Hybrid colloidal plasmonic-photonic crystals

We review the recently emerged class of hybrid metal-dielectric colloidal photonic crystals. The hybrid approach is understood as the combination of a dielectric photonic crystal with a continuous metal film. It allows to achieve a strong modification of the optical properties of photonic crystals by involving the light scattering at electronic excitations in the metal component into moulding of the light flow in series to the diffraction resonances occurring in the body of the photonic crystal. We consider different realizations of hybrid plasmonic-photonic crystals based on two- and three-dimensional colloidal photonic crystals in association with flat and corrugated metal films. In agreement with model calculations, different resonance phenomena determine the optical response of hybrid crystals leading to a broadly tuneable functionality of these crystals.     

3D-printable colloidal photonic crystals

The architecture of the colloidal photonic crystals (CPCs) is of paramount importance to their functionality and applications. Nevertheless, the realization of CPCs with arbitrarily designed, volumetrically sophisticated structures at the macroscale remains challenging. In this work, a printable CPC ink was developed. By combining this ink with a digital light processing (DLP)-based three-dimensional (3D) printing system, we were able to fabricate the CPC superstructures featuring both digitally defined macroscale geometries and structural colors originating from the ordered structures at the sub-micron scale. Moreover, besides the arbitrarily adjustable and precisely designable architectures, the optical properties, mechanical performances, and stimuli-responsiveness of the printed objects could also be facilely tuned by the composition of the ink or the printing parameters of the DLP system. This technology endows us the ability to fabricate CPCs with a multitude of desirable functions as well as mimic the hierarchical structures and color-manipulation strategies of some creatures in nature, which paves the way for potentially broad applications in intelligent color displays, 3D integrated sensors, biomimetic color-morphing soft robots, and smart anti-counterfeiting labels, among others.     

Three-dimensional reduced-symmetry of colloidal plasmonic nanoparticles

Owing to their novel optical properties, three-dimensional plasmonic nanostructures with reduced symmetry such as a nanocrescent and a nanocup have attracted considerable current interest in biophotonic imaging and sensing. However, their practical applications have been still limited since the colloidal synthesis of such structures that allows, in principle, for in vivo application and large-scale production has not been explored yet. To date, these structures have been fabricated only on two-dimensional substrates using micro/nanofabrication techniques. Here we demonstrate an innovative way of breaking symmetry of colloidal plasmonic nanoparticles. Our strategy exploits the direct overgrowth of Au on a hybrid colloidal dimer consisting of Au and polystyrene (PS) nanoparticles without the self-nucleation of Au in an aqueous solution. Upon the overgrowth reaction, the steric crowding of PS leads to morphological evolution of the Au part in the dimer ranging from half-shell, nanocrescent to nanoshell associated with the appearance of the second plasmon absorption band in near IR. Surface-enhanced Raman scattering signal is obtained directly from the symmetry-broken nanoparticles solution as an example showing the viability of the present approach. We believe our concept represents an important step toward a wide range of biophotonic applications for optical nanoplasmonics such as targeting, sensing/imaging, gene delivery, and optical gene regulations.     

Three-dimensional atomic imaging of colloidal core-shell nanocrystals

Colloidal core-shell semiconductor nanocrystals form an important class of optoelectronic materials, in which the exciton wave functions can be tailored by the atomic configuration of the core, the interfacial layers, and the shell. Here, we provide a trustful 3D characterization at the atomic scale of a free-standing PbSe(core)-CdSe(shell) nanocrystal by combining electron microscopy and discrete tomography. Our results yield unique insights for understanding the process of cation exchange, which is widely employed in the synthesis of core-shell nanocrystals. The study that we present is generally applicable to the broad range of colloidal heteronanocrystals that currently emerge as a new class of materials with technological importance.     

单分散SiO2微球的合成及胶体晶体的生长

对传统的"Stober-Fink"合成SiO2微球的工艺进行了改进,运用"籽晶生长法"合成了单分散SiO2微球,该法可以准确地控制微球尺寸,提高微球的球形度.采用垂直沉积法制备了胶体晶体,并对样品的结构和光学性能进行了表征.研究了微球尺寸对垂直沉积SiO2胶体晶体光子带隙的影响,结果表明,通过控制微球粒径,可调节光子晶体的带隙位置.     

Patterning microsphere surfaces by templating colloidal crystals

By using the upper single or double layers in colloidal crystals as masks during Au vapor deposition, various Au patterns have been successfully constructed on the surfaces of the lower spheres. The dimension and geometry of the Au patterns obtained are dependent on the orientation of the colloidal crystal templates. Our patterning procedure is independent of the curvature and chemical composition of the surfaces, which definitely pave a promising way to pattern highly curved surfaces.     

