Development of high sensitivity tin oxide based sensors for gas/odour detection at room temperature

An effort has been made to develop thick film tin oxide gas sensors which could detect various gases/odours at room temperature. To achieve this, the fabricated sensors were annealed in oxygen plasma for various durations. It was then found that, the room temperature sensitivity of such sensors was increased to about ten times as compared to the sensitivity of the non-annealed sensors. Further, plasma annealed sensors are found to be practically independent of temperature and the room temperature sensitivity of these sensors are found to be about 1.5 times the sensitivity of the conventional sensors at its operating temperature of 300°C. Studies on the variation of d.c. resistance, sensitivity, temporal response, current–temperature characteristics and impedance spectroscopy with the annealing time have also been made. These studies reveal that, with the increase in annealing time, there is a permanent gradual reduction in the d.c. resistance of annealed sensors. Further, it is also observed that with the increase in annealing time, the response time improves, barrier height reduces, barrier capacitance increases and the dependence of the sensitivity with temperature reduces while the sensitivity itself improves many-fold.     

Gas sensing properties at room temperature of a quartz crystal microbalance coated with ZnO nanorods

Gas sensors based on a quartz crystal microbalance (QCM) coated with ZnO nanorods were developed for detection of NH₃ at room temperature. Vertically well-aligned ZnO nanorods were synthesized by a novel wet chemical route at a low temperature of 90 °C, which was used to grow the ZnO nanorods directly on the QCM for the gas sensor application. The morphology of the ZnO nanorods was examined by field-emission scanning electron microscopy (FE-SEM). The diameter and length of the nanorods were 100 nm and 3 μm, respectively. The QCM coated with the ZnO nanorods gas sensor showed excellent performance to NH₃ gas. The frequency shift (Δf) to 50 ppm NH₃ at room temperature was about 9.1 Hz. It was found that the response and recovery times were varied with the ammonia concentration. The fabricated gas sensors showed good reproducibility and high stability. Moreover, the sensor showed a high selectivity to ammoniac gas over liquefied petroleum gas (LPG), nitrous oxide (N₂O), carbon monoxide (CO), nitrogen dioxide (NO₂), and carbon dioxide (CO₂).     

Ammonia sensing properties of polypyrrole thin films at room temperature

Polypyrrole thin films were synthesized in situ by chemical polymerization. Fourier transform infrared spectroscopy revealed formation of polypyrrole. The morphological studies by scanning electron microscopy showed formation of uniform granular structure with average grain size of 0.6 μm. The film composition was characterized by X-ray photoelectron spectroscopy for chemical composition in polypyrrole film. These films were investigated for their sensing behaviour towards NH₃ and NO at room temperature. It has been observed that these films are selective for NH₃ and the sensitivity exhibited a linear response in range of 4-80 ppm.     

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.     

Thin film polypyrrole/SWCNTs nanocomposites-based NH3 sensor operated at room temperature

A PPY/SWCNTs nanocomposite-based sensor with relatively high sensitivity and fast response–recovery was developed for detection of NH₃ gas at room temperature. The gas-sensitive composite thin film was prepared using chemical polymerization and spin-coating techniques, and characterized by Fourier transformed infrared spectra and field-emission scanning electron microscopy. The results reveal that the conjugated structure of the PPY layer was formed and the functionalized SWCNTs were well-embedded. The effects of film thickness, annealing temperature, and SWCNTs content on gas-sensing properties of the composite thin film were investigated to optimize the gas-sensing performance. The as-prepared thin film PPY/SWCNTs composite sensor with optimized process parameters had a response of 26–276% upon exposure to NH₃ gas concentration from 10 to 800 ppm, and their response and recovery times were around 22 and 38 s, respectively.     

Cerium oxide/SnO2-based semiconductor gas sensors with improved sensitivity to CO

SnO₂-based semiconductor gas sensors have been successfully fabricated and tested for detecting carbon monoxide and methane. The sensitivity and selectivity of the sensors are tailored by incorporation of different additives such as platinum and cerium oxide. While platinum enhances the sensor response to CH₄, ceria suppresses its sensitivity in favor of carbon monoxide. The effect of operating temperature on the performance of sensors is reported. Addition of 10% cerium oxide in the SnO₂ sample leads to an insignificant response to methane even at an elevated temperature of 450°C, while its response to CO remains intact.     

