Poly(vinyl alcohol) Rehydratable Photonic Crystal Sensor Materials

We developed a new photonic crystal hydrogel material based on the biocompatible polymer poly (vinyl alcohol) (PVA), which can be reversibly dehydrated and rehydrated, without the use of additional fillers, while retaining the diffraction and swelling properties of polymerized crystalline colloidal arrays (PCCA). This chemically modified PVA hydrogel photonic crystal efficiently diffracts light from the embedded crystalline colloidal array. This diffraction optically reports on volume changes occurring in the hydrogel by shifts in the wavelength of the diffracted light. We fabricated a pH sensor, which demonstrates a 350 nm wavelength shift between pH values of 3.3 and 8.5. We have also fabricated a Pb(+2) sensor, in which pendant crown ether groups bind lead ions. Immobilization of the ions within the hydrogel increases the osmotic pressure due to the formation of a Donnan potential, swelling the hydrogel and shifting the observed diffraction in proportion to the concentration of bound ions. The sensing responses of rehydrated PVA pH and Pb(+2) sensors were similar to that before drying. This reversibility of rehydration enables storage of these hydrogel photonic crystal sensors in the dry state, which makes them much more useful for commercial applications.     

Photochemically Controlled Photonic Crystals

We have developed photochemically controlled photonic crystals that may be useful in novel recordable and erasable memories and/or display devices. These materials can operate in the UV, visible, or near‐IR spectral regions. Information is recorded and erased by exciting the photonic crystal with ～ 360 nm UV light or ～ 480 nm visible light. The information recorded is read out by measuring the photonic crystal diffraction wavelength. The active element of the device is an azobenzene‐functionalized hydrogel, which contains an embedded crystalline colloidal array. UV excitation forms cis‐azobenzene while visible excitation forms trans‐azobenzene. The more favorable free energy of mixing of cis‐azobenzene causes the hydrogel to swell and to red‐shift the photonic crystal diffraction. We also observe fast nanosecond, microsecond, and millisecond transient dynamics associated with fast heating lattice constant changes, refractive index changes, and thermal relaxations.     

Photoswitchable Spirobenzopyran‐ Based Photochemically Controlled Photonic Crystals

We have developed a photochemically controlled photonic‐crystal material by covalently attaching spiropyran derivatives to polymerized crystalline colloidal arrays (PCCAs). These PCCAs consist of colloidal particles that self‐assemble into crystalline colloidal arrays (CCAs), which are embedded in crosslinked hydrogels. Photoresponsive PCCAs were made two ways: 1) by functionalizing the hydrogel network with spiropyran derivatives, and 2) by functionalizing the colloidal particles with spiropyran derivatives. These materials can diffract light in the UV, visible, or near‐IR spectral regions. The diffraction of the PCCAs is red‐shifted by exciting the spiropyran with UV light. Alternatively, the diffraction is blue‐shifted by exciting the spiropyran with visible irradiation. Thus, this material acts as a memory storage material where information is recorded by illuminating the PCCA and information is read out by measuring the photonic‐crystal diffraction wavelength. UV excitation forms the open spiropyran form while visible excitation forms the closed spiropyran form. The diffraction shifts result from changes in the free energy of mixing of the PCCA system as the spiropyran is photoexcited to its different stable forms.     

Stimuli‐Responsive Materials Based on Interpenetrating Polymer Liquid Crystal Hydrogels

Stimuli‐responsive materials based on interpenetrating liquid crystal‐hydrogel polymer networks are fabricated. These materials consist of a cholesteric liquid crystalline network that reflects color and an interwoven poly(acrylic acid) network that provides a humidity and pH response. The volume change in the cross‐linked hydrogel polymer results in a dimensional alteration in the cholesteric network as well, which, in turn, leads to a color change yielding a dual‐responsive photonic material. Furthermore a patterned coating having responsive and static interpenetrating polymer network areas is produced that changes both its surface topography and color.     

