Effect of aluminium doping on structural and gas sensing properties of zinc oxide thin films deposited by spray pyrolysis

A facile spray pyrolysis route is used to deposit aluminium doped ZnO (AZO) thin films on to the glass substrates. It is observed that on aluminium doping the particle size of ZnO reduces significantly; moreover, uniformity of particle also gets enhanced. Their XRD study reveals that intensity ratio of crystal planes depend on the aluminium doping concentration. The gas response studies of; ∼800 nm thick Al-doped ZnO films at different operating temperatures show that 5 at% Al-doped ZnO thin film exhibits highest response towards H₂S gas at 200 °C. The results suggest that the gas response strongly depends on the particle size and aluminium doping in the ZnO.     

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.     

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.     

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.     

Improving the ethanol sensing of ZnO nano-particle thin films—The correlation between the grain size and the sensing mechanism

ZnO and Sn doped ZnO (ZnO:Sn) thin films at various doping concentrations from 1 to 10 at.% were prepared by the sol-gel method for an ethanol sensing application. The Sn doping significantly influenced the film growth, grain size and response of the films. The XRD patterns showed that the hexagonal wurtzite structure of the ZnO film was retained even after the Sn doping. The crystallite grain sizes of the ZnO:Sn thin films at 0, 2 and 4 at.% were estimated by using the typical Scherrer's equation. The crystalline quality of the films at 6, 8 and 10 at.% of Sn was degenerated. Typical FESEM images demonstrated the different morphologies for the ZnO:Sn thin films at various Sn concentrations; many pores of various dimensions were observed depending on the doping level. A TEM analysis of the ZnO:Sn thin films at 0, 2 and 4 at.% was performed to verify the grain size. The optimum Sn doping level of ZnO:Sn thin film for ethanol sensing was estimated to be 4 at.%. The 4 at.% sample obtained the highest response to ethanol vapor in the 10-400 ppm level range at a low operating temperature of 250 °C. The sensing mechanism was explained by a variation in the sensitivity model from a neck-grain-boundary controlled sensitivity to a neck-controlled sensitivity. Our work demonstrates the ability to reduce the working temperature as well as to increase the response of ZnO thin film based gas sensors to detect ethanol, which would be of great merit for commercialized applications.     

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.     

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.     

Electrospun Cu-doped ZnO nanofibers for H2S sensing

Pure and Cu-doped ZnO nanofibers were synthesized via electrospinning technology. The morphology and structure of the as-synthesized nanofibers were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy. The effects of Cu doping on H₂S sensing properties at low concentration (1-10 ppm) were investigated at 230 °C. The results show that the H₂S sensing properties of ZnO nanofibers are effectively improved by Cu doping: 6 at% Cu-doped ZnO nanofibers show a maximum sensitivity to H₂S gas, and the response to 10 ppm H₂S is one order of magnitude higher than the one of pure ZnO nanofibers.     

Synthesis of nearly monodisperse Co3O4 nanocubes via a microwave-assisted solvothermal process and their gas sensing properties

Nearly monodisperse Co₃O₄ nanocubes have been prepared by a microwave-assisted solvothermal (MS) method at 180 °C for 20 min. The samples are characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD pattern and TEM images of the products illustrated that Co₃O₄ nanocubes had a cubic phase with a lateral size of ∼20 nm. The gas response of the Co₃O₄ nanocubes was studied to several typical organic gases. The Co₃O₄ nanocubes showed good gas sensing performance towards xylene and ethanol vapors with rapid and high responses at a low-operating temperature. The results showed that the Co₃O₄ nanocubes can be used to fabricate high performance gas sensors.     

Hydrothermal synthesis of hollow ZnSnO3 microspheres and sensing properties toward butane

Hollow ZnSnO₃ microspheres were successfully prepared by hydrothermal method at 160 °C for 12 h. The prepared material was characterized by field emission scanning electron microscope (FESEM), transmission electron microscope (TEM) and X-ray diffraction measurements (XRD). The average diameter of the hollow ZnSnO₃ microspheres was in the range of 400-600 nm. Compared with solid ZnSnO₃ microspheres structure, the hollow ZnSnO₃ microspheres showed better response (S) to butane. To 500 ppm butane, the sensor response (S) of the hollow ZnSnO₃ microspheres was 5.79 at the optimum operating temperature of 380 °C, and the response and recovery time were 0.3 s and 0.65 s, respectively. The sensitivities of sensors based on this material were linear with the concentration of butane in the range of 100-1000 ppm.     

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.     

Selective gas sensing response from different loading of Ag in sol-gel mesoporous titania powders

Bare and Ag loaded TiO₂ (0.05, 0.5, and 5.0 mol% Ag) powders prepared by sol-gel process have been used for the detection of ethanol, LPG, acetone and toluene gases. These materials were well characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS) and Brunauer-Emmett-Teller (BET) specific surface area analysis techniques. Specific surface area increased with increasing Ag loading in these mesoporous materials. A thorough TEM/HRTEM investigation with X-ray maps of the modified particles shows the extent of TiO₂ surface coverage by Ag nanoparticles. From the comparative study of the sensor response of Ag-TiO₂ powders for various gases, it is observed that each Ag loading resulted in the highest response towards a particular gas or in other words, every gas responded best towards a particular Ag loading of the sensor material, i.e. 0.05 mol% Ag-TiO₂ sensor showed highest response towards ethanol, 0.5 mol% Ag-TiO₂ sensor showed best response towards toluene, whereas, bare TiO₂ proved to be the best sensor for both acetone and LPG gases. This establishes that Ag loading is not required for detection of acetone and LPG gases. On the basis of detailed materials characterization, a mechanism for the gas sensing response of each analyte has been discussed.     

