声表面波气体传感器研究进展*

基于声表面波技术的气体传感器包括采用敏感膜和结合气相色谱两种方式。比较而言,采用敏感膜的声表面波气体传感器体积小、功耗低,适应小型化毒气报警器的发展要求,但可检测的气体种类少、灵敏度低、存在交叉干扰问题;声表面波与气相色谱联用的气体分析仪灵敏度高、可检测气体种类多、很好地解决交叉干扰问题,特别适合于复杂大气背景条件下的气体成分分析。本文从传感器响应机理分析与物理功能结构两方面出发介绍了两类声表面波气体传感器的研究进展情况。     

基于指条厚度优化的冷凝式SAW气体传感器灵敏度提升方法

该文通过对声表面波谐振器指条厚度的优化提升了冷凝式气体传感器的灵敏度。基于流固耦合理论,利用有限元商业软件建立了有液膜负载和无液膜负载下的多物理场三维周期模型,并提取了相应的耦合模参量,利用耦合模模型及P矩阵级联技术,计算了不同指条厚度下液膜负载引起的传感器响应,获得了冷凝式声表面波气体传感器灵敏度随指条厚度的变化关系。实验中制备了6种不同电极厚度的声表面波谐振器,并利用甲基膦酸二甲酯实验样品完成了传感器的响应测试,验证了理论分析的正确性。结果表明,冷凝式声表面波气体传感器的灵敏度随指条厚度的增加先变大后减小,最优归一化电极厚度为6.4%～7.6%之间。该研究结果对进一步提升传感器灵敏度具有重要意义。     

快速吸附与脱附的声表面波H2S传感器

本文主要研究了基于SnO₂/CuO薄膜的声表面波（SAW）传感器（室温下,工作频率约为147.8 MHz）检测H₂S气体的特性。以36°YXLiTaO₃为基片制作声表面波器件,通过采用射频磁控溅射法在其表面淀积SnO₂/CuO的复合薄膜制作出H₂S气体传感器。由场发射电子扫描电镜观察薄膜,薄膜连续均匀且表面分布大量微气孔,因而具有良好的吸附性。然后本文在85℃～205℃范围内对传感器的吸附和脱附速率、灵敏度及选择性等进行了实验研究。实验结果表明,所制备的传感器在较低温度下同时具备快速吸附和脱附特性,工作在190℃时气体吸附和脱附速率最快,检测20ppm H₂S的响应和恢复时间分别为30s、15s;工作在160℃时,传感器检测20ppmH₂S的灵敏度最高,工作频率变化约230 kHz,且对于低浓度2 ppm H₂S,频率变化可达45 kHz。同时,传感器也表现出良好的重复性和选择性。     

新型声表面波电流传感器*

将声表面波技术的快速响应特点与磁致伸缩薄膜的高磁敏特点相结合,可实现一种快速、高灵敏、稳定可靠的新型电流检测技术。传感器由双通道差分式振荡器与沉积在传感通道器件表面的声传播路径上的磁致伸缩薄膜组成。该文基于分层介质中声传播理论及磁致伸缩效应,对声表面波电流传感机理进行了分析,以实现对传感器结构的优化设计。实验研制了采用铁钴(FeCo)薄膜的声表面波电流传感器,测试结果表明,该传感器具有快速响应和高灵敏特点。为抑制磁致伸缩薄膜自身的剩磁效应所带来的高磁滞误差,采用的有效途径是将沉积的磁致伸缩薄膜进行图形化设计。实验结果表明,采用栅阵化FeCo薄膜结构的传感器表现出更高检测灵敏度、更好线性及更低的磁滞误差。     

声表面波免疫传感器的设计及应用

声表面波免疫传感器是一种新型生物免疫传感器，它利用声表面波振动的敏感性，同时结合了免疫反应的特异性，作为免疫检测的手段。可以对多种抗原或抗体进行快速的定量测定。具有高特异性，高灵敏度，响应快，小型简便等特点。本文利用声表面波延迟线振荡器作为传感器，检测溶液中人体免疫球蛋白IgG的含量。实验采用双通道系统进行频率变化的测定，并分别采用氨基硅烷膜，蛋白A两种方法将抗体固定到反应区域表面，根据实验结果，我们得到了频率变化和质量附着的定量关系。并与理论分析的结果相比较。     