Organic field-effect transistor with extended indium tin oxide gate structure for selective pH sensing

In this study, organic field-effect transistors (OFETs) with extended gate structure were fabricated for selective pH sensing applications. Indium tin oxide (ITO) was used as extended gate electrode as well as an active layer for H⁺ sensing. The threshold voltage of the fabricated ion-selective OFET was varied by the changes in the electrochemical potential at the ITO electrode surface upon its exposure to buffer solutions with variable pH values. The sensor showed excellent linearity and a high sensitivity of 57–59 mV/pH in the pH range of 2–12. The selectivity of the ITO sensing layer to H⁺ ions was also investigated by measuring the interfering effect of Ca²⁺ and K⁺ ions in the buffer pH solutions. The results showed that the Ca²⁺ and K⁺ ions weakly interfere with the selective pH sensing of the ITO-extended gate OFET sensor device.     

Quantum‐Dot‐Tagged Bioresponsive Hydrogel Suspension Array for Multiplex Label‐Free DNA Detection

A novel hydrogel suspension array, which possesses the joint advantages of quantum‐dot‐encoded technology, bioresponsive hydrogels, and photonic crystal sensors with full multiplexing label‐free DNA detection capability is developed. The microcarriers of the suspension array are quantum‐dot‐tagged DNA‐responsive hydrogel photonic beads. In the case of label‐free DNA detection, specific hybridization of target DNA and the crosslinked single‐stranded DNA in the hydrogel grid will cause hydrogel shrinking, which can be detected as a corresponding blue shift in the Bragg diffraction peak position of the beads that can be used for quantitatively estimating the amount of target DNA. The results of the label‐free DNA detection show that the suspension array has high selectivity and sensitivity with a detection limit of 10^?9 M . This method has the potential to provide low cost, miniaturization, and simple and real‐time monitoring of hybridization reaction platforms for detecting genetic variations and sequencing genes.     

Red‐ to NIR‐Emitting,BODIPY‐Based,K+‐Selective Fluoroionophores and Sensing Materials

Optical sensing materials for the selective measurement of potassium ions (K⁺) in water are presented. The indicator dyes are based on an aza‐crown ether as a receptor and borondipyrromethenes (BODIPY) dyes as fluorophores. Fluorescence enhancement is caused by the reduction of photoinduced electron transfer (PET) upon complexation with K⁺ ions. The family of new indicators possesses tuneable optical properties (green to red excitation, red to NIR emission) and PET efficiencies. They exhibit high brightness with quantum yields between 0.20 and 0.47 in the “on” state and a molar absorption coefficient between 30 000 and 290 000 m ^?1 cm^?1. The new indicator dyes are immobilized in biocompatible hydrogel matrices to obtain stable nonleaching and fast responding (t₉₀ ≈ 10 s) sensing materials for continuous measurements of potassium. They are realized in various formats such as planar optodes, fiber‐optic sensors, and water‐dispersible polymer‐based nanoparticles. Apart from fluorescence intensity measurements, self‐referenced read‐out of fluorescence decay time is demonstrated. All sensor materials display a high K⁺/Na⁺ selectivity and are not influenced by pH within the physiologically relevant range. Practical applicability of the materials is emphasized by application of a fiber‐optic sensor to quantification of K⁺ in serum, which shows excellent correlation with the reference measurements.     

An Optical Sensor Based on a Photonic Polymer Film to Detect Calcium in Serum

An optical calcium sensor is fabricated based on a cholesteric liquid crystalline (CLC) polymer containing benzoic acid metal binding sites. A chiral imprinted CLC polymer is made which is subsequently treated with KOH to yield a responsive green reflecting film. On investigation of various metal ions, the polymer film shows a high optical response, and selectivity for calcium ions, which is related to the preorganized binding sites in the ordered liquid crystalline phase, leading to a blue reflecting film. The photonic polymer film is sensitive to Ca²⁺ within the physiologically relevant concentration range of 10^?4 to 10^?2 m . Measurement of total calcium concentration in serum is also investigated using the film. The optical responses of normal serum and samples mimicking hypocalcemia and hypercalcemia can be clearly distinguished, providing a cheap, battery‐free, and easy‐to‐use alternative for calcium determination in clinical diagnostics.     

