Enhanced ammonia sensing performances of Pd-sensitized flowerlike ZnO nanostructure

We report the synthesis of flowerlike ZnO nanostructure using a facile hydrothermal process, and the investigation on the ammonia (NH₃)-sensing properties of the pure and palladium (Pd)-sensitized flowerlike ZnO nanostructure. The phase purity, morphology, and structure of the pure and Pd-sensitized ZnO nanostructure are investigated. The characterized results reveal that the flowerlike ZnO has a wurtzite structure and is composed of numerous aggregated single-crystalline ZnO nanorods with a diameter of about 60 nm. Having fabricated gas sensors based on the pure and Pd-sensitized flowerlike ZnO, we find that the Pd-sensitized sensor exhibits a response of 45.7-50 ppm NH₃ at 210 °C, which is about 8 times higher than that of pure ZnO at the optimal operating temperature of 350 °C. The enhanced NH₃-sensing performance demonstrates that the significant decrease in optimal operating temperature and the distinct increase in response are attributed to the sensitization effect of Pd.     

Room temperature ammonia sensors based on zinc oxide and functionalized graphite and multi-walled carbon nanotubes

In this work, different techniques are proposed to realize ammonia (NH₃) sensors working at room temperature and a preliminary electrical characterization under water vapor and in NH₃ atmospheres is presented. Three families of ceramic planar sensors based on a zinc oxide (ZnO) layer overlapped by screen-printed Pd-doped carboxyl groups functionalized multi-walled carbon nanotubes (Pd-COOH-MWCNTs) or by blocks of vertically aligned MWCNTs or by graphite as such and functionalized with fluorinated or nitrogenous functional groups were studied.These sensors were almost insensitive to humidity, while all of them gave a good response in NH₃ atmosphere, starting from about 45 ppm in the case of zinc oxide with fluorinated or nitrogenous MWCNTs and graphite or 50 ppm for Pd-COOH-MWCNTs sensors. These results are not actually as good as those reported in the literature, but this preliminary work proposes simpler and cheaper processes to realize NH₃ sensor for room temperature applications.     

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.     

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.     

LPG sensing properties of Pd-sensitized vertically aligned ZnO nanorods

One-dimensional (1-D) vertically aligned ZnO nanorods are synthesized on glass substrate through a simple chemical route and their liquefied petroleum gas (LPG) sensing properties are studied. The morphology and structure of vertically aligned ZnO nanorods has been characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. The LPG sensing properties of the vertically aligned ZnO nanorods are improved significantly after palladium (Pd) sensitization. The unsensitized vertically aligned ZnO nanorods exhibited the maximum response of 37% at 573 K upon exposure to 2600 ppm LPG, which improved to 60% at operating temperature of 498 K after the Pd sensitization. The Pd-sensitized vertically aligned ZnO nanorods showed more selectivity towards LPG as compared to CO₂. Our results demonstrate that the chemically grown vertically aligned ZnO nanorods along with Pd sensitization are promising material for the fabrication of cost effective and high performance gas sensors.     

Carbon dioxide gas sensor using a graphene sheet

In this article, we report on a high-performance graphene carbon dioxide (CO₂) gas sensor fabricated by mechanical cleavage. Unlike other solid-state gas sensors, the graphene sensor can be operated under ambient conditions and at room temperature. Changes in the device conductance are measured for various concentrations of CO₂ gas adsorbed on the surface of graphene. The conductance of the graphene gas sensor increases linearly when the concentration of CO₂ gas is increased from 10 to 100 ppm. The advantages of this sensor are high sensitivity, fast response time, short recovery time, and low power consumption.     

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.     

ZnO纳米棒修饰的QCM气体传感器检测NH_3研究

主要介绍了ZnO纳米棒修饰的石英晶体微天平(QCM)气体传感器的制备与测试。采用两步法在石英晶振片表面制备直径为100 nm的ZnO纳米棒敏感膜,构成QCM NH3传感器。检测系统为自主研发的基于LabVIEW平台的QCM气体传感器频率测试软件。检测NH3的体积分数为5×10-6~50×10-6,响应时间均在10 s以内,最大频差值为10.9 Hz,响应最大频差值与NH3体积分数呈现良好的线性关系。室温条件下,ZnO纳米棒敏感膜可以完全实现吸附解吸过程,具有可逆性。该传感器性能稳定,响应灵敏,具有重复性。     

Development and evaluation of piezoelectric-polymer thin film sensors for low concentration detection of volatile organic compounds related to food safety applications

In this study, the regioregular poly (3-hexyl thiophene) (rr-P3HT) based piezoelectric sensors were developed and evaluated to detect alcoholic volatile organic compounds (VOCs) associated with spoiled and Salmonella typhimurium contaminated packaged beef headspace. The drop coating technique was used to deposit thin films of rr-P3HT on both the sides of quartz crystal microbalance (QCM) electrode. The QCM polymer sensors were found to provide repeatable and reproducible sensor response to alcohol VOCs with a fast recovery (<2 min) at room temperature (25 °C). The principal component analysis on the sensors sensitivities was performed to discriminate the sensed alcohol VOCs, namely: 3-methyl-1-butanol from 1-hexanol. The QCM polymer sensors demonstrated selective response to low concentration of 3-methyl-1-butanol (average estimated lowest detection limit (LDL): 4.35 ppm) and to 1-hexanol (average estimated LDL: 3.20 ppm). The 30 days storage study performed on QCM sensors showed identical sensitivity responses for sensing 3-methyl-1-butanol and 1-hexanol at low concentrations.     

