沉积法自组装三维有序的Eu(DBM)3Phen/SiO2胶体球

采用修饰的St ber法合成了300 nm的Eu(DBM)3Phen/SiO2胶体杂化球,并通过沉积法将这种胶体杂化球组装成厚度为5 mm,面积为12 cm2的三维有序结构。通过扫描电子显微镜观察发现这些胶体球在垂直于烧杯底面的所有层面中都显示了立方密堆积的结构。元素分析进一步证实了荧光分子被包埋在SiO2胶体球中。在355 nm的激发下,这种三维有序结构具有铕离子的特征发射。     

Synthesis of PS colloidal crystal templates and ordered ZnO porous thin films by dip-drawing method

Polystyrene spheres (PS) were synthesized by an emulsifier-free emulsion polymerization technique and the PS colloidal crystal templates were assembled orderly on clean glass substrates by dip-drawing method from emulsion of PS. Porous ZnO thin films were prepared by filling the ZnO sol into the spaces among the close-packed PS templates and then annealing to remove the PS templates. The effects of ZnO precursor sol concentration and dipping time in sol on the porous structure of the thin films were studied. The results showed an ordered ZnO porous thin film with designed pore size that depended on the sol concentration and PS size could be obtained. And the shrinkage of pore diameter was about 30-43%. X-ray diffraction (XRD) spectra indicated the thin film was wurtzite structure. The transmittance spectrum showed that optical transmittance decreased with the decrease of wavelength, but kept above 80% optical transmittances beyond the wavelength of 550 nm. Optical band gap of the porous ZnO thin film (fired at 500 °C) was 3.22 eV.     

Solution Lithography for Colloidal Crystal Patterning: Revisiting Flory–Huggins Interaction Parameters and Co-Nonsolvent Systems

For fundamental studies and practical applications, colloidal crystal patterns on substrates are typically fabricated through etching and conventional lithography. However, a wet-chemical based method is necessary for simplifying the procedure, preserving the substrate structure, and reproducibly fabricating the colloidal crystal patterns. The present study demonstrates that colloidal crystal patterns can be conveniently generated using thermodynamic relationships between a polymer colloid and surrounding solvents. Close-packed colloidal monolayers in good solvents that cause colloidal swelling spontaneously transform into non–close-packed crystal patterns when non-solvents that cause their shrinkage replace the good solvents. The colloid diameter in the close-packed monolayer decreases significantly when the polymer in the colloid is passing thermodynamic theta conditions (when Flory–Huggins interaction parameters increase to higher than ≈0.5). The close-packed monolayers also transform into the patterns in co-nonsolvent conditions. The “solution lithography” might be particularly useful for patterning colloids on curved microstructures and plastic/flexible films. The colloidal shapes in the patterns vary with the solvent pairs and substrates. The method does not require special facilities to reproducibly fabricate the patterns. The study further suggests methods simultaneously fixing the patterns. The patterns exhibit anti-reflection properties. Therefore, the solution lithography is applicable to optics, electronics, analytical science, and energy systems.     

二氧化硅人工蛋白石晶体（opal)的制备及其结构性质的研究

运用胶体化学法合成了尺寸可控的二氧化硅（SiO2）亚微米溶胶小球.透射电子显微镜（TEM）结果显示样品平均尺寸可从200nm变化至600nm，单分散性较高、平均标准偏差小于5％.通过自然沉积法，由溶胶SiO2小球自组织晶化制备了人工蛋白石晶体（opal晶体）结构.样品的剖面扫描电子显微镜（SEM）检测表明，样品为面心立方（fcc）结构.分析表明，较高的单分散性和缓慢的沉积过程是SiO2溶胶小球自组织晶化成三维有序结构的关键因素.反射谱中峰位在1320nm处的反射峰的出现，意味着样品在宏观尺度上的有序排列， 关键词： 亚微米二氧化硅溶胶小球 人工蛋白石晶体 方向带隙     

Macroporous fluoropolymeric films templated by silica colloidal assembly: A possible route to super-hydrophobic surfaces

A super-hydrophobic surface was obtained on a three-dimensional (3D) polyvinylidene fluoride (PVDF) macroporous film. The porous films were fabricated through self-assembled silica colloidal templates. The apparent water contact angle of the surface can be tuned from 106° to 153° through altering the sintering temperature and the diameter of the colloidal templates. A composite structure of micro-cavities and nanoholes on the PVDF surface was responsible for the super-hydrophobicity. The wettability of the porous surfaces was described by the use of the Cassie-Baxter model and Wenzel's equation.     

