Photoswitching properties of photonic band gap material containing azo-polymer liquid crystal

A photochemically tunable photonic crystal was prepared by infiltration of the polymer liquid crystal (LC) having azo-chromophores in a SiO₂ inverse opal structure. The SiO₂ inverse opal film infiltrated with the polymer LC reflected a light corresponding to the periodicity as well as the refractive indices of the inverse opal structure. Linearly polarized light irradiation caused the shift of the reflection band to longer wavelength more than 15 nm. This is caused by the formation of uniaxially anisotropic molecular orientation of the polymer LC. The switched state was stable under interior light, and reversible switching of the reflection band can be achieved by the linearly and circularly polarized light irradiation. This photoswitching property will be suitable not only for various optical materials, but also for introduction of defects in the photonic crystals.     

带隙可调各向同性蛋白石光子晶体的制备与研究

用旋涂法将聚苯乙烯微球组装成光子晶体,研究了此光子晶体的特点,并分析了在单一微球粒径下旋涂参数对光子带隙的影响.结果表明:旋涂法制备的光子晶体具有各向同性特点,其光子带隙由旋涂参数决定.光子晶体的反射波段取决于乳液中微球的质量分数,而反射强度取决于旋涂层数.因此,在设计光子晶体时,可以根据需要,通过微球的质量分数和旋涂...     

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.     

基于胆甾相液晶的可调制光子晶体

将胆甾相液晶填充进胶体晶体内部空隙, 通过胆甾相液晶与胶体晶体的耦合, 构建了一种新型可调制液晶光子晶体. 填充于胶体晶体内部的胆甾相液晶织构呈现典型的手性近晶相(S)特征. 由于胆甾相液晶具有特定的选择性反射, 当胶体晶体的带隙处于胆甾相液晶的反射波长范围之内, 则随着温度的改变, 胶体晶体的带隙与胆甾相液晶的带隙同时发生蓝移. 在一定温度条件下, 胆甾相液晶的带隙将与胶体晶体的带隙发生耦合, 实现了光子晶体带隙在单峰与双峰之间的可逆切换.     

Standing wave enhancement of red absorbance and photocurrent in dye-sensitized titanium dioxide photoelectrodes coupled to photonic crystals

The light harvesting efficiency of dye-sensitized photoelectrodes was enhanced by coupling a TiO(2) photonic crystal layer to a conventional film of TiO(2) nanoparticles. In addition to acting as a dielectric mirror, the inverse opal photonic crystal caused a significant change in dye absorbance which depended on the position of the stop band. Absorbance was suppressed at wavelengths shorter than the stop band maximum and was enhanced at longer wavelengths. This effect arises from the slow group velocity of light in the vicinity of the stop band, and the consequent localization of light intensity in the voids (to the blue) or in the dye-sensitized TiO(2) (to the red) portions of the photonic crystal. By coupling a photonic crystal to a film of TiO(2) nanoparticles, the short circuit photocurrent efficiency across the visible spectrum (400-750 nm) could be increased by about 26%, relative to an ordinary dye-sensitized nanocrystalline TiO(2) photoelectrode.     

Fabrication and optical characterization of imprinted broad‐band photonic films via multiple gradient UV photopolymerization

A structured broad‐band photonic film is fabricated by a novel method using multiple gradient UV‐induced polymerization in the presence of cholesteric liquid crystals (CLCs). Here, imprinting and broadening of the reflection band of chiral nematic mesophase cells are achieved via controlled UV polymerization. The intensity gradient of UV light is modified by the distance between UV lamp and sample cell, which affects the polymerization rate and leads to the formation of imprinted helical constructions with different pitches. In this study, a comparison of new design process with traditional UV polymerization process is carried out. After seven cycles of gradient UV polymerization, the imprinted photonic construction exhibited a broadened reflection band and Bragg reflection, even for isotropic materials. Because of this, the reflection bandwidth showed a 70% improvement. Additionally, two stacked imprinted cells with different pitches can reflect incident light with a bandwidth over the visible wavelength range of 480–680 nm. A broad‐band photonic polymer film can be imprinted using multiple gradient UV photopolymerization in the presence of CLCs. Forming a UV intensity gradient and controlling the rate of photopolymerization are key factors in broadening the reflection band. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 1427–1434     

