MEMS-based formaldehyde gas sensor integrated with a micro-hotplate

This paper presents a novel micro-fabricated formaldehyde gas sensor with enhanced sensitivity and detection resolution capabilities. The device comprises a quartz substrate with Pt heaters as a micro-hotplate and deposited formaldehyde-sensing layer on it. A sputtered NiO thin film is used as the formaldehyde-sensing layer. A specific orientation of NiO becomes more apparent as the substrate temperature increases in the sputtering process, which helps the formation of NiO material with a correct stoichiometric ratio. The gas sensor incorporates Pt heating resistors integrated with a micro-hotplate to provide a heating function and utilizes Au inter-digitated electrodes. When formaldehyde is present in the atmosphere, oxydation happens near the sensing layer with a high temperature caused by the micro-hotplate and causes a change in the electrical conductivity of the NiO film. Therefore, the measured resistance between the inter-digitated electrodes changes correspondingly. The application of a voltage to the Pt heaters causes the temperature of the micro-hotplate to increase, which in turn enhances the sensitivity of the sensor. The nanometer scale grain size of the sputtered oxide thin film is conducive to improving the sensitivity of the gas sensor. The experimental results indicate that the developed device has a high stability (0.23%), a low hysteresis value (0.18%), a quick response time (13.0 s), a high degree of sensitivity (0.14 Ω ppm⁻¹), and a detection capability of less than 1.2 ppm.

     

Enhanced sensing characteristics in MEMS-based formaldehyde gas sensors

This paper presents a novel micro fabrication for formaldehyde gas sensors to enhance sensitivity and detection resolution capabilities. Therefore, two different types of fabrication sequences of gas sensors were considered, different positions of micro heaters and sensing layers to compare the effects of different areas of the sensing layers contact with the surrounding gas. The MEMS-based formaldehyde gas sensor consists of a quartz substrate, a thin-film NiO/Al₂O₃ sensing layer, an integrated Pt micro-hotplate, and Pt inter-digitized electrodes (IDEs) to measure the resistance variation of sensing layers caused by formaldehyde oxidation at the oxide surface. This abstract offers comparisons of the characteristics of sensors in different areas of the sensing layers contacting the surrounding gas as well as those to decrease the thickness of the sensing layer and deposits of the sensing layer using co-sputtering technology with NiO/Al₂O₃ to improve the sensitivity limits of the sensors. The experimental data indicated that increasing the area of the sensing layer that contacts with the surrounding gas and decreasing the thickness of the sensing layer in the sputtering process and then co-sputtered NiO/Al₂O₃ sensing layers, significantly enhanced the sensing characteristics of the developed formaldehyde sensor.     

中国微米纳米----氧化锡气敏薄膜的喷墨打印技术研究

喷墨打印技术具有无需掩膜图形化、室温加工、方便操作等优点.利用喷墨打印技术在微热板上打印SnO2多孔薄膜.根据打印机的定位精度和微热板的悬空尺寸设计了打印图形,根据目标厚度确定打印层数,以及打印后的干燥工艺参数;通过扫描电镜对薄膜结构进行微观表征,敏感薄膜表面平整,成膜均匀;最后对其进行气敏测试,当微热板工作在250 ℃时,打印的SnO2气敏薄膜对乙醇有良好的响应,检测到最低乙醇浓度为0.5×10-6,响应和恢复时间均在3 s左右.     

多层薄膜结构气敏效应研究

在SnO2气敏薄膜层上覆盖一层或多层钝化材料（SiO2,Al2O3) 薄膜，制成的多层膜气敏元件，可很好地排除大分子气体如乙醇等对小分子H2检测的干扰，使其具有单独检测H2的功能。本文还通过测量元件的升温曲线，推导出敏感体表面的氧吸附活化能；找出活化能与灵敏度、选择性的关系。根据实验现象和物性分析结果，试着探讨了元件的敏感机理。     

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.     

Flexible H2 sensor fabricated by layer-by-layer self-assembly of thin films of polypyrrole and modified in situ with Pt nanoparticles

A novel flexible H₂ gas sensor was fabricated by the layer-by-layer (LBL) self-assembly of a polypyrrole (PPy) thin film on a polyester (PET) substrate. A Pt-based complex was self-assembled in situ on the as-prepared PPy thin film, which was reduced to form a Pt-PPy thin film. Microstructural observations revealed that Pt nanoparticles formed on the surface of the PPy film. The sensitivity of the PPy thin film was improved by the Pt nanoparticles, providing catalytically active sites for H₂ gas molecules. The interfering gas NH₃ affected the limit of detection (LOD) of a targeted H₂ gas in a real-world binary gas mixture. A plausible H₂ gas sensing mechanism involves catalytic effects of Pt particles and the formation of charge carriers in the PPy thin film. The flexible H₂ gas sensor exhibited a strong sensitivity that was greater than that of sensors that were made of Pd-MWCNTs at room temperature.     

