Enhancing the Responsiveness of Thermoelectric Gas Sensors with Boron-Doped and Thermally Annealed SiGe Thin Films via Low-Pressure Chemical Vapor Deposition.

Thermoelectric gas sensor (THGS) devices with catalysts and Si0.8Ge0.2 thin films of different boron doping levels of 1018, 1019, and 1020 cm-3 were fabricated, and their transport properties are investigated. SiGe films were deposited on Si3N4/SiO2 multilayers on Si substrates using low-pressure chemical vapor deposition (LPCVD) and thermally annealed at 1050 °C. The Seebeck coefficients of the SiGe films were increased after thermal annealing, ranging from 191 to 275 µV/K at temperatures of 74 to 468 °C in air, and reaching the highest power factor of 6.78 × 10-4 W/mK2 at 468 °C. The thermal conductivity of the SiGe films varied from 2.4 to 3.0 W/mK at 25 °C. The THGS detection performance was tested for the H2 gas in air from 0.01 to 1.0%, and compared to the thermoelectric properties of the SiGe films. The high-temperature annealing treatment process was successful in enhancing the thermoelectric performance of both the SiGe films and sensor devices, achieving the best THGS performance with the sensor device fabricated from the annealed SiGe film with 1018 cm-3 boron-doped Si0.8Ge0.2.

Erratum: Effect of evaporation and condensation on a thermoacoustic engine: A Lagrangian simulation approach [J. Acoust. Soc. Am. 141 (6), 4398-4407 (2017)].

In the original paper [Yasui and Izu, J. Acoust. Soc. Am. 141(6), 4398-4407 (2017)], the temperature gradient in Rott equations was assumed as zero by mistake as an author error, although temperature gradient was adequately taken into account in the numerical simulations of thermal conduction between a fluid parcel and the wall of a stack. In the present erratum, the results of the corrected numerical simulations are shown. The results show that the pV work done by a fluid parcel is larger in a wet stack compared to that in a dry stack not only in a traveling-wave thermoacoustic engine but also in a standing-wave thermoacoustic engine. The pV work is determined not only by the volume oscillation amplitude of a fluid parcel but also by the change in the mean volume of a fluid parcel.

Self-assembly patterning of ultrafine zirconia nanocrystal films fabricated on chemically patterned templates.

Ultra-thin zirconia (ZrO2) nanocrystal films were fabricated by using a controlled dip-coating process. ZrO2 nanocrystals possess a cubic crystalline phase and large surface-to-volume area. The film composite with only several layers of nanocrystals were obtained by controlling the withdrawal speed and mass concentration of the colloidal solution. The optical properties of ZrO2 nanocrystal films were accessed by UV-vis spectroscopy, which indicated the dense and uniform structure of the nanocrystal films. The high reflection index suggested that the films could be used in the reflection coating industry. Furthermore, a micro-pattern of self-assembled monolayers of silane molecular was used as a chemical mold for selective deposition of ZrO2 nanocrystals. As a result, a self-assembly patterning of ZrO2 nanocrystals with a neat edge was fabricated on silicon substrate. The low-cost fabricating method is compatible with conventional very-large-scale integration processes and can be extended to other kinds of nanocrystals.

Effect of evaporation and condensation on a thermoacoustic engine: A Lagrangian simulation approach.

Acoustic oscillations of a fluid (a mixture of gas and vapor) parcel in a wet stack of a thermoacoustic engine are numerically simulated with a Lagrangian approach taking into account Rott equations and the effect of non-equilibrium evaporation and condensation of water vapor at the stack surface. In a traveling-wave engine, the volume oscillation amplitude of a fluid parcel always increases by evaporation and condensation. As a result, pV work done by a fluid parcel is enhanced, which means enhancement of acoustic energy in a thermoacoustic engine. On the other hand, in a standing-wave engine, the volume oscillation amplitude sometimes decreases by evaporation and condensation, and pV work is suppressed. Presence of a tiny traveling-wave component, however, results in the enhancement of pV work by evaporation and condensation.

Development of an Exhaled Breath Monitoring System with Semiconductive Gas Sensors, a Gas Condenser Unit, and Gas Chromatograph Columns.

Various volatile organic compounds (VOCs) in breath exhaled by patients with lung cancer, healthy controls, and patients with lung cancer who underwent surgery for resection of cancer were analyzed by gas condenser-equipped gas chromatography-mass spectrometry (GC/MS) for development of an exhaled breath monitoring prototype system involving metal oxide gas sensors, a gas condenser, and gas chromatography columns. The gas condenser-GC/MS analysis identified concentrations of 56 VOCs in the breath exhaled by the test population of 136 volunteers (107 patients with lung cancer and 29 controls), and selected four target VOCs, nonanal, acetoin, acetic acid, and propanoic acid, for use with the condenser, GC, and sensor-type prototype system. The prototype system analyzed exhaled breath samples from 101 volunteers (74 patients with lung cancer and 27 controls). The prototype system exhibited a level of performance similar to that of the gas condenser-GC/MS system for breath analysis.