声表面波梁式加速度传感器的优化设计

为获得传感器的优化设计,对一种声表面波梁式加速度传感器敏感机理进行了研究。从声波波动方程出发,结合有限元分析以及微扰理论对加速度作用力作用下声表面波传播特性进行分析,以此构建梁式声表面波加速度传感器敏感机理的理论模型,特别分析了压电梁材料及几何结构、振子质量对传感响应的贡献以确定传感器优化的几何参数。为验证理论分析结果,实验研制了基于ST-X石英悬臂梁结构的差分振荡式声表面波加速度传感器,并利用精密振动台对所研制传感器性能进行评价。实验结果显示,在给定加速度测试范围内,采用ST-X石英梁并延长梁长度、降低梁厚度以及采用较大的阵子质量将有效的改善传感器检测灵敏度,在±2 g范围内加速度灵敏度可达27 k Hz/g,且实验结果很好的验证了理论模型。     

基于声表面波的氢气传感器*

将钯基材料对氢气分子的特异选择性吸附能力与声表面波的快速响应特点相结合,可实现一种快速、高灵敏和低功耗的氢气检测与报警技术。传感器由双通道差分式振荡器与沉积在传感器件表面的声表面波传播路径上的钯基气敏薄膜组成。为提升传感器响应速度,该文探讨了采用钯镍合金薄膜与钯铜纳米线作为气敏材料的氢气传感器响应特性,通过对气敏材料制备方法及参数的优化,研制了两种沉积不同钯基气敏材料的氢气传感器件,并对其性能进行了评测。实验测试结果表明:钯铜纳米线气敏材料由于具有大体积表面积比和多孔结构,大幅提高了SAW氢气传感器响应速度,针对浓度为10%、4%以及0.5%的氢气响应时间可达～2s。     

应用于气体传感器的具有铝/金电极的单模式两端对声表面波谐振器

为改善气体传感器性能,通过器件优化设计获得了一种应用于气体传感器的具有低损耗、高品质因子(Q)的单模式两端对声表面波(SAW)谐振器。该谐振器由两个换能器、分置于换能器两边的短路栅反射器以及在换能器之间分布的用于敏感膜镀膜的约2.5mm金属薄层构成。谐振器采用铝/金双层电极以降低测试气体环境的腐蚀影响。利用经典耦合模(COM)理论对器件性能进行了仿真以提取优化的结构设计参数。基于仿真结果,实验研制了基于300MHz频率的新型铝/金电极SAW两端对谐振器,测试结果显示所研制器件具有较低损耗(〈7dB),较高Q值(-3000)以及单一谐振模式的特点,并且,以所研制的新型谐振器为频率控制单元的谐振器型振荡器表现出良好的频率稳定度(t15Hz/h),这对于改善气体传感器的检测下限及稳定性等性能指标具有重要意义。     

ZnO薄膜/金刚石在不同激励条件下声表面波特性的计算与分析

本文首先以刚度矩阵法为基础, 给出了ZnO薄膜/金刚石在四种不同激励条件下的有效介电常数计算公式. 然后以此为工具, 分别计算了多晶ZnO(002) 薄膜/多晶金刚石和单晶ZnO(002) 薄膜/多晶金刚石的声表面波特性, 并根据计算结果及设计制作声表面波器件的要求, 对ZnO膜厚的选择进行了详细地分析. 最后讨论了ZnO/金刚石/Si复合晶片可以忽略Si衬底对声表面特性影响时对金刚石膜厚的要求. 关键词： 声表面波 压电多层结构 有效介电常数 刚度矩阵法     

负折射率材料用于表面波传感的特性分析

利用严格电磁理论分析了负折射材料界面上激励表面波的相关特性,证明两种偏振入射都能在负折射材料与正折射材料界面上激发表面波,并推导出了相应表面波的传播波矢和激发条件.针对负折射材料在表面波传感方面的应用,对膜厚选择,偏振态,测量范围,线性度等性能参量进行了具体分析,与传统的金属表面等离子波传感器相比,使用负折射材料在灵敏度相当的情况下,能有效提高线性度,增大测量范围,提高信噪比.     

A Prussian blue-based amperometric sensor for the determination of hydrogen peroxide residues in milk

A highly selective, sensitive, fast, and stable amperometric sensor for the determination of hydrogen peroxide residues in aseptic milk is presented. To fabricate this amperometric sensor, a thin film of Prussian blue was first electrodeposited on a glassy carbon electrode and then a Nafion polymer layer was formed on the top. It was found that Nafion film greatly improves the anti-interference ability and the stability of the Prussian blue-modified electrode. Factors that influence the overall analytical performance of the sensor, such as the concentration of Nafion drop and pH value of the electrolyte, were examined. Results show that the prepared sensor possesses efficient electrocatalytic activity towards hydrogen peroxide with the detection limit as low as 0.2 μM and linear range from 0.8 μM to 0.12 mM. The developed sensor was applied to the determination of hydrogen peroxide in milk with satisfactory results.     

