预辐射接枝四氟乙烯-乙烯共聚物湿敏膜的制备及特性研究

利用2 MeV电子加速器, 在常温下采用预辐照引发接枝的方法, 在四氟乙烯-乙烯共聚物(ETFE)上接枝丙烯酸(AA)和对苯乙烯磺酸钠(SSS), 制备了一种含羧酸基团和磺酸基团的接枝膜. 傅里叶变换红外光谱(FTIR)分析结果证明了磺酸基团和羧酸基团的成功引入, 并对接枝膜的热力学和化学特性进行了研究. 结果表明, 随着接枝率的增加, 接枝膜的结晶度逐渐降低, 接触角逐渐减小, 接枝膜的亲水性逐渐增强. 利用制备的接枝膜构建了电阻型湿度传感器, 并测定了传感器的电学特性. 在相对湿度(RH)从5%变化到98%时, 传感器电阻线性变化范围接近4个数量级, 具有响应速度快(吸附<1 min, 解吸<2 min), 湿滞小(<2%RH)的特点.     

Optical Sol-Gel-Based Dissolved Oxygen Sensor: Progress Towards a Commercial Instrument

A dissolved oxygen sensor based on fluorescence quenching of the oxygen-sensitive ruthenium complex, [Ru(II)-tris(4,7-diphenyl-1,10-phenanthroline]2+, which has been immobilized in a porous silica sol-gel-derived film, is reported. Ormosil sensing films were fabricated using modified silica precursors such as methyltriethoxysilane (MTEOS) and ethyltriethoxysilane (ETEOS) and were dip-coated onto planar glass substrates. Tailoring of the films for dissolved oxygen (DO) sensing is described whereby sensor response is optimized by maximizing film hydrophobicity by the use of the modified precursors. Sensor performance parameters such as limit of detection and sensor resolution are reported. Issues such as dye leaching and photobleaching are discussed. Progress towards a commercial instrument is reported.     

Structurally integrated organic light emitting device-based sensors for gas phase and dissolved oxygen

A compact photoluminescence (PL)-based O2 sensor utilizing an organic light emitting device (OLED) as the light source is described. The sensor device is structurally integrated. That is, the sensing element and the light source, both typically thin films that are fabricated on separate glass substrates, are attached back-to-back. The sensing elements are based on the oxygen-sensitive dyes Pt- or Pd-octaethylporphyrin (PtOEP or PdOEP, respectively), which are embedded in a polystyrene (PS) matrix, or dissolved in solution. Their performance is compared to that of a sensing element based on tris(4,7-diphenyl-l,10-phenanthroline) Ru II (Ru(dpp)) embedded in a sol-gel film. A green OLED light source, based on tris(8-hydroxy quinoline Al (Alq3), was used to excite the porphyrin dyes; a blue OLED, based on 4,4'-bis(2,2'-diphenylviny1)-1,1'-biphenyl, was used to excite the Ru(dpp)-based sensing element. The O2 level was monitored in the gas phase and in water, ethanol, and toluene solutions by measuring changes in the PL lifetime tau of the O2-sensitive dyes. The sensor performance was evaluated in terms of the detection sensitivity, dynamic range, gas flow rate, and temperature effect, including the temperature dependence of tau in pure Ar and O2 atmospheres. The dependence of the sensitivity on the preparation procedure of the sensing film and on the PS and dye concentrations in the sensing element, whether a solid matrix or solution, were also evaluated. Typical values of the detection sensitivity in the gas phase, S(g) identical with tau(0% O2)/tau(100% O2), at 23 degrees C, were approximately 35 to approximately 50 for the [Alq3 OLED[/[PtOEP dye] pair; S(g) exceeded 200 for the Alq3/PdOEP sensor. For dissolved oxygen (DO) in water and ethanol, S(DO) (defined as the ratio of tau in de-oxygenated and oxygen-saturated solutions) was approximately 9.5 and approximately 11, respectively, using the PtOEP-based film sensor. The oxygen level in toluene was measured with PtOEP dissolved directly in the solution. That sensor exhibited a high sensitivity, but a limited dynamic range. Effects of aggregation of dye molecules, sensing film porosity, and the use of the OLED-based sensor arrays for O2 and multianalyte detection are also discussed.     