倾斜底涂法制备聚苯乙烯胶体晶体及其光学特性研究

采用倾斜底涂法将单分散的聚苯乙烯胶体微球自组装生长成为胶体晶体,并用扫描电子显微镜和紫外-可见光分光光度计对其形貌和光学特性进行测量。结果表明,聚苯乙烯微球自组装为面心立方密堆积结构,胶体晶体的光子带隙位于可见光波段。分别对不同胶体颗粒的粒径、悬浮液的浓度、基片倾斜角度及环境温度等制备条件下生成的聚苯乙烯光子晶体样品逐一分类对比,分析了影响光子带隙宽度和深度的因素。     

Pb1−xSnxSe-on-Si LWIR sensor arrays and thermal imaging with JFET/CMOS read-out

Long wavelength infrared (LWIR) sensor arrays were fabricated in Pb_1−xSn_xSe layers grown epitaxially on Si-substrates by MBE. A CaF2 intermediate buffer layer ≈30dgA thick was employed for compatibility reasons. The photovoltaic sensors are based on the blocking Pb-contact technique on p-type material. They were fabricated using simple wet-etching process steps only. Cut-off wave-lengths were about 10.5 μm, quantum efficiencies >60%, and resistance-aera products above 3 Ω-cm² at 90K. A demonstrational LWIR thermal imaging camera was assembled with a 256 element line array with 50 μm pitch. Low-noise signal processing was achieved with sensors with differential resistances in the 10 kOhm range by using JFET/CMOS technology. For each channel, an integrator, correlated multiple sampling and sample/hold amplifier was used before multiplexing to a common output.     

Nanoimprinted,Submicrometric, MOF‐Based 2D Photonic Structures: Toward Easy Selective Vapors Sensing by a Smartphone Camera

In this work, a soft‐lithographic approach to fabricate submicrometer metal organic framework (MOF)‐based 2D photonic structures is described. Nanometric zeolitic imidazole framework material ZIF‐8 (zinc) is chosen as the sensible MOF material because of its chemical stability and its vapor selective adsorption properties. Two different systems are fabricated: nanopatterned colloidal ZIF‐8 homo‐ and ZIF‐8/TiO₂ heterostructures. Several features (stripes, squares, etc.) with dimensions of 200 nm are replicated on different substrates such as silicon, flexible plastics, and even aluminum cans, over relatively large surfaces (up to 1 cm²). In addition, the use of these photonic MOF‐heterostructures as very low‐cost sensing platforms compatible with smartphone technology is demonstrated. This method relies on the evaluation of the change in diffraction efficiency of the photonic MOF‐patterns, induced by the MOF refractive index variation, which is simply detected by a charge coupled device (CCD) camera, as those integrated in smartphones, without need for complex optical instrumentations for transduction data processing. Performances of the sensors are first evaluated using isopropyl alcohol adsorption/desorption cycling as a model case. In addition, a “real” environmental issue is tackled. Selective detection of styrene in presence of interfering water is demonstrated at concentrations below the human permissible exposure limit. In situ ellispometric analyses are also carried out in order to confirm the sensor performances and to propose a mechanism for styrene uptake into the nanoMOFs.     

中红外完全光子带隙Ge反蛋白石三维光子晶体的制备

采用溶剂蒸发对流自组装法将单分散二氧化硅（SiO2）微球组装形成三维有序胶体晶体模板。以锗烷（GeH4）为先驱体气,用等离子增强化学气相沉积法向胶体晶体的空隙中填充高折射率材料Ge。酸洗去除二氧化硅微球,得到Ge反蛋白石三维光子晶体。通过扫描电镜、X射线衍射仪和傅立叶变换显微红外光谱仪对锗反蛋白石的形貌、成分和光学性能进行了表征。结果表明：Ge在SiO2微球空隙内填充致密均匀,得到的锗为多晶态,锗反蛋白石为三维有序多孔结构。锗反蛋白石的测试光谱图有明显的光学反射峰,表现出光子带隙效应。测试的完全光子带隙位于中红外3.4µm处,测试的光学性能与理论计算基本吻合。     

Large-area submicron replica molding of porous low-k dielectric films and application to photonic crystal biosensor fabrication

