Structural and properties of nanocrystalline WO3/TiO2-based humidity sensors elements prepared by high energy activation

Nanocrystalline WO₃/TiO₂-based powders have been prepared by the high energy activation method with WO₃ concentration ranging from 1 to 10 mol%. The samples were thermal treated in a microwave oven at 600 °C for 20 min and their structural and micro-structural characteristics were evaluated by X-ray diffraction, Raman spectroscopy, EXAFS measurements at the Ti K-edge, and transmission electron microscopy. Nitrogen adsorption isotherms and H₂ Temperature Programmed Reduction were also carried out for physical characterization. The crystallite and particle mean sizes ranged from 30 to 40 nm and from 100 to 190 nm, respectively. Good sensor response was obtained for samples with at least 5 mol% WO₃ activated for at least 80 min. Ceramics heat-treated in microwave oven for 20 min have shown similar sensor response as those prepared in conventional oven for 120 min, which is highly cost effective. These results indicate that WO₃/TiO₂ ceramics can be used as a humidity sensor element.     

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.     

Characterization and humidity sensing properties of Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3 powder synthesized by metal-organic decomposition

Bi_0.5Na_0.5TiO₃-Bi_0.5K_0.5TiO₃ (BNT-BKT) powder is synthesized by a metal-organic decomposition method and characterized by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). A humidity sensor, which is consisted of five pairs of Ag-Pd interdigitated electrodes and an Al₂O₃ ceramic substrate, is fabricated by spin-coating the BNT-BKT powder on the substrate. Good humidity sensing properties such as high response value, short response and recovery times, and small hysteresis are observed in the sensing measurement. The impedance changes more than four orders of magnitude within the whole humidity range from 11% to 95% relative humidity (RH) at 100 Hz. The response time and recovery time are about 20 and 60 s, respectively. The maximum hysteresis is around 4% RH. The results indicate that BNT-BKT powder is of potential applications for fabricating high performance humidity sensors.     

Influence of Cs doping in spray deposited SnO2 thin films for LPG sensors

Detection of low concentrations of petroleum gas was achieved using transparent conducting SnO₂ thin films doped with 0–4 wt.% caesium (Cs), deposited by spray pyrolysis technique. The electrical resistance change of the films was evaluated in the presence of LPG upon doping with different concentrations of Cs at different working temperatures in the range 250–400 °C. The investigations showed that the tin oxide thin film doped with 2% Cs with a mean grain size of 18 nm at a deposition temperature of 325 °C showed the maximum sensor response (93.4%). At a deposition temperature of 285 °C, the film doped with 3% Cs with a mean grain size of 20 nm showed a high response of 90.0% consistently. The structural properties of Cs-doped SnO₂ were studied by means of X-ray diffraction (XRD); the preferential orientation of the thin films was found to be along the (3 0 1) directions. The crystallite sizes of the films determined from XRD are found to vary between 15 and 60 nm. The electrical investigations revealed that Cs-doped SnO₂ thin film conductivity in a petroleum gas ambience and subsequently the sensor response depended on the dopant concentration and the deposition temperature of the film. The sensors showed a rapid response at an operating temperature of 345 °C. The long-term stability of the sensors is also reported.     

Electrical response of Sm2O3-doped SnO2 to C2H2 and effect of humidity interference

Pure and Sm₂O₃-doped SnO₂ are prepared through a sol–gel method and characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The sensor based on 6 wt% Sm₂O₃-doped SnO₂ displays superior response at an operating temperature of 180 °C, and the response magnitude to 1000 ppm C₂H₂ can reach 63.8, which is 16.8 times larger than that of pure SnO₂. This sensor also shows high sensitivity under various humidity conditions. These results make our product be a good candidate in fabricating C₂H₂ sensors.     

Sprayed CdIn2O4 thin films for liquefied petroleum gas (LPG) detection

Nanocrystalline cadmium indium oxide (CdIn₂O₄) thin films of different thicknesses were deposited by chemical spray pyrolysis technique and utilized as a liquefied petroleum gas (LPG) sensors. These CdIn₂O₄ films were characterized for their structural and morphological properties by means of X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. The dependence of the LPG response on the operating temperature, LPG concentration and CdIn₂O₄ film thickness were investigated. The results showed that the phase structure and the LPG sensing properties changes with the different thicknesses. The maximum LPG response of 46% at the operation temperature of 673 K was achieved for the CdIn₂O₄ film of thickness of 695 nm. The CdIn₂O₄ thin films exhibited good response and rapid response/recovery characteristics to LPG.     