TiO2纳米线阵列干涉传感器

开发一种新型TiO₂纳米线阵列干涉传感器。首先,通过水热合成法在FTO导电玻璃表面制备了TiO₂纳米线阵列薄膜。然后,以此复合结构作为传感芯片,利用Kretschmann 棱镜耦合结构,构建了基于Kretschmann结构的波长调制型薄膜干涉传感器。最后,以氯化钠水溶液为待测液体介质研究了该传感器对环境介质折射率的灵敏性能。结果表明：该传感器对1.333 5~1.360 4范围内的折射率有很好的响应。TM模式下,在0~3%与3~15%浓度范围内,氯化钠浓度与该传感器的反射光强度分别呈现了良好的线性关系。TE模式下,在0~3%浓度范围内,氯化钠浓度与吸收强度存在良好的线性关系,而波长基本不变;而在3~15%浓度范围内,随着氯化钠浓度的增加,波长逐渐红移,氯化钠浓度与波长也具有良好的线性关系。     

Optical fiber methane sensor based on SAN film containing cryptophane-E-（OEt）_6

A novel long-period fiber grating (LPFG) film methane sensor is designed and applied successfully. The sensor is constructed by depositing a thin styrene-acrylonitrile (SAN) film containing the new compound cryptophane-E-(OEt)6 onto the cladding surface of the LPFG. This film is sensitive to methane gas. Methane causes a change in the refractive index of the sensing film, which can be measured by shifting the resonance wavelength. Experimental results show that the resonant wavelength shifts to the longer wavelength, with increasing methane concentration at a range of 0.0%-3.5% (v/v). A linear relationship is obtained within the test range. Detection limit is estimated at 0.2%, and response time is 60 s. No significant interference is detected from dry air, O2 , CO, CO2 , and H2 . This novel methane sensing material has great application potential due to its advantages.     

Synthesis and Properties of Thermosensitive Poly(N-Isopropylacrylamide)/Waterborne Polyurethane Graded Concentration Hybrid Films

Temperature-sensitive hybrid films were synthesized with a concentration gradient by casting and UV curing of N-isopropylacrylamide (NIPAAm) monomers (0%–70%) on the free surface of waterborne polyurethane (WPU) films on a Teflon substrate. The surface hardness and contact angle of the free surface with a water drop increased asymptotically with the addition of NIPAAm, whereas those on the substrate side were virtually unchanged. The diffusion coefficient (D), rates of swelling at 20°C (below the lower critical solution temperature (LCST) of poly(N-isopropylacrylamide) (PNIPAM)) and deswelling at 50°C (above the LCST) increased with increasing NIPAM content, showing favorable thermosensitivity. In addition, the glassy state modulus and glass transition temperature (Tg) of the film increased with increasing NIPAM content, whereas the rubbery modulus decreased due to the increased molecular weight between the crosslinks. In addition, as the NIPAM content increased, the film showed a positive yield with an increased yield and fracture stress and decreased ductility. Above 50% NIPAM, the film became brittle, showing a linear stress–strain relationship.     

Impulse characteristic as a response of a liquid sensor based on shear-horizontal surface acoustic waves

The feasibility of using the impulse response of a liquid sensor based on shear-horizontal surface acoustic waves to identify liquids is justified. Identification of some liquid analytes with a single-channel sensor is experimentally demonstrated. The sensor is built around a delay line based on shear-horizontal surface acoustic waves that are excited in a 36°YX LiTaO₃-Al film-SiO₂ film-molecularly imprinted polymer film layered structure. By way of example, the concentration of the morpholine impurity (molecules of which are used as a template in synthesis of this molecularly imprinted polymer) in the liquids is measured. Impulse characteristics are derived by applying the fast inverse Fourier transformation to the amplitude-frequency responses of the sensor taken in a 60-MHz wide band at a center frequency of 105 MHz. The reproducibility of results obtained using such a technique and its application are discussed.     