Formaldehyde sensors based on nanofibrous polyethyleneimine/bacterial cellulose membranes coated quartz crystal microbalance

A novel formaldehyde sensor based on nanofibrous polyethyleneimine (PEI)/bacterial cellulose (BC) membranes coated quartz crystal microbalance (QCM) has been successfully fabricated. The nanoporous three-dimensional PEI/BC membranes are composed of nanofibers with diameter of 30-60 nm. The sensor showed high sensitivity with good linearity and exhibited a good reversibility and repeatability towards formaldehyde in the concentration range of 1-100 ppm at room temperature. Moreover, the results showed that the sensing properties were mainly affected by the content of PEI component in nanofibrous membranes, concentration of formaldehyde and relative humidity. Additionally, the nanofibrous PEI/BC membrane coated QCM sensors exhibited a good selectivity to formaldehyde when tested with competing vapors. The simple and feasible method to prepare and coat the PEI/BC sensing membranes on QCM makes it promising for mass production at a low cost.     

Effect of NH3 gas on the electrical properties of single-walled carbon nanotube bundles

This study deals with the fabrication of sensors from single-walled carbon nanotubes (SWNTs) of 1.2 nm in diameters by a screen-printing method. These sensors have been exposed to ammonia (NH₃) gas at room temperature with nitrogen as the carrier gas.It was found that the electrical properties of SWNTs alter with temperature or the adsorption of ammonia gas. The SWNT is very sensitive to NH₃ gas. It can detect NH₃ in as low as concentration of 5 ppm. The sensitivity increases with increasing concentration. A saturation state is established at a concentration of ∼40 ppm, and the sensitivity of the sensor continues to increase in conjunction with an increase in concentration levels. Both the heating and increasing flux rates of carrier gas are used to improve gas desorption. The adsorption mechanism of gaseous molecules on SWNT bundle is discussed.     

Electrical response of electrospun PEDOT-PSSA nanofibers to organic and inorganic gases

Electrospun isolated nanofibers of poly(3,4-ethylenedioxythiophene) doped with (poly styrene sulfonic acid)-PEDOT-PSSA were used to sense vapors of several aliphatic alcohols. Due to the large surface to volume ratio and small quantity of active material used in their fabrication, these sensors have a similar or faster response time when compared to alcohol sensors based on PEDOT. Increasing the size of the alcohol molecule leads to longer response times, which is attributed to slower diffusion of the larger molecule into the polymer. The sensors were annealed in air at 70 °C and used to sense NH₃, HCl and NO₂ gas. The response time for NH₃ was faster than HCl, and the sensors showed a large initial response to NO₂ at room temperature which is very desirable, as some NO₂ gas sensors only operate at elevated temperatures. Electrospinning is a simple and inexpensive method of preparing PEDOT-PSSA nanofibers making it an attractive technique to fabricate polymer based low cost, rapid response and reusable gas sensors.     

Sensitivity and selectivity improvement of rf sputtered WO3 microhotplate gas sensors

Active layers consisting of rf sputtered WO₃ were deposited on microhotplate substrates. The films were doped with seven different materials (Pt, Au, Ag, Ti, SnO₂, ZnO and ITO (indium tin oxide)). The eight types of sensors (including pure tungsten oxide ones) were tested in the presence of ammonia, hydrogen sulphide, nitrogen dioxide, carbon monoxide and methane. It was found that gold improved the sensitivity to H₂S. On the other hand, doping with Ag and Pt led to higher responses to NO₂ and NH₃, respectively. No response to CH₄ was observed. The sensitivity to CO was very low. The influence of the working temperature on the sensor response was also studied. Our study proves that selective gas detection is possible combining a few tungsten oxide sensors with different dopants.     

Oxygen functionalisation of MWNT and their use as gas sensitive thick-film layers

Multi-wall carbon nanotubes (MWNT) were functionalised in an oxygen-based atmosphere by an inductively coupled RF-plasma at 13.56 MHz. X-ray photoelectron spectroscopy analysis showed that the chemical composition of the nanotube surface depends on the plasma conditions used. The MWNT were then deposited onto microhotplate gas sensor substrates by the drop coating method. A well-adhered thick-film of carbon nanotubes mesh (∼17 μm) was obtained after annealing in air. The influence of the different plasma conditions on the responsiveness of gas sensors fabricated with the functionalised MWNT was studied. The gas sensing properties were investigated both experimentally and theoretically for NO₂, and NH₃ at room temperature.     

