INVERSE OPALINE STRUCTURE TITANIA PHOTONIC CRYSTALS BY FUNCTIONALLY MODIFIED COLLOIDAL CRYSTALS TEMPLATING

Ordered macroporous titania photonic crystals （PCs） and photonic balls were fabricated by functional modified polymer colloidal crystals. The TiO2 PCs and balls formed through this method exhibit no cracks and lacunae in large areas on their surface and their inner structures.

Fabrication of Large-area 3-D Ordered Silvercoated Colloidal Crystals and Macroporous Silver Films Using Polystyrene Templates

The highly ordered silver-coated colloidal crystals arrays and macroporous silver films were derived through an electrostatics-induced adsorption effect using polystyrene(PS) as templates. Carboxyl-modified PS microspheres were prepared by emulsifier-free emulsion polymerization using methacrylic acid(MAA) as the functional monomer. PS microspheres were self-assembled into close packing colloidal crystals of facecentered cubic arrays to the substrate with vertical deposition method. These colloidal crystals were modified using dopamine(DA) to form poly-dopamine(PDA) during its oxidative polymerization. Through electrostatic interaction, the silver nanoparticles were deposited and adsorbed onto the surfaces of colloidal crystals templates by exposing [Ag(NH_3)_2]^+solution to infrared irradiation. Removal of the polymeric template by etching with methylbenzene solvent resulted in 3D ordered macroporous silver films. The structural and properties of the ordered silver-coated arrays and macroporous silver films were characterized by field emission scanning electron microscopy(FE-SEM), X-ray diffraction(XRD), UV-vis spectroscopy and surface-enhanced Raman spectroscopy(SERS). The results indicate that the prepared silver-coated arrays and macroporous silver films possess the features of ordered multilayer arrangement, uniformity and repeatability as well as an ideal SERS effect.

Preparation and properties of polymeric colloidal crystals containing rare earth complexes

Rare earth organic complexes were introduced into the polymerization system, and the polymeric colloidal nanospheres containing rare earth complexes were prepared by emulsion copolymerization. The characterization results indicated that the polymeric spheres were small at nanometer size and the diameter was monodisperse, particularly the nanospheres possessed good fluorescent properties. Moreover, the polymeric nanospheres were self-assembled to fabricate the colloidal crystals, which were three-dimensional regular multilayer films. The polymeric colloidal crystal films exhibited excellent luminescent and novel optical properties.

Applied electric field to fabricate colloidal crystals with the photonic band-gap in communication waveband

The macropore silica colloidal crystal templates were assembled orderly in a capillary glass tube by an applied electric field method to control silica deposition. In order to achieve the photonic band gap （PBG） of colloidal crystal in optical communication waveband, the diameter of silica microspheres is selected by Bragg diffraction formula. An experiment was designed to test the bandgap of the silica crystal templates. This paper discusses the formation process and the close-packed fashion of the silica colloidal crystal templates was discussed. The surface morphology of the templates was also analyzed. The results showed that the close-packed fashion of silica array templates was face-centered cubic （FCC） structure： The agreement is very good between the experimental data and the theoretical calculation.

Preparation of polystyrene spheres in different particle sizes and assembly of the PS colloidal crystals

Monodisperse polystyrene (PS) colloidal spheres were successfully prepared through emulsifier-free emulsion polymerization by controlling the polymerization reaction time, ionic strength of the system, concentration of the ionic copolymer (sodium p-styrenesulfonate) and other factors. The PS colloidal spheres were assembled into colloidal crystals whose structures were mainly face-centered cubic (fcc) close-packed. Then FDTD method was used to calculate the color-rendering characteristics of the colloidal crystals surface. The calculated results were consistent with the experimental results.

Recent research progress in wettability of colloidal crystals

The wettability of solid surfaces has attracted extensive interest in both theoretical research and industrial applications. This paper reviews recent research progress in the fabrication and applications of the colloidal crystals with special wettability. Based on the modified equation of Wenzel and Cassie, the colloidal crystals with special wettability have been obtained by either application of the intrinsic rough structure or modification of the surface chemical composition. Some typical applications of colloidal crystals with special wettability have also been demonstrated.

