反蛋白石光子晶体的研究进展

反蛋白石晶体是一类重要的光子晶体,由于其制备材料的广泛性以及容易实现对光子禁带的多重调制而受到广泛关注.本文介绍了目前反蛋白石晶体结构的主要制备技术和方法,详细阐述了反蛋白石晶体结构的最新研究进展.     

二氧化钛反蛋白石薄膜的制备及其在化学传感器中的应用

用提拉成膜法将单分散295 nm聚甲基丙烯酸甲酯(PMMA)胶体微球自组装成蛋白石光子晶体膜. 在PMMA蛋白石光子晶体膜的空隙里填充15 nm二氧化钛纳米颗粒, 经500 ℃的处理除去PMMA膜板, 制备出大面积, 结构均一的二氧化钛反蛋白石光子晶体膜. 扫描电子显微镜(SEM)观察和X射线光电能谱(XPS)分析表明, 这种二氧化钛反蛋白石光子晶体薄膜是六方紧密堆积. 用这种二氧化钛反蛋白石光子晶体膜对溶液折射率的检测实验表明该传感膜分辨率可达0.01.     

硫化镉反蛋白石光子晶体制备及光解水制氢

对硫化镉反蛋白石结构光子晶体薄膜进行了可控合成,用巯基乙酸修饰的纳米晶和P(St-MMA-SPMAP)高分子小球共组装,成功地构筑了反蛋白石结构并用于可见光光解水产氢。结果表明,在可见光(λ≥420 nm)照射下,Cd S-310反蛋白石结构薄膜的光解水产氢性能比硫化镉纳米颗粒提高了一倍。这主要是因为等级孔结构反蛋白石光子晶体特性对催化剂的光催化性能的提升:首先,反蛋白石的周期性结构增加了光子在材料中的传播,提高了催化剂对太阳光的利用率;同时,大孔孔壁是由纳米颗粒堆积而成的,在反应中提供了更多的反应活性位点;此外,孔结构有利于物质的传输和分子的吸附。     

三联噻吩衍生物功能化SiO2反蛋白石光子晶体荧光薄膜的制备及应用

将单分散聚苯乙烯微球乳液与SiO₂溶胶均匀混合后, 于恒温恒湿条件下, 竖直沉积共组装制备得到蛋白石型光子晶体薄膜, 然后利用牺牲模板法制得SiO₂反蛋白石光子晶体薄膜. 该薄膜依次经过浓硫酸与过氧化氢混合液、 3-氨丙基三甲氧基硅烷的甲苯溶液、 三联噻吩的三氯甲烷溶液和硼氢化钠的甲醇溶液处理后, 得到三联噻吩衍生物功能化的SiO₂反蛋白石光子晶体. 结果表明, 制备得到的光子晶体薄膜在512 nm处有荧光发射, 经紫外辐射后荧光猝灭, 甲醛气氛下458 nm处又出现新的荧光发射峰. 在甲醛气氛下20 s即可观察到荧光发射, 空气氛围下可恢复, 10次循环仍可保持强的荧光发射, 可重复性良好. 以无反蛋白石光子晶体结构的三联噻吩衍生物的平滑膜与甲醛作用的体系作为参比, 以330和400 nm聚苯乙烯微球为模板制备的三联噻吩功能化反蛋白石光子晶体, 在甲醛气氛中发射的荧光分别增强47.5和78.6倍. 这是由于光子晶体光子禁带的红带边和蓝带边与荧光发射波长相重叠, 产生了慢光子效应, 极大地增强了发射的荧光强度.     

甲基丙烯酸/丙烯酰胺双单体共聚反蛋白石光子晶体的制备

以烧结后的二氧化硅光子晶体为模板,采用溶胶凝胶法向模板间隙填充以甲基丙烯酸(MAA)和丙烯酰胺(AM)为双功能单体,N,N’-亚甲基双丙烯酰胺(BIS)为交联剂的聚合物前驱液,制备了甲基丙烯酸/丙烯酰胺共聚(PMAM)双单体反蛋白石凝胶光子晶体.通过紫外可见光谱分析表明,反蛋白石结构的凝胶膜对pH响应范围在4.0～7.0之间.由于其不受离子强度的影响,除了可以作为pH传感器外,还可以作为金属离子及生物小分子等分子印迹光子晶体传感器的基体膜.     