聚苯乙烯多孔薄膜的密度梯度控制

利用单分散的SiO2微球自组装制备了含一种尺寸微球的SiO2胶体晶体和含多种尺寸微球的多层异质结构。对含一种尺寸微球的SiO2胶体晶体进行煅烧和刻蚀处理后,胶体晶体中空隙所占比例大于立方密堆结构的26%,形成了非密堆结构,而且刻蚀时间越长,空隙比例越大。在同样的热处理和刻蚀条件下,微球尺寸越小的胶体晶体被刻蚀的程度越高,结构中空气空隙所占的比例越大。对SiO2多层异质结构经过煅烧和刻蚀处理后,得到了空隙梯度变化的多层结构,以此为模板制备了密度梯度变化的聚苯乙烯多孔薄膜。薄膜各层之间形成了平滑的过渡,没有显示出明显的层间缺陷,且孔与孔之间没有出现3维有序多孔结构中常见的大的连通孔道。     

Synthesis of nanostructured polymer materials with different morphologies: Nanoporous ordered networks and hollow capsules

Nanostructured polymer materials with interesting morphological variation, which include three dimensionally interconnected uniform nanoporous network arrays (volume- and surface-templated ordered arrays) and hollow core spheres were synthesized by inducing different polymerization process of phenol and formaldehyde as a precursor over silica templates (ordered silica colloidal crystals or individual silica particles). The pore sizes of the resulting nanostructured polymer materials can be easily controlled by monitoring the sizes of silica spheres, while their morphologies were modulated by controlling the initiation sites of the acid-catalyzed condensation reaction of the same polymer precursor and by modifying silica templates.     

低压化学气相沉积技术制备锗反蛋白石三维光子晶体

采用溶剂蒸发对流自组装法将单分散SiO2微球组装形成三维有序胶体晶体模板,用低压化学气相沉积法填充高折射率材料锗,酸洗去除SiO2模板,获得了锗反蛋白石三维光子晶体.通过扫描电镜、X射线衍射仪和紫外-可见-近红外光谱仪对锗反蛋白石的形貌、成分、结构和光学性能进行了表征.结果表明：锗在SiO2微球空隙内具有较高的结晶质量,填充致密均匀.通过改变沉积工艺,可控制锗的填充率;制备的锗反蛋白三维光子晶体具有明显的光学反射峰,表现出光学带隙效应.测试的光学性能与理论计算基本吻合.     

采用溶胶凝胶协同自组装方法制备SiO2反蛋白石结构薄膜及其光学性质研究

研究了溶胶凝胶协同自组装制备大面积高质量SiO₂反蛋白石结构薄膜的方法. 向单分散的聚苯乙烯(PS)胶体溶液中添加SiO₂前驱物溶液,用垂直自组装法一步得到微球空隙中均匀填充有凝胶的 复合PS胶体晶体薄膜,在空气中烧结去除PS后得到SiO₂反蛋白石结构薄膜.通过对添加前驱物溶液比例、 自组装温度以及烧结温度等参数的研究,用不同粒径的PS微球制备了不同孔径的高质量SiO₂反蛋白石结构薄膜. 用扫描电子显微镜和X射线能量色散谱仪对制备得到的薄膜样品进行显微形貌和成分表征,并测试了其透射光谱. 结果表明:溶胶凝胶协同自组装法制备的SiO₂反蛋白石结构薄膜大面积高度有序,孔径可以控制且选择范围宽; 薄膜的透射光谱带隙明显,带隙中心波长与理论计算结果相符.     

Two-dimensional nanopatterning by PDMS relief structures of polymeric colloidal crystals

A new constructive method of fabricating a nanoparticle self-assembly on the patterned surface of a poly(dimethylsiloxane) (PDMS) relief nanostructure was demonstrated. Patterned PDMS templates with close-packed microwells were fabricated by molding against a self-assembled monolayer of polystyrene spheres. Alkanethiol-functionalized gold nanoparticles with an average particle size of 2.5 nm were selectively deposited onto a hydrophobic self-assembled monolayer printed on the substrate by the micro-contact printing (μCP) of the prepared PDMS microwell, in which the patterned gold nanoparticles consisted of close-packed hexagons with an average diameter of 370 nm. In addition, two-dimensional colloidal crystals derived from PMMA microspheres with a diameter of 380 nm and a negative surface charge were successfully formed on the hemispherical microwells by electrostatic force using positively charged PAH-coated PDMS as a template to produce multidimensional nanostructures.     

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.     

低温等离子体增强化学气相沉积法制备Ge反opal三维光子晶体及其光学性能

通过溶剂蒸发对流自组装法制备SiO2三维有序胶体晶体模板,采用等离子体增强化学气相沉积法在200℃低温条件下填充高折射率材料Ge,获得了Ge反opal三维光子晶体.实现了低于GeH4热分解温度的低温填充.通过扫描电镜、X射线衍射仪和傅里叶变换显微红外光谱仪对Ge反opal的形貌、成分和光学性能进行了表征.结果表明:沉积得到无定型态Ge,退火后形成多晶Ge,Ge在SiO2微球空隙内填充致密均匀.Ge反opal的反射光谱有明显的光学反射峰,表现出光子带隙效应,其带隙中心波长为1650nm和2640nm,测试的光学性能与理论计算基本符合.采用SU-8光刻胶薄膜也进行了Ge沉积,证实了SU-8模板可以耐受这一沉积温度.低温沉积降低了Ge的填充温度,可以直接采用不耐高温的高分子材料作为初始模板,单次复型制备得到多种构型的完全带隙三维光子晶体.     

