柔性PMMA反蛋白石结构薄膜的制备及表征

以粒径为270 nm的SiO_2微球胶体晶体作为模板,向其中填充过量单体MMA,热聚合后形成SiO_2/PMMA复合结构光子晶体,将此光子晶体浸泡入浓度为20%的HF溶液中,刻蚀半小时后得到脱离ITO玻璃基板的柔性PMMA反蛋白石结构薄膜.该薄膜为周期有序的三维多孔结构,孔径大小均一,约为210 nm,外观蓝紫色与测试得到的带隙位置相对应.分析其微观形貌可知,对模板的过量填充产生了一层附着于胶体晶体上表面的PMMA致密层,致密层与其下层PMMA反蛋白石结构骨架在热聚合过程中由于体积收缩产生一定的应力差,使反结构薄膜自发从原基板脱离,从而获得柔性反蛋白石结构光子晶体.该薄膜可用于柔性光子晶体器件的制备.     

热处理温度对蛋白石晶体的影响

 采用等体积快速混合法制备了不同粒径的单分散SiO₂微球,通过重力垂直沉降自组装形成了蛋白石模板,研究了热处理温度对蛋白石晶体模板形貌、结构与光学性能的影响。SEM,TG-DSC,UV-Vis等分析表明：热处理可提高组装微球的粘合性与模板的机械强度;SiO₂胶体模板煅烧温度在700～800 ℃较为合适;热处理能够改变蛋白石晶体光子带隙的位置,随着煅烧温度的升高,带隙发生蓝移并且带隙逐渐变窄。     

光子晶体对稀土上转换发光的调控

稀土掺杂上转换材料由于其高化学稳定性、低生物毒性,在发光显示、防伪和生物成像等领域得到了广泛的应用。稀土掺杂上转换材料的基质晶格和掺杂离子决定着其发光强度和颜色。光子晶体(PCs)是折射率不同的材料在空间周期性排列形成的有序结构,其最显著的特征是具有光子禁带(PBG)。波长位于光子禁带内的光不能透过光子晶体而被反射回来,因而光子晶体具有优异的光调控能力。本文综述了一维、二维和三维光子晶体对稀土上转换发光调控的进展,介绍了利用光子禁带与上转换荧光发射峰的相对位置对发光进行控制的方法。重点从蛋白石结构和反蛋白石结构两个方面论述了三维光子晶体对上转换发光的调控:对于反蛋白石光子晶体,综述了利用上转换材料构筑反蛋白和利用其他材料构筑反蛋白,通过布拉格反射调控上转换材料的发光;对于蛋白石光子晶体,论述了利用不同折射率胶体微球构筑三维光子晶体对稀土上转换发光进行调控。最后总结了利用等离子体共振和光子禁带共同作用调控上转换发光的研究现状,并展望了利用光子晶体调控上转换发光的发展方向。     

CeO_2:Eu~(3+)反蛋白石的制备与性质研究

以自组装法制备的面心立方结构的聚甲基丙烯酸甲酯(PMMA)蛋白石为模板,采用溶胶凝胶法制备二氧化铈(CeO2)掺杂铕离子(Eu3+)的反蛋白石结构光子晶体.利用XRD,SEM,UV-Vis等测量手段研究了光子禁带特性,样品在低温下的发光特性也被研究.结果表明CeO2:Eu3+反蛋白石的光子禁带是413nm,PMMA蛋白石的光子禁带是612nm,与理论计算结果十分吻合.且随着温度的降低,Eu3+离子所处晶体场的对称性下降.     

