声表面波NO_2传感器敏感膜研究进展

由于工业检测、环境监测、医学监测等领域的需求,高性能NO2传感器得到了广泛的研究。声表面波传感器技术的发展为研发高灵敏度、高稳定性、响应快速、小型化的NO2传感器提供了极大的潜能。总结了近30年来声表面波NO2传感器敏感膜的研究现状,并根据现有的研究和传感器的应用需求,深入探讨了声表面波NO2传感器敏感膜面临的挑战和发展趋势。     

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.     

Epitaxially grown graphene based gas sensors for ultra sensitive NO2 detection

Epitaxially grown single layer and multi layer graphene on SiC devices were fabricated and compared for response towards NO₂. Due to electron donation from SiC, single layer graphene is n-type with a very low carrier concentration. The choice of substrate is demonstrated to enable tailoring of the electronic properties of graphene, with a SiC substrate realising simple resistive devices tuned for extremely sensitive NO₂ detection. The gas exposed uppermost layer of the multi layer device is screened from the SiC by the intermediate layers leading to a p-type nature with a higher concentration of charge carriers and therefore, a lower gas response. The single layer graphene device is thought to undergo an n-p transition upon exposure to increasing concentrations of NO₂ indicated by a change in response direction. This transition is likely to be due to the transfer of electrons to NO₂ making holes the majority carriers.     

Polypyrrole functionalized with FePcTSA for NO2 sensor application

The nitrogen dioxide (NO₂) sensing capability of polypyrrole (PPy) was enhanced dramatically after functionalized with iron(III)phthalocyanine-4,4′,4″,4-tetrasulfonic acid monosodium salt (FePcTSA). The incorporated phthalocyanine was confirmed by different characterization techniques such as UV–vis spectroscopy, FTIR, GFAAS, EDAX, etc. The resistance of the functionalized PPy decreased spontaneously during exposure to NO₂ gas at room temperature. This material exhibited excellent stability, reversibility, and reproducibility. The lowest response time (t₅₀) thus obtained is 47 s with a highest response factor (ΔR/R₀ × 100) of 50.25.     

Development of a highly sensitive and selective optical chemical sensor for batch and flow-through determination of mercury ion

A very sensitive, highly selective and reversible optical chemical sensor (optode) for mercury ion is described. The sensor is based on the interaction of Hg²⁺ with 2-mercapto-2-thiazoline (MTZ) in plasticized PVC membrane incorporating a proton-selective chromoionophore (ETH5294) and lipophilic anionic sites (sodium tetraphenylborate, NaTPB). The membranes were cast onto glass substrates and used for the determination of mercury ion in aqueous solutions by batch and flow-through methods. The sensor could be used in the range 2.0 × 10⁻¹⁰ to 1.5 × 10⁻⁵ M (0.04 ng mL⁻¹ to 3 μg mL⁻¹) Hg²⁺ with a detection limit of 5.0 × 10⁻¹¹ M and a response time of <40 s. It can be easily and completely regenerated by dilute nitric acid solution. The sensor has been incorporated into a home-made flow-through cell for determination of mercury ion in flowing streams with improved sensitivity, precision and detection limit. The sensor showed excellent selectivity for Hg²⁺ with respect to several common alkali, alkaline earth and transition metal ions. The results obtained for the determination of mercury ion in river water samples using the proposed optode was found to be comparable with the well-established cold-vapor atomic absorption method.     

High aspect ratio In2O3 nanowires: Synthesis, mechanism and NO2 gas-sensing properties

Flexural In₂O₃ nanowires with high aspect ratios were synthesized via a hydrothermal–annealing route. The as-synthesized In₂O₃ nanowires had diameters of 30–50 nm and length up to several microns. Various reaction parameters, such as the kind of reagents, the time of hydrothermal treatment, annealing time and annealing temperature, were investigated by a series of control experiments. The as-synthesized In₂O₃ nanowires showed excellent gas-sensing properties to NO₂ in terms of sensor response and selectivity.     

