Koichi Suematsu

WO3 Nanolamella Gas Sensor: Porosity Control Using SnO2 Nanoparticles for Enhanced NO2 Sensing

Tungsten trioxide (WO3) is one of the important multifunctional materials used for photocatalytic, photoelectrochemical, battery, and gas sensor applications. Nanostructured WO3 holds great potential for enhancing the performance of these applications. Here, we report highly sensitive NO2 sensors using WO3 nanolamellae and their sensitivity improvement by morphology control using SnO2 nanoparticles. WO3 nanolamellae were synthesized by an acidification method starting from Na2WO4 and H2SO4 and subsequent calcination at 300 °C. The lamellae were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM), which clearly showed the formation of single-crystalline nanolamellae with a c-axis orientation. The stacking of each nanolamella to form larger lamellae that were 50-250 nm in lateral size and 15-25 nm in thickness was also revealed. From pore size distribution measurements, we found that introducing monodisperse SnO2 nanoparticles (ca. 4 nm) into WO3 lamella-based films improved their porosity, most likely because of effective insertion of nanoparticles into lamella stacks or in between assemblies of lamella stacks. In contrast, the crystallite size was not significantly changed, even by introducing SnO2. Because of the improvement in porosity, the composites of WO3 nanolamellae and SnO2 nanoparticles displayed enhanced sensitivity (sensor response) to NO2 at dilute concentrations of 20-1000 ppb in air, demonstrating the effectiveness of microstructure control of WO3 lamella-based films for highly sensitive NO2 detection. Electrical sensitization by SnO2 nanoparticles was also considered.

Nanoparticle Cluster Gas Sensor: Controlled Clustering of SnO2 Nanoparticles for Highly Sensitive Toluene Detection

Gas sensing with nanosized oxide materials is attracting much attention because of its promising capability of detecting various toxic gases at very low concentrations. In this study, using clustered SnO2 nanoparticles formed by controlled particle aggregation, we fabricated highly sensitive gas sensing films to detect large gas molecules such as toluene. A hydrothermal method using stanic acid (SnO2·nH2O) gel as a precursor produced monodispersed SnO2 nanoparticles of ca. 5 nm at pH 10.6. Decreasing the solution pH to 9.3 formed SnO2 clusters of ca. 45 nm that were assemblies of the monodispersed nanoparticles, as determined by dynamic light scattering, X-ray diffraction, and transmission electron microscopy analyses. Porous gas sensing films were successfully fabricated by a spin-coating method using the clustered nanoparticles due to the loose packing of the larger aggregated particles. The sensor devices using the porous films showed improved sensor responses (sensitivities) to H2 and CO at 300 °C. The enhanced sensitivity resulted from an increase in the films porosity, which promoted the gas diffusivity of the sensing films. Pd loading onto the clustered nanoparticles further upgraded the sensor response due to catalytic and electrical sensitization effects of Pd. In particular, the Pd-loaded SnO2 nanoparticle clusters showed excellent sensitivity to toluene, able to detect it at down to low ppb levels.

Effect of Water Vapor on Pd-Loaded SnO2 Nanoparticles Gas Sensor

The effect of water vapor on Pd-loaded SnO2 sensor was investigated through the oxygen adsorption behavior and sensing properties toward hydrogen and CO under different humidity conditions. On the basis of the theoretical model reported previously, it was found that the mainly adsorbed oxygen species on the SnO2 surface in humid atmosphere was changed by loading Pd, more specifically, for neat SnO2 was O(-), while for 0.7% Pd-SnO2 was O(2-). The water vapor poisoning effect on electric resistance and sensor response was reduced by loading Pd. Moreover the sensor response in wet atmosphere was greatly enhanced by loading Pd. It seems that the electron depletion layer by p-n junction of PdO-SnO2 may impede OH(-) adsorption.

