Cover Picture: Functionalization of Crystalline Colloidal Arrays through Click Chemistry (Adv. Mater. 21/2007)

Photonic crystals based on electrostatically‐stabilized colloidal arrays dispersed in a liquid medium are of interest to materials scientists partly because of the optical tuning afforded to theses systems with a variation in interparticle distance. On p. 3507, Stephen Foulger and co‐workers from Clemson University, USA report on a general strategy for the preparation of well‐defined and regioselectively functionalized ordered colloidal particles through the exploitation of “click” chemistry. Click transformations have found utility in the synthesis and/or functionalization of a range of systems. In addition, the solvochromic tuning of the ordered arrays is employed to modify the emission spectra of the surface‐attached photoluminescent dyes.     

Synthesis of amorphous silicon/magnesia based direct opals with tunable optical properties

The effective refractive index of silica based artificial opals can be strongly modulated through magnesiothermic and wet etching processes. The magnesiothermic reduction of silica spheres assembled in a fcc lattice produces amorphous silicon/magnesia matrix, which can be easily converted in oxidized porous silicon, preserving the ordered structure. These results are verified by electron microscopies and IR/Raman spectroscopies. The optical properties are analyzed in terms of the experimental reflectance spectra. By comparing the measured data to rigorous calculations, the good quality of the opaline replicas is demonstrated.     

Liquid crystal order in colloidal suspensions of spheroidal particles by direct current electric field assembly

DC electric fields are used to produce colloidal assemblies with orientational and layered positional order from a dilute suspension of spheroidal particles. These 3D assemblies, which can be visualized in situ by confocal microscopy, are achieved in short time spans (t < 1 h) by the application of a constant voltage across the capacitor-like device. This method yields denser and more ordered assemblies than had been previously reported with other assembly methods. Structures with a high degree of orientational order as well as layered positional order normal to the electrode surface are observed. These colloidal structures are explained as a consequence of electrophoretic deposition and field-assisted assembly. The interplay between the deposition rate and the rotational Brownian motion is found to be critical for the optimal ordering, which occurs when these rates, as quantified by the Peclet number, are of order one. The results suggest that the mechanism leading to ordering is equilibrium self-assembly but with kinetics dramatically accelerated by the application of the DC electric field. Finally, the crystalline symmetry of the densest structure formed is determined and compared with previously studied spheroidal assemblies.     

单分散SiO2胶体球制备及其胶体晶体组装

运用胶体化学法在乙醇介质中合成SiO2胶体球,将制得的样品在30℃下用双氧水浸泡处理48h.用扫描电子显微镜(SEM)、傅立叶红外光谱(FT-TR)、Zeta电位仪和标准氢氧化钠滴定法对其形貌、结构和表面电学性质进行分析.结果表明样品平均粒径为292nm,平均标准偏差小于5%;经双氧水浸泡处理后,SiO2胶体球表面羟基数目增多,在水溶液中的Zeta电位从-55.72mV提高到-63.26mV,表面电荷密度从0.19μC/cm2提高到0.28μC/cm2.通过垂直沉积法,在40℃和60%相对湿度条件下制备出有序性较好、密排结构的SiO2胶体晶体.在SEM下,观察到这种胶体晶体是面心立方(fcc)密排结构,其(111)晶面平行于基底.透射光谱表明,所制备的胶体晶体在(111)方向具有光子晶体的不完全带隙性质.     

Introducing Defects in 3D Photonic Crystals: State of the Art

3D photonic crystals (PhCs) and photonic bandgap (PBG) materials have attracted considerable scientific and technological interest. In order to provide functionality to PhCs, the introduction of controlled defects is necessary; the importance of defects in PhCs is comparable to that of dopants in semiconductors. Over the past few years, significant advances have been achieved through a diverse set of fabrication techniques. While for some routes to 3D PhCs, such as conventional lithography, the incorporation of defects is relatively straightforward; other methods, for example, self‐assembly of colloidal crystals (CCs) or holography, require new external methods for defect incorporation. In this review, we will cover the state of the art in the design and fabrication of defects within 3D PhCs. The figure displays a fluorescence laser scanning confocal microscopy image of a y‐splitter defect formed through two‐photon polymerization within a CC.     

High-speed fabrication of 3-dimensional colloidal photonic crystal films by slide coating of polymer microspheres with continuous feeding of colloidal suspension

A simple, yet rapid fabrication method for large area colloidal crystal film is demonstrated. Aqueous colloidal dispersion sandwiched between a hydrophobic top cell and a hydrophilic bottom substrate formed a flat meniscus at the drying front, from which high quality colloidal crystal films were obtained within 20 min due to the strong capillary force exerted by accelerated water evaporation aided by hot air blowing. Continuous supply of the suspension enabled the fabrication of the colloidal crystal over large area (> 4 cm²) without significant loss of colloids.     

The Control of Colloidal Grain Boundaries through Evaporative Vertical Self‐Assembly

Self‐assembly continuously gains attention as an excellent method to create novel nanoscale structures with a wide range of applications in photonics, optoelectronics, biomedical engineering, and heat transfer applications. However, self‐assembly is governed by a diversity of complex interparticle forces that cause fabricating defectless large scale (>1 cm) colloidal crystals, or opals, to be a daunting challenge. Despite numerous efforts to find an optimal method that offers the perfect colloidal crystal by minimizing defects, it has been difficult to provide physical interpretations that govern the development of defects such as grain boundaries. This study reports the control over grain domains and intentional defect characteristics that develop during evaporative vertical deposition. The degree of particle crystallinity and evaporation conditions is shown to govern the grain domain characteristics, such as shapes and sizes. In particular, the grains fabricated with 300 and 600 nm sphere diameters can be tuned into single‐column structures exceeding ≈1 mm by elevating heating temperature up to 93 °C. The understanding of self‐assembly physics presented in this work will enable the fabrication of novel self‐assembled structures with high periodicity and offer fundamental groundworks for developing large‐scale crack‐free structures.