A CO2 sensor based upon a continuous-wave thermoelectrically-cooled quantum cascade laser

A CO₂ sensor based upon a continuous-wave thermoelectrically-cooled distributed feedback quantum cascade laser operating between 2305 and 2310 cm⁻¹ and a 54.2 cm long optical cell has been developed. Two approaches for direct absorption spectroscopy have been evaluated and applied for monitoring of the CO₂ concentration in gas lines and ambient laboratory air. In the first approach optical transmittance was derived from the single channel laser intensity, whilst in the second approach a ratio of signal and reference laser intensities (balanced detection) was used. The optimum residual absorption standard deviation was estimated to be 1.9 × 10⁻⁴ for 100 averages of 1 ms duration and 0.1 cm⁻¹ scans over the P(46) CO₂ absorption line of the ν₃ vibrational band at 2306.926 cm⁻¹. A CO₂ detection limit (1 standard deviation) of 36 ppb was estimated for 0.1 s average and balanced detection.     

EPR and DRS evidence for NO2 sensing in Al-doped ZnO

Zinc oxide (ZnO) is a well-known semiconducting multifunctional material wherein properties right from the morphology to gas sensitivity can be tailor-made by doping or surface modification. Aluminum (Al)-incorporated porous zinc oxide (Al:ZnO) exhibits good response towards NO₂ at low-operating temperature. The NO₂ gas concentration as low as 20 ppm exhibits S = 17% for 5 wt.% Al-incorporated ZnO. The NO₂ response increases with operating temperature and concentration and reaches to its maximum at 300 °C without any interference from other gases such as SO₃, HCl, LPG and alcohol. Physico-chemical characterization likes differential thermogravimetric analysis (TG-DTA) electron paramagnetic resonance (EPR) and diffused reflectance spectroscopy (DRS) have been used to understand the sensing behavior for pure and Al-incorporated ZnO. The TG-DTA depicts formation of ZnO phase at 287 °C. The EPR study reveals distinct variation for O⁻ (g = 2.003) and Zn interstitial (g = 1.98) defect sites in pure and Al:ZnO. The DRS studies elucidate signature of adsorbed NO_x species in aluminium-incorporated zinc oxide indicating its tendency to adsorb these species even at low temperatures. This paper is an attempt to correlate the gas sensing behavior with the physico-chemical studies such as EPR and DRS.     

High sensitive optode for selective determination of Ni based on the covalently immobilized thionine in agarose membrane

A novel Ni²⁺ optode was prepared by covalent immobilization of thionine, 3,7-diamine-5-phenothiazoniom thionineacetate, in a transparent agarose membrane. Influences of various experimental parameters on Ni²⁺ sensing, including the reaction time, the solution pH and the concentration of reagents were investigated. Under the optimized conditions, a linear response was obtained for Ni²⁺ concentrations ranging from 1.00 × 10⁻¹⁰ to 1.00 × 10⁻⁷ mol l⁻¹ with an R² value of 0.9985. The detection limit (3σ) of the method for Ni²⁺ was 9.30 × 10⁻¹¹ mol l⁻¹. The influence of several potentially interfering ions such as Ag⁺, Hg²⁺, Cd²⁺, Zn²⁺, Pb²⁺, Cu²⁺, Mn²⁺, Co³⁺, Cr³⁺, Al³⁺ and Fe³⁺ on the determination of Ni²⁺ was studied and no significant interference was observed. The membrane showed a good durability and short response time with no evidence of reagent leaching. The membrane was successfully applied for the determination of Ni²⁺ in environmental water samples.     

Effect of annealing and temperature on the NO2 sensing properties of tellurium based films

Influences of temperature and annealing on the electrical and sensing properties toward NO₂ of tellurium based films were investigated. The annealing at temperatures more than 100 °C causes a sharp decrease both of electrical resistance and sensitivity of the films. SEM analyzes indicated that annealing induced structural evolution of the films, including growth of large crystals in the matrix. Temperature-dependent electrical conductivity is strongly affected by presence of an NO₂ environment. The sensitivity toward NO₂, being controlled by gas concentration, decreases with operating temperature increase. On the other hand, the increase of operating temperature leads to a reduction of response–recovery times.

The results are discussed taking into consideration the contributions of grain boundary as well as grain bulk and surface resistance to the total conductivity. It is assumed the surface, including grain boundary, hole-enriched region is formed as a result of dangling bond chalcogen’s lone-pair electron interaction. Chemisorption of NO₂ molecules is accompanied by hole enrichment of the surface and grain boundary region, due to interaction of these molecules with lone-pair electrons.     