Self-assembly of latex particles for colloidal crystals

Self-assembly of latex particles is of great importance for fabricating various functional colloidal crystals. In this paper, we review recent research on the self-assembly of latex particles for colloidal crystals, covering the assembly forces and various assembly approaches of latex particles, including self-assembly by gravity sedimentation, vertical deposition, physical confinement, electric field, and magnetic field. Furthermore, some simple methods for assembling latex particles such as spin coating, spray coating, and printing are also summarized.

The infrared transmission through gold films on ordered two-dimensional non-close-packed colloidal crystals

We studied the infrared transmission properties of gold films on ordered two-dimensional nonclose- packed polystyrene （PS） colloidal crystal. The gold films consist of gold half-shells on the PS spheres and gold film with 2D arrays of holes on the glass substrate. An extraordinary optical transmission phenomenon could be found in such a structure. Simulations with the finite-difference time-domain method were also employed to get the transmission spectra and electric field distribution. The transmission response of the samples can be adjusted by controlling the thickness of the gold films. Angle-resolved measurements were performed using polarized light to obtain more information about the surface plasmon polariton resonances of the gold films. As the angle changes, the transmission spectra change a lot. The transmission spectra of p-polarized light have quite different properties compared to those of s-polarized light.

Engineering particles towards 3D supraballs-based passive cooling via grafting CDs onto colloidal photonic crystals

Particle engineering has opened the floodgates to material science in both fundamental and application field. However, covalent interactions have not yet been adequately designed in the particle engineering for functional colloidal photonic crystals(CPCs). Herein, we achieved covalent coupling between carboxylrich poly(styrene-acrylic acid)(P(St-AA)) monodispersed colloidal particles and amine-rich carbon dots(CDs) based on an feasible and universal particle engineering strategy. The designed CDs-grafted P(St-AA)monodispersed colloidal particles initiate a hydrogen bond-driven assembly mode and ensure the construction of large-scale crack-free CPCs. Moreover, the CDs equipped with selective broad-band absorption capacity could improve the saturation of structural colors for high-visibility CPCs. Furthermore, an injectable photonic hydrogel(IPH) is developed to design CPC supraball hydrogel via integrating the CDsgrafted P(St-AA) CPC supraballs with supramolecular hydrogel. Combining superior flexibility, sufficient self-healing capacity of supramolecular hydrogel with visual optical information of our CPC supraballs, a cyclically reversible coding and decoding system was developed. Meanwhile, we firstly demonstrated the novel strategy of 3D supraballs-based passive cooling. The designed 3D CPC supraball hydrogel presents nearly full observation angle reflections behavior and excellent water evaporation capacity and achieves3.6 ℃ temperature drops, showing the application advantages in 3D thermal management. This work not only provides a new insight for manipulating optical properties of CPCs, but also demonstrates an easyto-perform platform, as well as indicates the direction for the promising application of CPCs.

High-quality SiO_2 Colloidal Crystal Fabricated by Controllable Vertical Deposition Method

Monodispersed silica microspheres with diameter of 353nm were assembled into photonic crystal in ethanol colloidal suspensions of varied silica volume fraction at different temperature and humidity by means of controllable vertical deposition method. The surface morphology and optical properties were studied by SEM and UV-Vis-NIR. It was found that the high-quality silica colloidal photonic crystals were obtained from ethanol solutions with environment temperature between 45℃ and 55℃, humidity between 66% and 76%, the volume fraction of microspheres is between 0.8% and 1.5%. The ordered close-packed photonic crystal fabricated by controllable vertical deposition method had the two photonic bandgaps in the visible light band and near infrared band.