Synthesis and enhanced gas sensing properties of crystalline CeO2/TiO2 core/shell nanorods

Crystalline CeO₂/TiO₂ core/shell nanorods were fabricated by a hydrothermal method and a subsequent annealing process under the hydrogen and air atmosphere. The thickness of the outer shell composed of crystal TiO₂ nanoparticles can be tuned in the range of 5-11 nm. The crystal core/shell nanorods exhibited enhanced gas-sensing properties to ethanol vapor in terms of sensor response and selectivity. The calculated sensor response based on the change of the heterojunction barrier formed at the interface between CeO₂ and TiO₂ is agreed with the experimental results, and thus the change of the heterojunction barrier at different gas atmosphere can be used to explain the enhanced ethanol sensing properties.     

Separate assessment of chemoresistivity and Schottky-type gas sensitivity in M–metal oxide–M′ structures

Maximum response levels reported for chemoresistive sensors span from less than 10 to over 10⁸. These differences are attributed to either the different micro- and nano-structured oxide pallets used or the properties of the metal–metal oxide junctions provided. Here, we report separate measurements and model-based estimations of the chemical responses arising from these different origins. The results quantitatively connect the observed responses to the parameters of the metal and metal oxide components of the device. It is shown that while the peak chemoresistive response is microstructure-dependent, the highest attainable Schottky-type gas sensitivity is almost microstructure-independent and is determined by the intrinsic properties of the materials involved. Measurements carried out on different Ag–TiO₂–Ti, Au–TiO₂–Ti and Ti–TiO₂–Ti structures verified the estimations: While chemoresistive responses in TiO₂ can hardly rise over 10², atmosphere-sensitive noble metal–TiO₂ junctions can cause responses as high as ∼10⁷.     

Novel solid-state manganese oxide-based reference electrode for YSZ-based oxygen sensors

Various Mn-based oxides have been screened to find a suitable all-solid-state gas-insensitive reference-electrode (RE) for yttria-stabilized zirconia (YSZ)-based potentiometric oxygen sensor. The experimental observation of tubular YSZ-based sensors attached with each of the outer Mn-based oxide sensing electrodes (SEs) and the inner Pt-RE revealed that Mn₂O₃-SE was insensitive to all gases including oxygen at operating temperatures below 550 °C. Thus, the planar-like rod-type YSZ-based sensor using Pt-SE, Au-SE and Mn₂O₃-RE was then fabricated and its sensing performances were evaluated at 550 °C. As a result, the planar sensor using a couple of Pt-SE and Mn₂O₃-RE exhibited excellent responses to oxygen in the concentration range of 0.05-21 vol.% obeying Nernst equation and gave negligible responses to other co-existing gases. Close similarity of the results for tubular and planar sensors operated in a wide range of air/fuel (A/F) ratio indicated that the tubular YSZ-based sensor using the inner Pt-RE could be successfully miniaturized to the planar one using Mn₂O₃-RE without sacrificing its performance.     

A selective room temperature formaldehyde gas sensor using TiO2 nanotube arrays

A new gas sensor using TiO₂ nanotube arrays was fabricated and explored for formaldehyde detection at room temperature. Highly ordered vertically grown TiO₂ nanotube arrays were synthesized by using the conventional electrochemical anodization process. The sensor using the fabricated nanotube arrays as the sensing elements demonstrated a good response to different concentrations of formaldehyde from 10 to 50 ppm and a very good selectivity over other reducing gas species such as ethanol and ammonia at room temperature. While the exact sensing mechanism is unclear, some possibilities are briefly discussed.     

SnO2 thin films modified by the SnO2–Au nanocomposites: Response to reducing gases

The influence of the SnO₂ surface modification by the SnO₂–Au nanocomposites on conductivity response to such reducing gases as CO and H₂ has been analyzed in the present paper. Both initial SnO₂ films, subjected for surface modification, and SnO₂–Au nanocomposites were deposited by Successive Ionic Layer Deposition (SILD) method. The SnO₂–Au nanocomposites with Au/Sn ratio 1 were synthesized using HAuCl₄ and SnCl₂ precursors. The thickness of the Au-SnO₂ nanolayers varied from 0.7–1.0 nm to 10–15 nm. It was established that the increase in the thickness of the SnO₂–Au nanocomposite layer formed on the surface of the SnO₂ films was accompanied by both the improvement of sensor response and the decrease in response and recovery times. An explanation of the observed effects has been proposed.     

