Pinecone-shaped ZnO nanostructures: Growth, optical and gas sensor properties.

Pinecone-shaped ZnO nanostructures have been fabricated on Si substrate by pulsed laser deposition. The scanning electron microscope images showed that pinecone-shaped ZnO nanostructure was 6-fold symmetry and has the rough surface on one end. X-ray diffraction, Raman spectra and X-ray photoelectron spectroscopy indicated that the ZnO nanostructures have high crystal quality and a large amount of surface states. Compared with ZnO nanowires and nanobelts, the oxygen gas sensor based on pinecone-shaped ZnO nanostructures has excellent selectivity, fast response and recover, and lower operating temperature. Meanwhile, the response properties are very stable over several circles.     

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.     

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.     

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.     

High-sensitivity NO2 gas sensors based on flower-like and tube-like ZnO nanomaterials

Hierarchical flower-like and 1D tube-like ZnO architectures were synthesized by a microemulsion-based solvothermal method. Technologies of XRD, SEM and TEM were used to characterize the morphological and structural properties of the products. The influence of the flower-like and tube-like morphologies on their NO₂ sensing properties was investigated. The experimental results showed that high-sensitivity NO₂ gas sensors were fabricated. The sensitivity of the tube-like ZnO gas sensor was much higher than that of the flower-like ZnO gas sensor and the tube-like ZnO gas sensor exhibited shorter response time. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technique was employed to investigate the NO₂ sensing mechanisms. Free nitrate ions, nitrate and nitrite were the main adsorbed species during the adsorption, and NO also existed in the initial period of surface reoxidation. Furthermore, N₂O was formed via NO⁻ and N₂O₂⁻ stemmed from NO and increased upon rising temperature. Moreover, the PL spectra and the XPS spectra further proved that the intensity of donors (oxygen vacancy (V_O) and zinc interstitial (Zn_i)) and surface oxygen species (O₂⁻ and O₂) involved in the gas sensing mechanism leaded to the different sensitivities.     

CdO activated Sn-doped ZnO for highly sensitive, selective and stable formaldehyde sensor

Sn-, Ni-, Fe- and Al-doped ZnO and pure ZnO are prepared by coprecipitation method, and characterized by scanning electron microscope (SEM), energy diffraction spectra (EDS) and X-ray diffraction (XRD). Their formaldehyde gas sensing properties are evaluated and the results show that 2.2 mol% Sn dopant can increase the response of ZnO by more than 2 folds, while other dopants increase little response or even decrease response. Further, CdO is used to activate ZnO based formaldehyde sensing material. It is demonstrated that 10 mol% CdO activated 2.2 mol% Sn-doped ZnO has the highest formaldehyde gas response, with a linear sensitivity of ∼10/ppm at lowered work temperature of 200 °C than 400 °C of pure ZnO, and high selectivity over toluene, CO and NH₃, as well as good stability tested in 1 month.     

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.     

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.     

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.     

Application of m-CNTs/NaClO4/Ppy to a fast response, room working temperature ethanol sensor

A new blended material, m-CNTs/NaClO₄/Ppy, was developed as a gas sensor to detect ethanol concentrations at room temperature. The sensing material polypyrrole (Ppy) was synthesized in situ by UV-photo-polymerization. The multiwall carbon nanotubes (m-CNTs) added enhanced the short-term repeatability of the Ppy-sensing material. The relative resistance variation (R_ethanol/R_air) of m-CNTs/NaClO₄/Ppy was 1.193 when exposed to ethanol of 30,000 ppm. The sensor response and recovery times (both 20 s) were very short to this concentration. An unstable baseline of the sensor was explained by theoretical calculation of molecular dynamics made for ethanol adsorption on polypyrrole, which revealed formation of a new bond, N–HO. Adsorption energy decreased with increasing the number of ethanol molecules adsorbed and was 0.8 kcal/mol at eight adsorbed molecules. Sensor responses of three different Ppy samples were measured to ethanol concentrations of 18,000–40,000 ppm.     

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.     

Using a TiO2/ZnO double-layer film for improving the sensing performance of ZnO based NO gas sensor

NO gas sensors, based on ZnO thin film (ZnO_film), TiO₂ nanoparticulate film (TiO₂NP), and TiO₂NP/ZnO_film double-layer film, were fabricated, and their sensing characteristics towards NO gas were investigated in this study. The maximal response of a ZnO_film deposited onto a rougher Al₂O₃ substrate, towards NO gas, was higher than that of a ZnO_film deposited on a smoother glass substrate. Although the sensing response of the TiO₂NPs itself towards NO gas was minute, the TiO₂NP/ZnO_film double-layer film showed enhanced response as compared with TiO₂NP or ZnO_film single-layer film. In addition, the sensor response of the TiO₂NP/ZnO_film double-layer film was strongly influenced by the annealing time for the film preparation; the maximum response to NO was enhanced about 6.2 times as the annealing time was increased from 30 min to 2 h. Based on the XPS results, the increase in the transition zone between TiO₂NP and ZnO_film along with the appearance of Ti³⁺ state was noticed when the annealing time was increased. With the high sensitive TiO₂NP/ZnO_film/Al₂O₃ electrode, the limit of detection (S/N = 3) can be achieved at 8.8 ppb. The double-layer TiO₂NP/ZnO_film also showed improved selectivities with respect to NO₂ and CO.     

