三氧化钨纳米薄膜制备与气敏性能的研究

讨论一种对二氧化氮具有高灵敏性的WO3纳米薄膜的制备方法.当基片温度为室温,溅射混合气体(O2/Ar)的比例为1:1时,用直流反应磁控溅射法制备的薄膜,经过两步热处理(300℃/600℃),得到纳米结构WO3气敏元件.通过XRD、XPS和SEM对该薄膜的晶体结构和化学成分进行分析,用静态配气法测试NO2气敏特性.在Si3N4基片上制备的这种薄膜对空气中较低浓度的NO2(体积分数为0.1×10-5～3×10-5)具有优异的敏感特性和响应特性,最佳工作温度为150℃,在此温度下对其他一些气体(如CO,C2H5OH,NH3)的敏感性很差,显示出良好的选择性.     

Cu20纳米晶制备及其在乙醇气体传感器中的应用

以CuCl2·H2O为主要原料,抗坏血酸作还原剂,聚乙二醇-20000（PEG-20000）作表面活性剂,利用化学混合法制备了纳米晶结构的Cu2O纳米立方体。研究了pH值对Cu2O纳米结构的影响,并用XRD和SEM对产物的物相和形貌进行了表征。将粉体制成气敏元件,气敏性能测试结果表明：该Cu20纳米晶对乙醇气体具有较高的灵敏度和选择性。600℃热处理2h材料气敏特性最好,在最佳工作温度（360℃）下对体积分数为0．006％的乙醇气体灵敏度可达到38％,达到了口腔乙醇气体体积分数检测限度0．008％的要求。     

ZnSnO3气敏薄膜的制备和性能

利用共沉淀法制备了ZnSnO3粉体,通过直流溅射制备了气敏薄膜.研究了老化温度、薄膜的组成对气体的灵敏度影响.实验结果表明:600℃老化后,气敏膜薄膜的主要成分是ZnSnO3,在450℃时,该薄膜对乙醇灵敏度约为650,有望开发成酒敏元件.     

溅射Au对SnO_2/Fe_2O_3薄膜气敏特性的影响

通过直流溅射Au对PCVD方法制备的SnO2/Fe2O3双层薄膜的SnO2表面进行了修饰,并对修饰后的Au SnO2/Fe2O3薄膜的气敏特性进行了观测。结果表明,Au的催化作用使Au SnO2/Fe2O3薄膜气敏器件对CO,H2,C2H5OH等气体的灵敏度增大2～3倍,相应于最大灵敏度的工作温度均降低约60℃。这显示直流溅射Au是改善SnO2/Fe2O3双层薄膜气敏性能的一种有效手段。     

稀土La掺杂SnO_2薄膜气敏特性

用真空热蒸发两步法在玻璃衬底制备SnO2和La掺杂SnO2薄膜。研究氧化、热处理工艺和La掺杂含量对SnO2薄膜结构、气敏特性的影响。结果显示:经T=550℃,t=45 min氧化、热处理后,得到n型金红石结构SnO2薄膜。适当掺La可改善SnO2薄膜结晶状况,掺La后SnO2薄膜对气体的选择性和灵敏性均得到明显的改善,在气体体积分数为1×10-2时,掺La(5%)的SnO2薄膜对乙醇的灵敏度为12;掺La(3%)的SnO薄膜对丙酮的灵敏度可达到14。     

直流反应磁控溅射法制备WO_3薄膜及其氢敏特性研究

采用直流反应磁控溅射法,在未抛光的A l2O3基片上制备WO3薄膜,在干燥空气中经过热处理;利用SEM观察薄膜表面形貌;通过XRD测量,对薄膜的晶体结构进行分析;薄膜氢敏特性测试采用静态配气法。经过400℃热处理,当工作温度在270℃时,对体积分数为3×10-4氢气的灵敏度达到了77,稳定性较高,选择性好,响应时间很快,在15 s以内,是一种较理想的氢敏材料。     

SnO2薄膜的电学气敏特性与光学气敏特性研究

用射频磁控反应溅射法制备了ＳｎＯ２薄膜,并分别测量薄膜在乙醇气体中的电学气敏特性和光学气敏特性。对实验结果的分析表明,ＳｎＯ２薄膜对乙醇气体有较强的电学气敏效应和光学气敏效应。利用ＳｎＯ２薄膜的电学气敏特性适合检测较低浓度乙醇气体,而利用ＳｎＯ２薄膜的光学气敏特性能检测较高浓度乙醇气体。     