We demonstrate a replica-molding method for submicron patterning of a low-index sol-gel nanoporous glass for the purpose of fabricating large-area (∼80 cm²) label-free photonic crystal optical biosensors. Scanning electron micrographs show the sol-gel exhibited minimal shrinkage and good substrate adhesion and depict precise and uniform pattern transfer over the fabricated area within the limits of measurement resolution. A unique characterization approach is described in which the photonic crystal optical resonance is used to accurately and quickly characterize the geometrical and material property uniformity over a large area. Uniformity within 1% was measured over an 80 cm² area. We suggest that this robust method is an excellent approach for photonic crystal sensor fabrication, and may also find applications in integrated optics and electronics.     

Photoinduced Tuning of Optical Stop Bands in Azopolymer Based Inverse Opal Photonic Crystals

Photo‐tunable photonic crystals were prepared from three dimensional (3D) colloidal crystal templates using a photoresponsive azopolymer. For the preparation of azopolymer infiltrated photonic crystals, silica colloidal crystals were fabricated by gravity sedimentation, a self‐assembly technique. The interstitial voids between colloidal particles were filled with azopolymer and azopolymer inverse opals were produced by treatment with aqueous hydrofluoric acid. These photonic crystals exhibited stop bands in their transmission spectra measured in the normal incidence to the (111) plane of face centered cubic (fcc). The photonic bandgap of the azopolymer infiltrated opal and inverse opal could be controlled by the refractive index change due to the photoinduced orientation of azobenzene chromophores. When the azopolymer photonic crystals were irradiated with linearly polarized light, their bandgap positions were shifted to shorter wavelength regions with increasing irradiation time. This behavior experimentally produced a photoinduced orientation of the azobenzene groups in parallel with the incidence of the excitation light. Through such an out‐of‐plane orientation of azo chromophores, parallel to the [111] fcc crystallographic axis, the effective refractive index of the photonic crystal medium was decreased. Therefore, a blue‐shift in bandgap positions was consequently induced with 20–40 nm tuning ranges. The out‐of‐plane orientation was confirmed by angular resolved absorption spectral measurements.     

Ultrasensitive and Stable Au Dimer‐Based Colorimetric Sensors Using the Dynamically Tunable Gap‐Dependent Plasmonic Coupling Optical Properties

A novel Au dimer‐based colorimetric sensor is reported that consists of Au dimers to a chitosan hydrogel film. It utilizes the ultrasensitively gap‐dependent properties of plasmonic coupling (PC) peak shift, which is associated with the dynamical tuning of the interparticle gap of the Au dimer driven by the volume swelling of the chitosan hydrogel film. The interparticle gap and PC peak shift of the Au dimer can be precisely and extensively controlled through the pH‐driven volume change of chitosan hydrogel film. This colorimetric sensor exhibits a high optical sensitivity and stability, and it works in a completely reversible manner at high pH values. Importantly, the sensitivity of the composite film can be tuned by controlling the crosslinking time of the composite film, and thus leading to a wide dynamic tuning sensitive range for different applications. This presented strategy paves a way to achieve the construction of high‐quality colorimetric sensors with ultrahigh sensitivity, stability and wide dynamic tuning sensitive range.     

弯曲长周期光子晶体光纤光栅传感器的研究

为了研究弯曲长周期光子晶体光纤光栅传感器谐振波长漂移量与光栅弯曲形变的关系,采用耦合模理论和计算机模拟方法进行了理论计算和仿真研究,推导出弯曲光子晶体光纤长周期光栅谐振波长表达式,设计了一般弯曲长周期光子晶体光纤光栅传感器系统模型,分析了弯曲长周期光子晶体光纤光栅传感器的基本工作原理,并计算了长周期光子晶体光纤光栅弯曲曲率、光栅有效折射率和谐振波长与弯曲应变的关系。结果表明,随着光栅弯曲形变的增加,光栅的曲率会增加,光栅传感器的谐振波长漂移量会增加,光栅每发生1变化,光栅谐振波长的漂移量变化0.014nm。     

Multicolor Printing Using Electric‐Field‐Responsive and Photocurable Photonic Crystals

