Hydrogen gas sensing properties of Pt/Ta2O5 Schottky diodes based on Si and SiC substrates

We developed Pt/tantalum oxide (Ta₂O₅) Schottky diodes for hydrogen sensing applications. Thin layer (4 nm) of Ta₂O₅ was deposited on silicon (Si) and silicon carbide (SiC) substrates using the radio frequency sputtering technique. We compared the performance of these sensors at different temperatures of 100 °C and 150 °C. At these operating temperatures, the sensor based on SiC exhibited a larger sensitivity, whilst the sensor based on Si exhibited a faster response toward hydrogen gas. We discussed herein, the experimental results obtained for these Pt/Ta₂O₅ based Schottky diodes exhibited that they are promising candidates for hydrogen sensing applications.     

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.

     

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.     

SnO2-based R134a gas sensor: Sensing materials preparation, gas response and sensing mechanism

Undoped SnO₂ and porous Al₂O₃ powders were obtained through a simple chemical precipitation process. SnO₂-based gas sensing materials and Al₂O₃ catalytic coating loaded with a noble metal were prepared by impregnation. The SnO₂ and Al₂O₃ powders were characterized by TEM, SEM, nitrogen adsorption-desorption experiment, FT-IR and in situ XRD. Gas responses of the SnO₂-based gas sensors were measured in a static state. The experimental results indicated that the response towards R134a of the SnO₂-based gas sensor can be significantly enhanced by loading noble metal and using catalytic coating. The sensor based on a double layer film SnO₂ (Au)/Al₂O₃ (Au) showed satisfactory results including large response, good selectivity, high long-term stability, fast response and recovery, revealing its potential application in the detection of refrigerants and the maintenance of air condition systems. Finally, a gas sensing mechanism for R134a is suggested and proved by bond energy data, FT-IR spectrum and in situ XRD.     

Enhanced H2S sensing characteristics of Pt doped SnO2 nanofibers sensors with micro heater

Gas sensors were designed and fabricated using oxide nanofibers as the sensing materials on micro platforms using micromachining technology. Pure and Pt doped SnO₂ nanofibers were prepared by electrospinning and their H₂S gas sensing characteristics were subsequently investigated. The sensing temperatures of 300 and 500 °C could be attained at the heater powers of 36 and 94 mW, respectively, and the sensors showed high and fast responses to H₂S. The responses of 0.08 wt% Pt doped SnO₂ nanofibers to 4-20 ppm H₂S, were 25.9-40.6 times higher than those of pure SnO₂ nanofibers. The gas sensing characteristics were discussed in relation to the catalytic promotion effect of Pt, nano-scale morphology of electrospun nanofibers, and sensor platform using micro heater.     

Modification of the oxygen diffusivity in limiting current oxygen sensors

Effect of sacrificial carbon on microstructure of protective layer and sensing properties of limiting current oxygen sensors were studied. Graphite and carbon nanofiber with different concentrations were examined as sacrificial layer. Therefore, several YSZ-based electrochemical gas sensors were fabricated with dissimilarity in the diffusivity of the layer covering their measuring electrodes.Gas sensors were tested as potentiometric and amperometric devices under O₂-N₂ mixtures, and synthetic gases similar to the exhaust gas mixtures from combustion engines. Sensors with low diffusivity (low concentration of sacrificial material) exhibit more abrupt and O₂-sensitive potentiometric responses. Indeed, less O₂-linear amperometric responses and higher response times are their characteristics. Sensors with high diffusion in their layers (high concentration of sacrificial material) show a less abrupt step-drop potentiometric response but a more linear O₂ dependence for the amperometric response and, in general, lower response times.Results suggest that the configuration of the diffusive layer shall be controlled in terms of the expected performance of the sensor, as an amperometric or potentiometric device. The controlling parameters are discussed and given in this study.     