Sensing properties of Pd-loaded Co3O4 film for a ppb-level NO gas sensor.

We prepared 0.1 wt%-30 wt% Pd-loaded Co3O4 by a colloidal mixing method and investigated the sensing properties of a Pd-loaded Co3O4 sensor element, such as the sensor response, 90% response time, 90% recovery time, and signal-to-noise (S/N) ratio, toward low nitric oxide (NO) gas levels in the range from 50 to 200 parts per billion. The structural properties of the Pd-loaded Co3O4 powder were investigated using X-ray diffraction analysis and transmission electron microscopy. Pd in the powder existed as PdO. The sensor elements with 0.1 wt%-10 wt% Pd content have higher sensor properties than those without any Pd content. The response of the sensor element with a 30 wt% Pd content decreased markedly because of the aggregation and poor dispersibility of the PdO particles. High sensor response and S/N ratio toward the NO gas were achieved when a sensor element with 10 wt% Pd content was used.

Elimination of flammable gas effects in cerium oxide semiconductor-type resistive oxygen sensors for monitoring low oxygen concentrations.

We have investigated the catalytic layer in zirconium-doped cerium oxide, Ce0.9Zr0.1O2 (CeZr10) resistive oxygen sensors for reducing the effects of flammable gases, namely hydrogen and carbon monoxide. When the concentration of flammable gases is comparable to that of oxygen, the resistance of CeZr10 is affected by the presence of these gases. We have developed layered thick films, which consist of an oxygen sensor layer (CeZr10), an insulation layer (Al2O3), and a catalytic layer consisting of CeZr10 with 3 wt% added platinum, which was prepared via the screen printing method. The Pt-CeZr10 catalytic layer was found to prevent the detrimental effects of the flammable gases on the resistance of the sensor layer. This effect is due to the catalytic layer promoting the oxidation of hydrogen and carbon monoxide through the consumption of ambient O2 and/or the lattice oxygen atoms of the Pt-CeZr10 catalytic layer.

Thermal balance analysis of a micro-thermoelectric gas sensor using catalytic combustion of hydrogen.

A thermoelectric gas sensor (TGS) with a combustion catalyst is a calorimetric sensor that changes the small heat of catalytic combustion into a signal voltage. We analyzed the thermal balance of a TGS to quantitatively estimate the sensor parameters. The voltage signal of a TGS was simulated, and the heat balance was calculated at two sections across the thermoelectric film of a TGS. The thermal resistances in the two sections were estimated from the thermal time constants of the experimental signal curves of the TGS. The catalytic combustion heat Q(catalyst) required for 1 mV of ∆V(gas) was calculated to be 46.1 µW. Using these parameters, we find from simulations for the device performance that the expected Q(catalyst) for 200 and 1,000 ppm H2 was 3.69 µW and 11.7 µW, respectively.

Calorimetric thermoelectric gas sensor for the detection of hydrogen, methane and mixed gases.

A novel miniaturized calorimeter-type sensor device with a dual-catalyst structure was fabricated by integrating different catalysts on the hot (Pd/θ-Al2O3) and cold (Pt/α-Al2O3) ends of the device. The device comprises a calorimeter with a thermoelectric gas sensor (calorimetric-TGS), combining catalytic combustion and thermoelectric technologies. Its response for a model fuel gas of hydrogen and methane was investigated with various combustor catalyst compositions. The calorimetric-TGS devices detected H2, CH4, and a mixture of the two with concentrations ranging between 200 and 2000 ppm at temperatures of 100-400 °C, in terms of the calorie content of the gases. It was necessary to reduce the much higher response voltage of the TGS to H2 compared to CH4. We enhanced the H2 combustion on the cold side so that the temperature differences and response voltages to H2 were reduced. The device response to H2 combustion was reduced by 50% by controlling the Pt concentration in the Pt/α-Al2O3 catalyst on the cold side to 3 wt%.

NO and NO2 sensing properties of WO3 and Co3O4 based gas sensors.

Semiconductor-based gas sensors that use n-type WO3 or p-type Co3O4 powder were fabricated and their gas sensing properties toward NO2 or NO (0.5-5 ppm in air) were investigated at 100 °C or 200 °C. The resistance of the WO3-based sensor increased on exposure to NO2 and NO. On the other hand, the resistance of the Co3O4-based sensor varied depending on the operating temperature and the gas species. The chemical states of the surface of WO3 or those of the Co3O4 powder on exposure to 1 ppm NO2 and NO were investigated by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. No clear differences between the chemical states of the metal oxide surface exposed to NO2 or NO could be detected from the DRIFT spectra.