Three-dimensional Ordered Silica Colloidal Film Self-assembly Deposited on a VerticalSubstrate

A method for preparation of particle crystal film constructed from monodisperse silica colloidal particles in diameter of about 300 nm is reported. The films were prepared from an ethanol suspension by vertical deposition that relies on capillary forces to assemble colloidal crystal particles on a vertical substrate. The 3D ordered films were characterized by transmission spectra and scanning electric microscope (SEM). The effect of evaporation temperature, particle concentration and sintered temperature on the quality of colloidal particle crystal film was investigated.

Facile Fabrication of Large Area Polystyrene Colloidal Crystal Monolayer via Surfactant-free Langmuir-Blodgett Technique

A facile and novel method for the production of a large area of well-ordered polystyrene （PS） colloidal crystal monolayer was established using the surfactant-free Langmuir-Blodgett （LB） technique. The hydrophobic property （film-forming ability） of PS spheres was improved by a thermo-rheology treatment before LB assembly, and a large film was obtained. In contrast to the traditional LB technique, no surfactant was needed in this method, which could eliminate the additional contamination of surfactants in the preparation process and provided the products with versa- tile applications in nanosphere lithography （NSL） for biosensor, surface plasmon resonance, and surface enhanced Raman spectroscopy .

Improving self-assembly quality of colloidal crystal guided by statistical design of experiments

A versatile and reliable approach is created to fabricate wafer-scale colloidal crystal that consists of a monolayer of hexagonally close-packed polystyrene （PS） spheres. Making wafer-scale colloidal crystal is usually challenging, and it lacks a general theoretical guidance for experimental approaches. To obtain the optimal conditions for self-assembly, a systematic statistical design and analysis method is utilized here, which applies the pick-the-winner rule. This new method combines spin-coating and thermal treatment, and introduces a mixture of glycol and ethanol as a dispersion system to assist self-assembly. By controlling the parameters of self-assembly, we improve the quality of colloidal crystal and reduce the effect of noise on the experiment. To our best knowledge, we are first to pave this path to harvest colloidal crystals. Importantly, a theoretical analysis using an energy landscape base on our process is also developed to provide insights into the PS spheres＇ self-assembly.

Fabrication of Macro-porous β-zeolite by Using Colloidal Polystyrene Spheres as a Template

A β-zeolite/polystyrene composite material was synthesized by co-deposition of mono-disperse polystyrene spheres and nano β-zeolite particles in aqueous suspension on a vertical substrate. Macro-porous β-zeolite was obtained after the polystyrene template was removed by calcination. The micro/macro-pore structure of the prepared β-zeolite was highly ordered. In comparison with other assembly methods, the co-deposition method could obtain a highly ordered macro-porous material with relatively large zeolite filling particles, and therefore the co-deposition of particles with different size is a promising method for the fabrication of macro-porous materials.

Modification of the spontaneous emission of quantum dots near the surface of a three-dimensional colloidal photonic crystal

This paper demonstrates experimentally and numerically that a significant modification of spontaneous emission rate can be achieved near the surface of a three-dimensional photonic crystal. In experiments, semiconductor coreshell quantum dots are intentionally confined in a thin polymer film on which a three-dimensional colloidal photonic crystal is fabricated. The spontaneous emission rate of quantum dots is characterised by conventional and time-resolved photoluminescence （PL） measurements. The modification of the spontaneous emission rate, which is reflected in the change of spectral shape and PL lifetime, is clearly observed. While an obvious increase in the PL lifetime is found at most wavelengths in the band gap, a significant reduction in the PL lifetime by one order of magnitude is observed at the short-wavelength band edge. Numerical simulation reveals a periodic modulation of spontaneous emission rate with decreasing modulation strength when an emitter is moved away from the surface of the photonic crystal. It is supported by the fact that the modification of spontaneous emission rate is not pronounced for quantum dots distributed in a thick polymer film where both enhancement and suppression are present simultaneously. This finding provides a simple and effective way for improving the performance of light emitting devices.

