Design and characterization of a humidity sensor realized in LTCC-technology

A new type of integrated temperature and humidity sensor applying Low Temperature Cofired Ceramics technology (LTCC) has been developed and characterized. The proposed device is based on the detection of the difference of thermal conductivity between water vapor and dry air. In this approach, sensing elements are implemented using heated metal film resistors (Pt-elements), where one is exposed to the humid environment that causes the sensor element to cool down with increased humidity, while the other one is sealed from the environment. LTCC-tapes are used for the formation of caps as well are acting as substrate. Sensor design is based on finite element analyses (FEA) where the critical design parameters have been analyzed with regard to the performance characteristic of the device.     

Zeolite based trace humidity sensor for high temperature applications in hydrogen atmosphere

We present a humidity sensor based on H-ZSM-5 type zeolite that is suitable to detect traces of humidity (10–110 ppm_V) under harsh conditions, e.g. reducing atmosphere (H₂) and high temperature (up to 600 °C). By means of complex impedance spectroscopy (IS) we show that the zeolite sensor responds linearly towards minimal changes in humidity. Therefore this result indicates that the zeolite sensor is capable to detect traces of humidity in processes where high temperatures in a hydrogen environment are required.     

Flexible humidity sensor in a sandwich configuration with a hydrophilic porous membrane

We constructed a wearable and flexible humidity sensor (thickness: 80 μm) in a sandwich configuration, with a hydrophilic poly-tetrafluoroethylene membrane placed between two gold deposited layers, using soft-MEMS techniques. The device was used to measure humidity level, via its electrical conductivity, using a multi-frequency LCR-meter at frequencies ranging from 100 Hz to 100 kHz. The device was calibrated at 100 Hz against moist air over the range of 30–85% RH, which includes normal humidity levels in the atmosphere and physiological air such as breath and evaporating sweat. The response sensitivity of the humidity device was extremely high, even for recovery to dry air; for example response time was less than 1 s for a conductivity shift between humid air of 80% RH and dry air of −60 °C dew point. The sensor performance was reproducible over multiple measurements, with a coefficient of variation of 1.77% (n = 5). The sensor was appropriate for physiological applications, and was successfully used in two non-invasive approaches: to monitor breath air at the mouth, and to measure sweat moisture from the nostrils.     

Influence of humidity on CO sensing with p-type CuO thick film gas sensors

A model for the detection of CO in the presence of humidity is proposed for thick porous film gas sensors based on p-type CuO. The sensing mechanism is investigated by means of simultaneous DC electrical resistance and work function changes measurements combined with appropriate modeling of the conduction in the polycrystalline sensing film. The experiments were performed at 150 °C in dry and humid air backgrounds. The conclusion is that, very similarly to the case of undoped SnO₂, the explanation of the cross-interference of water in the CO detection is the fact that both react with pre-adsorbed oxygen ions.     

Fiber optic humidity sensors for high-energy physics applications at CERN

This work is devoted to a feasibility analysis for the development of novel fiber optic humidity sensors to be applied in high-energy physics (HEP) applications and in particular in experiments actually running at the European Organization for Nuclear Research (CERN). On this line of argument and due to the wide investigations carried out in the last years aimed to assess the radiation hardness capability of fiber optic technology in high energy physics environments, our multidisciplinary research group has been recently engaged in the development of near-field fiber optic sensors based on particle layers of tin dioxide to perform the monitoring of low values of relative humidity RH even at low temperatures.While this sensor type has been successfully employed for ppm and sub-ppm chemical detection in air and water environments, it is the first reported use for relative humidity measurements.The RH sensing performance of fabricated probes was analyzed during a deep experimental campaign carried out in the laboratories of CERN, in Genève. A very good agreement was observed between humidity measurements provided by the optical fiber sensors and commercial polymer-based hygrometers at 20 °C and 0 °C, with limits of detection for low RH regimes below 0.1%.     