Fe3O4 octahedral colloidal crystals

We present a facile and controllable method for the large-scale fabrication of highly-ordered octahedral Fe₃O₄ colloidal “single crystals” without the assistance of a substrate. Oleic acid is used to reduce the solubility of the nano-building blocks in colloidal solution and to induce a “crystallization” process. Our colloidal crystals are of multimicron size and show typical crystallographic characteristics. They have a very robust structure and can serve as a novel ordered magnetic mesoporous material with a relatively narrow pore size distribution. The sample possesses an extremely high Verwey transition temperature (T _V) of 100 K and a high saturation magnetization (M _S) of 86 emu/g at 5 K based on its good crystallinity, as well as the interparticle dipolar interaction behavior arising from its unique structure. Electrochemical measurements have demonstrated the excellent capacity of the mesoporous colloidal crystals when used in lithium-ion batteries.      

二氧化硅胶体晶体制备方法进展

SiO2 胶体晶体制备过程的研究是许多新型功能材料发展的基础 ,对人们进一步了解物质在纳米、微米尺度的许多特殊性质也将具有指导意义。本文综述了SiO2 胶体晶体制备方法的进展。     

Electrophoretic deposition of colloidal crystals assisted by hydrodynamic flows

Latex-based colloidal crystals have been grown by electrophoretic deposition. The deposition has been assisted by hydrodynamic von Kármán-like flows, which lead to quantitative improvements. It has been studied the influence of applied voltage, deposition time and flow rate on the number of deposited layers and on the mean domain size. The samples were studied with microscopy and precision weight measurement. It has been found that there is a critical time after which the deposition mechanism changes, and the behavior of the system before and after this critical time is considered. The mean domain size and the deposition time were reduced to non-dimensional forms which show the collapse of the data for different applied voltages and flow rates into one curve.     

氘代聚苯乙烯胶体晶体的制备及光学性质研究

以水作为介质合成了高度单分散的氘代聚苯乙烯微球,并利用垂直沉积法制备了高质量的氘代聚苯乙烯胶体晶体.傅立叶变换红外光谱清楚地表明氘代苯乙烯单体发生了聚合反应;扫描电镜表面分析展示出胶体微球的高度有序排列,断面分析表明氘代聚苯乙烯胶体晶体为面心立方结构;光学透射谱显示出氘代聚苯乙烯胶体晶体的高次布拉格衍射特征,通过和理论计算的能带结构对比,进一步证实了氘代聚苯乙烯胶体晶体为面心立方结构;变角度光学透射谱测量显示,随着入射角的增大,(111)面的衍射峰蓝移,而(200)和(220)面的衍射峰发生红移.     

Observation and tuning of hypersonic bandgaps in colloidal crystals

Composite materials with periodic variations of density and/or sound velocities, so-called phononic crystals, can exhibit bandgaps where propagation of acoustic waves is forbidden. Phononic crystals are the elastic analogue of the well-established photonic crystals and show potential for manipulating the flow of elastic energy. So far, the experimental realization of phononic crystals has been restricted to macroscopic systems with sonic or ultrasonic bandgaps in the sub-MHz frequency range. In this work, using high-resolution Brillouin spectroscopy we report the first observation of a hypersonic bandgap in face-centred-cubic colloidal crystals formed by self-assembly of polystyrene nanoparticles with subsequent fluid infiltration. Depending on the particle size and the sound velocity in the infiltrated fluid, the frequency and the width of the gap can be tuned. Promising technological applications of hypersonic crystals, ranging from tunable filters and heat management to acousto-optical devices, are anticipated.     

Silica colloidal crystals for enhanced fluorescence detection in microarrays

Silica colloidal crystals were investigated for their potential as high surface area materials to enhance sensitivity over planar surfaces for microarrays using fluorescence detection. A relation was derived showing how crystal thickness and transmission, as well as colloid size, combine to determine the optically accessible surface area for enhancing sensitivity. Experimentally, crystals of 250-nm colloids were prepared with thicknesses determined by SEM to be 1.6, 4.2, and 11.0 microm. The material was sintered at 1000 degrees C to make it durable without affecting the crystalline structure, as confirmed by SEM. UV/visible spectrometry showed the depth of penetration (1/e) to be 8.4 microm at 488 nm for these materials. Fluorescein-labeled streptavidin and biotin were used as a model ligand-receptor pair. For the fluorescence measurements, biotin was covalently bonded to the silica surfaces, and the fluorescence was detected from the captured streptavidin-fluorescein. The observed fluorescence enhancement agreed well with the theory developed here. Compared to a planar surface, the colloidal crystal of 11.0 microm in thickness enhanced the fluorescence by nearly a factor of 80, with only a 0.3% increase in fluorescence background.     