Formaldehyde sensing properties of electrospun NiO-doped SnO2 nanofibers

Formaldehyde is a kind of hazardous gases dangerous to human health. Hence, gas sensor is an essential device to monitor formaldehyde in air, especially in indoor ambient. Semiconductor metal oxides are studied as gas-sensing material to detect most of key gases for decade years. For the purpose of actual application and meeting a variety of conditions, diverse additives added into host material are expected to improve the performance of gas sensors. The formaldehyde gas-sensing characteristics of undoped and NiO-doped SnO₂ (NSO) nanofibers synthesized via a simple electrospinning method were investigated in this study. It is noticed that the addition of NiO causes the distortion at the surface of SnO₂ nanofibers, which is responsible to adjust activation energy, grain sizes and chemical states of host material. The sensors fabricated from NSO nanofibers exhibited good formaldehyde sensing properties at operating temperature 200 °C, and the minimum-detection-limit was down to 0.08 ppm. The response time and recovery time of the sensors were about 50 s and 80 s to 10 ppm formaldehyde, respectively. The sensor shows a good long-term stability in 90 days. The simple preparation and excellent properties significantly advance the viability of electrospun nanofibers as gas sensing materials. The sensing mechanisms of NSO nanofibers to formaldehyde were discussed. The results indicated that NSO nanofibers could be used as a candidate to fabricate formaldehyde sensors in practice.     

New gas sensitive MIS structures Pt/Al2O3(M = Pt, Rh)/Si with a granular dielectric layer

New gas sensitive MIS structures Pt/Al₂O₃(M)/p-Si, where M = Pt, Rh, with granular dielectric Al₂O₃ layers doped with noble metals were obtained by an aerosol pyrolysis method. Surface morphology and composition of the structures were studied by TEM, AFM and EPMA. Sensor properties of the MIS structures were studied towards reducing gases (1000 ppm H₂, 300 ppm CO, 1000 ppm CH₄ in air) at 100 and 200 °C. The Pt/Al₂O₃(M = Pt, Rh)/Si structures showed a very high sensor response to reducing gases. A shift of C–V characteristics was up to 2.5 V under CO, 2.2 V under hydrogen and 0.7 V under methane. High values of shift of C–V curves can be related with cooperative influence of a change of surface state density in dielectric layer, reduction of platinum electrode and dipole layer formation.     

The influence of catalytic activity on the response of Pt/SnO2 gas sensors to carbon monoxide and hydrogen

The article presents the results of research studies on ceramics SnO₂ sensors with Pt catalysts. The role of catalysis in gas sensing mechanisms was investigated. In order to obtain samples with different catalytic activity but with identical Pt loading, the Pt/SnO₂ catalysts were calcined at different temperatures (400-800 °C). Structural analysis of these samples was performed. Among the sensors manufactured with Pt/SnO₂, the highest sensitivity was shown for the sensor obtained with Pt/SnO₂ sample sintered at 800 °C. The correlation between catalytic activity and sensor sensitivity is given.     

Fabrication of micro sensors on a flexible substrate

Flexible micro temperature and humidity sensors on parylene thin films were designed and fabricated using a micro-electro-mechanical-systems (MEMS) process. Based on the principles of the thermistor and the ability of a polymer to absorb moisture, the sensing device comprised gold wire and polyimide film. The flexible micro sensors were patterned between two pieces of parylene thin film that had been etched using O₂ plasma to open the contact pads. The sacrificial Cr spacer layer was removed from the Cr etchant to release the flexible temperature and humidity sensors from the silicon substrate. Au was used to form the sensing electrode of the sensors while Ti formed the adhesion layer between the parylene and Au. The thickness of the device was 7 ± 1 μm, so the sensors attached easily to highly curved surfaces. The sensitivities of the temperature and humidity sensor were 4.81 × 10⁻³ °C⁻¹ and 0.03 pF/%RH, respectively. This work demonstrates the feasibility and compatibility of thin film sensor applications based on flexible parylene. The sensor can be applied to fuel cells or components that must be compressed.     

Thin film SnO2-based gas sensors: Film thickness influence

The influence of the thickness of SnO₂ films deposited by a spray pyrolysis method on the operating characteristics of gas sensors is analyzed in this paper. It outlines how the thickness of metal oxides is an important parameter for gas sensors in determining the main operating parameters, such as the magnitude and rate of the sensor response and the optimal operating temperature. It is also shown that the optimal film thickness of a gas sensing layer depends on the required sensor parameters.     

Nano- and microsized metal oxide thin film gas sensors

Functional micro- and nanosized metal oxide thin film structures are very promising candidate for future gas-sensors. Their reduced size offers an increased surface to volume ratio thus improving sensitivity and sensor performance. Whilst most experimental nanostructures are produced using a bottom-up approach, a top-down sputtering technique for structuring nano-sized gas sensitive metal oxide areas is presented in this letter. Oxidised silicon wafers were used as substrates. The silicon dioxide film of 1 μm thickness was prepared by thermal oxidation in order to insulate the gas sensing elements from the substrate. The sensor chips had an overall size of (1.5 × 1.5) mm² onto which a Ta/Pt film (20/200 nm thickness) was deposited and patterned to act as electrodes, heater and temperature sensor. In a second step micro-scaled tin dioxide layers (60 nm thick, 5 μm width) were deposited by sputtering techniques and photolithographical patterning between the platinum micro-electrodes (4 μm gap). Finally, the width of the stripes was reduced using focused ion beam technology to obtain the desired size and structure. This enables the control of the dimensions of the structures down to the resolution limit of the FIB-system which is about 10 nm. The structural and electrical characterisation of the sensors and their responses during exposure to several test gases including O₂, CO, NO₂ and H₂O are presented as well.     