Enhancing performance of FSP SnO2-based gas sensors through Sb-doping and Pd-functionalization

Via flame spray pyrolysis (FSP), SnO₂ gas sensing layers have been doped with 0.01-4 wt% Sb as well as 0.01 wt% Pd in combination with 1 wt% Sb. Characterization of these materials through X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface analysis, and transmission electron microscopy (TEM) revealed particle grain sizes and crystallinity unchanged by the presence of Sb and/or Pd. The addition of Sb to SnO₂ resulted in the significant decrease in baseline resistance; up to two orders of magnitude in dry air at 300 °C and three orders of magnitude in humid air at 300 °C, which is significant for FSP-prepared gas sensors with high porosity and low particle coordination number since they typically suffer from high baseline resistance. While the baseline resistance was improved with Sb-doping, the sensor signal (R₀/R_gas) remained constant over all concentrations explored. Moreover, regarding the surface functionalization of SnO₂ with Pd in combination with Sb-doping, the reduction of baseline resistance was preserved without influencing sensor signal.     

Gas sensors based on anodic tungsten oxide

Nanostructured porous tungsten oxide materials were synthesized by the means of electrochemical etching (anodization) of tungsten foils in aqueous NaF electrolyte. Formation of the sub-micrometer size mesoporous particles has been achieved by infiltrating the pores with water. The obtained colloidal anodic tungsten oxide dispersions have been used to fabricate resistive WO₃ gas sensors by drop casting the sub-micrometer size mesoporous particles between Pt electrodes on Si/SiO₂ substrate followed by calcination at 400 °C in air for 2 h. The synthesized WO₃ films show slightly nonlinear current-voltage characteristics with strong thermally activated carrier transport behavior measured at temperatures between −20 °C and 280 °C. Gas response measurements carried out in CO, H₂, NO and O₂ analytes (concentration from 1 to 640 ppm) in air as well as in Ar buffers (O₂ only in Ar) exhibited a rapid change of sensor conductance for each gas and showed pronounced response towards H₂ and NO in Ar and air, respectively. The response of the sensors was dependent on temperature and yielded highest values between 170 °C and 220 °C.     

Effect of La2CuO4 electrode area on potentiometric NOx sensor response and its implications on sensing mechanism

The intent of this work is to look at the effects of varying the La₂CuO₄ electrode area and the asymmetry between the sensing and counter electrode in a solid state potentiometric sensor with respect to NO_x sensitivity. NO₂ sensitivity was observed at 500-600 °C with a maximum sensitivity of ∼22 mV/decade [NO₂] observed at 500 °C for the sensor with a La₂CuO₄ electrode area of ∼30 mm². The relationship between NO₂ sensitivity and area is nearly parabolic at 500 °C, decreases linearly with increasing electrode area at 600 °C, and was a mixture of parabolic and linear behavior 550 °C. NO sensitivity varied non-linearly with electrode area with a minima (maximum sensitivity) of ∼−22 mV/decade [NO] at 450 °C for the sensor with a La₂CuO₄ electrode area of 16 mm². The behavior at 400 °C was similar to that of 450 °C, but with smaller sensitivities due to a saturation effect. At 500 °C, NO sensitivity decreases linearly with area.We also used electrochemical impedance spectroscopy (EIS) to investigate the electrochemical processes that are affected when the sensing electrode area is changed. Changes in impedance with exposure to NO_x were attributed to either changes in La₂CuO₄ conductivity due to gas adsorption (high frequency impedance) or electrocatalysis occurring at the electrode/electrolyte interface (total electrode impedance). NO₂ caused a decrease in high frequency impedance while NO caused an increase. In contrast, NO₂ and NO both caused a decrease in the total electrode impedance. The effect of area on both the potentiometric and impedance responses show relationships that can be explained through the mechanistic contributions included in differential electrode equilibria.     

