Reversibly strain-tunable elastomeric photonic crystals

Reversibly strain-tunable polymeric photonic crystals made of thermoplastic polyester elastomer (TPEE) were fabricated by using the self-assembled silica opals as templates. The stop band of the polymeric photonic crystal locates at the near infrared (IR) regime in its transmission spectrum, and exhibits a blue shift with the increase of the incident angle. Because of the elasticity of the TPEE, the stop band of the TPEE photonic crystal can also be reversibly tuned at ambient temperature through to and fro uniaxially or biaxially stretching and recovering by changing the lattice spacing and the symmetry of the crystal along (1 1 1) plane.

Non-affine structural evolution of soft colloidal crystalline latex films under stretching as observed via synchrotron X-ray scattering

A polymer dispersion consisting of soft latex spheres with a diameter of 135 nm was used to produce a crystalline film with face-centered cubic (fcc) packing of the spheres. Different from conventional small-molecule and hardsphere colloidal crystals, the crystalline latex film in the present case is soft (i.e., easily deformable). The structural evolution of this soft colloidal latex film under stretching was investigated by in-situ synchrotron ultra-small-angle X-ray scattering. The film exhibits polycrystalline scattering behavior corresponding to fcc structure. Stretching results not only in a large deformation of the crystallographic structure but also in considerable nonaffine deformation at high draw ratios. The unexpected nonaffine deformation was attributed to slippage between rows of particles and crystalline grain boundaries. The crystalline structure remains intact even at high deformation, suggesting that directional anisotropic colloidal crystallites can be easily produced.

Tunable photonic crystals by mixed liquids

Tunable photonic crystals were prepared by infiltrating mixed liquids into the voids of silica opals. The stop bands of the tunable photonic crystals were continuously tuned by changing the relative refraction index contrast n(mix)/ns(pheres) of the spheres and the mixed liquids by varying the volume fraction of the component of the mixed liquids. The peak wavelengths of the stop band have a red shift as the refractive index of the mixed liquids increases. The transmittance at the stop band decreases with the increase of the refractive index contrast n(mix)/n(spheres). The larger the diameter of silica opals is, the wider the tunable range of the stop band is. The position and transmittance of the peak wavelength obtained by the photonic band calculations agreed very well with the experimental data.

Complex materials via colloidal crystallization

The work presented in this thesis deals with complex materials, which were obtained by self-assembly of monodisperse colloidal particles, also called colloidal crystallization. Two main fields of interest were investigated, the first dealing with the fabrication of colloidal monolayers and nanostructures, which derive there from. The second turned the focus on the phononic properties of colloidal particles, crystals, and glasses. For the fabrication of colloidal monolayers a method is introduced, which is based on the sparse distribution of dry colloidal particles on a parent substrate. In the ensuing floating step the colloidal monolayer assembles readily at the three-phase-contact line, giving a 2D hexagonally ordered film under the right conditions. The unique feature of this fabrication process is an anisotropic shrinkage, which occurs alongside with the floating step. This phenomenon is exploited for the tailored structuring of colloidal monolayers, leading to designed hetero-monolayers by inkjet printing. Furthermore, the mechanical stability of the floating monolayers allows the deposition on hydrophobic substrates, which enables the fabrication of ultraflat nanostructured surfaces. Densely packed arrays of crescent shaped nanoparticles have also been synthesized. It is possible to stack those arrays in a 3D manner allowing to mutually orientate the individual layers. In a step towards 3D mesoporous materials a methodology to synthesize hierarchically structured inverse opals is introduced. The deposition of colloidal particles in the free voids of a host inverse opal allows for the fabrication of composite inverse opals on two length scales. The phononic properties of colloidal crystals and films are characterized by Brillouin light scattering (BLS). At first the resonant modes of colloidal particles consisting of polystyrene, a copolymer of methylmethacrylate and butylacrylate, or of a silica core-PMMA shell topography are investigated, giving insight into their individual mechanical properties. The infiltration of colloidal films with an index matching liquid allows measuring the phonon dispersion relation. This leads to the assignment of band gaps to the material under investigation. Here, two band gaps could be found, one originating from the fcc order in the colloidal crystal (Bragg gap), the other stemming from the vibrational eigenmodes of the colloidal particles (hybridization gap).

