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.

Examination of VOC Concentration of Aroma Essential Oils and Their Major VOCs Diffused in Room Air.

This study analyzed temporal variation of the composition of volatile organic compounds (VOCs) at different diffusion time of gaseous phase of aroma compounds of four essential oils, lavender, tea tree, eucalyptus, and melissa. GC/MS methodology with the trace gas sampling by a thermal desorption tube is used to quantitatively determine the concentration of the corresponding 14 kinds of major and original VOCs in four essential oils. This study revealed for the first time that the concentration level of gaseous phase composition is varied, with a diffusion time from that of the liquid phase at equilibrium with it and the VOCs in the essential oils are classified into two groups, depending on whether their concentration with the time. It is verified that the total concentration of VOCs of these essential oils in the room air diffused by the ultrasonic diffuser is as low as 0.6 ppb and decreased soon below 0.1 ppb.

High Temperature Electrical Properties of Co-Substituted La4BaCu5O13+δ Thin Films Fabricated by Sputtering Method.

The high-temperature conductivity of the perovskite oxides of a La4BaCu5O13+δ (LBCO) thin film prepared by RF sputtering deposition and thermal annealing has been studied. While the bulk LBCO compound was metallic, the LBCO film deposited on a Si substrate by sputtering and a post annealing process showed semiconductor-like conduction, which is considered to be due to the defects and poor grain connectivity in the LBCO film on the Si substrate. The LBCO film deposited on a SrTiO3 substrate was of high film quality and showed metallic conduction. When the cation site Cu was substituted by Co, the electrical conductivity of the LBCO film increased further and its temperature dependence became smaller. The transport properties of LBCO films are investigated to understand its carrier generation mechanism.

Development of Na0.5CoO2 Thick Film Prepared by Screen-Printing Process.

The Na0.5Co0.9Cu0.1O2 thick film with the same thermoelectric performance as a Na0.5CoO2 bulk was formed on an alumina substrate by the screen-printing process. The power factor exceeded 0.3 mW/K2m, with the resistivity of 3.8 mΩcm and the thermopower of 108 µV/K. The thick film without any cracks strongly adhered to the substrate. The high-quality thick film had been realized through the carefully designed and improved process, mixing NaCl to promote the anisotropic sintering of Na0.5Co0.9Cu0.1O2, inserting a CuO interlayer to adhere the film and substrate, and Co-Cu substituting Cu for Co to control the sintering temperature.

Selective Detection of Target Volatile Organic Compounds in Contaminated Air Using Sensor Array with Machine Learning: Aging Notes and Mold Smells in Simulated Automobile Interior Contaminant Gases.

We investigated the selective detection of target volatile organic compounds (VOCs) which are age-related body odors (namely, 2-nonenal, pelargonic acid, and diacetyl) and a fungal odor (namely, acetic acid) in the presence of interference VOCs from car interiors (namely, n-decane, and butyl acetate). We used eight semiconductive gas sensors as a sensor array; analyzing their signals using machine learning; principal-component analysis (PCA), and linear-discriminant analysis (LDA) as dimensionality-reduction methods; k-nearest-neighbor (kNN) classification to evaluate the accuracy of target-gas determination; and random forest and ReliefF feature selections to choose appropriate sensors from our sensor array. PCA and LDA scores from the sensor responses to each target gas with contaminant gases were generally within the area of each target gas; hence; discrimination between each target gas was nearly achieved. Random forest and ReliefF efficiently reduced the required number of sensors, and kNN verified the quality of target-gas discrimination by each sensor set.

Breath analysis using a spirometer and volatile organic compound sensor on driving simulator.

In this study the correlation between the condition of drivers and their expiration was evaluated by analyzing the exhalation of car drivers in a simulation setting using a spirometer and a volatile organic compound (VOC) gas sensor. Participants wore exhalation masks and their expiration was monitored for fluctuations in breath measurements, including VOC concentration, oxygen intake, carbon dioxide excretion, and respiration rate. Participants used a driving simulator on four different courses of varying difficulty for approximately five min each, with the mean and standard deviation (SD) being calculated for each parameter during the cruising section of the course. After driving each course, participants assessed the 'enjoyment' and 'difficulty' of their experience. It was verified whether the state of the participants during driving can be determined from exhalation by comparing the questionnaire results. The mean and SD of all exhalation parameters were analyzed using box-and-whisker plots and any statistical significance between these parameters and driver experience was tested using the analysis of variance. There was no significant difference in the correlation between the questionnaire result of 'difficulty' and each exhalation parameter. By contrast, the low assessment group of 'enjoyment' showed large SDs in all parameters from both the VOC gas sensor and spirometer.