H2 sensors using Fe2O3-based thin film

This paper describes the fabrication procedure as well as the sensing properties of new hydrogen sensors using Fe₂O₃-based thin film. The film is deposited by the r.f. sputtering technique; its composition is Fe₂O₃, TiO₂(5 mol%) and MgO(0–12 mol%). The conductance change of the film is examined in various test gases. The sensitivity to hydrogen gas is enhanced by treating the film in vacuum at 550 °C for 4 h and then in air at 700 °C for 2 h. The sputtered film is identified to be polycrystalline -Fe₂O₃ based on X-ray diffraction patterns. However, the surface layer is considered to be changed to Fe₃O₄ after heating in vacuum and then to γ-Fe₂O₃ after heating in air. The film is thus a multilayer one with a thin γ-Fe₂O₃ layer on a -Fe₂O₃ layer. The sensing mechanism is discussed based on measurements of the physical properties of the film, such as the temperature dependence of the sensor conductance, X-ray diffraction pattern, surface morphology, RBS (Rutherford back-scattering) spectrum and optical absorption spectrum.     

热蒸发石墨烯基SnOx-Sn传感器气敏性研究

通过化学气相沉积法制备石墨烯并采用热蒸发法在石墨烯上沉积锡(Sn)及其氧化物,得到石墨烯基SnOx-Sn气敏传感器,研究其在室温下对低体积分数甲醛和二氧化氮(NO2)气体的气敏性及SnOx-Sn膜厚和基底加热温度对传感器气敏性的影响.通过场发射扫描电镜(FESEM)、原子力显微镜(AFM)等表征手段研究了石墨烯基SnOx-Sn气敏传感器的形态结构.     

基于环形微热板的ZnO微气体传感器设计

提出一种新型的设有环形结构微热板的硅基ZnO微气体传感器。利用ANSYS软件,将环形电极结构与传统的蛇形结构进行温度分布的模拟仿真,发现该结构能供给传感器更高的温度且中心温度分布均匀,进而解决了现有传感器功耗大的缺点。通过对RF磁控溅射ZnO薄膜的工艺摸索,得出了适宜作气敏薄膜的制备参数。该传感器在250℃下对（200-1000）×10-6CH4气体有很好的响应。     

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.     

Characterization of ozone sensors based on WO3 reactively sputtered films: influence of O2 concentration in the sputtering gas, and working temperature

We report on electrical responses of tungsten oxide thin film ozone sensors based on a tungsten trioxide (WO₃)/tin oxide (SiO₂)/Si structure with interdigitated Pt electrodes. The influence of O₂ concentration in the sputtering gas and working temperature of the sensor are investigated. Sensitivity to ozone increases with O₂ content in the sputtering gas. It reaches its highest value for sensors fabricated with 50% O₂. For these sensors, the best ozone sensitivity and shortest response and recovery times are obtained at a working temperature of 523 K. Ozone sensitivity is compared to other ozone sensors.     

Low power highly sensitive platform for gas sensing application

This paper reports a low power miniaturized MEMS based integrated gas sensor with 36.84 % sensitivity (ΔR/R₀) for as low as 4 ppm (NH₃) gas concentration. Micro-heater based gas sensor device presented here consumes very low power (360 °C at 98 mW/mm²) with platinum (Pt) micro-heater. Low powered micro-heater is an essential component of the metal oxide based gas sensors which are portable and battery operated. These micro-heaters usually cover less than 5 % of the gas sensor chip area but they need to be thermally isolated from substrate, to reduce thermal losses. This paper elaborates on design aspects of micro fabricated low power gas sensor which includes ‘membrane design’ below the microheater; the ‘cavity-to-active area ratio’; effect of silicon thickness below the silicon dioxide membrane; etc. using FEM simulations and experimentation. The key issues pertaining to process modules like fragile wafer handling after bulk micro-machining; lift-off of platinum and sensing films for the realization of heater, inter-digitated-electrodes (IDE) and sensing film are dealt with in detail. Low power platinum microheater achieving 700 °C at 267 mW/mm² are fabricated. Temperature calculations are based on experimentally calculated thermal coefficient of resistance (TCR) and IR imaging. Temperature uniformity and localized heating is verified with infrared imaging. Reliability tests of the heater device show their ruggedness and repeatability. Stable heater temperature with standard deviation (σ) of 0.015 obtained during continuous powering for an hour. Cyclic ON–OFF test on the device indicate the ruggedness of the micro-heater. High sensitivity of the device for was observed for ammonia (NH₃), resulting in 40 % response for ~4 ppm gas concentration at 230 °C operating temperature.     

