Interparticle interactions and direct imaging of colloidal phases assembled from microsphere-nanoparticle mixtures

We investigate the interparticle interactions, phase behavior, and structure of microsphere-nanoparticle mixtures that possess high size and charge asymmetry. We employ a novel Monte Carlo simulation scheme to calculate the effective microsphere interactions in suspension, yielding new insight into the origin of the experimentally observed behavior. The initial settling velocity, final sediment density, and three-dimensional structure of colloidal phases assembled from these binary mixtures via gravitational settling of silica microspheres in water and index-matched solutions exhibit a strong compositional dependence. Confocal laser scanning microscopy is used to directly image and quantify their structural evolution during assembly. Below a lower critical nanoparticle volume fraction (phi(nano) < phi(L,C)), the intrinsic van der Waals attraction between microspheres leads to the formation of colloidal gels. These gels exhibit enhanced consolidation as phi(nano) approaches phi(L,C). When phi(nano) exceeds phi(L,C), an effective repulsion arises between microspheres due to the formation of a dynamic nanoparticle halo around the colloids. From this stable fluid phase, the microspheres settle into a crystalline array. Finally, above an upper critical nanoparticle volume fraction (phi(nano) > phi(U,C)), colloidal gels form whose structure becomes more open with increasing nanoparticle concentration due to the emergence of an effective microsphere attraction, whose magnitude exhibits a superlinear dependence on phi(nano).     

Size ratio effects on interparticle interactions and phase behavior of microsphere-nanoparticle mixtures

We investigate the interparticle interactions and phase behavior of microsphere-nanoparticle mixtures of high charge asymmetry and varying size ratio. In the absence of nanoparticles, negligibly charged microspheres flocculate as a result of van der Waals interactions. Upon addition of a lower critical nanoparticle volume fraction, the microspheres are stabilized by the formation of nanoparticle halos around each microsphere. , A weak attraction between the two species leads to a pronounced enhancement of the effective nanoparticle concentration near the microsphere surface relative to the bulk solution. Above an upper critical nanoparticle volume fraction, the microspheres undergo reentrant gelation. Binary mixtures, in which the effective nanoparticle size is reduced at a fixed microsphere diameter, exhibit a narrow window of stability that ultimately disappears with increasing ionic strength. By contrast, binary mixtures of varying microsphere diameter are stabilized at similar nanoparticle volume fractions and exhibit a broader window of stability with decreasing size ratio. This unexpected observation may arise from the reduced attraction between smaller microspheres because negligible differences in nanoparticle halo formation are observed in these mixtures.     

Electrostatically tuned interactions in silica microsphere-polystyrene nanoparticle mixtures

We explore the generality of nanoparticle haloing as a novel colloidal stabilization mechanism in binary mixtures of silica microspheres and polystyrene nanoparticles. By selectively tuning their electrostatic interactions, both the initial microsphere stability and the role of nanoparticle additions are varied. Adsorption isotherm and zeta potential measurements indicate that highly charged nanoparticles exhibit a weak (haloing) association with negligibly charged microspheres, whereas they either strongly adsorb onto oppositely charged or are repelled by like-charged microsphere surfaces, respectively. Bulk sedimentation and confocal scanning fluorescence microscopy reveal that important differences in system stability emerge depending on whether the added nanoparticles serve as haloing, bridging, or depletant species.     

Phase behavior and 3D structure of strongly attractive microsphere-nanoparticle mixtures

We investigate the phase behavior and 3D structure of strongly attractive mixtures of silica microspheres and polystyrene nanoparticles. These binary mixtures are electrostatically tuned to promote a repulsion between like-charged (microsphere-microsphere and nanoparticle-nanoparticle) species and a strong attraction between oppositely charged (microsphere-nanoparticle) species. Using confocal fluorescence scanning microscopy, we directly observe the 3D structure of colloidal phases assembled from these mixtures as a function of varying composition. In the absence of nanoparticle additions, the charged-stabilized microspheres assemble into a polycrystalline array upon sedimentation. With increasing nanoparticle volume fraction, nanoparticle bridges form between microspheres, inducing their flocculation. At even higher nanoparticle volume fractions, the microspheres become well coated with nanoparticles, leading to their charge reversal and subsequent restabilization. We demonstrate how this fluid-gel-fluid transition can be utilized to control the morphology of the colloidal phases formed under gravity-driven sedimentation.     