Ceria-doped SnO2 sensor highly selective to ethanol in humid air

In our earlier study, we reported that at 300 °C, a 2.0 wt.% CeO₂-doped SnO₂ sensor is highly selective to ethanol in the presence of CO and CH₄ gases [F. Pourfayaz, A. Khodadadi, Y. Mortazavi, S.S. Mohajerzadeh, CeO₂ doped SnO₂ sensor selective to ethanol in presence of CO, LPG and CH₄, Sens. Actuators B 108 (2005) 172–176]. In the present investigation, we report the influence of ambient air humidity on the ethanol selective SnO₂ sensor doped with 2.0 wt.% CeO₂. Maximum response to ethanol occurs at 300 °C which decreases with the relative humidity. The relative humidity was changed from 0 to 80% for different ambient air temperatures of 30, 40 and 50 °C and the response of the sensor was monitored in a 250–450 °C temperature range. As the relative humidity in 50 °C air increased from 0 to 30%, a 15% reduction in the maximum response to ethanol was observed. A further increase in the relative humidity no longer reduced the response significantly. The presence of humidity improved the sensor response to both CO and CH₄ up to 350 °C after which the extent of improvement became smaller and at 450 °C was almost diminished. The sensor is shown to be quite selective to ethanol in the presence of humid air containing CO and CH₄. The selectivity passes a maximum at 300 °C; however it declines at higher operating temperatures.     

Facile synthesis of hierarchical SnO2 semiconductor microspheres for gas sensor application

Hierarchical SnO₂ microspheres were synthesized by a hydrothermal method at 140 °C using stannic chloride hydrate and sodium hydroxide as starting materials. The individual hierarchical SnO₂ microsphere ranged from 700 to 900 nm in diameter. After these microspheres were heated at 600 °C for 2 h, the spheres were cross-linked into clusters by short SnO₂ nanorods as revealed by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Most importantly, SnO₂ hierarchical microsphere sensor exhibits excellent selectivity and fast response to ethanol. Response and recovery times were 0.6 s and 11 s when the sensor was exposed to 50 ppm ethanol at an operating temperature of 300 °C. Thus, hierarchical structures play a significant role in the field of gas sensing.     

Pulsed laser deposited Y-doped BaZrO3 thin films for high temperature humidity sensors

Pulsed laser deposited (PLD) Y-doped BaZrO₃ thin films (BaZr_1-xY_xO_3-y/2, x = 0.2, y > 0), were investigated as to their viability for reliable humidity microsensors with long-term stability at high operating temperatures (T > 500 °C) as required for in situ point of source emissions control as used in power plant combustion processes. Defect chemistry based models and initial experimental results in recent humidity sensor literature [1] and [2]. indicate that bulk Y-doped BaZrO₃ could be suitable for use in highly selective, high temperature compatible humidity sensors. In order to accomplish faster response and leverage low cost batch microfabrication technologies we have developed thin film deposition processes, characterized layer properties, fabricated and tested high temperature humidity micro sensors using these thin films. Previously published results on sputtering Y-doped BaZrO₃ thin films have confirmed the principle validity of our approach [3]. However, the difficulty in controlling the stoichiometry of the films and their electrical properties as well as mud flat cracking of the films occurring either at films thicker than 400 nm or at annealing temperature above 800 °C have rendered sputtering a difficult process for the fabrication of reproducible and reliable thin film high temperature humidity microsensors, leading to the evaluation of PLD as alternative deposition method for these films.X-ray Photoelectron Spectroscopy (XPS) data was collected from as deposited samples at the sample surface as well as after 4 min of Ar⁺ etching. PLD samples were close to the desired stoichiometry. X-ray diffraction (XRD) spectra from all as deposited BaZrO₃:Y films show that the material is polycrystalline when deposited at substrate temperatures of 800 °C. AFM results revealed that PLD samples have a particle size between 32 nm and 72 nm and root mean square (RMS) roughness between 0.2 nm and 1.2 nm. The film conductivity increases as a function of temperature (from 200 °C to 650 °C) and upon exposure to a humid atmosphere, supporting our hypothesis of a proton conduction based conduction and sensing mechanism. Humidity measurements are presented for 200–500 nm thick films from 500 °C to 650 °C at vapor pressures of between 0.05 and 0.5 atm, with 0.03–2% error in repeatability and 1.2–15.7% error in hysteresis during cycling for over 2 h. Sensitivities of up to 7.5 atm⁻¹ for 200 nm thick PLD samples at 0.058 atm partial pressure of water were measured.     