Surface patterning with colloidal monolayers

This thesis focuses on the controlled assembly of monodisperse polymer colloids into ordered two-dimensional arrangements. These assemblies, commonly referred to as colloidal monolayers, are subsequently used as masks for the generation of arrays of complex metal nanostructures on solid substrates.rnThe motivation of the research presented here is twofold. First, monolayer crystallization methods were developed to simplify the assembly of colloids and to produce more complex arrangements of colloids in a precise way. Second, various approaches to colloidal lithography are designed with the aim to include novel features or functions to arrays of metal nanostructures.rnThe air/water interface was exploited for the crystallization of colloidal monolayer architectures as it combines a two-dimensional confinement with a high lateral mobility of the colloids that is beneficial for the creation of high long range order. A direct assembly of colloids is presented that provides a cheap, fast and conceptually simple methodology for the preparation of ordered colloidal monolayers. The produced two-dimensional crystals can be transformed into non-close-packed architectures by a plasma-induced size reduction step, thus providing valuable masks for more sophisticated lithographic processes. Finally, the controlled co-assembly of binary colloidal crystals with defined stoichiometries on a Langmuir trough is introduced and characterized with respect to accessible configurations and size ratios. rnSeveral approaches to lithography are presented that aim at introducing different features to colloidal lithography. First, using metal-complex containing latex particles, the synthesis of which is described as well, symmetric arrays of metal nanoparticles can be created by controlled combustion of the organic material of the colloids. The process does not feature an inherent limit in nanoparticle size and is able to produce complex materials as will be demonstrated for FePt alloy particles. Precise control over both size and spacing of the particle array is presented. rnSecond, two lithographic processes are introduced to create sophisticated nanoparticle dimer units consisting of two crescent shaped nanostructures in close proximity; essentially by using a single colloid as mask to generate two structures simultaneously. Strong coupling processes of the parental plasmon resonances of the two objects are observed that are accompanied by high near-field enhancements. A plasmon hybridization model is elaborated to explain all polarization dependent shifts of the resonance positions. Last, a technique to produce laterally patterned, ultra-flat substrates without surface topographies by embedding gold nanoparticles in a silicon dioxide matrix is applied to construct robust and re-usable sensing architectures and to introduce an approach for the nanoscale patterning of solid supported lipid bilayer membranes. rn

Structure and dynamics of thin colloidal films

This thesis begins by studying the thickness of evaporative spin coated colloidal crystals and demonstrates the variation of the thickness as a function of suspension concentration and spin rate. Particularly, the films are thicker with higher suspension concentration and lower spin rate. This study also provides evidence for the reproducibility of spin coating in terms of the thickness of the resulting colloidal films. These colloidal films, as well as the ones obtained from various other methods such as convective assembly and dip coating, usually possess a crystalline structure. Due to the lack of a comprehensive method for characterization of order in colloidal structures, a procedure is developed for such a characterization in terms of local and longer range translational and orientational order. Translational measures turn out to be adequate for characterizing small deviations from perfect order, while orientational measures are more informative for polycrystalline and highly disordered crystals. Finally, to obtain an understanding of the relationship between dynamics and structure, the dynamics of colloids in a quasi-2D suspension as a function of packing fraction is studied. The tools that are used are mean square displacement (MSD) and the self part of the van Hove function. The slow down of dynamics is observed as the packing fraction increases, accompanied with the emergence of 6-fold symmetry within the system. The dynamics turns out to be non-Gaussian at early times and Gaussian at later times for packing fractions below 0.6. Above this packing fraction, the dynamics is non-Gaussian at all times. Also the diffusion coefficient is calculated from MSD and the van Hove function. It goes down as the packing fraction is increased.