Sedimentation and drying dissipative patterns of binary suspensions of colloidal silica spheres having different sizes

The sedimentation and drying dissipative structural patterns were formed during the course of drying binary mixtures among colloidal silica spheres of 183 nm, 305 nm, and 1.205 μm in diameter in aqueous suspension on a watch glass, a glass dish, and a cover glass, respectively. The broad ring-like sedimentation patterns were formed within several hours in suspension state for all the substrates used. Colorful macroscopic broad ring-like drying patterns were formed for the three substrates. In a watch glass, macroscopic drying patterns were composed of the outer and inner layers of small and large spheres, respectively. The two colored layers were ascribed to the Bragg diffractions of light by the dried colloidal crystals of the corresponding spheres. The width ratio of the layers changed in proportion to the mixing ratio of each spheres. In a glass dish, wave-like macroscopic drying patterns were observed in the intermediate areas between the outside edges of the broad ring and the inner wall of the cell. On a cover glass, the sphere mixing ratios were analyzed from the widths of the drying broad rings of the small spheres at the outside edge. High and distinct broad rings of small spheres and the low and vague broad one formed at the outer edges and in the inner area, respectively. Drying dissipative pattern was clarified to be one of the novel analysis techniques of colloidal size in binary colloidal mixtures.     

Direct-write fabrication of colloidal photonic crystal microarrays by ink-jet printing

An array of the colloidal photonic crystals was directly fabricated using an ink-jet printing. The colloidal ink droplets containing the monodispersed polystyrene latex particles were selectively deposited on a hydrophobic surface. Solvent evaporation from each ink droplet leads to a formation of microdome-shaped colloidal assembles of close-packed structures. Microspectroscopic analysis has confirmed that the individual assembly serves as a photonic crystal and its optical properties can be correlated with the microstructural features. Unlike other techniques of patterned growth of colloidal photonic crystal, the substrate does not need to be patterned first and no template is needed in the direct writing by the ink-jet printing. Using our strategy, we have rapidly produced the colloidal photonic crystal microarrays composed of different-sized spheres addressably patterned on the same substrate.     

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.     

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.     

TiO2掺杂调控聚苯乙烯微球折射率及胶体光子晶体结构色

胶体光子晶体由于其可调变的结构色在绿色印刷、印染等领域备受关注,而其光子带隙的宽度和位置由光子晶体的晶格参数(晶面间距,通常受胶体微球尺寸影响)和介质的折射率决定。现有人工胶体光子晶体主要基于SiO_2和高分子(如聚苯乙烯(PS)等)微球的组装制备,由于胶体微球材质种类有限,折射率调控受限,因而目前调控胶体光子晶体结构色主要靠改变胶体微球的尺寸来实现。本文首先制备高折射率(2.6)的TiO_2纳米晶,在乳液聚合制备单分散的PS(折射率1.6)微球过程中,将所制备的TiO_2纳米晶掺杂于PS微球中,通过TiO_2的掺杂量有效调控胶体微球的折射率,进而实现胶体光子晶体的结构色调控。以多色胶体光子晶体微球的水溶液为墨水,采用彩色喷墨打印技术打印了电脑设计的光子晶体彩画。本文发展的光子晶体结构色调控新技术拓展了胶体光子晶体的应用。     

胶体光子晶体的平面介电常数缺陷

为引入特殊的光学性质,通常需要在三维光子晶体中人为可控地引入缺陷.通过改变局部结构单元的尺寸或介电常数,相应地引入给体或受体掺杂,带来不同的缺陷态.以前文献报道的向胶体光子晶体中引入缺陷,常会因为同时引入尺寸和介电常数掺杂,给掺杂性质的界定带来困难.本文中,我们结合对流自组装法和L-B膜法,在实心二氧化硅微球组成的三维光子晶体内引入尺寸相同的二氧化硅空心球(与实心球相比具有不同折光率)组成的单层平面缺陷,或者在空心球晶体内引入实心球缺陷层,构成实心-空心-实心或空心-实心-空心的三明治结构,在不破坏整体晶格的同时,在三维胶体光子晶体中引入单一的平面介电常数缺陷.     