A metallic oxide gas sensor array for a selective detection of the CO and NH3 gases

An analysis of single gases using non-selective sensor elements is presented. It contains two steps: the identification of an unknown substance and the estimation of its concentration. To prepare the identification step, a calibration procedure is done to associate a class with each definite gas. In order to do this classification, the signals of the sensor array are transformed into quantities independent of the gas concentration but characteristic for its chemical compound. Then, the analysis parameters of an unknown substance allow to identify it with one of the calibration classes. After the identification of the gas, its concentration can be estimated with the model which is specific for each class of a single gas. The accuracy of this estimation is discussed.     

Design and performances of a mid-infrared CH4 detection device with novel three-channel-based LS-FTF self-adaptive denoising structure

A novel mid-infrared (MIR) CH₄ concentration detection device using three-channel-based least-square fast transverse filtering (LS-FTF) self-adaptive denoising structure was proposed. By introducing an additional noise-channel besides the traditional detection-channel and reference-channel, the noises can be well removed using the LS-FTF denoising algorithm. The detection procedure was described, and the key modules including the optical part and electrical part were designed and fabricated. Thorough experiments performed for the fabricated device show that the absolute detection error is less than 5%, and by quantifying the detected voltage using software, the minimum detection level is 8 ppm and the detection sensitivity is 9 ppm within the detection range of 8-1000 ppm. The measured maximum response time is less than 10 s, and the absolute detection error with temperature-compensation is less than 5%. The proposed three-channel-based LS-FTF denoising structure can also be adapted to other similar detection systems for noise elimination.     

Synthesis of novel SnO2/ZnSnO3 core-shell microspheres and their gas sensing properities

Large-scale novel core-shell structural SnO₂/ZnSnO₃ microspheres were successfully synthesized by a simple hydrothermal method with the help of the surfactant poly(vinyl pyrrolidone) PVP. The as-synthesized samples were characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). The results indicate that the shell was formed by single crystalline ZnSnO₃ nanorods and the core was formed by aggregated SnO₂ nanoparticles. The effects of PVP and hydrothermal time on the morphology of SnO₂/ZnSnO₃ were investigated. A possible formation mechanism of these hierarchical structures was discussed. Moreover, the sensor performance of the prepared core-shell SnO₂/ZnSnO₃ nanostructures to ethanol was studied. The results indicate that the as-synthesized samples exhibited high response and quick response-recovery to ethanol.     

Dispersive SnO2 nanosheets: Hydrothermal synthesis and gas-sensing properties

SnO₂ nanosheets with the thickness of 10 nm were successfully synthesized by a simple hydrothermal process at 180 °C for 12 h. The samples were characterized by X-ray power diffraction, scanning electron microscopy, transmission electron microscopy, and high-resolution transmission electron microscopy. The sensor performance of the as-prepared SnO₂ nanosheets for ethanol and carbon monoxide was measured. The results indicate that the sensor exhibited high response, quick response-recovery kinetics, and good repeatability.     

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.     

Synthesis of quantum size ZnO crystals and their gas sensing properties for NO2

Quantum size ZnO crystals have been synthesized successfully by a room temperature sol-gel process. Oleic acid (OA) has been used as capping agent to control the particle size of ZnO. The crystal structure and size of the ZnO are characterized by the X-ray diffraction (XRD) and transmission electron microscope (TEM). The XRD results show the as-synthesized ZnO has hexagonal wurtzite structure and the average crystallite size is 5.7 nm which is little less than TEM result. It is testified by photoluminescence (PL) and Raman spectra that the quantum size ZnO keeps the crystal structure of the bulk ZnO and possesses more surface defects. The quantum size ZnO has the highest response of 280 to NO₂ and the highest selectivity of 31 and 49 corresponding to CO and CH₄ at operating temperature of 290 °C. The effect of calcination temperatures on sensing property and transient response of the ZnO sensor are also investigated.     

Mechanism of CO and O3 sensing on WO3 surfaces: First principle study

The microscopic mechanism of O₃ and CO sensing on WO₃ surfaces is clarified by a first principle study. It is shown that ozone reduces to O₂ on the (0 0 1) surface of WO₃ decreasing in such a way the number of oxygen vacancies and the conductivity (since oxygen vacancies act as donors in WO₃). The mechanism of CO sensing is just the opposite: the CO molecule is oxidized to CO₂ on the WO₃ surface increasing the number of oxygen vacancies and the conductivity. The reaction enthalpy for the reduction process of O₃ is found to be −2.54 eV in local density approximation (LDA) and −2.86 in generalized gradient approximation (GGA). The corresponding values for CO are −1.73 eV (LDA) and −1.52 eV (GGA). The adsorptions of O₃ and CO without reduction or oxidation are also calculated but the related energies are much smaller.     

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.