Enhancement of the fluorescence intensity of DNA intercalators using nano-imprinted 2-dimensional photonic crystal

We have fabricated polymer-based 2-dimensional photonic crystals that play a key role in enhancing the fluorescence of DNA intercalators. Highly ordered 2-dimensional photonic crystals possessing triangle-shaped and nm-sized hole arrays were fabricated on a 100 μm thick polymer film using nano-imprint lithography. Samples of double-stranded DNAs (sizes: 4361 and 48502 bp; concentration: 1 pM to 10 nM) were adsorbed on the surface of the 2-dimensional photonic crystal by electrostatic interactions and then treated with intercalators. It is found that the fluorescence intensity of the intercalator is enhanced by a factor of up to 10 compared to the enhancement in the absence of the 2-dimensional photonic crystal. Fluorescence intensity increases with increasing length and concentration of the DNAs. If the 2-dimensional photonic crystal is used as a Bragg reflection mirror, the enhancement of fluorescence intensity can be easily observed using a conventional spectrofluorometer. These results suggest that the printed photonic crystal offers a great potential for highly sensitive intercalator-based fluorescent detection of DNAs.

光子晶体薄膜的制备以及在编码载体中的应用

通过将由聚苯乙烯纳米粒子构成的光子晶体膜镶嵌在聚二甲基硅氧烷(PDMS)薄膜中制备得到了具有PDMS/光子晶体/PDMS夹心结构的可用于多重生物分析的光子晶体编码载体. 用编码载体进行了大肠杆菌3种基因的杂交检测: 以3种光子晶体膜作为编码载体固定核酸探针, 然后在含有荧光标记的目标分子的缓冲液中进行杂交反应. 杂交反应后以光子晶体膜的特征反射谱为核酸编码, 以荧光信号的有无来确定目标分子的存在与否. 实验结果表明PDMS/光子晶体/PDMS夹心结构是一种有效的构建悬浮载体的方法.     

Fluorescence enhancement for the complex PAMAM-BSA in the presence of photonic crystal heterostructures

The paper presents the optical characterization of the multilayer film composed of styrene (ST)-poly(ethylene glycol) methyl ether methacrylate (PEGMA 1100)-gold nanoparticles (Au)-poly(amidoamine) PAMAM (G4)-bovine serum albumin (BSA). The addition of the last layer composed of BSA resulted in an unusual optical behaviour, i.e. increase of the fluorescence emission intensity, respectively the intensity of the UV-vis reflection, compared with the ST-PEGMA 1100-Au-G4 film. The explanation could be attributed to the presence of photonic crystal heterostructures. The multilayer film has been characterized by optical microscopy, AFM, UV-vis, and fluorescence.     

Fabrication of tunable colloid crystals from amine-terminated polyamidoamine dendrimers

A pH-responsive colloidal crystal was assembled using core-shell composite spheres, poly(styrene-methyl methacrylate-acrylic acid) (P(St-MMA-AA)) spheres covered by generation 4 amine-terminated polyamidoamine dendrimers. The light reflection of the colloidal crystal film can be tuned at different pH due to different protonation level of the dendrimers. The method shows a facile way to fabricate diffraction-based chemical and biological sensors by exploiting the effect of photonic crystal cooperated with tunable nanoparticles.     

Photonic band structures of colloidal crystals measured with angle-resolved reflection spectroscopy

We acquired angle- and polarization-resolved reflection spectra from a colloidal crystal made of polystyrene spheres along the two perpendicular directions corresponding to the LU and LW directions in the first Brillouin zone of an fcc lattice. Dispersion relations between the reflection peak positions and the wave vectors of the incident light were obtained from the measured spectra and compared with calculated photonic band structures. For the first stop band region in the spectra, the behavior of the reflection peak due to Bragg diffraction agreed with the calculated band structure and revealed some differences induced by the polarization and crystalline orientations. The spectral features observed in the higher energy regions also revealed these differences. In addition, dispersion relationships between the peak positions and the wave vectors were obtained from the results of fitting each spectrum with several Gaussian curves, compared with the calculated photonic band structures. The relationships obtained for the LU direction almost matched the calculated band structure, while the relationships obtained for the LW direction revealed the features of the mixed band structure calculated for the two perpendicular directions. These results indicate that angle- and polarization-resolved reflection spectroscopy has the potential to experimentally analyze the photonic band structures of actual photonic crystals.     