Facile fabrication of free-standing colloidal-crystal films by interfacial self-assembly

This paper reports a rapid and facile method of preparing free-standing colloidal crystals from monodisperse charged polystyrene (PS) microspheres. Mixed solvents (ethanol/water) were used as the dispersion medium in the self-assembly process of colloidal crystals. By a simple "floating self-assembly" method, PS microspheres floated on the surface of liquid and self-assembled into large area of three-dimensional (3D) ordered colloidal crystals within 15 min. Then epichlorohydrin was added in as a cross-linking agent to strengthen the colloidal-crystal film. After cross-linking reactions between the microspheres, the obtained colloidal-crystal film was free-standing and could be easily transferred to other substrates. Using tetrabutyl titanate as a titania precursor, 3D porous TiO(2) materials with rodlike skeletal structure were fabricated from the prepared free-standing colloidal crystal. This work provides a facile method to fabricate free-standing colloidal-crystal film, which can be used as an ideal template for the preparation of porous materials.     

表面富含羧基的单分散交联聚合物微球的快速自组装制备胶体晶的研究

在20～70℃范围内,用垂直沉积的方法可使表面富含羧基的单分散交联聚合物微球在不同的基底上快速自组装成三维有序的胶体晶.不同粒径的微球形成的胶体晶其光禁带峰位不同,因此可调控不同波长的光在胶体晶中的传播.利用紫外-可见光谱研究了胶体晶的光禁带峰位与组成其微球粒径之间的关系.结果表明,随着构成胶体晶微球粒径的增大,胶体晶光禁带峰位发生了红移,而随着入射光角度的增大,胶体晶的光禁带峰位发生了蓝移.利用原子力显微镜和扫描电子显微镜研究了其它条件对聚合物微球有序排列的影响,发现聚合物微球在pH值为3.0～13.0范围内可以形成三维有序自组装胶体晶.这是由于在不同的pH值下,聚合物微球表面发生羧基化及去羧基化反应,导致在自组装过程中微球之间和微球与介质之间作用力的变化     

流动控制沉积法制备PMMA叠层光子晶体薄膜及其光学性能研究

采用流动控制沉积法,通过调控泵速和聚甲基丙烯酸甲酯(PMMA)胶体微球溶液的浓度,制备出微球排列高度有序且薄膜紧密附着于基底的高质量光子晶体薄膜。获得了制备高质量PMMA光子晶体薄膜的组装条件范围,发现在该条件范围内,当泵速或胶体微球溶液浓度一定时,PMMA光子晶体薄膜的厚度随胶体微球溶液浓度的增加或泵速的降低而增加。研究了组装条件对PMMA光子晶体薄膜光学性能的影响,发现光子禁带位置随光子晶体薄膜厚度增加或减少而红移或蓝移。在此基础上,控制组装条件得到了不同尺寸微球堆叠而成的叠层光子晶体薄膜,并研究了其光学性能的变化规律。结果显示,叠层光子晶体薄膜的光子禁带峰为各层叠层光子晶体禁带峰的简单叠加,且峰强度受光入射角方向影响。     

A universal approach to fabricate ordered colloidal crystals arrays based on electrostatic self-assembly

We present a novel and simple method to fabricate two-dimensional (2D) poly(styrene sulfate) (PSS, negatively charged) colloidal crystals on a positively charged substrate. Our strategy contains two separate steps: one is the three-dimensional (3D) assembly of PSS particles in ethanol, and the other is electrostatic adsorption in water. First, 3D assembly in ethanol phase eliminates electrostatic attractions between colloids and the substrate. As a result, high-quality colloidal crystals are easily generated, for electrostatic attractions are unfavorable for the movement of colloidal particles during convective self-assembly. Subsequently, top layers of colloidal spheres are washed away in the water phase, whereas well-packed PSS colloids that are in contact with the substrate are tightly linked due to electrostatic interactions, resulting in the formation of ordered arrays of 2D colloidal spheres. Cycling these processes leads to the layer-by-layer assembly of 3D colloidal crystals with controllable layers. In addition, this strategy can be extended to the fabrication of patterned 2D colloidal crystals on patterned polyelectrolyte surfaces, not only on planar substrates but also on nonplanar substrates. This straightforward method may open up new possibilities for practical use of colloidal crystals of excellent quality, various patterns, and controllable fashions.     