Device characteristics for Pt–Ti–O gate Si–MISFETs hydrogen gas sensors

A novel Pt–Ti–O-gate Si–metal–insulator–semiconductor field-effect transistor (MISFET) hydrogen gas sensor has been proposed by Usagawa and Kikuchi (2010) [1]. The sensors consist of unique gate structures composed of Ti and oxygen accumulated regions around Pt grains on top of a novel mixing layer of nanocrystalline TiO_x and superheavily oxygen-doped amorphous Ti formed on SiO₂/Si substrates. The optimum Pt/Ti thickness and annealing conditions for most hydrogen safety monitoring sensor systems are obtained by annealing Pt(15 nm)/Ti(5 nm)-gate Si–MOS structures in air around 400 °C for 2 h. One of the advantages of the Pt–Ti–O-gate Si–MISFETs after 10 min of air-diluted 1000-ppm hydrogen exposure at 115 °C are reproducible and uniform threshold voltage of V_th in addition to large sensing amplitudes at a practically important hydrogen concentration range between 100 ppm and 1%. The analysis of device characteristics of the Pt–Ti–O-gate Si–MISFETs hydrogen sensors concludes that the oxidation process of the Ti layer is consistently explained by an oxidation model that the oxygen invasion into Ti layer comes from open air through Pt grain boundaries and at the same time Ti will evacuate into the Pt surface through Pt grain boundaries. During the course of this process, the invading oxygen will be balanced with the evacuating Ti so that the Ti layer keeps nearly the same thickness with the as grown states. Ti and oxygen will remains around Pt grains named Ti and oxygen merged corridors.     

Piezo-tunneling strain sensors integrated on plastic by combining vacuum thin film coatings and 3D printing technologies

There is a growing demand for the integration of sensor functions on flexible substrates for wearable electronics, robotics or medical monitoring. For this, it is necessary to develop strain gauges both sensitive and integrable at low cost with a low thermal budget. The gauge factor of metal/insulator/metal piezo-tunneling strain sensors is first measured as a function of applied current and polarity, for different electrode materials (Al, Pt or Pd) and insulator (Al₂O₃) thicknesses. A maximum gauge factor of 90 is obtained with an Al/Al₂O₃ (10 nm)/Al junction and top electrode injection. Results are discussed based on the Fowler–Nordheim model and it is shown that the electron effective mass in Al₂O₃ most likely plays a major role in the observed mechano-sensitivity. Next, the feasibility of a low-pressure sensor demonstrator based on a 3D-printing process on a polymer substrate is shown with a sensitivity of 0.19 bar⁻¹ in the 0–450 mbar range.

     

Fabrication at wafer level of miniaturized gas sensors based on SnO2 nanorods deposited by PECVD and gas sensing characteristics

SnO₂ nanorods were successfully deposited on 3″ Si/SiO₂ wafers by inductively coupled plasma-enhanced chemical vapour deposition (PECVD) and a wafer-level patterning of nanorods layer for miniaturized solid state gas sensor fabrication were performed. Uniform needle-shaped SnO₂ nanorods in situ grown were obtained under catalyst- and high temperature treatment-free growth condition. These nanorods have an average diameter between 5 and 15 nm and a length of 160-300 nm. The SnO₂-nanorods based gas sensors were tested towards NH₃ and CH₃OH and gas sensing tests show remarkable response, showing promising and repeatable results compared with the SnO₂ thin films gas sensors.     

