Influence of morphology and structure geometry on NO2 gas-sensing characteristics of SnO2 nanostructures synthesized via a thermal evaporation method

SnO₂ microwires, nanowires and rice-shaped nanoparticles were synthesized by a thermal evaporation method. The diameters of microwire and nanowire were 2 μm and 50-100 nm, respectively, with approximately the same length (∼20 μm). The size of nanoparticles was about 100 nm. It was confirmed that the as-synthesized products have SnO₂ crystalline rutile structure. The sensing ability of SnO₂ particle and wire-like structure configured as gas sensors was measured. A comparison between the particle and wire-like structure sensors revealed that the latter have numerous advantages in terms of reliability and high sensitivity. Although its high surface-to-volume ratio, the nanoparticle sensor exhibited the lowest sensitivity. The high surface-to-volume ratio and low density of grain boundaries is the best way to improve the sensitivity of SnO₂ gas sensors, as in case of nanowire sensor which exhibited a dramatic improvement in sensitivity to NO₂ gas.     

Gas sensing properties of SnO2 nanowires on micro-heater

The SnO₂ nanowires (NWs) network gas sensors were fabricated on a micro-electrode and heater suspended in a cavity. The sensors showed selective detection to C₂H₅OH at a heater power during sensor operation as low as 30-40 mW. The gas response and response speed of the SnO₂ NWs sensor to 100 ppm C₂H₅OH were 4.6- and 4.7-fold greater, respectively, than those of the SnO₂ nanoparticles (NPs) sensor with the same electrode geometry. The reasons for these enhanced gas sensing characteristics are discussed in relation to the sensing materials and sensor structures.     

Nanowire structured SnOx–SWNT composites: High performance sensor for NOx detection

A nanowire structured nanocomposite of tin oxide (SnO_x) and a single-walled carbon nanotube (SWNT) are fabricated using rheotaxial growth and thermal oxidation method for gas sensor application. The morphology, gas sensing properties, as well as the chemical and electrical properties are investigated. The oxidation temperature for Sn mainly determines the stoichiometry of the SnO_x nano-beads, and consequently the electrical and gas sensing properties of the nanocomposite sensors. The gas sensing to nitrogen oxide, hydrogen, oxygen, xylene, acetone, carbon monoxide, and ammonia are also examined to determine the gas selectivity of the sensor. The high sensitivity and selectivity towards NO_x of the nanocomposite sensor is realized via the porous structure of the SWNT template. The gas sensing mechanism of the nanocomposite structure is also discussed.     

One-step synthesis and gas sensing characteristics of hierarchical SnO2 nanorods modified by Pd loading

The hierarchical unloaded and Pd-loaded SnO₂ nanostructures, consisting of many aggregative nanorods were prepared by one-step hydrothermal method. A possible formation mechanism of these hierarchical structures was proposed. The butanone sensing properties of the sensors based on unloaded and hierarchical Pd-loaded SnO₂ nanorods were investigated. The results indicate that the response of sensor using hierarchical Pd-loaded SnO₂ nanorods to 1000 ppm butanone was 451 at 250 °C, which was about 10 times higher than that of sensor based on unloaded SnO₂. Such enhanced gas sensing performances can be attributed to both the chemical and the electrical contribution of Pd loading.     

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.     

Fabrication at wafer level of miniaturized gas sensors based on SnO2 nanorods deposited by PECVD and gas sensing characteristics

SnO₂ nanorods were successfully deposited on 3″ Si/SiO₂ wafers by inductively coupled plasma-enhanced chemical vapour deposition (PECVD) and a wafer-level patterning of nanorods layer for miniaturized solid state gas sensor fabrication were performed. Uniform needle-shaped SnO₂ nanorods in situ grown were obtained under catalyst- and high temperature treatment-free growth condition. These nanorods have an average diameter between 5 and 15 nm and a length of 160-300 nm. The SnO₂-nanorods based gas sensors were tested towards NH₃ and CH₃OH and gas sensing tests show remarkable response, showing promising and repeatable results compared with the SnO₂ thin films gas sensors.     

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.     