Design and optimization of heating plate for metal oxide semiconductor gas sensor

A thin film was coated onto the top of the heating electrodes to reduce the power consumption and improve the uniformity of temperature distribution. Finite element simulation software COMSOL was used to simulate the effect of coating materials and dependence of thicknesses of the coating film on the power consumption of the heating plate. On the basis of simulation, the temperature distribution of different heating plates was measured using infrared thermography. Experiments have showed that the power consumption of the heating plate can be significantly reduced and the temperature uniformity is promoted with adding the coating film on the top of the heating electrodes. The response of the gas sensor based on PdO-WO₃ nanoparticles was characterized with analyte of acetone. It was found that the addition of the coating film could enhance the response to acetone. In addition, the response speed of sensors was investigated with coating films and the results indicated that with the coating film sensor response speed became faster.

     

基于γ-Al_2O_3膜微加工煤油传感器研究

基于半导体式气体传感原理,提出了利用MEMS技术将电化学生长的Al2O3膜加工成微热板结构载体,采用平面薄膜工艺制做Pt薄膜加热电阻和信号电极。在微热板的2个电极上,涂敷γ-Fe2O3-SnO2-Pt-Pd形成煤油蒸气敏感单元,实现在微结构体上气体检测的二单元集成。传感器采用脉冲工作方式,工作周期为30 s,在加热峰值形成高温400℃的煤油检测条件。测试结果表明:煤油(标志物:癸烷)检测可实现体积分数(0～7000)×10-6范围,90%的吸附响应时间小于8s,脱附响应时间小于12s,传感器信号输出与煤油体积分数有对应的全对数线性关系。     

一种微型平面薄膜型酒敏器件的研制

粉末溅射有制靶简单、掺杂容易的特点,并有掺杂稳定的优点.利用反溅,发展了粉末溅射,制备了酒敏微型平面薄膜.对薄膜的相关特性进行了研究,给出了薄膜最佳掺杂范围、最佳灵敏度的膜厚以及响应时间与恢复时间随膜厚变化的规律,总结了最优参数.又测试了器件性能,通过实验对影响灵敏度测试的条件如测试电压和湿度影响灵敏度的规律进行了分析和讨论.结论认为,所研制的粉末溅射微型薄膜酒敏器件性能可靠、灵敏度高、稳定性好.     

A silicon-glass-based microfabricated wide range thermal distribution gas flow meter

Recently, there has been high demand on miniaturizations of bio-instruments and wide range gas flux measurement in the field of chemistry and mechanics. This paper presents the design, fabrication, and characterization of a silicon-glass-based thermal distribution gas flow meter (20 mm × 10 mm × 1.6 mm) with a wide detection range. To facilitate the fabrication and maintain the stability of the sensor, a platinum (Pt) thin film was adopted as the heater and thermometers. Both the thermal property and temperature sensitivity of Pt thin film were characterized. SiO₂ passivation layers were deposited on top of the Pt film to prevent thermal and electrical shift of sensitive elements. Three pairs of thermometers were constructed beside the heater. Sensitivity and gas flux range of the gas flow meter can be increased by alternate use of these three sensor pairs. We also introduced a specific hardware control circuit system for real-time gas flux monitoring through the connection with a computer interface. The proposed gas flow sensor device was capable of measuring gas flux within the range of 0.8-2800 ml/min, thus demonstrating the potential for a wide range of applications.     