Three-dimensional Si/Ge quantum dot crystals

Modern nanotechnology offers routes to create new artificial materials, widening the functionality of devices in physics, chemistry, and biology. Templated self-organization has been recognized as a possible route to achieve exact positioning of quantum dots to create quantum dot arrays, molecules, and crystals. Here we employ extreme ultraviolet interference lithography (EUV-IL) at a wavelength of lambda = 13.5 nm for fast, large-area exposure of templates with perfect periodicity. Si(001) substrates have been patterned with two-dimensional hole arrays using EUV-IL and reactive ion etching. On these substrates, three-dimensionally ordered SiGe quantum dot crystals with the so far smallest quantum dot sizes and periods both in lateral and vertical directions have been grown by molecular beam epitaxy. X-ray diffractometry from a sample volume corresponding to about 3.6 x 10(7) dots and atomic force microscopy (AFM) reveal an up to now unmatched structural perfection of the quantum dot crystal and a narrow quantum dot size distribution. Intense interband photoluminescence has been observed up to room temperature, indicating a low defect density in the three-dimensional (3D) SiGe quantum dot crystals. Using the Ge concentration and dot shapes determined by X-ray and AFM measurements as input parameters for 3D band structure calculations, an excellent quantitative agreement between measured and calculated PL energies is obtained. The calculations show that the band structure of the 3D ordered quantum dot crystal is significantly modified by the artificial periodicity. A calculation of the variation of the eigenenergies based on the statistical variation in the dot dimensions as determined experimentally (+/-10% in linear dimensions) shows that the calculated electronic coupling between neighboring dots is not destroyed due to the quantum dot size variations. Thus, not only from a structural point of view but also with respect to the band structure, the 3D ordered quantum dots can be regarded as artificial crystal.     

On the parameters influencing the deposition of polystyrene colloidal crystals

Colloidal crystals of polystyrene particles of 1.0, 1.4 and 2.8 μm diameter have been prepared by vertical deposition. The influence of parameters such as temperature, particle size and concentration as well as dispersion medium has been studied. The size of domain and the crystalline structure of the particle arrays have been analyzed by optical microscopy. The quality of the crystals has been improved (minimizing cracks) by controlling sedimentation (density matching), evaporation (volatility of the medium) and drying (co-solvents).     

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.     

Three-dimensional films of photoluminescent polyoxometalates fabricated by a colloidal crystal template

Three-dimensional ordered thin films based on 12-phosphotungstic acid (PW₁₂O₄₀/SiO₂) and lanthanide-substituted phosphotungstate (Eu(PW₁₁O₃₉)₂/SiO₂, Gd(PW₁₁O₃₉)₂/SiO₂ and Eu(P₂W₁₇O₆₁)₂/SiO₂) were constructed by an inverse opal method, using polystyrene colloidal crystal as a template. The samples were characterized by elemental analysis, XRD, IR spectra, UV–vis diffuse reflectance spectra (DR-UV–Vis) and SEM techniques. These thin films show well-defined lamellar array with inverse opal structure, and lanthanide polyoxometalate thin films exhibit photoluminescent properties.     

Lattice dynamics of colloidal crystals during photopolymerization of acrylic monomer matrix

The photoinitiated bulk polymerization process, which has been used recently in the manufacture of solid optical diffraction filters, is examined to understand the dynamics of both the crystalline colloidal arrays (CCA) and the host monomer species. Our analysis indicates that volume shrinkage of the monomer, changes in the dielectric properties of the monomer, and inhomogeneities of polymerization reaction rate across the dispersion during the polymerization process, are the major contributors for observed lattice compression and lattice disorder of the CCA of silica spheres in polymerized acrylic/methacrylic ester films. The effect of orientation of photocell with respect to the radiation source on Bragg diffraction of CCA indicated the presence of convective stirring in the thin fluid system during the photopolymerization that deleteriously affects the periodic array structures. To devise reproducible and more efficient optical filters, experimental methods to minimize or eliminate convective instabilities in monomeric dispersions during polymerization are suggested. © 1998 Chapman & Hall     

胶体晶体模板法制备有序多孔堇青石材料研究

采用乳液聚合法制备了单分散P(St-AA)微球,经自然沉降法制成胶体晶体模板,再利用胶晶模板法制备了有序多孔堇青石.利用FTIR、SEM、DSC、XRD等方法对P(St-AA)微球单分散性及有序多孔堇青石结构进行了研究.结果表明,当AA用量占单体总量的5.0%时,制备的P(St-AA)微球的单分散性及其胶体晶体微球结构最佳.经烧结去除P(St-AA)微球得到的有序多孔堇青石材料的孔径较单分散P(St-AA)微球稍小,约为200nm左右.当烧结温度为1200℃,多孔材料为堇青石相.