Investigation on nanocrystalline copper-doped zirconia thin films for optical sensing of carbon monoxide at high temperature

Nanocrystalline copper-doped zirconia (CDZ; Cu:Zr = 16:84) thin films have been synthesized on long-period fiber gratings (CDZ-LPFG) by a polymeric precursor method. The CDZ-LPFG device was demonstrated to have high sensitivity and good reversibility for low-concentration CO sensing at high temperatures. The CDZ-LPFG responds with red shifts of its resonant wavelength (λ_R) to CO-containing gases and the λ_R shift reverses when it is exposed to air. The optical response of the CDZ-LPFG to CO is due primarily to the CDZ refractive index variations resulted from the reversible redox reactions (i.e. Cu²⁺ ⇔ Cu⁺) in reducing and oxidizing atmospheres. The magnitude of the λ_R shift exhibited a strong dependence on CO concentration in a range from 0 to 1000 ppm that is potentially useful for quantitative measurement.     

表面改性四针状纳米ZnO结构与气敏性能研究

将4种质量分数(5%,10%,20%,30%)的Co(CH3COO)24H2O混合到四针状纳米ZnO原料里,采用超声化学浸泡法制备出表面改性四针状纳米ZnO颗粒。通过XRD和TEM分析了表面改性四针状纳米ZnO结构的物相和形貌特征。随着Co(CH3COO)24H2O质量分数增大,Co3O4相明显出现,Co3O4相沉积在ZnO表面上。研究表明:以表面改性四针状纳米ZnO粉末为原料制备的厚膜气敏元件,与纯ZnO气敏元件相比,Co(CH3COO)24H2O质量分数为5%的气敏元件对酒精和甲醇有较高的灵敏度,并讨论了表面改性对气敏性能的影响。     

Fabrication of polypyrrole-phenylalanine nano-films with NH3 gas sensitivity

Polypyrrole (PPy) films complexed with phenylalanine were successfully synthesized via one-step emulsion polymerization. By incorporating phenylalanine into the conductive PPy backbone, highly functionalized PPy films have been produced and found to respond to ammonia gas. The chemical sensors based on the PPy-phenylalanine nanoparticle films displayed enhanced reproducible and reversible responses upon exposure to NH₃ gas. Their response was strongly dependent on the amount of the phenylalanine. The PPy-phenylalanine films were characterized by UV, IR, and XPS spectroscopy and compared to the PPy films. The gas detection and reversible response mechanism are discussed on the basis of these analysis results.     

Fabrication of gas sensing devices with ZnO nanostructure by the low-temperature oxidation of zinc particles

A method for low-temperature synthesis of a mixture of high-density ZnO nanoflakes and nanowires was developed to produce low-cost and high-efficiency gas sensors with ZnO nanostructures. ZnO nanoflakes and nanowires were grown on glass substrates by the RF sputter deposition of Zn particles and localized oxidation at a low temperature of 300 °C. The synthesized ZnO nanoflakes and nanowires were polycrystalline and had nanometer dimensions, as revealed by X-ray diffraction (XRD) and field emission scanning electron microscope (FESEM) measuring. A gas sensor based on the mixture of ZnO nanoflakes/nanowires responded rapidly and sensitively to ethanol. The sensing properties of the ZnO nanostructure sensor were approximately 72% for 50 ppm ethanol gas at an operating temperature of 100 °C. The response to 10 ppm of ethanol gas was 42% at the same temperature.     

Love wave hydrogen sensors based on ZnO nanorod film/36°YX-LiTaO3 substrate structures operated at room temperature

Love wave hydrogen sensors based on ZnO nanorod layers deposited on 36°YX-LiTaO₃ substrates have been studied. The ZnO nanorod layers are prepared by two steps: first, the seed layers, as well the guiding layers of the Love wave devices, are deposited by RF magnetron sputtering; second, the nanostructural layers, as well the sensing layers of the sensors, are grown by hydrothermal synthesis. Two kinds of ZnO layers have been analyzed by XRD, SEM and XPS. The XRD shows that both ZnO layers have (0 0 2) oriented wurtzite structures. The SEM results reveal that the morphologies of the deposited ZnO seed layers are continuous and compact, while the hydrothermal treated layers are with nanorods almost perpendicular to the substrate surfaces. Finally, the hydrogen sensing responses of the Love wave sensors activated by Pt catalysts are measured for various concentrations of hydrogen in synthetic air at room temperature. The results show that the sensors have high sensitivity and repeatability as the nanorod layers are optimized, such as the frequency shift 8 kHz toward 0.04% of H₂ in synthetic air is obtained while the height of the nanorod layer is about 2.1 μm and the central frequency of the sensor is about 125.5 MHz. The XPS analyses of the sensitive layers show that there are oxygen vacancies in the layers, so the oxygen vacancy model is used to explain the hydrogen sensing mechanism of the Love wave sensors.     