Efficient and large scale printing of photonic crystal patterns with multicolor, multigrayscale, and fine resolution is highly desired due to its application in smart prints, sensors, and photonic devices. Here, an electric‐field‐assisted multicolor printing is reported based on electrically responsive and photocurable colloidal photonic crystal, which is prepared by supersaturation‐induced self‐assembly of SiO₂ particles in the mixture of propylene carbonate (PC) and trimethylolpropane ethoxylate triacrylate (ETPTA). This colloidal crystal suspension, named as E‐ink, has tunable structural color, controllable grayscale, and instantly fixable characteristics at the same time because the SiO₂/ETPTA‐PC photonic crystal has metastable and reversible assembly as well as polymerizable features. Lithographical printing with photomask and maskless pixel printing techniques are developed respectively to efficiently prepare multicolor and high‐resolution photonic patterns using a single‐component E‐ink.     

A Double‐Layer Mechanochromic Hydrogel with Multidirectional Force Sensing and Encryption Capability

Hydrogel‐based soft mechanochromic materials that display colorimetric changes upon mechanical stimuli have attracted wide interest in sensors and display device applications. A common strategy to produce mechanochromic hydrogels is through photonic structures, in which mechanochromism is obtained by strain‐dependent diffraction of light. Here, a distinct concept and simple fabrication strategy is presented to produce luminescent mechanochromic hydrogels based on a double‐layer design. The two layers contain different luminescent species—carbon dots and lanthanide ions—with overlapped excitation spectra and distinct emission spectra. The mechanochromism is rendered by strain‐dependent transmittance of the top‐layer, which regulates light emission from the bottom‐layer to control the overall hydrogel luminescence. An analytical model is developed to predict the initial luminescence color and color changes as a function of uniaxial strain. Finally, this study demonstrates proof‐of‐concept applications of the mechanochromic hydrogel for pressure and contact force sensors as well as for encryption devices.     

Photonic crystal microcrystalline silicon solar cells

Enhancing the absorption of thin‐film microcrystalline silicon solar cells over a broadband range in order to improve the energy conversion efficiency is a very important challenge in the development of low cost and stable solar energy harvesting. Here, we demonstrate that a broadband enhancement of the absorption can be achieved by creating a large number of resonant modes associated with two‐dimensional photonic crystal band edges. We utilize higher‐order optical modes perpendicular to the silicon layer, as well as the band‐folding effect by employing photonic crystal superlattice structures. We establish a method to incorporate photonic crystal structures into thin‐film (~500 nm) microcrystalline silicon photovoltaic layers while suppressing undesired defects formed in the microcrystalline silicon. The fabricated solar cells exhibit 1.3 times increase of a short circuit current density (from 15.0 mA/cm² to 19.6 mA/cm²) by introducing the photonic crystal structure, and consequently the conversion efficiency increases from 5.6% to 6.8%. Moreover, we theoretically analyze the absorption characteristics in the fabricated cell structure, and reveal that the energy conversion efficiency can be increased beyond 9.5% in a structure less than 1/400 as thick as conventional crystalline silicon solar cells with an efficiency of 24%. © 2015 The Authors. Progress in Photovoltaics: Research and Applications published by John Wiley & Sons Ltd.     

单分散性sio2胶体微球自组装光子晶体的实验研究

光子晶体是一种周期性电介质材料,具有光子带隙和光子局域等一系列优异的光学特性。制备了多种不同直径的单分散二氧化硅胶体微球,采用垂直沉积法将不同直径,以及同一直径不同浓度的二氧化硅胶体微球自组装成多种光子晶体薄膜,并用扫描电子显微镜和紫外—可见—近红外分光光度计对其微观结构和光学特性进行了表征,结果表明所得晶体薄膜具有三维有序结构,其表面存点、线缺陷。自组装得到的光子晶体薄膜存在明显的光子带隙特征,带隙位置与二氧化硅胶体微球直径有关,带隙中心波长与理论值一致。随着二氧化硅胶体微球浓度的增加,光子带隙深度增加,特性更好,但是,当浓度大于10%时,光子带隙的深度反而减小。