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.     

Sensing of CO2 at room temperature using work function readout of (hetero-)polysiloxanes sensing layers

Organically modified silicates based on primary amino groups are known to be CO₂ sensitive, as they can undergo a reversible acid base reaction. In order to generate detectable CO₂ signals and to limit the cross-sensitivity to humidity, some sources suggest that these materials should be operated at higher temperatures (50-70 °C). In this paper, a new variant of CO₂ sensing is to be presented, namely a combination of work function readout and organically modified silicates, which yields CO₂ detection even at room temperature. Kelvin probe measurements are used for work function readout. The layers are intended to be used in a “Floating Gate Field Effect Transistors” (FGFETs) sensing platform (mySens) by Micronas. The reversible interaction of CO₂ with spin-coated heteropolysiloxane sensitive layers results in changes of the work function with typical signal heights of 15-20 mV (change from 400 to 4000 ppm CO₂) and response times of only a few minutes. Also, results will be presented regarding variations in the chemical nature of the films. The findings summarized in this paper point towards the possibility of a new room temperature CO₂ sensor, which comprises fast response times and sufficient sensitivity for ambient CO₂ variations.     

A novel thick-film ceramic humidity sensor

The paper describes the results of studies on the fabrication and characterisation of a thick-film humidity sensor based on the semiconducting metal oxide MnWO₄. The sensor element possesses a novel ‘sandwich’-configuration with a 40 μm porous MnWO₄ ceramic layer sandwiched by two 10 μm polarity-reversed, interdigitated metal films. Instead of traditional glass frits, LiCl powders are used as adhesion promoters for sintering the sensor paste. With this method, MnWO₄ powders with an average particle size of 3.0 μm are sintered at the standard thick-film firing temperature of 850°C. The sintered ceramic layer exhibits a porous structure. The novel electrode arrangement combines the advantages of humidity sensors in the form of a parallel capacitor with those in the form of an interdigital capacitor, permitting a high sensitivity and a fast response. The influence of temperature on the sensor characteristics has been compensated for by integrating a thick-film NTC resistor. The humidity sensor shows no cross-sensitivity to organic vapour. The organic contamination on the sensor surface can be burned out by heating the sensor element at about 400°C with the refresh heater printed on the back side of the substrate.     

Gas sensing properties of nanostructured bismuth oxychloride

In this work, nanostructured bismuth oxychloride (BiOCl) was prepared by a surfactant-assisted method. Bismuth trichloride and dioctyl sulfosuccinate (AOT) were dissolved in non-aqueous media, producing a fine precipitate. The calcination of the precipitated particles at 180 °C produced 3D hierarchical BiOCl semi-spherical architectures, assembled by microplates. The increase of the calcination temperature to 600 °C produced nanostructured ribbons, which are formed by the stacking of several BiOCl layers. Other microstructures can be formed at different calcination temperatures or by using other surfactants. Thick-films of the as-prepared BiOCl ribbons were made by its direct deposition on alumina substrates. The gas sensing characterization was performed at 300 and 400 °C using alternating current (AC). The tests gases were compressed air, CO, CO₂ and O₂. Humidity effects were discarded by using the extra dry version of these gases. At 300 °C, reproducible CO gas sensing patterns were obtained; however, the detection of CO₂ and O₂ produced unreliable results. At 400 °C, reliable gas sensing patterns were obtained in CO, CO₂ and O₂. According to its gas response, BiOCl behaved as a p-type seminconductor material.     

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.     