Phase diagram of a two-species lattice model with a linear instability

We discuss the properties of a one-dimensional lattice model of a driven system with two species of particles in which the mobility of one species depends on the density of the other. This model was introduced by Lahiri and Ramaswamy (Phys. Rev. Lett., 79, 1150 (1997)) in the context of sedimenting colloidal crystals, and its continuum version was shown to exhibit an instability arising from linear gradient couplings. In this paper we review recent progress in understanding the full phase diagram of the model. There are three phases. In the first, the steady state can be determined exactly along a representative locus using the condition of detailed balance. The system shows phase separation of an exceptionally robust sort, termed strong phase separation, which survives at all temperatures. The second phase arises in the threshold case where the first species evolves independently of the second, but the fluctuations of the first influence the evolution of the second, as in the passive scalar problem. The second species then shows phase separation of a delicate sort, in which long-range order coexists with fluctuations which do not damp down in the large-size limit. This fluctuation-dominated phase ordering is associated with power law decays in cluster size distributions and a breakdown of the Porod law. The third phase is one with a uniform overall density, and along a representative locus the steady state is shown to have product measure form. Density fluctuations are transported by two kinematic waves, each involving both species and coupled at the nonlinear level. Their dissipation properties are governed by the symmetries of these couplings, which depend on the overall densities. In the most interesting case,, the dissipation of the two modes is characterized by different critical exponents, despite the nonlinear coupling.

二元体系胶体晶体性质的实验研究

利用Kossel衍射技术和反射光谱对由总体积分数为0.02的二元聚苯乙烯胶体体系(94 nm+141 nm)形成的胶体晶体的性质进行了研究,实验结果显示胶体晶体的形成时间,平均粒子间距,晶体结构都与二元胶体体系中两种粒子的数密度比相关,当94 nm聚苯乙烯粒子相对于141 nm聚苯乙烯粒子的数密度比趋向1∶1时,胶体晶体的形成时间延长,当94 nm聚苯乙烯粒子相对于141 nm聚苯乙烯粒子的数密度比由1∶0向0∶1变化时,胶体晶体的平均粒子间距变大,另外实验中发现在两种粒子的数密度比为5∶1时,胶体晶体出现了超晶格结构. 

Characterization Of Crystal Structure In Binary Mixtures Of Latex Globules

Colloidal crystals formed by two types of polystyrene particles of different sizes (94 and 141 nm) at various number ratios (94:141 nm) are studied. Experiments showed that the formation time of crystals lengthens as the number ratio of the two components approaches 1:1. The dependence of the mean interparticle distance (D-0), crystal structure and alloy structure on the number ratio of the two types of particles was Studied by means of Kossel diffraction technique and reflection spectra. The results showed that as the number ratio decreased, the mean interparticle distance (D-0) became larger. And the colloidal crystal in binary mixtures is more preferably to form the bcc structure. This study found that binary systems form the substitutional solid solution (sss)-type alloy structure in all cases except when the number ratio of two types of particles is 5:1, which results instead in the superlattice structure. (C) 2008 Elsevier Inc. All rights reserved.

Rapidly Infrared-Assisted Cooperatively Self-Assembled Highly Ordered Multiscale Porous Materials

In this paper, cooperative self-assembly (CSA) of colloidal spheres with different sizes was studied. It was found that a complicated jamming effect makes it difficult to achieve an optimal self-assembling condition for construction of a well-ordered stacking of colloidal spheres in a relatively short growth time by CSA. Through the use of a characteristic infrared (IR) technique to significantly accelerate local evaporation on the growing interface without changing the bulk growing environment, a concise three-parameter (temperature, pressure, and IR intensity) CSA method to effectively overcome the jamming effect has been developed. Mono- and multiscale inverse opals in a large range of lattice scales can be prepared within a growth time (15-30 min) that is remarkably shorter than the growth times of several hours for previous methods. Scanning electron microscopy images and transmittance spectra demonstrated the superior crystalline and optical qualities of the resulting materials. More importantly, the new method enables optimal conditions for CSA without limitations on sizes and materials of multiple colloids. This strategy not only makes a meaningful advance in the applicability and universality of colloidal crystals and ordered porous materials but also can be an inspiration to the self-assembly systems widely used in many other fields, such as nanotechnology and molecular bioengineering.

带电胶体粒子结晶过程的实验研究

利用带电单分散聚苯乙烯胶体粒子,通过自组装机理,制备了体积百分比为4·8%的具有多晶结构的胶体晶体,并用Kossel衍射技术和紫外可见分光光度计分别对晶体的生长过程进行了监测.通过对Kossel的图像分析检测不同阶段相应的晶格结构,发现胶体结晶过程晶体结构演变顺序为由液态—随机层结构—堆无序结构—面心立方孪晶结构到面心立方结构.定量地确定了结晶过程中晶体不同晶面的晶面间距和晶体的晶格常数,通过紫外可见分光光度计测量的晶体透射谱图,计算得到111晶面的晶面间距和晶体的晶格常数,与用Kossel衍射技术得到的结果相一致,还发现随样品放置时间的延长,衰减峰变窄和加深,并向短波方向移动,对应着晶体的晶格常数减小的现象.

