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.     

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.     

一种室温下制备多孔锐钛矿型TiO2薄膜的方法

 采用具有锐钛矿晶粒的TiO2溶胶与聚苯乙烯球形粒子混合制得涂膜液,通过浸渍提拉法制备薄膜,然后在超声波振荡条件下,以甲苯为溶剂,将薄膜中的聚苯乙烯球选择性地溶解去除,在室温下获得了锐钛矿型多孔TiO2薄膜. 与致密的TiO2薄膜相比,该多孔TiO2薄膜具有较高的光催化活性. 该方法有以下两方面的优点: 一是实现了多孔TiO2薄膜的室温制备,增大了薄膜基材的选择范围; 二是可以通过添加不同粒径的聚苯乙烯球,较为方便地实现了对薄膜孔径的调节.     

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.     

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.     

Crystallization of colloidal crystal on hydrogel surface

A dip-coating method to fabricate wet and dry type of colloidal crystal films was developed. The wet type of colloidal crystal film was fabricated by lifting an agarose-hydrogel-coated substrate out of an aqueous suspension containing monodisperse polymer spheres and the dry type of colloidal crystal film was derived by following desiccation of the wet film. Monodisperse spheres formed ordered structures in the both type of the films, which contributed sharp reflection peaks. Brilliant colors were observed when the reflection peaks fell in the visible region. Formation mechanism of the colloidal crystal and their optical properties were discussed.     

Drying dissipative structures of colloidal crystals of silica spheres coated with polymer brushes of poly(carboxymethyl betaine)

Drying patterns of colloidal crystals of colloidal silica spheres coated with the brushes of zwitterionic poly(carboxymethyl betaine) (SiP-PCMB) and their parent silica spheres (SiP) were studied on a cover glass, a watch glass, and a Petri glass dish. Crystal structures kept the whole process of dryness of the suspensions of SiP-PCMB and SiP. Crystal structures of the dried films of SiP-PCMB were kept stable even when the initial suspensions contained 5 mM of sodium chloride, which is the important role of the excluded volume effects of the shells of the polymer brushes. On the other hand, crystal structures of SiP spheres in the dried films were much unstable and melted in the presence of 5 mM sodium chloride. In the suspension state, colloidal crystallization of SiP-PCMB took place stably by the contribution of the excluded volume effects besides the extended electrical double layers compared with that of SiP spheres, where only the double layer effect contributes to the crystallization. The fractal patterns of the complexation of SiP-PCMB or SiP spheres with sodium chloride were observed microscopically in the dried films. Several kinds of dissipative crystallization such as array and/or accumulation of the crystallites were observed, and the importance of the convectional and sedimentation processes during the course of dryness was demonstrated.     

Ion transport in sulfonated nanoporous colloidal films

The surface of self-assembled nanoporous silica colloidal crystalline films comprised of 184-nm-diameter silica spheres has been sulfonated using 1,3-propanesultone. The transport of ions through the sulfonated films has been studied using cyclic voltammetry in water as a function of ion charge, pH, and solution ionic strength. We found that the flux of anions through the sulfonated colloidal films is reduced, while the flux of cations is increased, compared to the unmodified colloidal films. This behavior is pH-dependent and is due to electrostatic repulsion/attraction that can be modulated by changing the ionic strength of the contacting solution.     

胶体晶体模板法制备三维有序大孔复合氧化物*

胶体晶体模板法是制备三维有序大孔（3DOM）复合氧化物材料的有效方法。制备过程一般包括3个步骤：首先,将单分散微球堆积成三维有序排列的胶体晶体;其次,将液态前驱体填充到胶体晶体的间隙,并在原位转化为固体骨架;最后,将微球去除,在原来微球间的空隙位置得到固体骨架,原来微球占据的位置则成为相互连接的孔穴。其中,胶体晶体模板的组装、前驱体的填充以及模板的去除都是制备3DOM复合氧化物的关键影响因素。本文针对这几个控制因素对胶体晶体模板法制备3DOM复合氧化物的影响进行了概述,并对孔结构的表征以及材料在催化和电极材料等方面的应用作了简单介绍。     