新型室温硫化氢纳米传感器的制备及性能

采用溶胶-凝胶法在叉指金电极表面制备纳米二氧化钛(TiO₂)多孔薄膜, 并用浓度为2.5×10⁴ mol/L的花青素对其进行敏化, 制备了一种能在室温条件下检测硫化氢(H₂S)的高灵敏度传感器. 从材料的光谱特性、 微观结构和传感器的灵敏度等方面对该传感器的性能进行了评价, 并讨论了传感器的响应机理以及温度和湿度对灵敏度的影响. 结果表明, 材料表面的可见吸收光谱比花青素红移了约50 nm, 吸收能力有所提高; 纳米TiO₂颗粒呈层状堆积排列, 颗粒之间具有较多缝隙, 比表面积大. 在室温下, 该气体传感器对浓度为5~50 mL/m³的H₂S具有良好的敏感特性, 传感器灵敏度与H₂S浓度呈线性相关, 相关系数为0.939, 响应时间为50~70 s, 恢复时间为160~180 s. 计算和测试结果表明, 环境湿度约为50%时传感器的灵敏度最佳; 在10~50 ℃范围内, 温度与传感器的灵敏度存在负相关性. 该方法为简单、 经济制备室温条件下工作的气体传感器提供了新思路和新方法.     

Modeling of hydrocarbon sensors based on p-type semiconducting perovskites

In the scope of the present contribution, perovskite SrTi(1-x)Fe(x)O(3-delta) was investigated as a model material for conductometric hydrocarbon sensing at intermediate temperatures between 350 and 450 degrees C. To explain the observations made during sensor optimization in a quantitative way, a novel sensor model was proposed. At the microscopic scale, the local gas concentration affects local conductivity of the gas sensitive material. In the case of n-type tin oxide sensors, this interaction is commonly attributed to a redox reaction between the reducing analyte gas and adsorbed oxygen. In contrast, a reduction process affecting the entire bulk was assumed to govern gas sensitivity of SrTi(1-x)Fe(x)O(3-delta) films. Although very few variables needed to be assumed or fitted, the present bulk-type model was found to represent well sensor functionality of p-type conducting SrTi(0.8)Fe(0.2)O(3-delta) films. In addition to the temperature dependence of sensor response, the hydrocarbon sensitivity, m, was predicted with good accuracy. The different sensor responses towards hydrocarbons with a different chemical reactivity and other cross-interfering species, such as NO, was explained as well as the dependence on film thickness for screen printed films.     

A resistive-type humidity sensor using composite films prepared from poly(2-acrylamido-2-methylpropane sulfonate) and dispersed organic silicon sol

A composite material of dispersed organic silicon sol and poly(2-acrylamido-2-methylpropane sulfonate) (poly-AMPS) was used to make humidity sensor without protective film or complicated chemical procedures. The organic silicon sol was dispersed well in the poly-AMPS without using dispersion agent. Parameters that may affect the water-resistive but humidity-sensitive characteristic of composite material, the adding amount of organic silicon sol solution and the film of thermal treatment time, were investigated. The microstructure of the material was analyzed, and the humidity sensing and electrical properties of the sensor were measured. The sensor well responded to humidity with a relatively good linearity, though it depended on the applied frequency. The temperature influence between 15 and 35 °C was within −0.17 % relative humidity (RH)/°C in the range of 30–90% RH. The activation energy was maximum around 40% RH. The sensor showed the hysteresis within 5.9%, fast response time, long-term stability (75 days at least) and satisfactory resistance to high humidity atmosphere (97% RH) and chemical environment (20% C₂H₅OH vapor). Analyzing the structure and complex impedance plots of organic silicon sol/poly-AMPS was used to explain improvement in humidity sensing properties in comparison with nano-sized SiO₂ powder/poly-AMPS films.     

Ozone- and thermally activated films of palladium monolayer-protected clusters for chemiresistive hydrogen sensing

Here we describe the chemiresistive H2-sensing properties of drop-cast films comprised of 3.0 nm average diameter hexanethiolate-coated Pd monolayer-protected clusters (C6 Pd MPCs) bridging a pair of electrodes separated by a 23 microm gap. The gas-sensing properties were measured for 9.6-0.11% H2 in a H2/N2 mixture. The sensing mechanism is based on changes in the resistance of the film upon reaction of Pd with H2 to form PdH(x), which is known to be larger in volume and more resistive than pure Pd. As-prepared Pd MPC films are highly insensitive to H2, requiring O3 and thermal treatment to enhance changes in film resistance in the presence of H2. Exposure to O3 for 15 min followed by activation in 100% H2 leads to an increase in film conductivity in the presence of H2, with a detection limit of 0.11% H2. When exposed to temperatures of 180-200 degrees C, the conductivity of the film increases and a decrease in conductivity occurs in the presence of H2 with a detection limit of 0.21%. The sensing behavior reverses after further heating to 260 degrees C, exhibiting an increase in conductivity in the presence of H2 as in O3-treated films and a detection limit of 0.11%. The sensitivity of the variously treated films follows the order O3 > high temp > low temp, and the response times at 1.0% H2 range from 10 to 50s, depending on the treatment. FTIR spectroscopy, Raman spectroscopy, and atomic force microscopy provide information about the C6 monolayer, Pd metal, and film morphology, respectively, as a function of O3 and heat treatment to aid in understanding the observed sensing behavior. This work demonstrates a simple chemical approach toward fabricating a fast, reversible sensor capable of detecting low concentrations of H2.     