带电悬浮粒子胶体晶体的固定化

采用光固化技术, 以丙烯酰胺单体与亚甲基双丙烯酰胺交联剂在紫外光的照射下发生光聚合反应, 嵌入聚苯乙烯胶体晶体, 实现了胶体晶体的固定化. 结合反射光谱和Kossel衍射技术研究对照了固定化前后胶体晶体的变化, 实验结果表明, 通过这种水凝胶固定化的胶体晶体保存了未固定前悬浮液中胶体晶体的结构. 但固定化后的胶体晶体的晶面间距和晶体的尺寸都略微减小. 通过对固定化后的水凝胶长时间的反射光谱观测, 发现固定化后胶体晶体在Milli-Q水中起初会发生溶胀, 经过2-5天溶胀-消溶胀过程达到平衡, 平衡后的水凝胶胶体晶体十分稳定, 可以长时间保持胶体晶体的结构. 因此, 胶体晶体固定化不但极大地提高了悬浮液中胶体晶体的抗剪切能力, 还克服了悬浮液中胶体晶体对离子、外界干扰的敏感性, 扩大了胶体晶体的实际应用价值.

Tunable Multiresponsive Methacrylic Acid Based Inverse Opal Hydrogels Prepared by Controlling the Synthesis Conditions

Methacrylic acid based inverse opal hydrogels (MIOHs) have been prepared by controlling the synthesis conditions, including cross-linker content, solvent content, and water content in solvent mixtures to explore the effect of the synthesis conditions (especially solvent content and mixture) on the response performance. Various response events (pH, solvent, ionic strength, 1,4-phenylenediamine dihydrochloride (PDA) response) have been investigated. For pH, solvent response, the same response behaviors have been observed: both the increased solvent (only ethanol) content and the enhanced water content in solvent will lead to the reduced response level of MIOHs compared to that of the increased cross-linker content. However, two different kinds of response behaviors for ionic strength response have been found by adjusting the synthesis conditions. The kinetics of pH response shows characteristics of a diffusion-limited process, and the equilibrium response time is about 20 min, which cannot be reduced by changing the synthesis conditions.

Formation and characterisation of ordered porous vanadium oxide inverse opal materials for Li-ion batteries

This thesis presents several routes towards achieving artificial opal templates by colloidal self-assembly of polystyrene (PS) or poly(methyl methacrylate) (PMMA) spheres and the use of these template for the fabrication of V2O5 inverse opals as cathode materials for lithium ion battery applications. First, through the manipulation of different experimental factors, several methods of affecting or directing opal growth towards realizing different structures, improving order and/or achieving faster formation on a variety of substrates are presented. The addition of the surfactant sodium dodecyl sulphate (SDS) at a concentration above the critical micelle concentration for SDS to a 5 wt% solution of PMMA spheres before dip-coating is presented as a method of achieving ordered 2D PhC monolayers on hydrophobic Au-coated silicon substrates at fast and slow rates of withdrawal. The effect that the degree of hydrophilicity of glass substrates has on the ordering of PMMA spheres is next investigated for a slow rate of withdrawal under noise agitation. Heating of the colloidal solution is also presented as a means of affecting order and thickness of opal deposits formed using fast rate dip coating. E-beam patterned substrates are shown as a means of altering the thermodynamically favoured FCC ordering of polystyrene spheres (PS) when dip coated at slow rate. Facile routes toward the synthesis of ordered V2O5 inverse opals are presented with direct infiltration of polymer sphere templates using liquid precursor. The use of different opal templates, both 2D and 3D partially ordered templates, is compared and the composition and arrangement of the subsequent IO structures post infiltration and calcination for various procedures is characterised. V2O5 IOs are also synthesised by electrodeposition from an aqueous VOSO4 solution at constant voltage. Electrochemical characterisation of these structures as cathode material for Li-ion batteries is assessed in a half cell arrangement for samples deposited on stainless steel foil substrates. Improved rate capabilities are demonstrated for these materials over bulk V2O5, with the improvement attributed to the shorter Li ion diffusion distances and increased electrolyte infiltration provided by the IO structure.