SiO2胶体晶体垂直沉积自组装方法的改进

采用垂直沉积技术及相应的改进方法,使用化学合成的400 nm单分散二氧化硅微球自组装制备了胶体晶体薄膜。通过扫描电镜与分光光度计对样品的微观结构与透过光谱进行了表征,并对比研究了不同的垂直沉积方法对胶体晶体的影响。结果表明,通过温度与流量控制两种改进手段,均能制备具有六方密堆结构周期排列的胶体晶体薄膜。在垂直沉积过程中适当的升高温度有利于降低胶体粒子的用量,而通过流量控制的垂直沉积技术则可以有效缩短自组装时间。通过调节蠕动泵改变液面与基板的相对运动速度,或者调控温度改变胶体溶液的蒸发速率,可在材料表面形成单层或多层的胶体晶体薄膜。改进的垂直沉积技术将有望应用于快速沉积大面积、高质量的胶体晶体材料。     

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．     

Electron Microscopic Study on Aerosol-Assisted Synthesis of Aluminum Organophosphonates Using Flexible Colloidal PS-b-PEO Templates

A wide variety of synthetic approaches from homogeneous precursor solutions have so far been developed for precise structural design of materials in multiscale. In organic templating approaches for porous materials design, we have recently developed a new approach to fabricate colloidal polystyrene-block-poly(oxyethylene) (PS-b-PEO) templated large pores that can be controlled in thick films of aluminum organophosphonate (AOP). In this study, we extended this approach using colloidal PS-b-PEO aggregates to aerosol-assisted synthesis for the fabrication of spherical particles. Structural variations (morphology and porous structure) depended on the synthetic conditions, which were mainly investigated by using electron microscopies (SEM and TEM). In addition to the insight on the colloidal PS-b-PEO templating of spherical pores in AOP spheres, it was found that colloidal PS-b-PEO aggregates were flexible for further design of pore shape that was strongly affected by external morphology. In this context, we proposed this method as flexible colloidal PS-b-PEO templating to fabricate unusual macroporous structures during morphological control from precursor solutions containing colloidal PS-b-PEO aggregates. The insights will be promising for precise construction of unique devices using porous materials templated by colloidal organic aggregates. In addition, we found a useful water adsorption-desorption behavior over the macroporous AOP bulky powders when the macropores were connected through large pores, which is also significant for future development of AOP-based porous materials.     

Self-assembly of two- and three-dimensional particle arrays by manipulating the hydrophobicity of silica nanospheres

The surface hydrophobicity of colloidal silica (SiO2) nanospheres is manipulated by a chemical graft of alkyl chains with silane coupling agents or by physical adsorption of a cationic surfactant. The surface-modified SiO2 spheres can be transferred from the aqueous phase to organic solvents and readily self-assemble at the water-air interface to form two-dimensional (2D) particle arrays. Closely packed particle monolayers are obtained by adjusting the hydrophilic/hydrophobic balance of the synthesized SiO2 spheres and may further be transferred onto solid substrates layer by layer to form three-dimensional (3D) ordered particle arrays with a hexagonal close-packed (hcp) crystalline structure. The 2D monolayer and 3D multilayer SiO2 films exhibit photonic crystal properties, which were determined by the UV-visible spectroscopic analysis in transmission mode. In the multilayer films, the Bragg diffraction maxima increased with an increase in thickness of the particle layers. The experimentally observed diffraction positions are in good agreement with those that were theoretically calculated.     

Temperature-assisted photochemical construction of CdS-based ordered porous films with photocatalytic activities on solution surfaces

Taking a colloidal monolayer floating on the surface of a precursor solution as template, free-standing CdS/Cd composites and pure CdS (CdS-based) ordered porous films had been prepared by a temperature-assisted photochemical strategy. After irradiation with UV-light and heat treatment, the films formed hemi-spherical pores due to the preferable deposition of CdS and Cd onto the PS spheres during the photochemical and interfacial reactions. When the temperature increased from 15 to 60°C, the air/water interface gradually changed into a vapor/water interface on the surface of the solution, resulting in variations of the final compositions. The optical properties of the films were hence changed. Because of the free-standing characteristic, the ordered porous films were first transferred on surface of polluted solutions as photocatalysts, which was a new mode in application of photocatalysts. The photocatalytic activities of films showed regular variations with the compositions in photodegradation of Rhodamine B. This method provides a simple route for tuning the properties of porous films through control of its composition and a flexible application of films on any surface.     