CO responses of sensors based on cerium oxide thick films prepared from clustered spherical nanoparticles.

Various types of CO sensors based on cerium oxide (ceria) have been reported recently. It has also been reported that the response speed of CO sensors fabricated from porous ceria thick films comprising nanoparticles is extremely high. However, the response value of such sensors is not suitably high. In this study, we investigated methods of improving the response values of CO sensors based on ceria and prepared gas sensors from core-shell ceria polymer hybrid nanoparticles. These hybrid nanoparticles have been reported to have a unique structure: The core consists of a cluster of ceria crystallites several nanometers in size. We compared the characteristics of the sensors based on thick films prepared from core-shell nanoparticles with those of sensors based on thick films prepared from conventionally used precipitated nanoparticles. The sensors prepared from the core-shell nanoparticles exhibited a resistance that was ten times greater than that of the sensors prepared from the precipitated nanoparticles. The response values of the gas sensors based on the core-shell nanoparticles also was higher than that of the sensors based on the precipitated nanoparticles. Finally, improvements in sensor response were also noticed after the addition of Au nanoparticles to the thick films used to fabricate the two types of sensors.

Application of V2O5/WO3/TiO2 for resistive-type SO2 sensors.

A study on the application of V(2)O(5)/WO(3)/TiO(2) (VWT) as the sensitive material for resistive-type SO(2) sensor was conducted, based on the fact that VWT is a well-known catalyst material for good selective catalytic nitrogen oxide reduction with a proven excellent durability in exhaust gases. The sensors fabricated in this study are planar ones with interdigitated electrodes of Au or Pt. The vanadium content of the utilized VWT is 1.5 or 3.0 wt%. The resistance of VWT decreases with an increasing SO(2) concentration in the range from 20 ppm to 5,000 ppm. The best sensor response to SO(2) occurs at 400 °C using Au electrodes. The sensor response value is independent on the amount of added vanadium but dependent on the electrode materials at 400 °C. These results are discussed and a sensing mechanism is discussed.

Resistive oxygen gas sensors for harsh environments.

Resistive oxygen sensors are an inexpensive alternative to the classical potentiometric zirconia oxygen sensor, especially for use in harsh environments and at temperatures of several hundred °C or even higher. This device-oriented paper gives a historical overview on the development of these sensor materials. It focuses especially on approaches to obtain a temperature independent behavior. It is shown that although in the past 40 years there have always been several research groups working concurrently with resistive oxygen sensors, novel ideas continue to emerge today with respect to improvements of the sensor response time, the temperature dependence, the long-term stability or the manufacture of the devices themselves using novel techniques for the sensitive films. Materials that are the focus of this review are metal oxides; especially titania, titanates, and ceria-based formulations.

Effects of high-humidity aging on platinum, palladium, and gold loaded tin oxide--volatile organic compound sensors.

This study is an investigation of high-humidity aging effects on the total volatile organic compound (T-VOC) gas-sensing properties of platinum, palladium, and gold-loaded tin oxide (Pt,Pd,Au/SnO(2)) thick films. The sensor responses of the high-humidity aged Pt,Pd,Au/SnO(2), a non-aged Pt,Pd,Au/SnO(2), and a high-humidity aged Pt/SnO(2) to T-VOC test gas have been measured. The high-humidity aging is an effective treatment for resistance to humidity change for the Pt,Pd,Au/SnO(2) but not effective for the Pt/SnO(2). The mechanism of the high-humidity aging effects is discussed based on the change of surface state of the SnO(2) particles.

Resistive oxygen sensor using ceria-zirconia sensor material and ceria-yttria temperature compensating material for lean-burn engine.

Temperature compensating materials were investigated for a resistive oxygen sensor using Ce(0.9)Zr(0.1)O(2) as a sensor material for lean-burn engines. The temperature dependence of a temperature compensating material should be the same as the sensor material; therefore, the Y concentration in CeO(2)-Y(2)O(3) was optimized. The resistance of Ce(0.5)Y(0.5)O(2-δ) was independent of the air-to-fuel ratio (oxygen partial pressure), so that it was confirmed to function as a temperature compensating material. Sensor elements comprised of Ce(0.9)Zr(0.1)O(2) and Ce(0.5)Y(0.5)O(2-δ) were fabricated and the output was determined to be approximately independent of the temperature in the wide range from 773 to 1,073 K.