Unusually Small Thermal Expansion of Ordered Perovskite Oxide CaCu3Ru4O12 with High Conductivity.

We measured the coefficient of thermal expansion (CTE) of conducting composite ceramics 30 vol.% CuO-mixed CaCu3Ru4O12 together with CaCu3Ru4O12 and CuO. Although conducting ceramics tend to show higher CTE values than insulators, and its CTE value does not match with other ceramic materials, the CTE of CaCu3Ru4O12 (7⁻9 × 10-6/K) was as small as those of insulators such as CuO (9 × 10-6/K), alumina (8 × 10-6/K), and other insulating perovskite oxides. We propose that the thermal expansion of CaCu3Ru4O12 was suppressed by the Cu-O bond at the A-site due to the Jahn⁻Teller effect. This unusually small CTE of CaCu3Ru4O12 compared to other conducting oxides plays a vital role enabling successful coating of 30 vol.% CuO-mixed CaCu3Ru4O12 thick films on alumina substrates, as demonstrated in our previous study.

Trial of an All-Ceramic SnO2 Gas Sensor Equipped with CaCu3Ru4O12 Heater and Electrode.

We have constructed a gas sensor of SnO2 equipped with ceramic electrodes and a heater made of CaCu3Ru4O12, which demonstrated good device performance at high temperature. The CaCu3Ru4O12-based electrodes and heater were formed on Al2O3 substrates using a screen-printing process, which is cost-effective and suitable for mass-production. This all-ceramic device reached 600 °C at the lowest, and remained intact after one week of operation at 500 °C and rapid thermal cycling of 500 °C temperature changes within 10 s. We propose CaCu3Ru4O12 as a robust and reliable conducting material that can be a substitute for Pt in various devices.

Thermoelectric Array Sensors with Selective Combustion Catalysts for Breath Gas Monitoring.

Inflammable breath gases such as H2 and CH4 are used as bio markers for monitoring the condition of the colon. However, their typical concentrations of below 100 ppm pose sensitivity and selectivity challenges to current gas sensing systems without the use of chromatography. We fabricated a compact, gas-selective thermoelectric array sensor (TAS) that uses micro-machined sensor devices with three different combustion catalysts to detect gases such as H2, CO, and CH4 in breath. Using Pt/Pt-W thin-film micro-heater meanders, Pd/Al2O3, Pt,Pd,Au/Co3O4, and Pt/Al2O3 catalysts were heated to 320, 200, and 125 °C, respectively, and the gas sensing performances of the TAS for each gas and for a model breath gas mixture of 100 ppm H2, 25 ppm CO, 50 ppm CH4, and 199 ppm CO2 in air were investigated. Owing to its high catalyst temperature, the Pd/Al2O3 catalyst burned all three gases, while the Pt,Pd,Au/Co3O4 burned CO and H2 and the Pt/Al2O3 burned H2 selectively. To calibrate the gas concentration of the mixture gas without the use of a gas separation tool, linear discriminant analysis was applied to measure the sensing performance of TAS. To enhance the gas selectivity against H2, a double catalyst structure was integrated into the TAS sensor.

Thin Film Coating with Highly Dispersible Barium Titanate-Polyvinylpyrrolidone Nanoparticles.

Thin BaTiO3 (BT) coating layers are required in various multilayer ceramic technologies, and fine nanosized BT particles with good dispersion in solution are essential for this coating process. In this work, cubic and tetragonal phase monodispersed BT nanoparticles—which were referred to as LBT and HBT-PVP coated on their surface by polyvinylpyrrolidone (PVP) polymer—were prepared by low temperature synthesis (LTS) and hydrothermal method (HT) at 80 and 230 °C, respectively. They were applied for the thin film coating on polyethylene terephthalate (PET) and Si wafer substrates by a simple bar coating. The thickness of BT, LBT-PVP, and HBT-PVP films prepared by their 5 wt % coating agent on Si are around 268, 308, and 263 nm, and their surface roughness are 104.6, 91.6, and 56.1 nm, respectively. The optical transmittance of BT, LBT-PVP, and HBT-PVP films on PET are 55, 66, and 73% at 550 nm wavelength and the haze values are 34.89, 24.70, and 20.53% respectively. The mechanism of dispersant adsorbed on the BT surface for densification of thin film during the drying process of the film was discussed.

