. The concentration ratio of [NH2OH]:[HAuCl4] is critical for the formation of nonspherical particles as higher ratios produce lower yields and smaller of such particles. These concentrations also affect the reaction kinetics; the reaction rate increases with [NH2OH], while independent of [HAuCl4], which we believe is due to the specific adsorption of AuCl4- onto gold surface. These nonspherical particles come from the preferential growth of {111} facets as indicated by their TEM images and electron diffraction patterns. We propose this preferential growth is ascribed to the preferential adsorption of AuCl4- on {111} facets, and some competition which determines the yield of nonspherical particles exists between the AuCl4- adsorption and the AuCl4- reduction, faster reduction counteracting the effect of this preferential adsorption and thus suppressing nonspherical particle. This result probably provides some guidance to develop a shape-controlled synthesis of gold particles without any additives.     

Cooperative organic hydrogen bonds: the librational modes of cyclic methanol clusters

Intermolecular hydrogen bond libration modes of isolated cyclic methanol trimers (approximately 613 cm(-1)) and tetramers (695 and 760 cm(-1)) are observed in pulsed jet Fourier transform infrared spectra and found to exhibit sizeable anharmonicity and mode coupling effects, opening the way for a microscopic interpretation of the broad librational bands of alcohols. The correlation of experimental OH stretching and OH libration band intensities provides important constraints for theoretical band strengths, cluster densities, and size assignments.     

C 1s -->pi* excitation in variable size benzene clusters

The C 1s -->pi* transition in molecular benzene and benzene clusters is investigated by photoion yields at high energy resolution. The vibrationally resolved band shows the same shape in clusters as in the bare molecule, but it is redshifted by 50 meV in small clusters, i.e. near the threshold of cluster formation. This redshift increases to 70 meV with increasing cluster size. The results are assigned in comparison with ab initio calculations on model structures of dimers, trimers, and tetramers. These indicate that different carbon sites in the molecular moieties give rise to distinct spectral shifts, where carbon sites that are pointing to the pi-system of another molecule show a larger redshift than the other ones. Such structural properties are found in solid benzene, so that the gas-to-solid shift of C 1s -->pi* excited benzene is derived to be a redshift which is of the order of 100-180 meV.     

Low-birefringence liquid crystal mixtures for photonic liquid crystal fibres application

ABSTRACT

Series of low-birefringence liquid crystal mixtures composed of alkyl alkylbicyclohexyl carbonates and modified mixtures with other compounds have been formulated, their refractive indices and electric permittivity measured upon temperature. They exhibit the ordinary refraction index n_o lower than the refractive index of silica glass in a different range of temperature. This enables to observe in photonic liquid crystal fibres (PLCFs) a change in the light propagation mechanism from photonic band gap guiding to modified total internal reflection at different temperatures. Selected applications of PLCFs are also discussed.     

FABRICATION OF PHOTONIC CRYSTAL WITH SUPERLATTICES

A novel technique was used to fabricate three-dimensional photonic crystals with superlattices. The super structure was fabricated by assembling monodispersed microspheres in the grooves of the scales of morpho butterfly, which makes the photonic crystal being composed of two kinds of different photonic structures (natural groove structure of butterfly wing and artificial microspherical colloids arrangement). The superstructural photonic crystal exhibits some unique optical properties different from both the butterfly wing and the colloidal crystal. The approach exhibited here provides a new way for fabricate photonic crystals with superlattices.     

Re-entrant melting and freezing in a model system of charged colloids

We studied the phase behavior of charged and sterically stabilized colloids using confocal microscopy in a low polarity solvent (dielectric constant 5.4). Upon increasing the colloid volume fraction we found a transition from a fluid to a body centered cubic crystal at 0.0415+/-0.0005, followed by reentrant melting at 0.1165+/-0.0015. A second crystal of different symmetry, random hexagonal close packed, was formed at a volume fraction around 0.5, similar to that of hard spheres. We attribute the intriguing phase behavior to the particle interactions that depend strongly on volume fraction, mainly due to the changes in the colloid charge. In this low polarity system the colloids acquire charge through ion adsorption. The low ionic strength leads to fewer ions per colloid at elevated volume fractions and consequently a density-dependent colloid charge.     

Homogeneous, core-shell, and hollow-shell ZnS colloid-based photonic crystals

Ordered ZnS-based colloidal crystals from homogeneous, core-shell, and hollow building blocks were prepared via electrosteric colloid stabilization combined with a convective assembly technique. The polyelectrolyte stabilized colloids assembled into face-centered cubic arrays with the (111) face perpendicular to the substrate. Structure-property correlations were made using scanning electron microscopy, scanning transmission electron microscopy, and UV/visible/near-IR spectroscopy. Multilayer film growth, with film thickness of several micrometers, was achieved. Optical spectra showed (111) stopgaps along with pronounced higher order peaks. The spectral position of the photonic stopgap can be predicted using a volume average refractive index and the Maxwell-Garnett formula for the homogeneous and core-shell particles, respectively. This work holds the promise of harnessing ZnS for optical property engineering and enhanced photonic band gap materials.     

FABRICATION OF PHOTONIC CRYSTAL WITH SUPERLATTICES

1. INTRODUCTION The very latest subject of physics to surface in biology is the photonic crystal, which is ordered, subwavelength structured material capable of controlling the propagation of light in the similar manner as which atomic crystal control electrons [1,2]. Due to the application of the photonic crystal in laser, integrated optical circuit, it attracted great attention in the past decade. Photonic crystals can be fabricated by microfabrication methods, holographic methods, and c…