作为锂离子电池负极材料的三维有序大孔SnO2的 制备及表征

通过聚苯乙烯(PS)胶晶模板法合成了三维有序大孔(3DOM) SnO2. 运用扫描电镜、热重分析、X射线衍射、电化学充放电等多种方法对其结构和性能进行了表征和研究. SEM图表明PS胶晶模板微球排列规整, 大小均匀(直径275±10 nm), 形成多层六方紧密堆积排列; 煅烧除去模板后的3DOM SnO2呈三维多孔网络结构, 具有圆型和六边形的孔隙形貌, 其孔径大小为(215±10) nm; 孔壁由SnO2纳米晶粒组成, 壁厚为20～30 nm. XRD图谱表明经过煅烧除去模板后, 形成了纯SnO2相. 当作为锂离子电池负极材料时, 3DOM SnO2表现出较好的充放电容量和库仑效率. 此外, 这种合成方法简单、经济, 可进一步应用于其它锂离子电池材料的合成.     

Generalized Hertzian model for the deformation and cracking of colloidal packings saturated with liquid

The process of drying colloidal dispersions generally produces particulate solids under stress as a result of capillary or interparticle forces. The derivation of a constitutive relation on the basis of Hertzian contact mechanics between spheres provides a model for quantitatively predicting the conditions under which close-packed colloidal layers form continuous void-free films or homogeneous porous films or crack under tensile stresses.     

Particle and substrate charge effects on colloidal self-assembly in a sessile drop

By direct video monitoring of dynamic colloidal self-assembly during solvent evaporation in a sessile drop, we investigated the effect of surface charge on the ordering of colloidal spheres. The in situ observations revealed that the interaction between charged colloidal spheres and substrates affects the mobility of colloidal spheres during convective self-assembly, playing an important role in the colloidal crystal growth process. Both ordered and disordered growth was observed depending on different chemical conditions mediated by surface charge and surfactant additions to the sessile drop system. These different self-assembly behaviors were explained by the Coulombic and hydrophobic interactions between surface-charged colloidal spheres and substrates.     

木质素基偶氮聚合物胶体球的制备

利用造纸废液中的碱木素(AL)合成了木质素基偶氮聚合物(AL-azo-COOEt), 并研究其自组装胶体化过程. 木质素偶氮聚合物的成功合成通过核磁共振氢谱(¹H NMR)、紫外-可见(UV-Vis)光谱、傅里叶变换红外(FTIR)光谱和元素分析等表征方法得到证实. 激光光散射(LLS)监测了AL-azo-COOEt的胶体化过程, 自组装形成的胶体球利用透射电镜(TEM)、扫描电镜(SEM)、X射线光电子能谱仪(XPS)和元素分析等进行表征. 结果表明,木质素偶氮聚合物通过疏水聚集作用可以形成规整的实心胶体球, 且为内部较疏水外部较亲水性质的结构. 木质素偶氮聚合物胶体球可以包载疏水性药物阿霉素(DOX), 且其缓释性能可以通过缓冲溶液的pH值来调控.     

Plasmonic films based on colloidal lithography

This paper reviews recent advances in the field of plasmonic films fabricated by colloidal lithography. Compared with conventional lithography techniques such as electron beam lithography and focused ion beam lithography, the unconventional colloidal lithography technique with advantages of low-cost and high-throughput has made the fabrication process more efficient, and moreover brought out novel films that show remarkable surface plasmon features. These plasmonic films include those with nanohole arrays, nanovoid arrays and nanoshell arrays with precisely controlled shapes, sizes, and spacing. Based on these novel nanostructures, optical and sensing performances can be greatly enhanced. The introduction of colloidal lithography provides not only efficient fabrication processes but also plasmonic films with unique nanostructures, which are difficult to be fabricated by conventional lithography techniques.     

Thermal phase transition behaviour of liquid crystals in submicron pores formed with stretched polymer fibrils

This paper discusses thermal phase transitions in a nematic liquid crystal material, filling a highly strained porous polyolefin film. Ruptured and aligned polymer fibrils, whose minimum diameter reaches several tens of nm, formed polymer networks in the porous film. From observations of temperature-controlled composite films using a polarizing microscope, it was noted that the isotropic-to-nematic phase transition temperatures of submicron liquid crystal domains, located in or near molecularly aligned streak-like polymer areas, were significantly higher than those located at some distance from these areas. It was assumed that the highly aligned polymer chains in the fine fibrils promote the nematic phase of the liquid crystal. The stretched porous polymer, exhibiting spatial ordering on a submicron scale, is thus suitable for the control of thermal phase transitions in a liquid crystal.