Is surface tension reduced by nanobubbles (ultrafine bubbles) generated by cavitation?

Nanobubbles (ultrafine bubbles) are produced by hydrodynamic or acoustic cavitation. They work as cavitation nuclei. Is the experimentally reported considerable reduction of surface tension of liquid water by nanobubbles real? It is theoretically suggested that nanobubbles partly covered with hydrophobic materials are concentrated at a surface of liquid water. A hydrophobic cap is directed toward a gas phase above a liquid surface. Uncovered surface of a nanobubble is directed into liquid water underneath the liquid surface. It is suggested that a liquid film is more easily ruptured by the presence of nanobubbles at the liquid surface, which reduces the value of surface tension in du Noüy ring method. A role of ionic surfactants on accumulation of nanobubbles at a liquid surface is also discussed.

Fabrication and H2-Sensing Properties of SnO2 Nanosheet Gas Sensors.

Vertically formed and well-defined SnO2 nanosheets are easy to fabricate, involving only a single process that is performed under moderate conditions. In this study, two different sizes of a SnO2 nanosheet were concurrently formed on a Pt interdigitated electrode chip, with interconnections between the two. As the SnO2 nanosheets were grown over time, the interconnections became stronger. The ability of the fabricated SnO2 nanosheets to sense H2 gas was evaluated in terms of the variation in their resistance. The resistance of a SnO2 nanosheet decreased with the introduction of H2 gas and returned to its initial level after the H2 gas was replaced with air. Also, the response-recovery behaviors were improved as a result of the growth of the SnO2 nanosheets owing to the presence of many reaction sites and strong interconnections, which may provide multipassages for the electron transfer channel, leading to the acceleration of the reaction between the H2 gas and SnO2 nanosheets.

Effect of Core-shell Ceria/Poly(Vinylpyrrolidone) (PVP) Nanoparticles Incorporated in Polymer Films and Their Optical Properties (2): Increasing the Refractive Index.

We investigated the preparation of well-dispersed core-shell ceria-poly(vinylpyrrolidone) (PVP) nanoparticles with an average particle size of around 20 nm which were used to produce a hybrid film with a polymer coating of dipentaerythritol hexaacrylate (DPHA). We obtained good dispersion of the nanoparticles in a mixed solvent of 48% 1-methoxy-2-propanol (MP), 32% 3-methoxy-3-methyl-1-butanol (MMB), and 20% methyl i-butyl ketone (MIBK). An ink of the polymer coating consisting of 68.7 wt% nanoparticles and 31.3 wt% DPHA with a polymerization initiator was prepared using this solvent mixture. The surface of the hybrid film showed low roughness and the nanoparticles formed a densely packed structure in the DPHA matrix. The resulting coating possessed excellent transparency and a high refractive index of 1.69.

Rapid Synthesis and Formation Mechanism of Core-Shell-Structured La-Doped SrTiO3 with a Nb-Doped Shell.

To provide a convenient and practical synthesis process for metal ion doping on the surface of nanoparticles in an assembled nanostructure, core-shell-structured La-doped SrTiO3 nanocubes with a Nb-doped surface layer were synthesized via a rapid synthesis combining a rapid sol-precipitation and hydrothermal process. The La-doped SrTiO3 nanocubes were formed at room temperature by a rapid dissolution of NaOH pellets during the rapid sol-precipitation process, and the Nb-doped surface (shell) along with Nb-rich edges formed on the core nanocubes via the hydrothermal process. The formation mechanism of the core-shell-structured nanocubes and their shape evolution as a function of the Nb doping level were investigated. The synthesized core-shell-structured nanocubes could be arranged face-to-face on a SiO2/Si substrate by a slow evaporation process, and this nanostructured 10 µm thick thin film showed a smooth surface.

Effect of Core-Shell Ceria/Poly(vinylpyrrolidone) (PVP) Nanoparticles Incorporated in Polymer Films and Their Optical Properties.

We fabricated hybrid films of pentaerythritol triacrylate (PETA) with core-shell ceria/poly(vinylpyrrolidone) (PVP) nanoparticles, which consist of cerium oxide as the core and PVP as the shell, and investigated the film optical properties. In this study, we used ceria/PVP nanoparticles with average diameters of 37, 49 and 91 nm. We obtained translucent films consisting of PETA with core-shell ceria/PVP nanoparticles. The core-shell ceria/PVP nanoparticles can reduce the transmittance of near-ultraviolet light. The transmittance of visible light and haze values depends not only on the thickness of the films, but also on the average diameter of the nanoparticles. A SEM observation and the optical analyses prove that the core-shell ceria/PVP nanoparticles do not aggregate into the PETA matrix.