Pd Size Effect on the Gas Sensing Properties of Pd-Loaded SnO2 in Humid Atmosphere

Pd particles of different nanosizes were loaded on the SnO2 surface by using different Pd precursors for the purpose of investigating the Pd size effect on gas sensing properties in humid atmosphere. One kind of Pd-loaded SnO2 nanoparticle was characterized by smaller Pd particles (2.6 nm) with high dispersion, while another kind was characterized by larger Pd particles (5-10 nm) with low dispersion. It was found that both kinds of Pd on the SnO2 surface let the mainly adsorbed oxygen species change from O(-) to O(2-) in humid atmosphere at 350 °C. In addition, the water vapor poisoning effect on electric resistance and sensor response was greatly reduced by loading Pd. Interestingly, for the CO response at 350 °C, Pd-SnO2 with small Pd size showed almost constant sensor response with varying humidity (0.5-4 vol % H2O). While the CO response of Pd-SnO2 with large Pd size even increased with increasing amount of water vapor. Moreover, the former CO response was increased from 300 to 350 °C, but the later response decreased with increase in operating temperature. These behaviors were analyzed by temperature programed reduction (TPR) in H2 and CO atmospheres, and they were supported by the different catalytic activities of different nanosized Pd particles.

Surface-modification of SnO2 nanoparticles by incorporation of Al for the detection of combustible gases in a humid atmosphere

Inhibition of hydroxyl poisoning of SnO2 nanoparticles is important to develop a highly sensitive combustible gas sensor that functions in a humid atmosphere. For this purpose, we incorporated Al into SnO2 nanoparticles (Al-doped SnO2) by a precipitation method, and fabricated a thick-film-type sensor using a screen printing method. Bare SnO2 nanoparticles and Al2O3-loaded SnO2 nanoparticles were also prepared for comparison. The oxygen adsorption amount clearly decreased after Al doping and Al2O3 loading, according to temperature programmed desorption measurements. Al doping enhanced the sensor response (sensitivity) to H2, CO and C2H5OH in a humid atmosphere by almost five to ten times. Al2O3 loading also slightly increased the sensor response to each gas in a humid atmosphere. The enhancement of the sensor response was attributed to both Al and Al2O3 acting as hydroxyl absorbers on the surface of the nanoparticles, thereby providing an oxygen adsorption site for surface combustion reactions in a humid atmosphere. Based on the relationship between the sensor response and C2H5OH concentration, it was estimated that Al-doped SnO2 can detect less than one ppm C2H5OH in a humid atmosphere. Therefore, doping with Al, which protects and holds the adsorbed oxygen on the surface of the SnO2, is important as a surface modification to obtain humidity-tolerant semiconductor gas sensors.

Ultrasensitive Detection of Volatile Organic Compounds by a Pore Tuning Approach Using Anisotropically Shaped SnO2 Nanocrystals

Gas sensing with oxide nanostructures is increasingly important to detect gaseous compounds for safety monitoring, process controls, and medical diagnostics. For such applications, sensor sensitivity is one major criterion. In this study, to sensitively detect volatile organic compounds (VOCs) at very low concentrations, we fabricated porous films using SnO2 nanocubes (13 nm) and nanorods with different rod lengths (50-500 nm) that were synthesized by a hydrothermal method. The sensor response to H2 increased with decreasing crystal size; the film made of the smallest nanocubes showed the best sensitivity, which suggested that the H2 sensing is controlled by crystal size. In contrast, the responses to ethanol and acetone increased with increasing crystal size and resultant pore size; the highest sensitivity was observed for a porous film using the longest nanorods. Using the Knudsen diffusion-surface reaction equation, the gas sensor responses to ethanol and acetone were simulated and compared with experimental data. The simulation results proved that the detection of ethanol and acetone was controlled by pore size. Finally, we achieved ultrahigh sensitivity to ethanol; the sensor response (S) exceeded S = 100 000, which corresponds to an electrical resistance change of 5 orders of magnitude in response to 100 ppm of ethanol at 250 °C. The present approach based on pore size control provides a basis for designing highly sensitive films to meet the criterion for practical sensors that can detect a wide variety of VOCs at ppb concentrations.