Luminescence Quenching Behavior of Oxygen Sensing ORMOSIL Films Based on Ruthenium Complex

An organically modified silicate(ORMOSIL) based optical sensor response to gaseous O2 or O2 dissolved in water is presented. The oxygen sensing film mechanism is based on the principle of fluorescence quenching of tris(4,7-diphenyl-l , 10-phenanthroline) ruthenium ( ) ([Ru(dpp)3]2+), which has been entrapped in a porous ORMOSIL film. In order to establish optimum film-processing parameters, comprehensive investigations, including the effects of the polarity and the hydrophobicity of the sensing film on oxygen quenching response and response time, were carried out. The film hydrophobicity increased as a function of dimethyl-dimethoxysilane (DiMe-DMOS) content, which is correlated with enhanced oxygen sensor performance. The sensor developed in the present work exhibits the advantages of fast response time and good reversibility. The detection limits are 0. 5 % and 0. 3 g/mL for O2 in the gaseous and the aqueous phases, respectively.     

Gas sensing properties of MWCNTs decorated with gold or tin oxide nanoparticles

Gas sensors based on oxygen plasma functionalised MWCNTs and plasma-treated nanotubes decorated either with gold nanoclusters or tin oxide nanoparticles were evaluated for the detection of NO₂, CO and ethylene. The sensor active layers were deposited by airbrushing onto micro-machined silicon transducers. Sensitivity, linearity, selectivity, response and recovery times and humidity effect were studied. XPS and TEM were employed to analyse the gas sensitive films. Among the different sensors tested, those based on tin oxide decorated MWCNTs showed the highest sensitivity to NO₂ (at ppb level) and the lowest humidity cross-sensitivity when operated at room temperature.     

Optimization of Ormosil Films for Optical Sensor Applications

Recent work has indicated that Ormosil films, fabricated from organically modified precursors, produce better sensor performance for some specific applications, compared to films fabricated from conventional sol-gel precursors such as TEOS or TMOS. This paper aims to compare film properties and sensor behavior for films fabricated from tetraethoxysilane (TEOS) and tetramethoxysilane (TMOS) silica precursors and both methyltrimethoxysilane (MTMS) and methyltriethoxysilane (MTES) organically modified precursors. Microstructural differences, for example, porosity changes due to the different precursor backbone structures, are interrogated by monitoring oxygen gas and aqueous-phase sensor response. Oxygen sensing using these films is enabled by incorporating in the films an oxygen-sensitive ruthenium dye whose fluorescence is quenched in the presence of oxygen. Film properties such as thickness, thickness stabilization time, as well as sensor response, are discussed in terms of relative hydrolysis and condensation behavior for the different precursors. Film hydrophobicity, an issue which has been identified as being of crucial importance for optimum dissolved oxygen sensor response, is discussed and contact angle measurements are used to investigate the degree of hydrophobicity for different film types. The main motivation for this work is film optimization for optical gas-phase and dissolved oxygen sensors.     

Self-assembly of TiO2/polypyrrole nanocomposite ultrathin films and application for an NH3 gas sensor

TiO₂/polypyrrole (PPy) nanocomposite ultrathin films for NH₃ gas detection were fabricated by the in situ self-assembly technique. The films were characterized by UV–Vis absorption, FT–IR spectroscopy, and atomic force microscopy (AFM). The electrical properties of TiO₂/PPy ultrathin film NH₃ gas sensors, such as sensitivity, selectivity, reproducibility, and stability were investigated at room temperature in air as well as in N₂. The results showed that the optimum gas-sensing characteristics of TiO₂/PPy ultrathin film were obtained in the presence of 0.1?wt% colloidal TiO₂ for 20-min deposition. Compared with pure PPy thin-film sensors, the TiO₂/PPy film gas sensor has a shorter response/recovery time. It was also found that both humidity and temperature had an effect on the operation of the TiO₂/PPy film gas sensor at low NH₃ concentrations.     