Monodispersed ZnSe colloidal microspheres: preparation, characterization, and their 2D arrays

Uniform and monodispersed ZnSe colloidal microspheres were prepared via a hot injection route by using trioctylamine as solvent and with a relatively higher concentration of the monomer precursors. The size of the colloidal ZnSe spheres was tuned from 138 to 629 nm by varying the concentration of the precursors, and the size increased linearly with the concentration of Zinc oleate in the range from 0.05 to 0.10 kg/L with the molar ratio of Zn to Se of 0.5. The colloidal microspheres were well characterized by SEM, TEM, HRTEM, EDS, UV-vis, and PL techniques. Detailed examination confirmed that the colloidal microspheres were formed by the in-situ aggregation of ZnSe nanoparticles. Furthermore, the 2D ordered assembly of the ZnSe microspheres was realized via a simple vertical precipitation technique. Due to the high refractive index and absence of absorption in the visible region, the monodispersed ZnSe colloidal microspheres could be potential building blocks to construct photonic band gap crystals and other functional devices.     

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.     

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…     

Automated preparation method for colloidal crystal arrays of monodisperse and binary colloid mixtures by contact printing with a pintool plotter

Photonic crystals and photonic band gap materials with periodic variation of the dielectric constant in the submicrometer range exhibit unique optical properties such as opalescence, optical stop bands, and photonic band gaps. As such, they represent attractive materials for the active elements in sensor arrays. Colloidal crystals, which are 3D gratings leading to Bragg diffraction, are one potential precursor of such optical materials. They have gained particular interest in many technological areas as a result of their specific properties and ease of fabrication. Although basic techniques for the preparation of regular patterns of colloidal crystals on structured substrates by self-assembly of mesoscopic particles are known, the efficient fabrication of colloidal crystal arrays by simple contact printing has not yet been reported. In this article, we present a spotting technique used to produce a microarray comprising up to 9600 single addressable sensor fields of colloidal crystal structures with dimensions down to 100 mum on a microfabricated substrate in different formats. Both monodisperse colloidal crystals and binary colloidal crystal systems were prepared by contact printing of polystyrene particles in aqueous suspension. The array morphology was characterized by optical light microscopy and scanning electron microscopy, which revealed regularly ordered crystalline structures for both systems. In the case of binary crystals, the influence of the concentration ratio of the large and small particles in the printing suspension on the obtained crystal structure was investigated. The optical properties of the colloidal crystal arrays were characterized by reflection spectroscopy. To examine the stop bands of the colloidal crystal arrays in a high-throughput fashion, an optical setup based on a CCD camera was realized that allowed the simultaneous readout of all of the reflection spectra of several thousand sensor fields per array in parallel. In agreement with Bragg's relation, the investigated arrays exhibited strong opalescence and stop bands in the expected wavelength range, confirming the successful formation of highly ordered colloidal crystals. Furthermore, a narrow distribution of wavelength-dependent stop bands across the sensor array was achieved, demonstrating the capability of producing highly reproducible crystal spots by the contact printing method with a pintool plotter.     

Microwave-assisted self-organization of colloidal particles in confining aqueous droplets

Monodisperse aqueous emulsion droplets encapsulating colloidal particles were produced in the oil phase, and controlled microwave irradiation of the aqueous drop phase created spherical colloidal crystals by so-called evaporation-induced self-organization of the colloidal particles. Unlike usual colloidal crystals, colloidal crystals in spherical symmetry (or photonic balls) possessed photonic band gaps for the normal incident light independent of the position all over the spherical surface. While the consolidation of colloidal particles in emulsion droplets in an oven took several hours, the present microwave-assisted evaporation could reduce the time for complete evaporation to a few tens of minutes. Under the microwave irradiation, the aqueous phase in emulsions was superheated selectively and the evaporation rate of water could be controlled easily by adjusting the microwave intensity. The result showed that the packing quality of colloidal crystals obtained by the microwave-assisted self-organization was good enough to show photonic band gap characteristics. The reflectance of our photonic balls responded precisely to any change in physical properties including the size of colloidal particles, refractive index mismatch, and angle of the incident beam. In particular, for polymeric particles, the photonic band gap could be tuned by the intensity of microwave irradiation, and the reflection color was red-shifted with stronger microwave irradiation. Finally, for better photonic band gap properties, inverted photonic balls were prepared by using the spherical colloidal crystals as sacrificial templates.