面缺陷对三维胶体晶体光学性质的影响

利用化学自组装方法和旋涂技术,成功地将二氧化硅(SiO2)微球体植入聚苯乙烯微球组成的蛋白石中,获得了嵌有面缺陷的三维胶体晶体.经SiO2渗透后,煅烧除去聚苯乙烯微球,获得了反相结构的光子晶体.胶体球粒直径增大时,无论晶体中有无缺陷态的存在,蛋白石及其反相结构透射谱中峰的位置发生红移,反之则产生蓝移.在胶体球粒直径一定时,对于降低折射率的缺陷,其透射谱峰中缺陷态的位置发生红移;对于增加折射率的缺陷,其透射谱峰中缺陷态的位置发生蓝移.透射谱还与缺陷层的厚度等因素有关.     

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.     

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.     

圆柱形蛋白石和反蛋白石结构光子晶体的制备及其光学性质

研究了在圆柱曲面基底上自组装空心和实心的圆柱形蛋白石和反蛋白石结构光子晶体的方法. 用垂直沉积法在不同曲率半径的毛细管内自组装了空心圆柱形聚苯乙烯(PS)蛋白石结构光子晶体薄膜和二氧化硅 (SiO₂) 反蛋白石结构薄膜; 用类重力沉积法制得实心圆柱形蛋白石和反蛋白石结构光子晶体, 并讨论了这一生长方式中的状态变化过程及影响因素. 用扫描电子显微镜对样品内部结构进行了表征, 用光谱仪测试了光子晶体薄膜的反射光谱, 结果表明: 基底曲率半径和微球粒径的大小是影响空心蛋白石和反蛋白石薄膜质量的主要因素; 微球大小是影响实心结构有序性的主要因素. 关键词： 反蛋白石 空心圆柱 溶胶凝胶协同自组装     

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.     

蛋白石型光子晶体红外隐身材料的制备

基于光子晶体的红外隐身材料,主要采取一维层层堆叠结构和三维木堆结构等来实现对红外波段电磁波辐射性能的调控.本文报道了一种操作简易、成本低廉的光子晶体红外隐身材料制备方法.通过优化的垂直沉积法,微米级SiO_2胶体微球自组装成高质量的蛋白石型光子晶体结构.对SiO_2胶体微球进行优选,成功制备了禁带位于2.8—3.5μm,8.0—10.0μm的SiO_2胶体晶体蛋白石型光子晶体材料.该材料可改变目标相应波段的红外辐射特征,具有目标红外波段的隐身效果.     

Enhanced photoluminescence from three-dimensional ZnO photonic crystals

We have fabricated optically active ZnO inverse opals by infiltrating polystyrene (PS) opal templates using an electrodeposition process. Compared with bare ZnO films also prepared by electrodeposition, the three-dimensional (3D) ordered ZnO structure exhibits markedly enhanced photoluminescence. The effect of photonic band gap on PL spectra is also clearly observed from the ZnO inverse opal structure.     

Enhancing fluorescence of tricolor fluorescent powders by silica inverse opals

Silica inverse opal photonic crystals (PCs) were fabricated by using a sacrificial polymer template method, and were characterized by scanning electron microscopy and reflection spectra. The fluorescence of tricolor fluorescent powders has been enhanced obviously by silica inverse opals as the emission wavelengths of the tricolor fluorescent powders are in the range of stop bands of the inverse opal PCs, which demonstrates that the PCs will be efficient and selective reflection mirrors. A promising application of the strategy would be in novel effective lighting devices. PACS 42.70.Qs; 78.55.-m; 78.55.Mb; 78.68.+m; 78.67.-n An erratum to this article can be found at     

Development of highly-ordered, ferroelectric inverse opal films using sol–gel infiltration

Highly-ordered, ferroelectric, Pb-doped Ba_0.7Sr_0.3TiO₃, inverse opal films were fabricated by spin-coating a sol–gel precursor into a polystyrene artificial opal template followed by heat treatment. Thin films of the ferroelectric were independently studied and were shown to exhibit good dielectric properties and high refractive indices. The excellent quality of the final inverse opal film using this spin-coating infiltration method was confirmed by scanning electron microscopy images and the good correspondence between optical reflection data and theoretical simulations. Using this method, the structural and material parameters of the final ferroelectric inverse opal film were easily adjusted by template heating and through repeated infiltrations, without changes in the initial template or precursor. Also, crack-free inverse opal thin films were fabricated over areas comparable to that of the initial crack-free polystyrene template (100 by 100 m²). PACS  78.67.n; 81.20.Fw; 77.84.Dy     