氧化钨纳米线修饰多孔硅结构的制备及NO2气敏性能研究

针对多孔硅气敏传感器在室温下对NO2气体灵敏度较低、选择性不强的问题,采用双槽电化学腐蚀法制备多孔硅,然后在多孔硅顶部溅射沉积金属钨薄膜并经高温热处理氧化形成WO3纳米线,制备出WO3纳米线修饰多孔硅结构及其气敏传感器,对WO3纳米线/多孔硅材料进行了SEM和XRD分析,测试了传感器室温下对NO2的气敏特性。结果表明,制备WO3纳米线的最佳热处理条件是700℃,此温度下增加金属钨膜溅射时间可提升WO3纳米线的生长密度? 所制备的传感器对NO2气体表现出反型气敏响应,特别是溅射1min金属钨的样品显示出优异的NO2室温探测能力与选择性,对4×10-6NO的气敏灵敏度是单纯多孔硅样品的 5.8倍。     

稀土Nd掺杂纳米ZnO薄膜气敏特性

研究了用真空气相沉积法在玻璃衬底上制备掺稀土Nd的ZnO薄膜的气敏特性,实验给出,经温度为500℃,时间为45min的氧化、热处理的掺Nd的ZnO薄膜的晶粒尺寸、结构特性均发生变化。随掺Nd质量分数的增大,薄膜的晶粒尺寸从53nm减小至20nm。经掺Nd(质量分数为4.96×10-2)后纳米ZnO薄膜对乙醇气体的选择性和灵敏性均得到明显的改善。在1.5×10-3体积分数的乙醇气体中最高灵敏度为34,相应的薄膜工作温度为200℃。     

Ag掺杂的SnO_2酒敏薄膜敏感特性研究

采用非醇盐溶胶—凝胶工艺在A l2O3基片上旋转涂敷制得掺Ag的SnO2薄膜。原子力显微镜和扫描电子显微镜分析显示:薄膜晶粒呈球形,600℃热处理粒径为20 nm左右。热处理温度升高,晶粒尺寸增大。气敏性能采用静态法测试,掺Ag薄膜对体积分数为50×10-6乙醇和汽油气体的灵敏度分别为32.7和4.9,与未掺Ag薄膜的14.4和7.2相比较,提高了乙醇气体灵敏度,抑制了汽油气体灵敏度,使选择性得到改善。直流加热条件下,试样电阻和电容在老化初期变化较大,数天后趋于稳定,复阻抗分析表明:长期稳定性与晶粒间界处电阻和电容值的变化有关,来源于晶界势垒高度和势垒宽度的变化,其本质可能是直流偏压作用下晶界层中的离子迁移。     

WO3基臭氧敏感元件的研制

在三氧化钨粉体材料中加入金属氧化物,以恒温600℃烧结1小时制成傍热式厚膜O3气体敏感元件.采用静态电压测量法,研究了加入一定质量分数的Nb2O5、Fe2O3、Co3O4、TiO2、Sb2O3后元件的加热电压与电导率、元件灵敏度、60 s后回复几率的关系,讨论了掺杂成分和杂质的质量分数对材料的气敏性能和环境适应能力的影响.实验结果显示:2%TiO2- 3% Nb2O5-WO3元件能开发成理想的O3敏感元件.     

SnO_2-ZnO复合膜特性研究

用真空蒸发的方法,在1.33×10-3Pa的真空中,蒸发SnO2,ZnO获得超微粒结构的SnO2-ZnO复合膜。当复合膜中ZnO质量分数为20%时,SnO2-ZnO复合膜对乙醇气体的灵敏度为40,膜的方电阻值也较低,为0.01×103Ω/□。复合膜经热处理后,其电学性能也得到改善,当温度t=600℃时,ZnO质量分数为20%的SnO2-ZnO复合膜热处理后,其膜对乙醇气体有较高的选择性,灵敏度为60。当t=400℃时,对掺有Sb2O5质量分数为450×10-6,ZnO质量分数为20%的SnO2-ZnO复合膜进行热处理,其方电阻仅为0.003×103Ω/□,具有优良的导电性能。     

NiCrAlY薄膜应变计的研制

采用射频磁控溅射法在Ni基高温合金拉伸件上制备NiCrAlY薄膜应变计。研究了热稳定处理对NiCrAlY薄膜结构、表面形貌的影响,并且测试了NiCrAlY薄膜应变计的电学与应变性能。结果表明：热稳定处理后 NiCrAlY 薄膜应变计由于在表面形成了一层 Al2 O3膜,具有抗高温氧化的特性,在室温～800℃范围内,应变计电阻同温度呈线性变化,电阻温度系数（ TCR）约为290×10－6/℃,室温下的应变计系数（ GF）为2.1。     