Gas sensing properties of a clad modified fiber optic sensor with Ce, Li and Al doped nanocrystalline zinc oxides

Spectral characteristics of a clad modified fiber optic gas sensor are studied for various concentrations (0-500 ppm) of ammonia, methanol and ethanol at room temperature. Cerium, aluminum and lithium doped (6 at.%) nanocrystalline zinc oxides are replaced with a clad and used as gas sensing materials. The study shows that the spectral intensity increases linearly with concentration for ammonia whereas it decreases for methanol and ethanol. The Ce doped ZnO exhibits higher gas sensitivity compared to Al and Li doped zinc oxides. The time response of the sensor is presented for a Ce doped ZnO with ammonia gas. A model is proposed for understanding the spectral intensity variations.     

Theoretical approach to the gas response of oxide semiconductor film devices under control of gas diffusion and reaction effects

Gas response of semiconductor film devices to reducing gas under control of gas diffusion and reaction effects was investigated in the light of recently developed theory of receptor function of small semiconductor crystals. The conventional gas diffusion and reaction equation is applicable consistently to the analysis of this issue provided that the size of the crystals and the partial pressure of reducing gas are small enough. Under this condition, gas response can be estimated as a function of film thickness and operating temperature. The bell-shaped correlations between response and temperature as well as depth dependence of the response are simulated and discussed.     

Selective detection of HCHO gas using mixed oxides of ZnO/ZnSnO3

Mixed oxides of ZnO/ZnSnO₃ doped with Au element were prepared by a hydrothermal process. The crystal structure, composition and ceramic microstructure of the powders obtained were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The results show that the product is the mixture of ZnO/ZnSnO₃; its particle size is about 500 nm with good dispersivity in shape. The sensitivity, selectivity, response and recovery properties of the ZnO/ZnSnO₃-based sensors were investigated by mixing a target gas in air. It is found that the sensors have remarkable sensitivity to HCHO vapor and satisfactory selectivity to other gases.     

ZnO hierarchical nanostructures grown at room temperature and their C2H5OH sensor applications

Highly crystalline ZnO hierarchical nanostructures were prepared at room temperature through the alkaline hydrolysis of zinc salt by the forced mixing of two immiscible solutions: Zn-nitrate aqueous solution and oleic-acid-dissolved n-hexane solution. The oleic acid acted as a surfactant in the room-temperature formation of well-defined ZnO hierarchical nanostructures, which subsequently demonstrated a sensitive and selective detection of C₂H₅OH. The responses of these hierarchical nanostructures to 10-100 ppm C₂H₅OH ranged from 15.7 to 177.7, which were 7-9 times higher than those of the agglomerated nanoparticles.     

Enhanced room temperature response of SnO2 thin film sensor loaded with Pt catalyst clusters under UV radiation for LPG

The room temperature response characteristics of SnO₂ thin film sensor loaded with platinum catalyst clusters are investigated for LPG under the exposure of ultraviolet radiation. The SnO₂-Pt cluster sensor structures have been prepared using rf sputtering. Combined effect of UV radiation exposure (λ = 365 nm) and presence of Pt catalyst clusters (10 nm thick) on SnO₂ thin film sensor surface is seen to lead to an enhanced response (4.4 × 10³) for the detection of LPG (200 ppm) at room temperature whereas in the absence of UV illumination a comparable response (∼5 × 10³) could be obtained but only at an elevated temperature of 220 °C. The present study therefore investigates the effect of UV illumination on LPG sensing characteristics of SnO₂ sensors loaded with Pt clusters of varying thickness values. Results indicate the possibility of utilizing the sensor structure with novel dispersal of Pt catalyst clusters on SnO₂ film surface for efficient detection of LPG at room temperature under the illumination of UV radiations.     

