Reversible control of light reflection of a colloidal crystal film fabricated from monodisperse mesoporous silica spheres

In this letter, we report a novel method for controlling the light reflection of a colloidal crystal. Highly monodisperse mesoporous silica spheres have been successfully organized into a hexagonally close-packed colloidal crystal film. Just by introducing water vapor into the fabricated colloidal film, the structural color and reflection spectra were changed dramatically because of water vapor adsorption occurring in the mesoporous channels. This phenomenon can be observed reversibly over five cycles. We are convinced that this is the first report on controlling the light reflection of a colloidal crystal film dynamically by taking advantage of adsorption properties inherent to mesoporous silica spheres.     

Connected open structures from close-packed colloidal crystals by hyperthermal neutral beam etching

We report the fabrication of connected open structures from close-packed colloidal crystals by hyperthermal neutral beam etching. Colloidal crystal films of polystyrene microspheres were prepared by a vertical deposition method. Exposure of the colloidal crystal films to hyperthermal neutral beam made isolated microspheres in the face-centered cubic lattice, each of which was connected with its twelve nearest neighbors through very thin cylinders. Due to the charge neutrality of impinging gas molecules of the hyperthermal neutral beam, the spherical shape of polymer microspheres was almost maintained during the etching process. The Bragg reflection peaks were modulated by the etched volume of colloidal crystals. Finally, the inverse structures of such open structures were replicated by a simple room-temperature chemical vapor deposition and subsequently burning out polymer template spheres.     

Fabrication of tunable colloid crystals from amine-terminated polyamidoamine dendrimers

A pH-responsive colloidal crystal was assembled using core-shell composite spheres, poly(styrene-methyl methacrylate-acrylic acid) (P(St-MMA-AA)) spheres covered by generation 4 amine-terminated polyamidoamine dendrimers. The light reflection of the colloidal crystal film can be tuned at different pH due to different protonation level of the dendrimers. The method shows a facile way to fabricate diffraction-based chemical and biological sensors by exploiting the effect of photonic crystal cooperated with tunable nanoparticles.     

基于温敏水凝胶的可调胶体晶体制备

基于单分散胶体粒子悬浊液在温敏水凝胶表面可以形成湿润型胶体晶体的现象, 利用温敏水凝胶对水的控释作用制备了温度敏感的可调制胶体晶体. 在室温下利用提拉法在温敏水凝胶聚N-异丙基丙烯酰胺(PNIPAAm)表面制备湿润型胶体晶体膜. 由于胶体粒子的有序排列, 胶体晶体显示出一个尖锐的反射峰. 当温度上升到34 ℃以上时, 由于PNIPAAm水凝胶中的水被释放, 导致胶体晶体中粒子浓度降低, 粒子间距增加; 反射峰发生红移. 这些特性可以通过温度变化进行调制.     

Large-domain colloidal crystal films fabricated using a fluidic cell

The growth of colloidal crystal films from a dispersion of monodispersed silica spheres using a simple cell with one opening was investigated. Colloidal crystal films with large domain sizes were successfully fabricated almost over the cell (approximately 10 cm2) without applying any external force at room temperature. During the drying process, three distinct conditions were observed, in each of which the films exhibited different optical properties. Films with high transmittance were formed in the first stage. Upon further solvent evaporation, the films entered a medium transmittance state via an extremely low transmittance state. Angle-resolved reflection spectroscopy, which was used to analyze the three conditions, revealed that close-packed arrays with water-filled spaces between were formed in the first stage. One-directional flow was generated in the cell because water evaporation occurred only at the opening. The flow caused the spheres to be arranged epitaxially, resulting in a large domain size.     

Dry etching of colloidal crystal films

Two types of non-close-packed colloidal crystal films were prepared by etching the films made of polystyrene nanospheres using a hyperthermal neutral beam of oxygen gas. Etching without sintering above glass transition temperature of the polymer particles resulted in the non-close-packed structure of the nanospheres, in which polystyrene nanospheres in different lattice planes touched each other due to the reduction in the size of the nanospheres that occurred during the etching process. In contrast, a different non-close-packed structure with inter-connecting networks between etched nanospheres was generated by annealing of the colloidal crystal and a subsequent etching process. The photonic bandgap could be tuned during this dry etching of colloidal photonic crystals. This connected open structure could be used as a template for a silica inverse opal by chemical vapor deposition. An alternative dry etching process, reactive ion etching, mainly affected the morphology of particles near the top surface, and only a slight change in the stop band position of the colloidal crystal film was observed.     