Semiconducting metal oxides as sensors for environmentally hazardous gases

This article extensively reviews the recent development of semiconductor metal oxide gas sensors for environmentally hazardous gases including NO₂, NO, N₂O, H₂S, CO, NH₃, CH₄, SO₂ and CO₂. The gas sensing properties of differently-prepared metal oxides and loaded metal oxides towards nine environmentally hazardous gases have been individually compared and digested. Promising materials for sensitive and selective detection of each hazardous gas have been identified. For instance, unloaded WO₃ nanostructures are the most promising candidates for NO₂ sensing while metal catalyst loaded WO₃ and gold-loaded SnO₂ sensors are among the most effective for NO and N₂O sensing, respectively. Moreover, related gas-sensing mechanisms are comprehensively discussed.     

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.     

Mixed-potential-type zirconia-based NO2 sensor with high-performance three-phase boundary

This paper focuses on the gas sensing properties of the mixed-potential-type NO₂ sensor based on yttria stabilized zirconia (YSZ) and NiO electrode. The sensing performance of the sensor was improved by modifying the three-phase boundary (TPB). Hydrofluoric acid with different concentrations (10%, 20% and 40%) was used to corrode YSZ substrate to obtain large superficial area of TPB. The scanning electron microscope and atomic force microscopic images showed that the 40% HF could form the largest superficial area at the same corroding time (3 h). The sensitivity of the sensor using the YSZ plate corroded with 40% hydrofluoric acid to 20-500 ppm NO₂ was 76 mV/decade at 850 °C, which was the largest among the examined HF concentrations. It was also seen that the sensor showed a good selectivity and speedy response kinetics to NO₂. On the basis of the measurements of anodic and cathodic polarization curves, as well as the complex impedance of the device, the sensing mechanism was confirmed to involve a mixed potential at the oxide sensing electrode.     

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.     

SnO2-based R134a gas sensor: Sensing materials preparation, gas response and sensing mechanism

Undoped SnO₂ and porous Al₂O₃ powders were obtained through a simple chemical precipitation process. SnO₂-based gas sensing materials and Al₂O₃ catalytic coating loaded with a noble metal were prepared by impregnation. The SnO₂ and Al₂O₃ powders were characterized by TEM, SEM, nitrogen adsorption-desorption experiment, FT-IR and in situ XRD. Gas responses of the SnO₂-based gas sensors were measured in a static state. The experimental results indicated that the response towards R134a of the SnO₂-based gas sensor can be significantly enhanced by loading noble metal and using catalytic coating. The sensor based on a double layer film SnO₂ (Au)/Al₂O₃ (Au) showed satisfactory results including large response, good selectivity, high long-term stability, fast response and recovery, revealing its potential application in the detection of refrigerants and the maintenance of air condition systems. Finally, a gas sensing mechanism for R134a is suggested and proved by bond energy data, FT-IR spectrum and in situ XRD.     

The effect of La2CuO4 sensing electrode thickness on a potentiometric NOx sensor response

In order to further understand the different contributions to NO_x sensing mechanism as well as the importance of electrode geometry, solid state potentiometric sensors with varying La₂CuO₄ sensing electrode thicknesses were studied. These sensors (with a Pt counter electrode) showed a dependence of NO₂ sensitivity which decreased with increasing thickness in the temperature range of 550-650 °C. They also showed NO sensitivity that was independent of thickness at 400 °C and 600 °C, but varied at temperatures between. This behavior was attributed to multiple mechanistic contributions explained by Differential Electrode Equilibria.     

The low temperature polysilicon (LTPS) thin film MOS Schottky diode on glass substrate for low cost and high performance CO sensing applications

The Au/SnO₂/n-LTPS MOS Schottky diode prepared on a glass substrate for carbon monoxide (CO) sensing applications is studied. The n-LTPS (n-type low temperature polysilicon) is prepared by excimer laser annealing and PH₃ plasma treatment of an amorphous Si thin film on glass substrate. The developed Schottky diode exhibits a high relative response ratio of ∼546% to 100 ppm CO ambient under condition of 200 °C and −3 V bias. The response ratio is better than the reported SnO₂ based resistive type CO sensors of 100% and 37%, respectively on poly-alumina and glass substrates or comparable to 390% of Pt-AlGaN/GaN Schottky diode CO sensor. Thus, the Au/SnO₂/n-LTPS Schottky diode has the potential to develop a low cost high performance CO sensor.     