Pulse-Driven Micro Gas Sensor Fitted with Clustered Pd/SnO2 Nanoparticles

Real-time monitoring of specific gas concentrations with a compact and portable gas sensing device is required to sense potential health risk and danger from toxic gases. For such purposes, we developed an ultrasmall gas sensor device, where a micro sensing film was deposited on a micro heater integrated with electrodes fabricated by the microelectromechanical system (MEMS) technology. The developed device was operated in a pulse-heating mode to significantly reduce the heater power consumption and make the device battery-driven and portable. Using clustered Pd/SnO2 nanoparticles, we succeeded in introducing mesopores ranging from 10 to 30 nm in the micro gas sensing film (area: ϕ 150 μm) to detect large volatile organic compounds (VOCs). The micro sensor showed quick, stable, and high sensor responses to toluene at ppm (parts per million) concentrations at 300 °C even by operating the micro heater in a pulse-heating mode where switch-on and -off cycles were repeated at one-second intervals. The high performance of the micro sensor should result from the creation of efficient diffusion paths decorated with Pd sensitizers by using the clustered Pd/SnO2 nanoparticles. Hence we demonstrate that our pulse-driven micro sensor using nanostructured oxide materials holds promise as a battery-operable, portable gas sensing device.

A micro gas sensor using TiO2 nanotubes to detect volatile organic compounds

To develop a portable gas sensor with low power consumption, we deposited a micro size sensing film (100×100 µm2) on a Si substrate with an integrated micro heater and electrodes constructed using micro-electro-mechanical system (MEMS) technology. TiO2 nanotubes ca. 500 nm long with a 50 nm diameter were used to sense and detect volatile organic compounds (VOCs). We demonstrate that the MEMS sensor responded well to ethanol and toluene in air at elevated temperatures, such as 500 °C, which suggests that it is a promising battery-operable micro gas sensor for detecting VOCs.

Effect of humid aging on the oxygen adsorption in SnO2 gas sensors

To investigate the effect of aging at 580 °C in wet air (humid aging) on the oxygen adsorption on the surface of SnO2 particles, the electric properties and the sensor response to hydrogen in dry and humid atmospheres for SnO2 resistive-type gas sensors were evaluated. The electric resistance in dry and wet atmospheres at 350 °C was strongly increased by humid aging. From the results of oxygen partial pressure dependence of the electric resistance, the oxygen adsorption equilibrium constants (K1; for O− adsorption, K2; for O2− adsorption) were estimated on the basis of the theoretical model of oxygen adsorption. The K1 and K2 in dry and wet atmospheres at 350 °C were increased by humid aging at 580 °C, indicating an increase in the adsorption amount of both O− and O2−. These results suggest that hydroxyl poisoning on the oxygen adsorption is suppressed by humid aging. The sensor response to hydrogen in dry and wet atmosphere at 350 °C was clearly improved by humid aging. Such an improvement of the sensor response seems to be caused by increasing the oxygen adsorption amount. Thus, the humid aging offers an effective way to improve the sensor response of SnO2 resistive-type gas sensors in dry and wet atmospheres.

Unexpected gas sensing properties of SiO2/SnO2 core–shell nanofibers under dry and humid conditions

SiO2/SnO2 core–shell nanofibers were synthesized using TEMPO-oxidized cellulose nanofibers as templates. The gas sensing properties of the synthesized SiO2/SnO2 core–shell nanofibers were evaluated under dry and humid conditions and compared to practical SnO2 nanoparticles produced by a hydrothermal method. The sensor responses were analyzed by monitoring the electric resistance changes upon the introduction of H2 or CO analytes. Surprisingly, the SiO2/SnO2 nanofibers showed a prominent sensor response at a higher temperature at which the adsorbed oxygen on the SnO2 nanoparticles desorbs under dry conditions. Unexpectedly, the SiO2/SnO2 nanofibers are available in humid atmosphere since they are less influenced by H2O poisoning compared to the SnO2 nanoparticles. Such an intriguing phenomenon could be interpreted in terms of the lower susceptibility of the major adsorbed oxygen species toward water vapor.