DEFORMATION OF SOFT COLLOIDAL CRYSTALLINE STRUCTURE-THEORETICAL CONSIDERATIONS AND EXPERIMENTAL EVIDENCES BY SYNCHROTRON SMALL-ANGLE X-RAY SCATTERING ON TENSILE STRETCHED POLYMERIC LATEX FILM

Films obtained via drying a polymeric latex dispersion are normally colloidal crystalline where latex particles are packed into a face centered cubic (fcc) structure.Different from conventional atomic crystallites or hard sphere colloidal crystallites,the crystalline structure of these films is normally deformable due to the low glass transition temperature of the latex particles.Upon tensile deformation,depending on the drawing direction with respect to the normal of specific crystallographic plane,one obs...

Influence of Gravity on Structure of Colloidal Crystal Using Simulated Microgravity

Liquid mixtures of water and deuterium oxide as the liquid phase, were used to match the density of charged colloidal particles. Kossel diffraction method was used to detect the crystal structures. The experiments under the density-matched （g=0） and unmatched （g=1） conditions are compared to examine the influence of gravity on the crystal structures formed by self-assembly of 110 nm （in diameter） polystyrene microspheres. The result shows that the gravity tends to make the lattice constants of colloidal crystals smaller at lower positions, which indicates that the effect of gravity should be taken into account in the study of the colloidal crystals.

Influence of Sedimentation on Crystallization of Charged Colloidal Particles

The method of density matching between the solid and liquid phases is often adopted to effectively eliminate the effect of sedimentation of suspensions on dynamic behavior of a colloidal system. Experiments on crystallization of charged colloidal microspheres with di- ameter of 98 nm dispersed in density-matched and -unmatched media （mixtures of H20 and D20 in proper proportion） are compared to examine the influence of sedimentation. Reflection spectra of colloidal suspensions were used to monitor the crystallization process. Results showed that the crystal size of the density-unmatched （namely, in the presence of sedimentation） sample grew faster than that of the density-matched （in the absence of sedi- mentation） case at the initial stage of the crystallization, and then the latter overtook and outstripped the former. To explain these observations, we assume that in the settling of crystals sedimentation facilitates result in more particles getting into the crystal structures. However, as the crystals increase to varying sizes, the settling velocities become large and hydrodynamic friction strips off some particles from the delicate crystal structures. Overall, the sedimentation appears to accelerate the crystal size growth initially and then retard the growth. In addition, the crystal structures formed under microgravity were more closely packed than that in normal gravity.

Observations of defect propagation in [100]-oriented opal-type photonic crystals

Charged colloidal suspensions have been used as experimental models for the study of crystal nucleation. Here we propose that the technique of template-assisted colloidal self-assembly can be used to visualize the effects of defect propagation in atomic crystal films produced using epitaxial growth. Templates with periodic line defects were used to grow [100]-oriented three-dimensional photonic crystals by means of the template-assisted colloidal self-assembly method, aided by capillary and gravitational forces. The defect propagation in the [100]-oriented photonic crystal was observed using scanning electron microscopy, both at the surface of the crystal and on cleaved facets. This method is useful in the understanding of defect propagation in the growth of colloidal films on templates - and the same approach may also prove useful for the understanding of atomic crystal growth on substrates with defects. Additionally, the deliberate incorporation of line defects may prove valuable as a way of introducing waveguide channels into three-dimensional photonic crystals.

Influence of colloidal particle transfer on the quality of self-assembling colloidal photonic crystal under confined condition

The relationship between colloidal particle transfer and the quality of colloidal photonic crystal（CPC） is investigated by comparing colloidal particle self-assembling under the vertical channel（VC） and horizontal channel（HC） conditions.Both the theoretical analyses and the experimental measurements indicate that crystal quality depends on the stability of mass transfer.For the VC,colloidal particle transfer takes place in a stable laminar flow,which is conducive to forming high-quality crystal.In contrast,it happens in an unstable turbulent flow for the HC.Crystals with cracks and an uneven surface formed under the HC condition can be seen from the images of a field emission scanning electron microscope（SEM） and a three-dimensional（3D） laser scanning microscope（LSM）,respectively.