Gas Sensing Properties of Co3O4-loaded SnO2 to Ethanol and Acetone

A series of Co3O4-loaded SnO2 nanocomposite thick films were prepared by grinding, screen-printing and sintering at 700 ±C for 3 h. XRD data showed the nanocomposite thick films were rutile structure of SnO2 and cubic Co3O4. The composite films were found to exhibit good response to alcohol and acetone at 300 ±C. The film went through a sharp sensitivity maximum at 5 mol%CoO4=3 with a change in Co3O4 content. At 300 ±C, the maximum sensor response to alcohol and acetone, each 1000 ppm in air, was 301 and 235, respectively, which was about 7 and 5 times as large as that of the pure SnO2 respectively. The selectivity to alcohol and acetone over H2 and CO also was promoted by the addition of Co3O4 to SnO2. The mechanism of such strong promotion of sensor response (electronic sensitization) is discussed.     

A Novel Thin Film Resistive Humidity Sensor Based on Soluble Conjugated Polymer:(propionic acid)-co-(propargyl alcohol)

In recent years, humidity sensors have found wide applications in industrial and agricultural production, process control, household electric appliances, etc., therefore the research on humidity sensitive materials has attracted more and more attentions, and many polymers, including polymer electrolytes, conjugated polymers have been investigated as sensing materials1-3. However the doped conjugated polymers in general were insoluble and can not be used to prepare thin film humidity sensors, wh…     

Electrical and humidity characterization of m-NA doped Au/PVA nanocomposites

The Meta-Nitroaniline (m-NA) doped (by varying weight percentage (wt. %)) gold/polyvinyl alcohol (Au/PVA) nanocomposites were synthesized using gold salt and hydrazine hydrate (HH) by in situ process. The composite was coated on ceramic rods having two end electrodes by drop casting method for studying their electrical behavior at different relative humidity (RH) levels, ranging from 4 to 95% RH at room temperature. The optimized wt. % was used to prepare coatings of various thicknesses (20-40 μm) of the films. As the humidity decreases, the resistance increases. The low humidity sensing characteristic can be tailored by varying wt. % of m-NA and thicknesses of the nanocomposite films. The resistive-humidity sensor shows two regions of sensitivity having highest sensitivity for lower RH. The sensor response and recovery time is about 6-10 s and 52 s respectively. The dynamic range of variation of the resistance allows a promising use of the films as a humidity sensor. The material was characterized by X-ray diffraction (XRD) and impedance spectroscopy at 60% RH.     

A sensitive enzymeless hydrogen-peroxide sensor based on epitaxially-grown Fe3O4 thin film

A novel and facile approach has been developed to synthesize thin films of magnetite (Fe(3)O(4)) with epitaxial needle-like columnar grains on titanium nitride (TiN) buffered substrate using DC magnetron reactive sputtering. TiN buffer layer was first sputtered onto a substrate at 550 °C as a preferable substrate for growth following sputtering of epitaxial crystalline Fe(3)O(4) at 300 °C. The as-synthesized epitaxial Fe(3)O(4) was extensively characterized. The electrocatalytic activity of the epitaxial Fe(3)O(4) thin-film sensor against hydrogen peroxide (H(2)O(2)) reduction was rapid with a response time less than 5 s. The sensor also exhibited an acceptable stability, a satisfying sensitivity of 432.2 μA mM(-1) cm(-2), good specificity to the substrate, a dynamic working range of up to 0.7 mM and a low detection limit of 1.0 μM. The sensor performance correlated well (R(2)=0.996) with results obtained using a commercial HPLC-UV device. The sensor performance was robust and accurate in measuring H(2)O(2) in some complex matrices. The advantages of relative simplicity and ease of mass production make the epitaxial Fe(3)O(4) thin film promising candidate for use in sensing applications.     

Highly sensitive acetone gas sensor based on ultra-low content bimetallic PtCu modified WO3·H2O hollow sphere

Acetone is an important industrial raw material as well as biomarker in medical diagnosis. The detection of acetone has great significance for safety and health. However, high selectivity and low concentration (ppb level) detection remain challenges for semiconductor gas sensor. Herein, we present a novel sensitive material with bimetallic PtCu nanocrystal modified on WO₃·H₂O hollow spheres (HS), which shows high sensitivity, excellent selectivity, fast response/recovery speed and low limit of detection (LOD) to acetone detection. Noteworthy, the response (R_a/R_g) of WO₃·H₂O HS sensor increased by 9.5 times after modification with 0.02% bimetallic PtCu nanocrystals. The response of PtCu/WO₃·H₂O HS to 50 ppm acetone is as high as 204.9 with short response/recovery times (3.4 s/7.5 s). Finally, the gas-sensitivity mechanism was discussed based on gas sensitivity test results. This research will offer a new route for high efficient acetone detection.     