Influence of the measurement conditions on the sensitivity of SnO2 gas sensors operated thermo-cyclically

The conductance of several tin oxide gas sensitive layers was simultaneously measured in thermo-cyclic and isothermal operation mode at various concentrations of CO and propene in air, respectively. Different measurement conditions were set by the cycle time, the gas flow rate, the humidity and the thickness of the sensitive layer. The sensor response is expressed by the conductance-over-time profiles (CTPs), the gas sensitivity or by the sum of the CTP sampling points. The resultant sensitivities from the CTPs were found to be higher than those of the isothermal measurements. The CTPs considerably change with the kind of gas as well as with the variation of the measurement conditions. This is discussed for both types of target gases with respect to the temperature, the adsorbates assumed and the reaction kinetics in relation to the gas transport conditions in the porous gas sensitive layer.     

Fabrication of ultraviolet photoconductive sensor using a novel aluminium-doped zinc oxide nanorod-nanoflake network thin film prepared via ultrasonic-assisted sol-gel and immersion methods

Unique and novel thin films with aluminium (Al)-doped zinc oxide (ZnO) nanostructures consisting of nanorod-nanoflake networks were prepared for metal-semiconductor-metal (MSM)-type ultraviolet (UV) photoconductive sensor applications. These nanostructures were grown on a glass substrate coated with a seed layer using a combination of ultrasonic-assisted sol-gel and immersion methods. The synthesised ZnO nanorods had diameters varying from 10 to 40 nm. Very thin nanoflake structures were grown vertically and horizontally on top of the nanorod array. The thin film had good ZnO crystallinity with a root mean square roughness of approximately 13.59 nm. The photocurrent properties for the Al-doped ZnO nanorod-nanoflake thin films were more than 1.5 times greater than those of the seed layer when the sensor was illuminated with 365 nm UV light at a density of 5 mA/cm². The responsivity of the device was found to be dependent on the bias voltage. We found that similar photocurrent curves were produced over eight cycles, which indicated that the UV sensing capability of the fabricated sensor was highly reproducible. Our results provide a new approach for utilising the novel structure of Al-doped ZnO thin films with a nanorod-nanoflake network for UV sensor applications. To the best of our knowledge, UV photoconductive sensors using Al-doped ZnO thin films with a nanorod-nanoflake network have not yet been reported.     

Growth and gas sensing characteristics of p- and n-type ZnO nanostructures

ZnO nanoparticles (NPs) of 5-15 nm size and nanowires (NWs) of 50-100 nm dia., exhibiting p and n-type characteristics, respectively, have been synthesized using simple chemical process. ZnO NW-films exhibited good sensitivity and selectivity towards H₂S in ppm range with fast response and recovery times. Interestingly, ZnO NP-films showed p-type conductivity that has been obtained for the first time without intentional doping while NW-films showed n-type conduction as has also been reported in various earlier studies. The p- and n-type conductivities in NP- and NW-films have been confirmed using hot probe and Kelvin probe measurements. The n-type behavior of NW-films is attributed to oxygen vacancies, whereas the p-type nature of NP-films is attributed to the zinc vacancy, surface acceptor levels created by the adsorbed oxygen and/or the unintentional carbon doping in ZnO.     

Selectivity of flame-spray-made Nb/ZnO thick films towards NO2 gas

Unloaded ZnO and Nb/ZnO nanoparticles containing 0.25, 0.5 and 1 mol.% Nb were produced in a single step by flame-spray pyrolysis (FSP) technique. The nanoparticles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The BET surface area (SSA_BET) of the nanoparticles was measured by nitrogen adsorption. FSP yielded small Nb particles attached to the surface of the supporting ZnO nanoparticles, indicating a high SSA_BET. The morphology and accurate size of the primary particles were further investigated by TEM. Nb/ZnO nanoparticles paste composed of ethyl cellulose and terpineol as binder and solvent respectively was coated on Al₂O₃ substrate interdigitated with gold electrodes to form thick films by spin coating technique. After the sensing tests, the morphology and the cross-section of sensing film were analyzed by SEM and EDS analyses. The influence on a low dynamic range of Nb concentration on NO₂ response (0.1-4 ppm) of thick film sensor elements was studied at the operating temperatures ranging from 250 to 350 °C in the presence of dry air. The optimum Nb concentration was found be 0.5 mol.% and 0.5 mol.% Nb exhibited an optimum NO₂ response of ∼1640 and a short response time (27 s) for NO₂ concentration of 4 ppm at 300 °C.