Ammonia identification using shear horizontal surface acoustic wave sensor and quantum neural network model

The ammonia detection at room temperature employing a shear horizontal surface acoustic wave (SH-SAW) sensor coated with polyaniline (PANI) film and the recognition of ammonia concentrations in humid environments based on quantum neural network (QNN) have been investigated in this study. Studies were performed in the ranges of 0–67.5% relative humidity and 15–72 ppm ammonia. The frequency shift of SH-SAW was measured to detect the presence of ammonia. The SH-SAW sensor in this study responded to the ammonia gas and could be recovered using dry nitrogen. Detecting at an ammonia concentration of 40.91 ppm in dry environment, the frequency shift was 0.75 ppm and the noise level was 0.08 ppm. In humid environment, the frequency shift increased as the humidity increased. In order to recognize the ammonia in humid environment, the QNN was used as the identifier. From the performance results shown, the neural model we proposed can effectively perform the identification of ammonia in a common ambience and overcome the inference of humidity caused.     

High-performance liquefied petroleum gas sensing based on nanostructures of zinc oxide and zinc stannate

Toxic and combustible gas detection plays a major role in environmental air quality monitoring. Real-time monitoring of hazardous gases and signal of accidental leakages is of great importance owing to the concern for safety requirements in industries and household applications. A simple and economical method for the fabrication of highly sensitive zinc oxide (ZnO) nanorods based gas sensors for detecting low concentrations of Liquefied Petroleum Gas (LPG) was studied in this work. Platinum (Pt) nanoparticles were deposited on the sensing medium which acts as catalysts to improve the sensor performance. The change in electrical resistance of the metal oxide semiconductor for varying concentrations of LPG was measured. Maximum response of 59% was achieved for 9000 ppm LPG at 250 °C. Further to improve the sensing performance of the sensor towards LPG, surface modification of ZnO nanorods using zinc stannate (Zn₂SnO₄) microcubes was performed. High response of 63% was observed for 3000 ppm LPG at 250 °C. Significant improvement in response of the sensor with Zn₂SnO₄ microcubes on ZnO nanorods was observed when compared to sensor with ZnO nanorods.     

Interaction of CO with hydrous ruthenium oxide and development of a chemoresistive ambient CO sensor

Hydrated ruthenium oxide (RuO_x(OH)_y), the material of interest in this study was prepared by reaction of an aqueous solution of ruthenium chloride with base. This material was amorphous, made up of 20-50 nm particles and contains Ru(III) and Ru(IV), as determined by X-ray photoelectron spectroscopy. The conductivity of thick films of RuO_x(OH)_y decreased in the presence of CO in a background of air and this change was reversible. Infrared spectroscopy showed the formation of carbonates in the presence of CO, which disappeared upon replacement of CO with O₂. Upon heating RuO_x(OH)_y, there was a gradual conversion to crystalline RuO₂ beyond 200 °C. With these heated materials, the resistance change in the presence of CO at room temperature also gradually diminished. We propose that oxidation of CO on RuO_x(OH)_y leads to reduction of the ruthenium and a decrease in conductivity. With the conversion to crystalline RuO₂ upon heating, the material becomes metallic and conductivity changes are diminished. The change in conductivity of RuO_x(OH)_y with CO provides a convenient platform for an ambient CO sensor. Such a device also does not show interference from hydrocarbons (2000 ppm), ammonia (150 ppm), CO₂ (2000 ppm), NO (15 ppm) and NO₂ (15 ppm).     

Silicon hotplates for metal oxide gas sensor elements

 Low-power-consumption metal oxide gas sensors and gas sensor arrays can be produced by combining micromachining and thin-film technologies. In the present paper the state-of-the art in this field is reviewed. In the first part the problem of thermal losses from a heated metal oxide film is addressed and the necessity of miniaturisation of gas sensing devices is pointed out. The thermal properties of realized silicon hotplates are compared and analysed with respect to thermal equivalent circuit models. In addition, the results of accelerated thermal ageing tests are presented. These latter results demonstrate that micromachined heater elements are likely to exhibit device lifetimes of the order of 30 years when operated at membrane temperatures around 400 °C. In the second part of the paper attention is drawn to novel methods of gas detection which are enabled by employing stacks of different thin film materials on micromachined hotplates. In this context, recent results on temperature-and field-effect modulated gas detection experiments are discussed. Received: 16 May 1997 / Accepted: 22 May 1997