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.     

Synthesis of ZnO nanorods and its application in NO2 sensors

One-dimensional (1D) ZnO nanorods with pencil-like shape and high aspect ratio were successfully synthesized using a cetyltrimethylammonium bromide (CTAB)-assisted hydrothermal process at 90 °C. The surface morphology and structure of nanocrystals were characterized by FE-SEM, XRD and XPS analysis. Experimental results show that the surfactant and base concentration play important roles in the formation and growth orientation of ZnO nanorods. The ZnO nanorods synthesized exhibits high response and selectivity to NO₂, the highest response to 40 ppm NO₂ reached 206 and the selectivity with respect to CO and CH₄ at same concentration reached 10.3 and 30 times, respectively. The effects of synthesis method, surfactant and calcination condition on sensing properties were systematically investigated. The results indicate that the CTAB-assisted low temperature hydrothermal process is a potentially facile method for synthesis of 1D ZnO nanorods and excellent potential candidates as gas sensing materials.     

Acetylene sensor based on Pt/ZnO thick films as prepared by flame spray pyrolysis

ZnO nanoparticles loaded with 0.2-2.0 at.% Pt have been successfully produced in a single step by flame spray pyrolysis (FSP) technique using zinc naphthenate and platinum(II) acetylacetonate, as precursors dissolved in xylene and their acetylene sensing characteristics have been investigated. The particle properties were analyzed by XRD, BET, TEM, SEM and EDS. Under the 5/5 (precursor/oxygen) flame condition, ZnO nanoparticles and nanorods were observed. The crystallite sizes of ZnO spherical and hexagonal particles were found to be ranging from 5 to 20 nm while ZnO nanorods were seen to be 5-20 nm in width and 20-40 nm in length. In addition, very fine Pt nanoparticles with diameter of ∼1 nm were uniformly deposited on the surface of ZnO particles. From gas-sensing characterization, acetylene sensing characteristics of ZnO nanoparticles is significantly improved as Pt content increased from 0 to 2  at.%. The 2 at.% Pt loaded ZnO sensing film showed an optimum C₂H₂ response of ∼836 at 1% acetylene concentration and 300 °C operating temperature. A low detection limit of 50 ppm was obtained at 300 °C operating temperature. In addition, Pt loaded ZnO sensing films exhibited good selectivity towards hydrogen, methane and carbon monoxide.     

Highly sensitive and selective LPG sensor based on α-Fe2O3 nanorods

The α-Fe₂O₃ nanorods were successfully synthesized without any templates by calcining the α-FeOOH precursor in air at 300 °C for 2 h and their LPG sensing characteristics were investigated. The α-FeOOH precursor was prepared through a simple and low cost wet chemical route at low temperature (40 °C) using FeSO₄·7H₂O and CH₃COONa as starting materials. The formation of α-FeOOH precursor and its topotactic transformation to α-Fe₂O₃ upon calcination was confirmed by X-ray diffraction measurement (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) analysis. The α-Fe₂O₃ nanorods exhibited outstanding gas sensing characteristics such as, higher gas response (∼1746-50 ppm LPG at 300 °C), extremely rapid response (∼3-4 s), relatively slow recovery (∼8-9 min), excellent repeatability, good selectivity and lower operating temperature (∼300 °C). Furthermore, the α-Fe₂O₃ nanorods are able to detect up to 5 ppm for LPG with reasonable response (∼15) at the operating temperature of 300 °C and they can be reliably used to monitor the concentration of LPG over the range (5-60 ppm). The experimental results clearly demonstrate the potential of using the α-Fe₂O₃ nanorods as sensing material in the fabrication of LPG sensors. Plausible LP G sensing mechanism of the α-Fe₂O₃ nanorods is also discussed.     

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.     

Vanadia doped tungsten-titania SCR catalysts as functional materials for exhaust gas sensor applications

Urea-SCR systems (selective catalytic reduction) are required to meet future NO_x emission standards of heavy-duty and light-duty vehicles. It is a key factor to control the SCR systems and to monitor the catalysts’ functionalities to achieve low emissions. The novel idea of this study is to apply commercially available SCR catalyst materials based on vanadia-doped tungsten-titania as gas sensing films for impedimetric thick-film exhaust gas sensor devices. The dependence of the impedance on the surrounding gas atmosphere, especially on the concentrations of NH₃ and NO₂, is investigated, as well as cross interferences from other components of the exhaust. The sensors provide a good NH₃ sensitivity at 500 °C. The sensor behavior is explained in light of the literature combining the fields of catalysts and semiconducting gas sensors.