Increase in breath hydrogen concentration was correlated with the main pancreatic duct stenosis.

BACKGROUND: Hydrogen is produced from unabsorbed carbohydrates in the intestine through degradation and metabolism by hydrogenase of intestinal bacteria. The hydrogen is then partially diffused into blood flow and released and detected in exhaled breath. Pancreatic juice production is decreased in patients with reduced pancreatic exocrine function, including those with pancreatic cancer, thus decreasing digestion and absorption of nutrients including carbohydrates, which may increase undigested carbohydrates in the intestine and increase breath hydrogen concentration (BHC). The aim of this study was to investigate the association between BHC and pancreatic diseases. METHODS: A retrospective study was designed and 68 patients underwent morning fasting breath hydrogen test. Since there is no clear standard, normal BHC, the median of the measured values from the subjects (9 ppm) was adopted as the standard. The subjects were classified into those with a value exceeding the median (BHC high group: 32 patients) and a value equal to or below the median (BHC low group: 36 patients). Patients characteristics, blood test results and imaging findings characteristic of pancreatic diseases were compared between the groups. RESULTS: The age was significantly higher (P = 0.010) and the incidences of pancreatic ductal adenocarcinoma and autoimmune pancreatitis were significantly higher (P = 0.018 and P = 0.004, respectively) in the BHC high group. With respect to the blood test items, the Alb level was significantly lower in the BHC high group (P = 0.005). With respect to the characteristic imaging findings of pancreatic diseases, the proportions of patients with pancreatic enlargement, the main pancreatic duct (MPD) stenosis, and the MPD dilatation were significantly higher in the BHC high group (P = 0.022, P < 0.001, and P = 0.002, respectively). On univariate analysis, only the MPD stenosis was extracted as an independent factor (P = 0.014). CONCLUSION: It was suggested that the fasting BHC is associated with pancreatic diseases causing stenosis of the MPD, including pancreatic cancer (UMIN000020777).

Formation Mechanism and Dispersion of Pseudo-Tetragonal BaTiO3-PVP Nanoparticles from Different Titanium Precursors: TiCl4 and TiO2.

Nano-sized tetragonal BaTiO3 (BT) particles that are well dispersed in solution are essential for the dielectric layer in multilayer ceramic capacitor technology. A hydrothermal process using TiCl4 and BaCl2, as source of Ti and Ba, respectively, or the precursor TiO2 as seed for the formation of BT, and poly(vinylpyrrolidone) (PVP) as a surfactant, was employed in this study to enhance both the dispersibility and tetragonality (c/a) simultaneously in a single reaction process. The process parameters, i.e., the ratio of TiO2 substitution of TiCl4, the reaction time, and PVP content were systematically studied, and the growth mechanism and relation between the tetragonality and the particle size are discussed. Dynamic light scattering (DLS) analysis was used to show that truncated pseudo-tetragonal BT-PVP particles with an average size of 100 nm, having a narrow size distribution and a coefficient of variation (CV) as low as 20% and being mono-dispersed in water, were produced. The narrow particle size distribution is attributed to the ability of PVP to inhibit the growth of BT particles, and the high c/a of BT-PVP to heterogeneous particle growth using TiO2 seeds.

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.

Selective Detection of Target Volatile Organic Compounds in Contaminated Humid Air Using a Sensor Array with Principal Component Analysis.

We investigated selective detection of the target volatile organic compounds (VOCs) nonanal, n-decane, and acetoin for lung cancer-related VOCs, and acetone and methyl i-butyl ketone for diabetes-related VOCs, in humid air with simulated VOC contamination (total concentration: 300 µg/m³). We used six "grain boundary-response type" sensors, including four commercially available sensors (TGS 2600, 2610, 2610, and 2620) and two Pt, Pd, and Au-loaded SnO2 sensors (Pt, Pd, Au/SnO2), and two "bulk-response type" sensors, including Zr-doped CeO2 (CeZr10), i.e., eight sensors in total. We then analyzed their sensor signals using principal component analysis (PCA). Although the six "grain boundary-response type" sensors were found to be insufficient for selective detection of the target gases in humid air, the addition of two "bulk-response type" sensors improved the selectivity, even with simulated VOC contamination. To further improve the discrimination, we selected appropriate sensors from the eight sensors based on the PCA results. The selectivity to each target gas was maintained and was not affected by contamination.