Effects of liquid bridge between colloidal spheres and evaporation temperature on fabrication of colloidal multilayers

For the application of colloidal crystal films as "photonic band gap" materials, their domain size and thickness are significant. The substrate withdrawing speed, the colloidal suspension volume fraction, and the colloidal suspension temperature have been studied for the domain size and thickness controls of colloidal crystals in this study. Stable dispersions of monodispersed polystyrene spheres with a diameter of 245 nm were synthesized according to a general emulsion polymerization for colloidal crystal films. By experimental results and the theoretical relationship between the number of layers and other parameters, we could know that the water bridge between colloidal spheres (which is formed by capillary force) influences the number of colloidal crystal layers significantly.     

Monitoring the transformation of colloidal crystals by styrene vapor using atomic force microscopy

The stages of transformation of a colloidal crystalline film of latex spheres to a new periodic structure were imaged by atomic force microscopy. Colloidal crystalline films were prepared with 320 nm diameter poly(styrene-co-2-hydroxyethyl methacrylate) (PSt/HEMA) spheres. The hexagonally ordered surfaces of the colloidal crystalline films were transformed with styrene vapor at room temperature to a new morphology having holes in the surface and the same periodicity as the original films. The surfaces of colloidal crystals and the transformed films have a raspberry-like texture superposed on the 320 nm hexagonal periodicity. Both height images and phase images reveal that the latex spheres shrink and the transformation proceeds by an order-disorder-order sequence. The final structure is an interconnected colloidal array with smaller polystyrene particles dispersed in a continuous PSt/HEMA matrix.     

Facile fabrication of mechanochromic-responsive colloidal crystal films

This paper presents a simple approach to fabricate a reversible mechanochromic-responsive crystal film based on the room-temperature film-formation of monodisperse polymer latex by the aid of nanosilica particles. In this approach, when the "soft" colloidal polymer spheres were blended with colloidal silica particles and then cast on a substrate, followed by drying at room temperature for self-assembly, an elastic crystal film was directly obtained. This crystal film has not only reversible and repeatable mechanochromic-responsive property, but also tunable color and peak position covering almost entire visible spectral region, depending upon the sizes of polymer spheres and strains. This optical response is attributed to the variation of lattice spacing during deformation.     

Colloidal crystallization of poly(n-butyl acrylate) spheres in deionized aqueous suspension and the melting during dryness

Colloidal crystallization of poly(n-butyl acrylate) spheres (ammonium persulfate-poly(n-butyl acrylate) (APS-PBA), 320?±?50 nm in diameter) was studied in deionized aqueous suspension. Coexistence of the crystal and distorted crystal structures was observed by the reflection spectroscopy. The critical concentrations of melting were ca. 0.01 and 0.03 in volume fraction in the presence of ion-exchange resins and in their absence, respectively. Crystal structures melted away during dryness by fusion of each spheres on the substrates, i.e., cover glass, watch glass, and Petri glass dish. Thickness profiles of the dried film changed sharply from the broad ring to the round hill as sphere concentration increased. The sharpness parameter S was evaluated from the ratio of the film size (diameter) against the full width at half maximum in the thickness profiles of the ring and/or the round hill. The S values decreased sharply from 30 to 1.2 as initial volume fraction of the spheres increased from 0.0005 to 0.1. The S values were significantly low compared with those of typical colloidal spheres, which supports the aggregate and/or fusion of the spheres resulting in their low convectional flow during dryness. The round hill profile at the high sphere concentration also supports that the fusion takes place easier during dryness. Microscopic observation of the dried film supports the formation of the homogeneous fused structures. It was clarified that colloidal crystallization of APS-PBA spheres takes place by the extended electrical double layers around the spheres like typical colloidal crystals of hard spheres. However, APS-PBA spheres are not so stable by the fusion especially at the high sphere concentrations and on the substrates.     

PAM-PAA microgel inverse opal photonic crystal and pH response

The colloidal crystal template or opal with a closed-packed face-centered cubic (fcc) lattice was prepared from monodisperse polystyrene (PS) spheres by vertical sedimentation.The template provided void space for infiltration of monomer precursor composed of acrylate acid,acrylamide and ammonium persulfate,as well as microgel from the subsequent copolymerization.The sample was immersed in dimethylbenzene for completely removing PS spheres to form PAM inverse opal hydrogels (IOH_(PAM)) or PAM/PAA inverse opal hydrogels (IOH_(PAM/PAA)) photonic crystals.The PS spheres were replaced by air spheres,which interconnected each other through the windows.The study of responses to pH show that there are two peaks for both IOH_(PAM) and IOH_(PAM/PAA) films,but the IOH(PAM/PAA) peaks shift to higher pH,and the peaks are independent with the AA content. (?)2007 Xiao Dong Wang.Published by Elsevier B.V.on behalf of Chinese Chemical Society.All rights reserved.     