掺杂对WO_3基气敏元件敏感特性的影响

在WO3粉体材料中加入质量分数为4%的瓷粉和不同质量分数的金属氧化物(SnO2,SiO2,Al2O3),以恒温600℃烧结1 h制成旁热式厚膜可燃性气敏元件。采用静态电压测量法,研究了元件的加热电压与元件灵敏度的关系。实验结果表明:WO3基元件掺入一定量的金属氧化物在加热功率为600mW时能提高元件的灵敏度。     

Gas sensing properties of ZnO thin films prepared by microcontact printing

In situ patterned zinc oxide (ZnO) thin films were prepared by precipitation of Zn(NO₃)₂/urea aqueous solution and by microcontact printing of self-assembled monolayers (SAMs) on Al/SiO₂/Si substrates. The visible precipitation of Zn(OH)₂ from the urea containing Zn(NO₃)₂ solution was enhanced by increasing the reaction temperature and the amount of urea. The optimized condition for the ZnO thin films was found to be the Zn(NO₃)₂/urea ratio of 1/8, the precipitation temperature of 80 °C, the precipitation time of 1 h and the annealing temperature of 600 °C, respectively. SAMs are formed by exposing Al/SiO₂/Si to solutions comprising of hydrophobic octadecylphosphonic acid (OPA) in tetrahydrofuran and hydrophilic 2-carboxylethylphosphonic acid (CPA) in ethanol. The ZnO thin film was then patterned with the heat treatment of Zn(OH)₂ precipitated on the surface of hydrophilic CPA. The ZnO gas sensor was exposed to different concentrations of C₃H₈ (5000 ppm), CO (250 ppm) and NO (1000 ppm) at elevated temperatures to evaluate the gas sensitivity of ZnO sensors. The optimum operating temperatures of C₃H₈, CO and NO gases showing the highest gas sensitivity were determined to be 350, 400 and 200 °C, respectively.     

Sensing characteristics of dc reactive sputtered WO3 thin films as an NOx gas sensor

In order to apply WO₃ thin films to the NO_x gas sensor, WO₃ thin films (3000 Å) were fabricated by using dc reactive sputtering method on alumina substrate and assembled as a unit of an NO_x gas sensor by adopting a patterned heater on the back side of substrate. The deposition temperatures of WO₃ thin film were changed from 200°C to 500°C, and then post-annealed for the crystallization for 4 h at 600°C. There were no WO₃ phases at the substrate temperature of 200°C, but the crystalline phases of WO₃ thin film were appeared with the increase of substrate temperature from 200°C to 500°C. The post-annealing of as-deposited WO₃ thin films at 600°C resulted in the enhancements of crystallinity, but it was observed that the quality of the final phases severely depends on the initial formation of phase during deposition. From the SEM images, crack free morphologies were found, which was different from the room temperature growth films. The sensitivity (R_gas/R_air) of as-deposited thin films was ranged from 4 to 10 for the 5 ppm NO test gas at the measuring temperature of 200°C. However, after post-annealing process at the temperature of 600°C, the sensitivities were increased around the values of 70–180 at the same test condition. These results show the WO₃ thin films need to be processed at least at the temperature of 600°C for the well-improved sensitivity against NO_x gas. It was also observed that the recovery rate of a sensing signal after measuring sensitivity was faster in the in-situ sputtered films than in the evaporated films or room temperature sputtered films.     

Tin oxide microsensor for LPG monitoring

A silicon-based SnO₂ gas sensor has been fabricated for monitoring liquified petroleum gas (LPG), commonly used as town gas. The gas sensor is made by silicon IC technology together with SnO_f2 thin-film processing. The whole chip with a size of 9 mm x 9 mm consists of nine sensors (three by three array). each sensor is supported by a thin membrane of SiO₂/Si₃N₄/SiO₂ layers that provides a low thermal mass and prevents heat conduction through the surrounding substrate material. Tin oxide thin film is prepared by thermal evaporation of metallic tin granules and subsequent thermal oxidation of the metallic film at 600 °C. To form the SnO₂(Pt) thin film, a layer of Pt with a thickness of several tens of angstroms is sputtered onto the tin oxide film and heat treated at 500 °C in air for several hours in order to stabilize its electrical response. The fabricated SnO₂(Pt) microsensors exhibit about 85 and 92% sensitivities to 5000 ppm C₃H₈ and 5000 ppm C₄H₁₀ (the main components of LPG) at 250 °C, respectively, and show a rapid response time of less than 5 s.     

Pt/Pd对WO_3燃气敏感元件的影响

在WO3粉体材料中加入Pt,PtO2,Pd,PdCl2,以恒温600℃烧结1h制成旁热式厚膜可燃性气敏元件。采用静态电压测量法,研究了元件的加热电压与元件灵敏度的关系。实验结果表明:WO3元件掺入质量分数为0.5%的Pt/Pd,在加热功率为600 mW时,能提高元件的灵敏度2~10倍。