Love wave hydrogen sensors based on ZnO nanorod film/36°YX-LiTaO3 substrate structures operated at room temperature

Love wave hydrogen sensors based on ZnO nanorod layers deposited on 36°YX-LiTaO₃ substrates have been studied. The ZnO nanorod layers are prepared by two steps: first, the seed layers, as well the guiding layers of the Love wave devices, are deposited by RF magnetron sputtering; second, the nanostructural layers, as well the sensing layers of the sensors, are grown by hydrothermal synthesis. Two kinds of ZnO layers have been analyzed by XRD, SEM and XPS. The XRD shows that both ZnO layers have (0 0 2) oriented wurtzite structures. The SEM results reveal that the morphologies of the deposited ZnO seed layers are continuous and compact, while the hydrothermal treated layers are with nanorods almost perpendicular to the substrate surfaces. Finally, the hydrogen sensing responses of the Love wave sensors activated by Pt catalysts are measured for various concentrations of hydrogen in synthetic air at room temperature. The results show that the sensors have high sensitivity and repeatability as the nanorod layers are optimized, such as the frequency shift 8 kHz toward 0.04% of H₂ in synthetic air is obtained while the height of the nanorod layer is about 2.1 μm and the central frequency of the sensor is about 125.5 MHz. The XPS analyses of the sensitive layers show that there are oxygen vacancies in the layers, so the oxygen vacancy model is used to explain the hydrogen sensing mechanism of the Love wave 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.     

A compact tri‐band microwave resonator for ethanol gas detection

This article presents the design, simulation, fabrication, and testing of a compact two‐port microwave resonator coated with nanomaterials for ethanol gas sensing applications. The proposed gas sensor consists of a transmission line loaded with three triangular split ring resonators for ethanol detection at three frequency bands viz. 2.2, 4.6, and 6.3 GHz. The transmission line has all‐pass characteristics in which band gaps are introduced using three split ring resonators. The TiO₂ and ZnO nanorods are used as sensitive layers for the proposed sensing application. The nanorods, which are grown on a glass substrate of thickness 1 mm, are loaded on to the two‐port microwave resonator making the device sensitive to ethanol. The microwave behavior of the sensor is analyzed using the scattering parameters. The absorption of the ethanol gas causes frequency detuning which is used to analyze the presence of ethanol and its concentration. From the experiments, it is understood that there is an increase in the frequency shift with an increase in the concentration of ethanol gas. The sensing device with ZnO as a sensitive layer showed a higher average sensitivity of 2.35 compared to TiO₂ whose average sensitivity is 1.29.     

Nanostructured spinel ZnCo2O4 for the detection of LPG

Nanostrucutred spinel ZnCo₂O₄ (∼26-30 nm) was synthesized by calcining the mixed precursor (consisting of cobalt hydroxyl carbonate and zinc hydroxyl carbonate) in air at 600 °C for 5 h. The mixed precursor was prepared through a low cost and simple co-precipitation/digestion method. The transformation of the mixed precursor into nanostructured spinel ZnCo₂O₄ upon calcinations was confirmed by X-ray diffraction (XRD) measurement, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HRTEM). To demonstrate the potential applicability of ZnCo₂O₄ spinel in the fabrication of gas sensors, its LPG sensing characteristics were systematically investigated. The ZnCo₂O₄ spinel exhibited outstanding gas sensing characteristics such as, higher gas response (∼72-50 ppm LPG gas at 350 °C), response time (∼85-90 s), recovery time (∼75-80 s), excellent repeatability, good selectivity and relatively lower operating temperature (∼350 °C). The experimental results demonstrated that the nanostructured spinel ZnCo₂O₄ is a very promising material for the fabrication of LPG sensors with good sensing characteristics. Plausible LPG sensing mechanism is also discussed.     

Optimization of a wafer-level process for the fabrication of highly reproducible thin-film MOX sensors

Thin-film metal oxide semiconductor (MOX) gas sensors are characterized by high sensitivity and fast response. Those characteristics make them very promising among the several existing technologies for the production of solid state gas sensors. Furthermore, by means of silicon micro-machining technology, MOX sensors can be made on micro hotplates, allowing to reach very low-power consumption, and the batch production guaranties a high yield. However, reproducibility and reliability are still major issues preventing the use of thin-film MOX sensors in mass-market applications.

In this work, a wafer-level fabrication process for micro-machined low-power consumption thin-film MOX sensor arrays is reported. Different solutions for the optimization of the fabrication process are investigated, aiming to increase the reproducibility. The critical technological steps related to signal generation and acquisition, like the thin-film definition and positioning and the definition of the sensing layer electrodes, have been optimized. The devices considered are 4-sensor arrays based on thin films of SnO₂ deposited by a modified rheotaxial growth and thermal oxidation (M-RGTO) technique on micro-machined low-power hotplates.

The different fabrication techniques are described in detail. 45 sensors from 3 wafers, made using the different fabrication techniques, are comparatively characterized. The spread of the main sensor functional parameters values shows an evident decrease when the optimized fabrication process is used.