流动控制沉积法制备PMMA叠层光子晶体薄膜及其光学性能研究

采用流动控制沉积法, 通过调控泵速和聚甲基丙烯酸甲酯(PMMA)胶体微球溶液的浓度, 制备出微球排列高度有序且薄膜紧密附着于基底的高质量光子晶体薄膜. 获得了制备高质量PMMA光子晶体薄膜的组装条件范围, 发现在该条件范围内, 当泵速或胶体微球溶液浓度一定时, PMMA光子晶体薄膜的厚度随胶体微球溶液浓度的增加或泵速的降低而增加. 研究了组装条件对PMMA光子晶体薄膜光学性能的影响, 发现光子禁带位置随光子晶体薄膜厚度增加或减少而红移或蓝移. 在此基础上, 控制组装条件得到了不同尺寸微球堆叠而成的叠层光子晶体薄膜, 并研究了其光学性能的变化规律. 结果显示, 叠层光子晶体薄膜的光子禁带峰为各层叠层光子晶体禁带峰的简单叠加, 且峰强度受光入射角方向影响.     

A temperature and pH double sensitive cholesteric polymer film from a photopolymerizable chiral hydrogen-bonded assembly

In this study, a novel H-bonded cholesteric polymer film responding to temperature and pH by changing the reflection color was fabricated. The H-bonded cholesteric polymer film was achieved by UV-photopolymerizing a cholesteric liquid crystal (Ch-LC) monomers mixture containing a photopolymerizable chiral H-bonded assembly (PCHA). The cholesteric polymer film based on PCHA can be thermally switched to reflect red color from the initial green/yellow color as temperature is increased, which is due to a change in helical pitch induced by the weakening of H-bonded interaction in the polymer film. Additionally, the selective reflection band (SRB) of the cholesteric polymer film in solution with pH > 7 showed an obvious red shift with increasing pH values. While the SRB of the cholesteric polymer film in solutions with pH = 7 and pH < 7 hardly changed. This pH sensitivity in solutions with pH > 7 could be explained by the breakage of H-bonds in the cholesteric polymer film and the structure changes induced by―OH and―K + ions in the alkaline solution. In contrast, it couldn’t happen in the neutral and acidic solutions. The cholesteric polymer film in this study can be used as optical/photonic papers, optical sensors and LCs displays, etc.     

Tuning of Photonic band gap via combined effect of electric and optical fields in a blue phase liquid crystal composite

ABSTRACT

Blue phase liquid crystals are soft 3D photonic crystals in which the liquid crystal molecules self-assemble to form a cubic structure with lattice spacing of a few hundred nanometers resulting in selective reflection of colours in the visible spectrum. The corresponding wavelength or the ‘photonic band gap’ can be tuned using various external stimuli such as thermal, electric, magnetic and optical fields. Here, we report efficient tuning of photonic band gap by utilising the combination of electric and optical fields in a blue phase liquid crystalline system. The studies indicate that the chirality of the medium has a direct bearing on the direction of the wavelength shift and the extent of the photonic band gap tunability. More importantly, the synergistic effect of the two fields helps in reversible tuning of the band gap.     

梯度结构胶体光子晶体的制备及光子禁带调节

以改进的对流自组装方法制备层数可控的胶体光子晶体, 并通过各向同性氧等离子体(O₂ Plasma)刻蚀构造出梯度结构, 进一步通过金(Au)及无定形硅(Si)的可控沉积调节梯度结构胶体光子晶体的光子禁带, 并将该梯度结构用于罗丹明B的荧光发射增强.     