HCl/NH_3敏感的卟啉-二氧化硅反蛋白石光子晶体荧光传感器

将反蛋白石结构的光子晶体引入到腐蚀性气体检测体系,制备得到卟啉-二氧化硅反蛋白石光子晶体(TPP-SiO_2IOPCs)荧光传感器。相对于空白样,TPP-SiO_2IOPCs传感器实现了氯化氢(HCl)气体检测信号200倍的增强,这主要归因于反蛋白石型光子晶体的大孔结构和慢光子效应。同时,TPP-SiO_2IOPCs传感器对于HCl气体的猝灭效率可达75%,比空白样的提高了25%,而且经HCl气体处理后的传感器通入氨气(NH_3)后,初始的荧光强度几乎完全恢复。在HCl和NH_3条件下进行5个循环后,TPP-SiO_2IOPCs传感器表现出良好的可重复使用性。该研究对于发展高效的荧光传感器提供了新的思路。     

反蛋白石结构光催化剂的制备与应用进展

光子晶体是一种具有光子禁带的周期性结构,在一定的波长范围内,光在晶体的某些方向上是不允许传播的;反蛋白石结构作为一种典型的光子晶体结构,具有慢光效应、多次散射效应和放大光子吸收、发射等特性,可以提高催化剂的传质效率、活性中心的曝光率和其集光性能,因此其在光催化领域受到越来越多的关注.我们综述了反蛋白石结构的光学性质;将反蛋白石结构光催化剂的制备方法归结为三步法和两步法两大类,列举了所包含的具体方法,总结了各自的优缺点;同时阐述了反蛋白石结构光催化剂的应用领域,最后对其在光催化领域的研究和发展趋势做出了展望.     

TiO_2反蛋白石光子晶体最新研究进展

TiO_2反蛋白石光子晶体的研究近年来受到广大科技工作者的关注。它具有TiO_2的无毒、高折射率、良好的生物相容性,并且在电化学、光催化等方面有着优良的特性,而且具有光子晶体的光子带隙、光子局域、慢光效应、超棱镜效应、负折射效应等光学特性,使其在化学传感器、太阳能电池、光催化、高效率微波电线以及光子晶体纤维等方面具有广阔的应用前景。本文总结了TiO_2反蛋白石光子晶体的制备方法、改性方法,同时介绍了其近年来在各领域的应用研究进展。     

反蛋白石光子晶体凝胶的pH响应

首先采用Stber方法制备了一系列亚微米级单分散二氧化硅小球,而后通过垂直沉降自组装方法制备了颜色鲜艳的二氧化硅三维有序结构胶体晶体模板,最后再采用模板聚合法在220 nm二氧化硅小球自组装的阵列间隙中共聚甲基丙烯酸和乙二醇二甲基丙烯酸酯,经氢氟酸刻蚀二氧化硅模板后得到多孔有序的反蛋白石光子晶体.当pH值从5升至8时,反蛋白石凝胶光子晶体的反射峰波长从514 nm移动至590 nm,颜色变化显著,从蓝绿色变成红色,突变点为pH=6.5,而且pH响应在100 s左右即可达到平衡.对交联剂用量的研究结果表明,随着交联剂乙二醇二甲基丙烯酸酯用量从4%增加到16%,光子晶体响应pH时的红移量减小.     

聚苯乙烯光子晶体高效制备

以苯乙烯单体为原料,采用一步聚合自组装法制备了具有蛋白石结构的聚苯乙烯(PS)光子晶体(1);以1为模板制备了反蛋白石结构的TiO2光子晶体(2)来验证1的有序性;探讨了1的制备机理。1和2的结构和形貌经IR,SEM和TEM表征。讨论了乳化剂SDS的用量对PS微球排列有序性的影响。结果表明,SDS用量在30 mg～74 mg时,PS微球的粒径不断减小,微球排列的有序性受到影响;当SDS用量为52 mg时,PS微球排列的有序性最佳,能够形成蛋白石结构的1;2在大范围内有序排列进一步证明了1的高度有序性。     

Photo-induced Birefringence of Azo-dye Based on Three-dimensional Opal Photonic Crystals

A series of three-dimensional opal photonic crystals based on the polymer was synthesized and applied in the field of photo-induced birefringence. The data show that the photo-induced birefringence(PIB) of pure Sudan III film could be enhanced by increasing the thickness of azo films. When Sudan III was distributed on the three-dimensional opal photonic crystals, the photo-induced birefringence process could be modulated. In addition, the data also exhibit that the PIB processes with different pumping polarization directions are sensitive to the role of photonic crystals. The results could be beneficial to further understanding the photo-induced birefringence and utilizing the photonic crystals.     

化学响应性光子晶体

光子晶体是一种具有光子带隙结构的周期性电介质材料,如果将响应性材料组装到光子晶体结构中,所形成的光子晶体的带隙结构则对外界环境的变化具有响应性,而被称为响应性光子晶体。响应性光子晶体作为光子晶体的一个新领域,由于其在传感器,生物医学,临床检测等方面的潜在应用,近几年受到广泛关注。根据外界环境的不同,响应性光子晶体可简单分为化学响应性光子晶体、物理响应性光子晶体和生物响应性光子晶体等。本文将对化学响应性光子晶体的国内外研究动态做一简要介绍,重点介绍以下五种化学响应性光子晶体:金属离子响应光子晶体、pH响应光子晶体、氧化还原响应光子晶体、葡萄糖响应光子晶体和光化学响应光子晶体。     

Fabrication of BaTiO3 Inverse Opal Photonic Crystal

The colloidal crystal template or opal with a closed-packed face centered cubic (fcc) lattice, was prepared from monodisperse polystyrene (PS) spheres by gravity sedimentation. The template was used for the generation of photonic crystal. The template provided void space for infiltration of liquid precursor composed of titanium butyloxide, barium acetate, ethanol, and acetic acid. The opal composite was hydrolyzed, dried, sintered by heating for completely removing PS spheres to form BaTiO3 photonic crystals with inverse opal structure. The PS spheres were replaced by air spheres, which interconnected each other through the windows on the BaTiO3 wall.So both the BaTiO3 wall and air void constitute continuous phases.     