A highly sensitive and selective hydrogen gas sensor from thick oriented films of MoS2

A new process is developed to fabricate a highly sensitive and selective hydrogen sensor by depositing a partially crystalline and highly oriented film of MoS₂ from its single layer suspension on an alumina substrate. When these films are promoted with some catalysts selected from Pt-group metals (Pt, Pd, Ru or any combination of these metals) they exhibit a high sensitivity and selectivity to hydrogen gas. Unlike other metal oxide sensors which are sensitive to many reducing and oxidizing gases and operate at a temperature of 350 °C or higher; this sensor is highly selective to hydrogen gas and its operating temperature is from 25 to 150°C. The lower operating temperature enhances safety when dealing with hydrogen gas. The sensor response to hydrogen at 120 °C is linear in concentration from 30 to 10⁴ ppm with a 10 to 30 second response time and a 45 to 90 second recovery time. Above 10⁴ ppm the sensor is still linear but the slope of conductance versus hydrogen concentration changes.     

Confinement and processing effects on glass transition temperature and physical aging in ultrathin polymer films: Novel fluorescence measurements

Fluorescence intensity measurements of chromophore-doped or -labeled polymers have been used for the first time to determine the effects of decreasing film thickness on glass transition temperature, T _g, the relative strength of the glass transition, and the relative rate of physical aging below T _g in supported, ultrathin polymer films. The temperature dependence of fluorescence intensity measured in the glassy state of thin and ultrathin films of pyrene-doped polystyrene (PS), poly(isobutyl methacrylate) (PiBMA), and poly(2-vinylpyridine) (P2VP) differs from that in the rubbery state with a transition at T _g. Positive deviations from bulk T _g are observed in ultrathin PiBMA and P2VP films on silica substrates while substantial negative deviations from bulk T _g are observed in ultrathin PS films on silica substrates. The relative difference in the temperature dependences of fluorescence intensity in the rubbery and glassy states is usually reduced with decreasing film thickness, indicating that the strength of the glass transition is reduced in thinner films. The temperature dependence of fluorescence intensity also provides useful information on effects of processing history as well as on the degree of polymer-substrate interaction. In addition, when used as a polymer label, a mobility-sensitive rotor chromophore is demonstrated to be useful in measuring relative rates of physical aging in films as thin as 10 nm. Received 21 August 2001     

Sn掺杂ZnO薄膜的室温气敏性能及其气敏机理

采用化学气相沉积方法在预制好电极的玻璃基底上制备出Sn掺杂ZnO薄膜和纯ZnO薄膜. 两种样品典型的形貌为四足状ZnO晶须, 其直径约为150-400 nm, 呈疏松状结构. 气敏测试结果显示Sn掺杂ZnO薄膜具有优良的室温气敏性, 并对乙醇具有良好的气敏选择性, 而纯ZnO薄膜在室温条件下对乙醇和丙酮均没有气敏响应. X射线衍射结果表明两种样品均为六方纤锌矿结构. Sn掺杂ZnO样品中没有出现Sn及其氧化物的衍射峰, 其衍射结果与纯ZnO样品对比, 衍射峰向小角度偏移. 光致发光结果表明, Sn掺杂ZnO薄膜与纯ZnO薄膜均出现紫外发光峰和缺陷发光峰, 但是Sn的掺杂使得ZnO的缺陷发光峰明显增强. 将Sn掺杂ZnO样品在空气中退火后, 其室温气敏性消失, 说明Sn掺杂ZnO样品的室温气敏性可能与其缺陷含量高有关. 采用自由电子散射模型解释了Sn掺杂ZnO薄膜的室温气敏机理.     

环糊精复合薄膜光波导元件的气敏性研究

采用旋转甩涂法在钾离子(K+)交换玻璃光波导表面制备了聚乙烯吡咯烷酮(PVP)-环糊精复合薄膜,研制了PVP-环糊精薄膜/K+交换玻璃光波导传感元件,并对挥发性有机气体进行了检测。该气敏元件对苯乙烯和二甲苯具有较好的响应,并能够检测到体积比为1×10-6的苯乙烯和1×10-5的二甲苯。还具有响应及恢复速度快、容易制备等特点。     

一种基于相位测量的角漂移自适应结构表面等离子体共振气体折射率测量系统

提出了一种可抑制角漂移的表面等离子体传感器结构,并结合相位测量设计了相应的气体折射率测量系统。分析表明激光入射角、金膜厚度以及反射光p、s分量的相位差与气体折射率之间的固有非线性是影响相位响应度与折射率测量精度的主要因素。计算表明所提出的自适应结构将角漂移引起的误差降低了一个数量级并很大程度提高了测量灵敏度。同时分析设计了金膜厚度参数,并评估了反射光p、s分量的相位差与气体折射率之间固有非线性带来的误差。应用于空气折射率的测量比对实验显示其测量精度达到了10-6量级。