Enhanced photochemical‐shift of reflection band from an inverse opal film based on larger birefringent polymer liquid crystals: Effect of tolane group on the photochemical shift behavior

Photo‐chemically tunable photonic band gap materials are prepared by infiltration of liquid crystal polymers having azobenzene groups into voids of SiO₂ inverse opal films. Linearly polarized (LP) light irradiation results in transformation from a random to an anisotropic molecular orientation of azobenzene side chains in the voids of the SiO₂ inverse opal film, leading to the reversible and stable shift of the reflection peak to longer wavelength more than 15 nm. To improve switching properties, we use copolymers of azobenzene monomer and tolane monomer, which have higher birefringence, as infiltration materials into the voids. The azobenzene‐tolane copolymers are found to show higher birefringence than azobenzene homopolymers by the LP light irradiation at higher temperature. Consequently, the reflection band of the SiO₂ inverse opal film infiltrated with the azobenzene‐tolane copolymer can be shifted to longer wavelength region more than 55 nm by the irradiation of LP light. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1981–1990, 2009     

High effective sensors based on photonic crystals

Photonic crystals have been extensively studied as high effective sensors for environmental monitoring and chemical and biological detections. This paper reviews recent achievements on photonic crystal sensors. Especially, the band gap responsiveness and the ability in amplifying spontaneous emission are demonstrated in the reported photonic crystal monitors/sensors. They are of great importance for optical monitors/sensors visualized by the naked eye and sensors based on fluorescence applications. The photonic crystal sensors are promising for low-cost and high effective sensors and detection methods, although challenges still exist in practical applications.     

利用局域光效应增强全光谱光催化的ZnO/PVDF反蛋白石结构薄膜

随着环境污染与能源危机的问题日益严重,利用清洁能源太阳能的光催化技术得到了研究者的广泛关注.然而,半导体光催化剂的带隙严重限制了其利用整个太阳光谱的能力.尽管通过能带工程、上转换等技术,已经有部分可见光可以被利用,但其本身的效率却并不高.太阳光谱中的近红外光有着显著的光热效应,可提高光催化反应的温度,促进光生载流子的分离,进而提升光催化的效果.光子晶体是一种周期性结构,通过调节其折射率以及孔径大小,可以对不同波段的光实现增强吸收或反射的效果.人们已制备了二氧化钛的反蛋白石结构用于光催化降解污染物,其光催化效率明显提高.但是,通过利用反蛋白石结构光子晶体增强近红外光的吸收,进而实现全光谱利用的光热协同催化目前还未有报道.本文以二氧化硅单分散微球为模板,制备了以苯胺黑-聚偏氟乙烯为基底、氧化锌为光催化剂的反蛋白石结构光子晶体薄膜,采用扫描电镜、XRD和XPS等技术表征了薄膜的结构,并通过透射光谱与镜面反射光谱验证了苯胺黑的加入可增强全光谱的利用率.结果发现,当苯胺黑掺量为0.5%时,微反应器中的薄膜温度在60 min内上升了13.6℃,而空气中的薄膜温度在2 min内升了24.5℃,表明苯胺黑在近红外光生热中起着重要作用.对比普通薄膜,Z0.5A-369在微反应器与空气中的温度分别提升了14.7和26.8℃,证实了光子晶体对于光谱吸收的增强效应.就光催化性能来看,Z0.5A-369比普通薄膜的效率提高了1.63倍,而微反应器也比普通反应器提升了5.85倍.可见,薄膜和反应器的设计实现了协同催化.光热协同光催化发现,利用近红外光的光热效应来提高光催化反应过程中的温度可有效促进光催化反应,是一种高效利用太阳光谱的方法.光子晶体因其多孔结构、高比表面积、限光效应和慢光效应而增强了对光的吸收,进一步提高了光催化效率.另外,微反应器通过其局域的热效应和缩短的传质路径有效地增加了反应速率.     

Synthesis and photochromism of novel unsymmetrical diarylethenes with an azaindole unit

A new class of unsymmetrical photochromic diarylethenes with an azaindole moiety has been firstly synthesized. Their properties, including photochromism, crystal structure, as well as fluorescence, were investigated systematically. The azaindole was connected directly to the central cyclopentene ring as a heteroaryl moiety and available to participate in the photoisomerization reaction. Each of the diarylethenes exhibited favorable photochromism, good thermal stability, remarkable fatigue resistance, and notable fluorescence switches in both solution and solid media. The substituents at the para-position of the terminal benzene ring affected evidently their properties: the electron-donating methoxy could be effective to enhance the cyclization quantum yield, while the electron-withdrawing cyano could shift the absorption maximum to a longer wavelength in both hexane and solid film. The results revealed that the introduction of azaindole moieties and different substituents played an important role in the photoisomerization process of these diarylethenes.