Single-crystalline Te microtubes: Synthesis and NO2 gas sensor application

Tellurium tubular crystals were grown by direct thermal evaporation of tellurium metal in an inert atmosphere on quartz substrates at ambient pressure without employing any catalyst. Tellurium powder was evaporated by heating at 600 °C and was condensed at a substrate temperature of 300–350 °C in the downstream of argon gas at a flow rate of 100 mL/min. The structure and chemical composition of the as-synthesized samples were examined by X-ray diffraction analysis, scanning electron microscopy, energy-dispersive X-rays microanalysis and micro-Raman spectroscopy. Scanning electron microscopy images and X-ray diffraction patterns showed that the as-synthesized Te had a tubular single-crystalline morphology with a hexagonal cross-section. The Te microtubes were typically 0.5–6 mm long, 30–70 μm in external diameter, and 5–20 μm thick. NO₂ gas-sensing properties of the Te microtubes at room temperature were also investigated. They showed a promising sensitivity and response towards tested gas.     

Highly sensitive gas sensors based on hollow SnO2 spheres prepared by carbon sphere template method

Hollow SnO₂ spheres were prepared in dimethylfomamide (DMF) by controlled hydrolysis of SnCl₂ using newly made carbon microspheres as templates. The phase composition and morphology of the material particles were characterized by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The gas sensing properties of sensors based on the hollow SnO₂ spheres were investigated. It was found that the sensor exhibited good performances, characterized by high response, good selectivity and very short response time to dilute (C₂H₅)₃N operating at 150 °C, especially, the response to 1 ppb (C₂H₅)₃N attained 7.1 at 150 °C. It was noteworthy that the response to 0.1 ppm C₂H₅OH of the sensor was 2.7 at 250 °C.     

Effect of surface modification on NO2 sensing properties of SnO2 varistor-type sensors

NO₂ sensing properties of SnO₂-based varistor-type sensors have been investigated in the temperature range of 400-650°C and in the NO₂ concentration range of 15–30 ppm. Pure SnO₂ exhibited a weak nonlinear I–V characteristic in air, but clear nonlinearity in NO₂ at 450°C. The breakdown voltage of SnO₂ shifted to a high electric field upon exposure to NO₂ and the magnitude of the shift was well correlated with NO₂ concentration. Thus, SnO₂ exhibited some sensitivity to NO₂ as a varistor-type sensor. When SnO₂ particles coated with a SiO₂ thin film were used as a raw material for fabricating a varistor, the breakdown voltage in air was approximately the double that of pure SnO₂ and the sensitivity to 15 ppm NO₂ was enhanced slightly. However, the sensitivity to 30 ppm NO₂ decreased. The Cr₂O₃-loading on SnO₂ also led to an increase in the breakdown voltage in air, but the Cr₂O₃ addition was not effective for promoting the NO₂ sensitivity under the present experimental conditions.     

Necked ZnO nanoparticle-based NO2 sensors with high and fast response

The NO₂ gas sensing characteristics of semiconductor type gas sensors with channels composed of necked ZnO nanoparticles (NPs) were investigated in this study. The heat treatment of the NPs at 400 °C led to their necking and coarsening. The response of the necked-NP-based sensors was as high as 100 when exposed to 0.2 ppm of NO₂ at 200 °C. As the concentration of NO₂ increased to 5 ppm, their response was enhanced to approximately 400. During the repeated injection of NO₂ gas with a concentration of 0.4 ppm, the sensors exhibited stable response characteristics. Furthermore, the 90% response and recovery times of the gas sensor were as fast as 13 and 10 s, respectively. These observations indicate that the non-agglomerated necking of the NPs induced by the heat treatment significantly enhances the gas sensing characteristics of the NP-based gas sensors.     

Highly sensitive and fast responding CO sensor using SnO2 nanosheets

A highly sensitive and fast responding CO sensor was fabricated from a sheet-like SnO₂. The SnO sheets were prepared by a room temperature reaction between SnCl₂, hydrazine and NaOH, and they were subsequently oxidized into SnO₂ sheets at high temperature (600 °C). The morphology and size of the SnO₂ sheets could be controlled during the formation of SnO, which influence the sensor response (R_a/R_g) and response time to a great extent. The sensor response of SnO nanosheets to 10 ppm CO was enhanced up to 2.34, and the 90% sensor response time could be reduced to 6 s, which are significantly higher and shorter than those of SnO₂ powders (1.57 and 88 s), respectively. The realization of both a high sensitivity and rapid response were explained in terms of rapid gas diffusion onto the entire sensing surface due to the less-agglomerated and very thin structure of SnO₂ nanosheets and the catalytic effect of Pt.     