光子晶体研究进展

光子晶体是最近10余年间提出的新概念和新材料。本文简述了光子晶体的主要特性,重点阐述了光子晶体的制作方法,特别是高分子材料制作分子晶体的几种新方法。     

Opal and inverse opal photonic crystals: Fabrication and characterization

Three-dimensional photonic crystals made of close-packed polymethylmethacrylate (PMMA) spheres or air spheres in silica, titania and ceria matrices have been fabricated and characterized using SEM, XRD, Raman spectroscopy and UV–Vis transmittance measurements. The PMMA colloidal crystals (opals) were grown by self-assembly from aqueous suspensions of monodisperse PMMA spheres with diameters between 280 and 415 nm. SEM confirmed the PMMA spheres crystallized uniformly in a face-centred cubic (fcc) array, and UV–Vis measurements show that the colloidal crystals possess pseudo photonic band gaps in the visible and near-IR regions. Inverse opals were prepared by depositing silica (SiO₂), titania (TiO₂) or ceria (CeO₂) in the voids of the PMMA colloidal crystals using sol-gel procedures, then calcining the resulting structure at 550 °C to remove the polymer template. The resulting macroporous materials showed fcc ordering of air spheres separated by thin frameworks of amorphous silica, nanocrystalline titania or nanocrystalline ceria particles, respectively. Optical measurements confirmed the photonic nature of the inverse opal arrays. UV–Vis data collected for the opals and inverse opals obeyed a modified Bragg’s law expression that considers both diffraction and refraction of light by the photonic crystal architectures. The versatility of the colloidal crystal template approach for the fabrication of macroporous oxide structures is demonstrated.     

Fabrication and characterization of core-shell photonic crystals via a dipping process

High-quality polystyrene (PS) colloidal photonic crystals in large area were fabricated in 24 h via a capillary-enhanced process. Then, the photonic crystals with core-shell structure were obtained by incorporating silica nanoparticles into the interstitial space of opal template via a dipping process. The filling ratio (V_silica) of interstitial space could be manipulated by dipping colloidal crystals into suspensions with different concentrations of silica nanoparticles, which in turn renders the obtained core-shell photonic crystals. The absorptive peak of opal without dipping process is at 445 nm as measured by UV–vis spectrometry. The filling ratios of 0.130, 0.167 and 0.253 can be calculated according to the modified Bragg's Law, which corresponds to the absorptive peaks for core-shell opals at 453, 463 and 469 nm obtained from suspensions with silica nanoparticles of 0.017, 0.122, and 0.244 wt%, respectively. Therefore, by using this dipping process, the characteristic absorption wavelength for photonic crystal will be varied easily, efficiently and cost effectively than that by traditional methods for constructing opal from monodispersed colloids of different diameters.     

光子晶体的制备及应用

光子晶体（PC）是具有光子带隙的周期性电介质结构，频率落在光子带隙中的光将被禁止传播。本文对光子晶体的能带结构、带隙的产生、制备方法及应用作了简要的介绍，重点介绍了光子晶体的制备技术及其在光电领域中的应用前景。     

三维SiO2欧泊模板溶剂热法制备硫化锌光子晶体

以单分散二氧化硅微球在重力场下自组装得到的三维有序欧泊(opal)为模板，采用溶剂热法在模板空隙内生长ZnS晶体，从而制备高质量的硫化锌基光子晶体. 通过X射线衍射(XRD)和Raman光谱证明ZnS晶体为闪锌矿结构且晶体质量较好，并对其生长机理进行了讨论. 通过场发射扫描电子显微镜(FESEM)和紫外-可见分光光度计对所合成的ZnS/opal复合物与ZnS反欧泊结构进行了表征，结果表明两种结构都保持了欧泊三维有序性，并且在Г-L方向(垂直于(111)方向)上出现了布拉格衍射峰，说明其具有良好的光子晶体特性.     

Emission and Energy Transfer Characteristics of Coumarin 6 Molecules Doped in Opal Polymer Photonic Crystal

The emission of coumarin 6(C-6) doped in opal polymethylmethacrylate(PMMA) photonic crystal(PC) was effectively manipulated. Meanwhile the energy transfer(ET) of C-6 in PCs, which are infiltrated with sulforhodamine B(S-B), was influenced by the concentration of energy acceptor in solution, the size of PMMA microsphere(SM) and the photonic stop band(PSB). The results should be beneficial to people to further understand the potential application of PCs in optoelectronic fields.