基于金银合金薄膜的高灵敏度宽光谱表面等离子体共振成像传感器

报道了一种基于金银合金薄膜的宽光谱表面等离子体共振成像(SPRI)传感器,该传感器能够对吸附在薄膜局部或整个表面上的生化分子进行原位定量检测,而且与常规的金膜SPRI传感器相比,检测成本更低,检测灵敏度更高。利用质量比1:1的金银合金溅射靶在玻璃基板上淀积了厚约50 nm的均匀的金银合金薄膜。利用实验室自制的Krestchmann结构多功能平台在不同入射角下测试了金银合金薄膜被纯水覆盖后的SPR光谱和SPR彩色图像。基于色相算法计算获得了每个SPR彩像的二维色相分布及其平均色相,从而使得宽光谱SPRI传感器能够利用平均色相作为灵敏度参数进行定量检测。实验确定了平均色相对溶液折射率(RI)变化和分子吸附最为敏感的光谱区间是595–610 nm之间。在这个窄光谱范围内,平均色相与共振波长呈线性关系,其斜率为?hue/?λR=7.52 nm~(-1),这意味着基于色相的RI灵敏度是基于共振波长的RI灵敏度的7.52倍,这一结论已被实验证明。将SPRI传感器的起始共振波长设定在色相敏感光谱区间内之后,实验测得基于色相的RI灵敏度为S=29879 RIU~(-1),比在相同条件下测得的金膜SPRI的灵敏度高8倍。利用时间分辨宽光谱SPRI方法实时监测了牛血清白蛋白(BSA)分子在金银合金薄膜表面的非特异性吸附,从实验测得的平均色相随时间的变化曲线可知BSA吸附达到平衡所需时间约15 min。研究结果表明,基于金银合金薄膜的SPRI传感器具有动态定量检测蛋白质分子吸附过程的功能。     

Embedding 1D Conducting Channels into 3D Isoporous Polymer Films for High‐Performance Humidity Sensing

Isoporous block copolymer (BCP) films have received exponential interest as highly selective membranes, stemming from their unique morphological features, but their applications in functional devices remain to be realized. Now single‐walled carbon nanotubes (CNTs) were efficiently incorporated into isoporous block copolymer films for chemiresistive sensing at room temperature. Leveraging the efficient charge extraction ability of CNTs together with nanochannel arrays aligned perpendicular to the surface of the films, an ultrafast response time of 0.3 s was achieved for humidity detection with a sensor response of about 800 on changing humidity from 10 % to 95 %. Furthermore, the sensor also responds to various organic vapors, underscoring its promising detection capability.     

基于纳米金自组装膜固定辣根过氧化物酶的生物传感研究

将辣根过氧化物酶(HRP)通过纳米技术和自组装技术固定于电极表面,制得了酶修饰电极.纳米金与HRP形成了静电复合物并高效地保持了HRP的生物活性,以对苯二酚作为电子媒介体,差示脉冲伏安法(DPV)研究生物酶电极测定H2O2的线性范围为5.0×10-6～1.0×10-3 mol/L,检测限为2.5×10-6 mol/L,线性方程为△I=0.34765+4.05553CH2O2(mM).酶电极的表观米氏常数(K(app))为0.0675 mmol/L.实验同时证明该生物酶电极具有良好的稳定性和使用寿命.     

Humidity sensors using in situ synthesized sodium polystyrenesulfonate/ZnO nanocomposites

Thin film humidity sensors have been prepared using in situ synthesized inorganic/organic nanocomposites of sodium polystyrenesulfonate (NaPSS) and ZnO. Its humidity sensing characteristics and the sensing mechanism have been investigated by measuring the complex impedance spectra of the sensor at different humidities. The logarithm of the impedance of sensor based on composite film changes linearly by four-orders of magnitude over almost whole humidity range (11-97% RH). Furthermore, the sensor exhibits a quick response (absorption: 2 s, desorption: 2 s) and small hysteresis (less than 2% RH). The composite film shows better sensing properties than NaPSS film, such as better linearity, quicker response. Explanation to the improvement is attempted by taking into account of the composition and structure of the nanocomposites.