H2 sensing characteristics of highly textured Pd-doped SnO2 thin films

The effects of the crystallographic orientation on the H₂ gas sensing properties were investigated in highly oriented polycrystalline Pd-doped SnO₂ films, which were obtained using rf magnetron sputtering of a Pd (0.5 wt%)-SnO₂ target on various substrates (a-, m-, r-, and c-cut sapphire and quartz). All the films had a similar thickness (110 nm), root-mean-square (rms) roughness (1.3 nm), surface area, and chemical status (O, Sn, and Pd). However, the orientation of the films was strongly affected by the orientation of the substrates. The (1 0 1), (0 0 2), and (1 0 1) oriented films were grown on (a-cut), (m-cut), and (r-cut) Al₂O₃ substrates, respectively, and rather randomly oriented films were deposited on (0 0 0 1) (c-cut) Al₂O₃ and quartz substrates. In addition, the oriented Pd-doped SnO₂ films were highly textured and had in-plane orientation relationships with the substrates similar to the epitaxial films. The (1 0 1) Pd-doped SnO₂ films on and Al₂O₃ showed a considerably higher H₂ sensitivity, and their gas response decreased with increasing sensing temperature (400–550 °C). The films deposited on and (0 0 0 1) Al₂O₃ showed the maximum sensitivity at 500 °C. The comparison of the H₂ gas response between undoped and Pd-doped SnO₂ films revealed that the Pd-doping shifted the optimum sensing temperature to a lower value instead of improving the gas sensitivity.     

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.     

Au-doped WO3-based sensor for NO2 detection at low operating temperature

Pure and Au-doped WO₃ powders for NO₂ gas detection were prepared by a colloidal chemical method, and characterized via X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The NO₂ sensing properties of the sensors based on pure and Au-doped WO₃ powders were investigated by HW-30A gas sensing measurement. The results showed that the gas sensing properties of the doped WO₃ sensors were superior to those of the undoped one. Especially, the 1.0 wt% Au-doped WO₃ sensor possessed larger response, better selectivity, faster response/recovery and better longer term stability to NO₂ than the others at relatively low operating temperature (150 °C).     

Ab initio calculations of NO2 and SO2 chemisorption onto non-polar ZnO surfaces

The authors present an ab initio study of NO₂ and SO₂ chemisorption onto non-polar ZnO and ZnO surfaces with the aim of providing theoretical hints for further developments in gas sensors. From first principles calculations (DFT-GGA approximation), the most relevant surface reduction scenarios are analyzed and, subsequently, considered in the chemisorption study. First, calculations indicate that NO₂ adsorbs avidly onto Zn surface atoms. This is compatible with the oxidizing character of NO₂. Second, results also explain the sensor poisoning by SO₂ adsorption (since this molecule competes with NO₂ for the same adsorption sites) and indicate that poisoning can only be reverted at typical operation temperatures (T ≤ 700 °C) in the case of stoichiometric ZnO surfaces.     

Ceria-doped SnO2 sensor highly selective to ethanol in humid air

In our earlier study, we reported that at 300 °C, a 2.0 wt.% CeO₂-doped SnO₂ sensor is highly selective to ethanol in the presence of CO and CH₄ gases [F. Pourfayaz, A. Khodadadi, Y. Mortazavi, S.S. Mohajerzadeh, CeO₂ doped SnO₂ sensor selective to ethanol in presence of CO, LPG and CH₄, Sens. Actuators B 108 (2005) 172–176]. In the present investigation, we report the influence of ambient air humidity on the ethanol selective SnO₂ sensor doped with 2.0 wt.% CeO₂. Maximum response to ethanol occurs at 300 °C which decreases with the relative humidity. The relative humidity was changed from 0 to 80% for different ambient air temperatures of 30, 40 and 50 °C and the response of the sensor was monitored in a 250–450 °C temperature range. As the relative humidity in 50 °C air increased from 0 to 30%, a 15% reduction in the maximum response to ethanol was observed. A further increase in the relative humidity no longer reduced the response significantly. The presence of humidity improved the sensor response to both CO and CH₄ up to 350 °C after which the extent of improvement became smaller and at 450 °C was almost diminished. The sensor is shown to be quite selective to ethanol in the presence of humid air containing CO and CH₄. The selectivity passes a maximum at 300 °C; however it declines at higher operating temperatures.