Template assisted fabrication technique towards Si-inverse opals with diamond structure

A method to fabricate silicon (Si) inverse opals with diamond structure is introduced. The method is based on the arrangement of silica particles in a template consisting of Si pillars periodically distributed. The profile of the pillars is specially designed to induce the self-organized growth of the particles in a diamond lattice along the (1 1 0) direction. Afterwards, the inverse structure is achieved by infiltrating the opal with Si and subsequently removing the silica by chemical means. Different from a former approach based on robotic manipulation, this method allows the fabrication of large samples available for integration in planar photonic devices.     

Large-scale ZnO inverse opal films fabricated by a sol–gel technique

We demonstrate that high-quality large-scale ZnO inverse opals can be fabricated by a simple sol–gel technique, comprising infiltration of polystyrene colloidal crystal films with zinc nitrate solution, drying and annealing at 300 C. This simple method yields continuous films, which consist of inverse opal domains (up to several hundreds of μm² in size), separated by small cracks filled with zinc oxide. Microradian X-ray diffraction was employed to verify the crystalline quality of ZnO inverse opals on the macroscale, revealing that the samples have a predominant face-centered cubic structure, and that the majority of domains have the same crystallographic orientation. The samples exhibit bright iridescence and possess photonic stop-bands in the visible to near-infrared spectrum.     

Controlling the photoluminescence spectroscopy of quinacrine dihydrochloride by SiO_2 inverse opal photonic crystal

Manipulation of the photoluminescence spectra of light-emitting materials doped in three-dimensional （3D） inverse opal photonic crystals is investigated. Quinacrine dihydrochloride molecules doped highly ordered SiO2 inverse opal is successfully synthesized by co-assembly combined with double-substrate vertical infiltrate method. The quinacrine dihydrochloride-doped and-undoped SiO2 inverse opals each exhibit an apparent photonic band gap （PBG） in the visible light region. Significant suppression of the emission is observed when the PBG is overlapped with the quinacrine dihydrochloride emission bands. The mechanism of suppression effect of PBG in inverse opal on the fluorescence intensity of quinacrine dihydrochloride molecules is studied.     

金属有机化学气相沉积法在欧泊空隙中生长磷化铟的影响因素

制备磷化铟(InP)反欧泊三维光子晶体的关键是提高InP在欧泊空隙中的填充率。使用低压金属有机化学气相沉积(MOCVD)系统在人工欧泊空隙中生长了InP晶体,分析了影响InP在欧泊空隙中填充的因素及确定了InP的最佳生长条件。实验和理论分析的结果较为符合。磷化铟在人工欧泊空隙中的填充率越高,二氧化硅球和空隙间的折射率差越大,人工欧泊光子晶体光学性能的变化就越显著;周期生长、低压、使用和InP失配小的衬底以及异质同构现象有助于InP在欧泊空隙中的填充。在优化的生长条件下制备了填充率较高的SiO₂-InP光子晶体。研究结果为制备InP反欧泊结构积累了有益的经验。     

Low-temperature heat capacity and heat conductivity of single-crystal synthetic opals

The heat capacity at constant pressure (in the range 3–50 K) and the lattice heat conductivity (from 5 to 75 K) of a single-crystal synthetic opal are measured. It is shown that the heat capacity of the opal behaves at these temperatures in a way similar to porous amorphous materials. The data on the heat conductivity suggest that single-crystal opals can be related to a class of semicrystalline (partially crystallized amorphous) materials. However, because of specific features of their crystal structure, the opals form a nonstandard type of semicrystalline material which we termed semiamorphous.