Diagnosis by Volatile Organic Compounds in Exhaled Breath from Lung Cancer Patients Using Support Vector Machine Algorithm.

Monitoring exhaled breath is a very attractive, noninvasive screening technique for early diagnosis of diseases, especially lung cancer. However, the technique provides insufficient accuracy because the exhaled air has many crucial volatile organic compounds (VOCs) at very low concentrations (ppb level). We analyzed the breath exhaled by lung cancer patients and healthy subjects (controls) using gas chromatography/mass spectrometry (GC/MS), and performed a subsequent statistical analysis to diagnose lung cancer based on the combination of multiple lung cancer-related VOCs. We detected 68 VOCs as marker species using GC/MS analysis. We reduced the number of VOCs and used support vector machine (SVM) algorithm to classify the samples. We observed that a combination of five VOCs (CHN, methanol, CH3CN, isoprene, 1-propanol) is sufficient for 89.0% screening accuracy, and hence, it can be used for the design and development of a desktop GC-sensor analysis system for lung cancer.

Mixed-Potential Gas Sensors Using an Electrolyte Consisting of Zinc Phosphate Glass and Benzimidazole.

Mixed-potential gas sensors with a proton conductor consisting of zinc metaphosphate glass and benzimidazole were fabricated for the detection of hydrogen produced by intestinal bacteria in dry and humid air. The gas sensor consisting of an alumina substrate with platinum and gold electrodes showed good response to different hydrogen concentrations from 250 parts per million (ppm) to 25,000 ppm in dry and humid air at 100-130 °C. The sensor response varied linearly with the hydrogen and carbon monoxide concentrations due to mass transport limitations. The sensor responses to hydrogen gas (e.g., -0.613 mV to 1000 ppm H2) was higher than those to carbon monoxide gas (e.g., -0.128 mV to 1000 ppm CO) at 120 °C under atmosphere with the same level of humidity as expired air.

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.

CO Sensing Performance of a Micro Thermoelectric Gas Sensor with AuPtPd/SnO2 Catalyst and Effects of a Double Catalyst Structure with Pt/α-Al2O3.

The CO sensing properties of a micro thermoelectric gas sensor (micro-TGS) with a double AuPtPd/SnO2 and Pt/α-Al2O3 catalyst were investigated. While several nanometer sized Pt and Pd particles were uniformly dispersed on SnO2, the Au particles were aggregated as particles measuring >10 nm in diameter. In situ diffuse reflectance Fourier transform Infrared spectroscopy (DRIFT) analysis of the catalyst showed a CO adsorption peak on Pt and Pd, but no clear peak corresponding to the interaction between CO and Au was detected. Up to 200 °C, CO combustion was more temperature dependent than that of H2, while H2 combustion was activated by repeated exposure to H2 gas during the periodic gas test. Selective CO sensing of the micro-TGS against H2 was attempted using a double catalyst structure with 0.3-30 wt% Pt/α-Al2O3 as a counterpart combustion catalyst. The sensor output of the micro-TGS decreased with increasing Pt content in the Pt/α-Al2O3 catalyst, by cancelling out the combustion heat from the AuPtPd/SnO2 catalyst. In addition, the AuPtPd/SnO2 and 0.3 wt% Pt/α-Al2O3 double catalyst sensor showed good and selective CO detection. We therefore demonstrated that our micro-TGS with double catalyst structure is useful for controlling the gas selectivity of CO against H2.

SnO2 Nanosheet/Nanoparticle Detector for the Sensing of 1-Nonanal Gas Produced by Lung Cancer.

A sensor has been developed for detecting 1-nonanal gas present in the breath of lung cancer patients by combining SnO2 nanosheets with SnO2 nanoparticles and noble metal catalysts. A significant change in the electrical resistance of this sensor was observed with increasing 1-nonanal gas concentration; the resistance decreased by a factor of 1.12 within the range of 1 to 10 ppm at 300 °C. The recovery of the sensor's resistance after detecting 1-nonanal gas concentrations of 0.055, 0.18, 1, and 9.5 ppm was determined to be 86.1, 84.2, 80.4 and 69.2%, respectively. This high sensitivity is attributed to the accelerated oxidation of 1-nonanal molecules caused by the (101) crystal faces of the SnO2 nanosheets and should provide a simple and effective approach to the early detection of lung cancer.

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.