Development of a novel piezoresistive thin film sensor system based on hydrogenated carbon

Thin film sensor systems based on hydrogenated carbon have the advantage to combine two very important characteristics in order to be used in measurement engineering: Firstly, the sensory layer demonstrates piezoresistive behavior and secondly its good properties related to hardness and wear resistance lead in a tribologically stable system. Therefore, the thin film sensor systems can be applied into the main distribution of force within machine parts or used for universal interchangeable sensor systems, e.g. sensory washers. In this article the deposition of a self-contained thin film sensor system on a large technical component (spindle shaft) is shown. The spindle shaft with a length of 480 mm and an outer diameter of 90 mm is part of a belt driven machining spindle for planing machines in woodworking industries. In order to establish a measurement system, which allows monitoring the clamping force of the tool holder and the imbalance of the mounted tool, the thin film sensor system was directly applied to the front surface of the spindle shaft. For this application a novel self-contained thin film sensor system was developed, which consists of an alumina layer for electrical isolation, a chromium layer to establish internal sensor electrodes, a piezoresistive hydrogenated carbon layer (1 μm) and a second covering wear resistance and insulation layer (silicon and oxygen modified carbon layer). The piezoresistive sensor layer and the top layer are part of the diamond like carbon layer family (Robertson, Diam Relat Mater 12:79–84, 2003; Bewilogua et al. DLC based coatings for tribological applications, pp. 67–75, 2006; Biehl et al. Thin Solid Films 515(3):1171–1175, 2006, Novel measurement and monitoring system for forming processes based on piezoresistive thin film systems. Springer Verlag, pp. 879–883, 2010).     

Liquid film thickness measurement underneath a gas slug with miniaturized sensor matrix in a microchannel

Measurement of liquid film thickness is essential for understanding the dynamics of two-phase flow in microchannels. In this work, a miniaturized sensor matrix with impedance measurement and MEMS technology to measure the thin liquid film underneath a bubble in the air–water flow in a horizontal microchannel has been developed. This miniaturized sensor matrix consists of 5 × 5 sensors where each sensor is comprised of a transmitter and a receiver electrode concentrically. The dimension and performance of the sensor electrodes were optimized with simulation results. The maximum diameter of the sensor ring is 310 µm, allowing a measurable range of liquid film thickness up to 83 µm. These sensors were distributed on the surface of a wafer with photolithography technology, covering a total length of 8 mm and a width of 2 mm. A spatial resolution of 0.5 × 2.0 mm² and a temporal resolution of 5 kHz were achieved for this sensor matrix with a measurement accuracy of 0.5 µm. A series of microchannels with different heights were used in the calibration in order to achieve the signal-to-thickness characteristics of each sensor. This delicate sensor matrix can provide detailed information on the variation of film thickness underneath gas–water slug directly, accurately and dynamically.     

High temperature stability of electrically conductive Pt–Rh/ZrO2 and Pt–Rh/HfO2 nanocomposite thin film electrodes

Nanocomposite films made up of either Pt–Rh/ZrO₂ or Pt–Rh/HfO₂ materials were co-deposited using multiple e-beam evaporation sources onto langasite (La₃Ga₅SiO₁₄) substrates, both as blanket films and as patterned interdigital transducer electrodes for surface acoustic wave sensor devices. The films and devices were tested after different thermal treatments in a tube furnace up to 1,200 °C. X-ray diffraction and electron microscopy results indicate that Pt–Rh/HfO₂ films are stabilized by the formation of monoclinic HfO₂ precipitates after high temperature exposure, which act as pinning sites to retard grain growth and prevent agglomeration of the conductive cubic Pt–Rh phase. The Pt–Rh/ZrO₂ films were found to be slightly less stable, and contain both tetragonal and monoclinic ZrO₂ precipitates that also helps prevent Pt–Rh agglomeration. Film conductivities were measured versus temperature for Pt–Rh/HfO₂ films on a variety of substrates, and it was concluded that La and/or Ga diffusion from the langasite substrate into the nanocomposite films is detrimental to film stability. An Al₂O₃ diffusion barrier grown on langasite using atomic layer deposition was found to be more effective than a SiAlON barrier layer in minimizing interdiffusion between the nanocomposite film and the langasite crystal at temperatures above 1,000 °C.     

AlN陶瓷微热板MEMS传感器阵列设计与工艺实现

针对陶瓷基微热板MEMS器件难以微加工,器件表面加热Pt膜使用普通正性光刻胶难以实现光刻剥离的工艺难点问题,提出了激光微加工和柔性机械剥离相结合的微加工方法。以AlN陶瓷为衬底基片,采用激光微加工技术实现热隔离刻蚀体加工,刻蚀梁宽可达0.2 mm。采用柔性机械剥离工艺制备方法解决普通正性光刻胶形成倒梯形凹槽Pt膜难实现图形化问题,可在复杂表面特性的陶瓷基衬底上实现Pt膜剥离线宽10μm。同时利用有限元法进行传感器阵列设计和热结构仿真,验证设计工艺的可行性。