Zeolite-modified WO3 gas sensors – Enhanced detection of NO2

Solid-state metal oxide gas sensors with zeolite overlayers have been developed as a means to improve sensor selectivity. Screen printed tungsten oxide (WO₃) sensors were modified by the addition of acidic and catalytic zeolite layers. The sensors were characterised before and after sensing experiments using X-ray diffraction, energy dispersive X-ray analysis and scanning electron microscopy. The sensors were tested against various gases and gas mixtures to assess their discriminatory behaviour. The results show that the sensors response can be tailored to be selective towards specific target gases by changing the zeolite; for example the H-ZSM-5 sensor gave a response 19 times greater to NO₂ than an unmodified control sensor. It was observed that the WO₃ based gas sensors showed a remarkable selectivity towards NO₂ in a gas mixture. The sensors also showed high levels of stability and sensitivity and have potential to be used in electronic nose technology.     

Highly sensitive NO2 sensor based on square-like tungsten oxide prepared with hydrothermal treatment

The square-like WO₃ nanosheets were synthesized by hydrothermal treatment of irregular WO₃ nanosheets prepared through acidification of Na₂WO₄·2H₂O. The obtained square-like and irregular WO₃ nanosheets were characterized with field emission scanning electron microscopy, X-ray powder diffraction and transmission electron microscopy. The gas sensing properties of sensors based on as-prepared samples were investigated. The results indicated that both samples exhibited high response to NO₂. The sensor based on square-like WO₃ nanosheets exhibited remarkably enhanced response and faster response/recovery time for NO₂ compared with that based on irregular nanosheets. Especially, the sensor based on square-like WO₃ nanosheets could detect NO₂ down to 40 ppb, which covered environmental standard. A possible reason for the influence of unique structure on the sensing properties of sensors based on square-like WO₃ was proposed.     

Growth kinetics of nanograins in SnO2 fibers and size dependent sensing properties

The present study investigates the growth kinetics of SnO₂ nanograins and determines the activation energy and mechanism of the growth in nanofiber form. The activation energy for the growth of the SnO₂ nanograins was estimated to be ∼28.28 kJ/mol, which is an order of magnitude smaller than that of bulk SnO₂. The estimated m value suggests that the growth mechanism of the nanograins is primarily through lattice diffusion in the pore control scheme. Precise control of the calcination temperature and time is necessary to maximize the efficiency of electrospinning-synthesized SnO₂ nanofibers for sensor applications. Importantly, the sensor fabricated with nanofibers of small nanograins showed much better sensing properties to CO and NO₂ comparing with the sensor fabricated with nanofibers of large nanograins. A mechanism to explain this finding is suggested.     

CuO/SnO2-In2O3 sensor for monitoring CO concentration in a reducing atmosphere

The CO sensing property of CuO-loaded SnO₂-In₂O₃ sensor was investigated in a reducing atmosphere. The sensor response to CO for CuO/SnO₂-In₂O₃ (8/2) was much higher than that for CuO/SnO₂ in the range of 200-1000 ppm of CO concentration. Such a high sensor response of CuO/SnO₂-In₂O₃ may originate from the high dispersion of CuO playing a role as sensing site.     

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.     

Enhanced sensor response of Ni-doped SnO2 hollow spheres

A novel sensing material of Ni-doped SnO₂ hollow spheres was prepared and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, inductively coupled plasma-optical emission spectroscopy and transmission electron microscopy. Gas sensing properties of the sensor fabricated from the as-prepared Ni-doped SnO₂ hollow spheres were systematically investigated and compared with those of pristine SnO₂ hollow spheres. Results showed that the Ni-doped sensor had a good selectivity to higher alcohols such as n-butanol with much higher response, while the undoped sensor exhibited poor response to all the tested gases with poor selectivity. The enhanced sensor performances are probably attributed to the formation of p-n heterojunctions between p-type NiO and n-type SnO₂. It also suggests that the Ni-dopant is a promising substitute for noble metal additives to fabricate sensor materials with a low cost.