Improved selective acetone sensing properties of Co-doped ZnO nanofibers by electrospinning

Pure and Co-doped (0.3 wt%, 0.5 wt%, and 1 wt%) ZnO nanofibers are synthesized by an electrospinning method and followed by calcination. The as-synthesized nanofibers are characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy dispersive X-ray (EDX) spectroscopy. Comparing with pure ZnO nanofibers, Co-doped nanofibers exhibit improved acetone sensing properties at 360 °C. The response of 0.5 wt% Co-doped ZnO nanofibers to 100 ppm acetone is about 16, which is 3.5 times larger than that of pure nanofibers (about 4.4). The response and recovery times of 0.5 wt% Co-doped ZnO nanofibers to 100 ppm acetone are about 6 and 4 s, respectively. Moreover, Co-doped ZnO nanofibers can successfully distinguish acetone and ethanol/methanol, even in a complicated ambience. The high response and quick response/recovery are based on the one-dimensional nanostructure of ZnO nanofibers combining with the Co-doping effect. The selectivity is explained by the different optimized operating temperatures of Co-doped ZnO nanofibers to different gases.     

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.     

Facile synthesis of hierarchical SnO2 semiconductor microspheres for gas sensor application

Hierarchical SnO₂ microspheres were synthesized by a hydrothermal method at 140 °C using stannic chloride hydrate and sodium hydroxide as starting materials. The individual hierarchical SnO₂ microsphere ranged from 700 to 900 nm in diameter. After these microspheres were heated at 600 °C for 2 h, the spheres were cross-linked into clusters by short SnO₂ nanorods as revealed by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Most importantly, SnO₂ hierarchical microsphere sensor exhibits excellent selectivity and fast response to ethanol. Response and recovery times were 0.6 s and 11 s when the sensor was exposed to 50 ppm ethanol at an operating temperature of 300 °C. Thus, hierarchical structures play a significant role in the field of gas sensing.     

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.     

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).     

Fabrication of N-type Fe2O3 and P-type LaFeO3 nanobelts by electrospinning and determination of gas-sensing properties

N-type Fe₂O₃ nanobelts and P-type LaFeO₃ nanobelts were prepared by electrospinning. The structure and micro-morphology of the materials were characterized by X-ray diffraction (XRD) and scanning of electron microscopy (SEM). The gas sensing properties of the materials were investigated. The results show that the optimum operating temperature of the gas sensors fabricated from Fe₂O₃ nanobelts is 285 °C, whereas that from LaFeO₃ nanobelts is 170 °C. Under optimum operating temperatures at 500 ppm ethanol, the response of the gas sensors based on these two materials is 4.9 and 8.9, respectively. The response of LaFeO₃-based gas sensors behaves linearly with the ethanol concentration at 10-200 ppm. Sensitivities to different gases were examined, and the results show that LaFeO₃ nanobelts exhibit good selectivity to ethanol, making them promising candidates as practical detectors of ethanol.     

Fe2O3 modified thick films of nanostructured SnO2 powder consisting of hollow microspheres synthesized from pyrolysis of ultrasonically atomized aerosol for LPG sensing

Nanostructured hollow spheres of SnO₂ with fine nanoparticles were synthesized by ultrasonic atomization. Thick film gas sensors were fabricated by screen printing technique. Different surface modified films (Fe₂O₃ modified SnO₂) were obtained by dipping them into an aqueous solution (0.01 M) of ferric chloride for different intervals of time followed by firing at 500 °C. The structural and microstructural studies of the samples were carried out using XRD, SEM, and TEM. The sensing performance of pure and modified films was studied by exposing various gases at different operating temperatures. One of the modified sample exhibited high response (1990) to 1000 ppm of LPG at 350 °C. Optimum amount of Fe₂O₃ dispersed evenly on the surface_, adsorption and spillover of LPG on Fe₂O₃ misfits and high capacity of adsorption of oxygen on nanostructured hollow spheres may be the reasons of high response.     

Effect of ‘Pt’ loading in ZnO-CuO hetero-junction material sensing carbon monoxide at room temperature

Sensing of carbon monoxide (CO) was carried out with ZnO-CuO and Pt/ZnO-CuO. Synthesized materials were characterized by temperature-programmed reduction (TPR), high-resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD). The composite materials of ZnO-CuO were found to have an active sensing center, The sensor response obtained for an optimized ratio of ZnO and CuO (1:1 weight ratio) yielded the highest response of 1.28 (R_co/R_air) for 1000 ppm of CO at room temperature; the response and recovery times were found to be 41 and 86 s, respectively. However, loading 1:1 ZnO-CuO with 0.4% Pt boosted the sensor response to 2.64 (R_co/R_air) for the same CO concentration. The sensor (0.4% Pt/ZnO-CuO) response was linear towards CO concentrations between 100 and 1000 ppm. In the Pt loaded case both the response and recovery times were found to be 81 s. A mechanism for CO sensor response was put forward with reference to CO adsorption and desorption.