Structural reorganization of a polymeric latex film during dry sintering at elevated temperatures

Structural rearrangement in a latex powder during dry sintering at temperatures higher than the minimum film formation temperature was investigated by means of synchrotron small-angle X-ray scattering. Two major effects were identified: (1) Deformation of latex particles leads to a closure of voids between them and an extensive perfectioning of the face centered cubic colloidal crystalline ordering. Such an improvement of the colloidal crystalline structure involves preferential crystal growth along certain crystallographic directions as was evidenced by the measured unmatched relative diffraction intensity distribution of the crystallographic (111) and (220) planes. (2) Interdiffusion of polymeric chains between adjacent particles promotes a nanometer sized aggregation of nonpolymeric materials previously located in the interstices between particles. Size and size distribution of the aggregates at different dry sintering conditions were evaluated by using a model considering spheres dispersed in the system.     

Drying dissipative patterns of the colloidal crystals of silica spheres in an dc-electric field

Drying dissipative structural patterns of the colloidal crystals of silica spheres were studied under an dc-electric field. Platinum plate electrodes of anode and cathode were set on a cover glass. The broad hills accumulated with the spheres were observed at the outer edges of the dried film without and also with the electric fields. The column-like structures were formed by the electric flux, and movement of the spheres took place toward anode. The dried film kept colloidal crystal structure, where the nearest-neighbored spheres contact each other more compactly in the areas closer to the anode. Drying times needed for the complete dryness of the suspensions decreased as the strength of the electric field increased. Addition of sodium chloride to the suspensions retarded the movement of spheres toward the anode substantially.     

Layer transfer approach to opaline hetero photonic crystals

By taking advantage of the hydrophobicity of dry polystyrene colloidal crystal (opal) films and the large surface tension of water, a convectively self-assembled polystyrene opal film on a hydrophilic glass substrate can be peeled off from the substrate and floated on the water surface. A layer transfer technique was developed to sequentially stack floating opal films of different sphere sizes, resulting in opaline hetero photonic crystals. The feasibility of this technique to planar defect engineering in a self-assembled colloidal photonic crystal was also demonstrated. Both structural observation and optical characterization confirmed the crystalline integrity of the resultant opaline heterostructures.     

Inward-growing self-assembly of colloidal crystal films on horizontal substrates

Colloidal crystal films have been fabricated on solid substrates with a horizontal deposition method. Scanning electron microscope images showed that the colloidal crystal films exhibit ordered face-centered cubic structures in large domains. Optical measurements demonstrated the presence of photonic band gap along the crystallographic [111] direction. The fabrication method described in this paper allows one to rapidly fabricate colloidal crystal films of different thicknesses, which can be controlled by varying colloidal suspension concentration or volume. In addition, the method also works well for growing colloidal crystal films on a hydrophilic solid substrate with a rough surface. Furthermore, the fabrication of colloidal crystal heterostructures has been demonstrated. An inward-growing mechanism responsible for self-assembly of colloidal spheres on horizontal substrates has been proposed to interpret the observed experimental results.     

Colloidal crystal films: advances in universality and perfection

For three-dimensional photonic crystals, made either by top-down microfabrication or by bottom-up self-assembly approaches, to comply with the stringent requirements of optical telecommunication applications, their degree of structural perfection and optical quality must meet an exceptionally high standard. Only with such superior quality photonic crystals can their unique optical properties be harnessed in optical devices and circuits constructed from micrometer-sized optical components. In this paper, we present a new strategy for making silica colloidal crystal films with a sufficiently high level of structural perfection and optical quality to make it competitive as a practical route to photonic crystal optical components. The attainment of this goal takes due cognizance of three key synergistic factors in the film formation process. The first recognizes the necessity to prepare high-quality silica spheres, which are highly monodisperse, with a polydispersity index significantly better than 2%, and the second recognizes that the population of spheres must be devoid of even the smallest fraction of substantially smaller or larger spheres or sphere doublets. The latter turns out to have a minimal effect on the polydispersity index, and yet a major detrimental effect on the overall structural order of the film. The third concerns the film-forming method itself, which necessitated the development of a novel process founded upon isothermal heating evaporation-induced self-assembly (IHEISA) of spheres on a planar substrate. This new method has several advantages over previously reported ones. It is able to deposit very high-quality silica colloidal crystal film rapidly over large areas, with a controlled thickness and without any restrictions on sphere sizes.     