Electro-optic behavior of liquid-crystal-filled silica opal photonic crystals: effect of liquid-crystal alignment

Photonic crystals made of nematic liquid crystal intercalated into the void space of close-packed silica spheres (synthetic porous opal) exhibit significant electric-field-induced shift of the optical Bragg reflection peak when the liquid crystal has the long molecular axis oriented parallel to the sphere surfaces. No such effect is observed for comparable fields when the long-axis orientation is normal to the sphere surfaces.     

Stimulated Raman scattering in light and heavy water under picosecond laser excitation

The spectra of stimulated Raman scattering in ordinary and heavy water under excitation by second harmonic of a picosecond Nd:YAG laser were compared. It was shown that when stimulated Raman scattering is excited in water in cavities of a photonic crystal (synthetic opal matrix constructed of silica nanoglobules) or a photonic glass in the form of close-packed monodimensional millimeter-size amorphous-quartz balls, the efficiency of stimulated Raman scattering increases significantly compared to a uniform liquid medium.     

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.     

Shape-controlled crystallisation pathways in dense fluids of ccp-forming hard polyhedra

Emergent directional entropic forces that favour facet-to-facet alignment of neighbouring colloidal particles – arising from multi-body interactions upon crowding – should cause the process by which colloidal crystals form from fluids of hard polyhedra to be different than that from fluids of hard spheres. We compute nucleation-free energy barriers for a family of shapes that all self-assemble the same cubic close-packed (ccp) crystal structure formed by hard spheres and find that changing rhombicuboctahedra into rhombic dodecahedra by successively removing facets that compete with the ccp structure cause a systematic decrease in barrier heights. We show that this decrease arises from the increased prominence of facets aligned with neighbouring shapes in the target crystal, which produce local environments in the fluid that facilitate crystallisation.     

Hard-sphere crystals with hcp and non-close-packed structure grown by colloidal epitaxy

We demonstrate the epitaxial growth of a metastable (with respect to the bulk) hcp crystal as well as any other close-packed stacking sequence of colloidal hard spheres. At certain stretched and compressed lattices we furthermore observed growth of a non-close-packed superstructure and of a perfect (100)-aligned fcc crystal. Perfect template-induced hcp-crystal growth occurs at lattice spacings that are larger than for bulk crystallization, indicative of prefreezing. Small mismatches lead to increased out-of-plane displacements. Large mismatches prevent crystallization in the surface layers.     

可变晶格常数乙醇-二氧化硅胶质光子晶体中的Raman散射

制备了乙醇 二氧化硅三维胶质光子晶体，其晶格常数随着晶体高度的变化而变化.用皮秒 脉冲激光在不同高度激发光子晶体中乙醇产生Raman信号，得到了两个结果：1）即使Raman 信号的中心频率与光子晶体的带隙中心频率一致，在其禁带方向上测得的强度也没有被抑制 到与带隙深度同样的量级；2）尽管单纯的具有Raman信号频率的入射光的透过率随着高度的 变化而剧烈变化，但在光子晶体中产生的Raman信号强度却几乎不随高度的变化而变化，即 光子晶体的赝带隙几乎没有影响在禁带方向上测得的Raman信号强度.基于“光子晶体 关键词： 光子晶体 Raman散射 赝带隙 内部光源     

A colloidal crystal double-heterostructure fabricated with the angle controlled inclined deposition method

A self-assembly method, named the angle controlled inclined deposition method, is developed for fabricating well-ordered silica and polystyrene colloidal crystals. A high-quality colloidal crystal with a flat and uniform surface over a large area can be produced rapidly using a minute quantity of suspension and without any additional equipment. By controlling the inclined angle, we can fabricate colloidal crystals with diverse numbers of layers. A colloidal crystal double-heterostructure (composed of three different colloidal photonic crystals) can be rapidly fabricated with this method. Both experimental and simulation results show that the photonic band gap of the double-heterostructure is not a simple superposition of that of the compositional colloidal crystals along the stacking direction.     

准完全带隙胶体非晶光子晶体

三维面心立方结构的固有的高对称性使其只具备非完全光子带隙,而非晶结构可降低对称性导致准完全光子带隙的出现.实验结果表明非晶胶状晶体具有准完全光子带隙.非晶胶状光子晶体中的光子带隙的禁带宽度与波长均不随光入射到样品池的角度的变化而明显变化.其禁带宽度比SiO₂小球面心单晶的禁带宽度宽得多 关键词： 光子带隙 非晶 光谱