Diesel engine dynamometer testing of impedancemetric NOx sensors

Prototype solid-state electrochemical sensors using a dense gold sensing electrode, porous yttria-stabilized zirconia (YSZ) electrolyte, and a platinum counter electrode (Au/YSZ/Pt) were evaluated for measuring NO_x (NO and NO₂) in diesel exhaust. Both electrodes were exposed to the test gas (i.e., there was no reference gas for the counter electrode). An impedancemetric method was used for NO_x measurements, where the phase angle was used as the response signal. A portion of the tailpipe exhaust from the dynamometer test stand was extracted and fed into a furnace containing the experimental sensor. The prototype sensor was tested along with a commercially available NO_x sensor. Simultaneous measurements for NO_x, O₂, CO₂, H₂O, CO, and CH₄ in a separate feed stream were made using Fourier transform infrared (FTIR) spectroscopy and an oxygen paramagnetic analyzer. The experimental sensor showed very good measurement capability for NO in the range of 25-250 ppm, with a response paralleling that of the FTIR and commercial sensor. The prototype sensor showed better sensitivity to NO_x at the lower concentration ranges. O₂ is an interferent for the experimental sensor, resulting in decreased sensitivity for measurement of NO_x. Methods to overcome this interference are discussed.     

Humidity sensing properties of mesoporous iron oxide/silica composite prepared via hydrothermal process

Mesoporous Fe₂O₃/SiO₂ composites with various Fe/Si molar ratios were synthesized via hydrothermal route and then studied as humidity sensor materials. The best result is obtained for the sample with a Fe/Si molar ratio of 0.5, which exhibits high humidity sensitivity, rapid response and recovery, small hysteresis and excellent linearity. The impedance of the sensor varies more than four orders of magnitude during the whole relative humidity (RH) from 11 to 95%. The response time and recovery time of the sensor is about 20 and 40 s, respectively. These results make our product a good candidate in fabricating high performance humidity sensors.     

α-MoO3/TiO2 core/shell nanorods: Controlled-synthesis and low-temperature gas sensing properties

Crystalline α-MoO₃/TiO₂ core/shell nanorods are fabricated by a hydrothermal method and subsequent annealing processes under H₂/Ar flow and in the ambient atmosphere. The shell layer is composed of crystalline TiO₂ particles with a diameter of 2-6 nm, and its thickness can be easily controlled in the range of 15-45 nm. The core/shell nanorods show enhanced sensing properties to ethanol vapor compared to bare α-MoO₃ nanorods. The sensing mechanism is different from that of other one-dimensional metal oxide core/shell nanostructures due to very weak response of TiO₂ nanoparticles to ethanol. The enhanced sensing properties can be explained by the change of type II heterojunction barrier formed at the interface between α-MoO₃ and TiO₂ in the different gas atmosphere. The present results demonstrate a novel sensing mechanism available for gas sensors with high performance.     

Epitaxially grown graphene based gas sensors for ultra sensitive NO2 detection

Epitaxially grown single layer and multi layer graphene on SiC devices were fabricated and compared for response towards NO₂. Due to electron donation from SiC, single layer graphene is n-type with a very low carrier concentration. The choice of substrate is demonstrated to enable tailoring of the electronic properties of graphene, with a SiC substrate realising simple resistive devices tuned for extremely sensitive NO₂ detection. The gas exposed uppermost layer of the multi layer device is screened from the SiC by the intermediate layers leading to a p-type nature with a higher concentration of charge carriers and therefore, a lower gas response. The single layer graphene device is thought to undergo an n-p transition upon exposure to increasing concentrations of NO₂ indicated by a change in response direction. This transition is likely to be due to the transfer of electrons to NO₂ making holes the majority carriers.     

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.     