聚苯乙烯胶晶膜及三维有序大孔SiO2膜的制备及表征

采用垂直沉积法组装了三维聚苯乙烯胶晶膜,并用其为模板制备了三维有序大孔（3DOM）SiO2膜．SEM观察表明,制备的胶晶膜和3DOMSiO2膜具有fcc结构,有序性很好．考察乳液浓度对胶晶膜结构的影响表明,浓度越高,胶晶膜越厚,有序性也越高,膜在30层内都能很好的粘附在载玻片上．通过调整前驱物溶液的浓度和滴加方式,可得到表面为球形或孔状的3DOM SiO2膜．     

Colloidal crystals of core-shell type spheres with poly(styrene) core and poly(ethylene oxide) shell

Elastic modulus and crystal growth kinetics have been studied for colloidal crystals of core–shell type colloidal spheres (diameter = 160–200 nm) in aqueous suspension. Crystallization properties of three kinds of spheres, which have poly(styrene) core and poly(ethylene oxide) shell with different oxyethylene chain length (n = 50, 80 and 150), were examined by reflection spectroscopy. The suspensions were deionized exhaustively for more than 1 year using mixed bed of ion-exchange resins. The rigidities of the crystals range from 0.11 to 120 Pa and from 0.56 to 76 Pa for the spheres of n = 50 and 80, respectively, and increase sharply as the sphere volume fraction increase. The g factor, parameter for crystal stability, range from 0.029 to 0.13 and from 0.040 to 0.11 for the spheres of n = 50 and 80, respectively. These g values indicate the formation of stable crystals, and the values were decreased as the sphere volume fraction increased. Two components of crystal growth rate coefficients, fast and slow, were observed in the order from 10⁻³ to 10¹ s⁻¹. This is due to the secondary process in the colloidal crystallization mechanism, corresponding to reorientation from metastable crystals formed in the primary process and/or Ostwald-ripening process. There are no distinct differences in the structural, kinetic and elastic properties among the colloidal crystals of the different core–shell size spheres, nor difference between those of core–shell spheres and silica or poly(styrene) spheres. The results are very reasonably interpreted by the fact that colloidal crystals are formed in a closed container owing to long-range repulsive forces and the Brownian movement of colloidal spheres surrounded by extended electrical double layers, and their formation is not influenced by the rigidity and internal structure of the spheres.     

Polymer-modified opal nanopores

The surface of nanopores in opal films, assembled from 205 nm silica spheres, was modified with poly(acrylamide) brushes using surface-initiated atom transfer radical polymerization. The colloidal crystal lattice remained unperturbed by the polymerization. The polymer brush thickness was controlled by polymerization time and was monitored by measuring the flux of redox species across the opal film using cyclic voltammetry. The nanopore size and polymer brush thickness were calculated on the basis of the limiting current change. Polymer brush thickness increased over the course of 26 h of polymerization in a logarithmic manner from 1.3 to 8.5 nm, leading to nanopores as small as 7.5 nm.     

镉离子响应性凝胶光子晶体传感膜的构建

将光子晶体与响应性水凝胶结合,采用“三明治”填充方法,以聚苯乙烯（PS）胶体晶体为模板,丙烯酰胺和烯丙基硫脲为单体制备得到一种对镉离子具有特异响应性的凝胶光子晶体传感膜,并对其进行了形貌表征和响应性研究。结果表明,该传感膜具有排列整齐的反蛋白石结构,可对不同浓度的Cd²⁺输出不同的光学信号。随着Cd²⁺浓度的增大,传感膜的Bragg衍射峰发生蓝移,并伴随有显著的颜色变化。在最优配比,适宜pH和离子强度条件下,衍射峰的最大位移值可达51.1 nm。在研究过程中发现其他干扰金属离子的存在不会影响传感膜对Cd²⁺的特异性响应,并且表现出了较快的响应速度。在多次循环实验中传感膜由于具备高度交联结构而表现出了良好的机械性和化学稳定性。该传感膜的构建为Cd²⁺的快速高效及裸眼可视检测提供了可能性。