A route to high sensitivity and rapid response Nb2O5-based gas sensors: TiO2 doping, surface embossing, and voltage optimization

We report a novel route for the fabrication of highly sensitive and rapidly responding Nb₂O₅-based thin film gas sensors. TiO₂ doping of Nb₂O₅ films is carried out by co-sputtering without the formation of secondary phases and the surface area of TiO₂-doped Nb₂O₅ films is increased via the use of colloidal templates composed of sacrificial polystyrene beads. The gas sensitivity of Nb₂O₅ films is enhanced through both the TiO₂ doping and the surface embossing. An additional enhancement on the gas sensitivity is obtained by the optimization of the bias voltage applied between interdigitated electrodes beneath Nb₂O₅-based film. More excitingly, such a voltage optimization leads to a substantial decrease in response time. Upon exposure to 50 ppm CO at 350 °C, a gas sensor based on TiO₂-doped Nb₂O₅ film with embossed surface morphology exhibits a very high sensitivity of 475% change in resistance and a rapid response time of 8 s under 3 V, whereas a sensor based on plain Nb₂O₅ film shows a 70% resistance change and a response time of 65 s under 1 V. Thermal stability tests of our Nb₂O₅-based sensor reveal excellent reliability which is of particular importance for application as resistive sensors for a variety gases.     

Electrical and CO gas sensing properties of nanostructured La1−xCexCoO3 perovskite prepared by activated reactive synthesis

A series of nanostructred La_1−xCe_xCoO₃ perovskite-type (x ranging from 0 to 0.2), with a crystallite size of around 10 nm and a specific surface area of up to 55 m²/g were prepared using the activated reactive grinding method. XRD results showed that Ce segregates as CeO₂ when the addition level exceeds 10 at%. CO was chosen as a typical reducing gas and its interaction with surface oxygen was investigated. TPD-O₂ was used to investigate the effect of Ce-doping on total surface oxygen. The experimental results confirmed a positive effect of Ce-doping of up to 10 at% on total surface oxygen (α-O₂). TPD-CO and XPS analyses were performed to find the total carbon adsorption (i.e. related to the adsorption of CO) on the surface of the synthesized samples. Both methods confirmed that more carbon adsorbs on the surface of doped formulations compared to the pure LaCoO₃. Ce-doping increases the surface oxygen, thereby facilitating the adsorption and oxidation processes. CO gas sensing properties of thick La_1−xCe_xCoO₃ films were performed. La_0.9Ce_0.1CoO₃ showed the highest conductivity and the lowest activation energy. The optimum CO sensing temperature for doped formulation was found to be 100 °C compared to 130 °C for pure perovskite. Ce-doped samples showed a maximum response ratio of 240% with respect to 100 ppm CO in air compared to 60% obtained with pure LaCoO₃.     

Development and application of micromachined Pd/SnO2 gas sensors with zeolite coatings

Zeolite A (LTA)-coated micromachined sensors have been prepared and used in the sensing of individual gases (H₂, CH₄, C₂H₅OH, C₃H₈ and CO, in the 10–1000 ppm range) and gas mixtures. Unlike previous works with conventional sensors, a hydrothermal synthesis was not used to prepare a zeolite film. Instead, a zeolite coating was formed on top of the Pd/SnO₂ surface by microdropping from a zeolite suspension. In spite of this, the response of the sensor with zeolite is significantly different from that of unmodified sensors, and essentially reproduces the performance of zeolite-coated conventional sensors. By avoiding the use of a hydrothermal synthesis the integrity of the sensor is better preserved, and the resulting non-continuous zeolite film has the added advantage of a strong reduction in response times.     

Necked ZnO nanoparticle-based NO2 sensors with high and fast response

The NO₂ gas sensing characteristics of semiconductor type gas sensors with channels composed of necked ZnO nanoparticles (NPs) were investigated in this study. The heat treatment of the NPs at 400 °C led to their necking and coarsening. The response of the necked-NP-based sensors was as high as 100 when exposed to 0.2 ppm of NO₂ at 200 °C. As the concentration of NO₂ increased to 5 ppm, their response was enhanced to approximately 400. During the repeated injection of NO₂ gas with a concentration of 0.4 ppm, the sensors exhibited stable response characteristics. Furthermore, the 90% response and recovery times of the gas sensor were as fast as 13 and 10 s, respectively. These observations indicate that the non-agglomerated necking of the NPs induced by the heat treatment significantly enhances the gas sensing characteristics of the NP-based gas sensors.