Synthesis and characterisation of nanosized TiO2-ZrO2 binary system prepared by an aqueous sol-gel process: Physical and sensing properties

Nanostructured TiO₂-ZrO₂ thin films and powders were prepared by a straightforward aqueous particulate sol-gel route. Titanium (IV) isopropoxide and zirconium (IV) acetate hydrate were used as precursors, and hydroxypropyl cellulose was used as a polymeric fugitive agent in order to increase the specific surface area. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy revealed that the powder were crystallised at the low temperature of 500 °C, containing anatase-TiO₂ and tetragonal-ZrO₂ phases. Furthermore, it was found that ZrO₂ retarded the anatase-to-rutile transformation up to 900 °C. The activation energies for crystallite growth of TiO₂ and ZrO₂ components in the binary system were calculated 10.16 and 3.12 kJ/mol, respectively. Transmission electron microscope (TEM) image showed that one of the smallest crystallite sizes was obtained for TiO₂-ZrO₂ binary mixed oxide, being 5 nm at 500 °C. Field emission scanning electron microscope (FESEM) analysis revealed that the deposited thin films had nanostructured morphology with the average grain size of 20 nm at 500 °C and 36 nm at 900 °C. Thin films produced under optimised conditions showed excellent microstructural properties for gas sensing applications. They exhibited a remarkable response towards low concentrations of CO and NO₂ gases at low operating temperature of 150 °C, resulted in an increase of thermal stability of sensing films as well as a decrease in the power consumption. Furthermore, calibration curves revealed that TiO₂-ZrO₂ sensor follows the power law, S = A[gas]^B (where S is sensor response, coefficients A and B are constants and [gas] is gas concentration) for the two types of gases, and it has excellent capability for the detection of low gas concentrations.     

SnO2 thin film sensor with enhanced response for NO2 gas at lower temperatures

Semiconducting SnO₂ thin films having higher value of electrical conductivity have been deposited using RF sputtering technique in the reactive gas environment (30% O₂ + 70% Ar) using a metallic tin (Sn) target for detection of oxidizing NO₂ gas. The effect of growth pressure (12-18 mTorr) on the surface morphology and structural property of SnO₂ film was studied using Atomic force microscopy (AFM), Scanning electron microscopy (SEM) and X-ray Diffraction (XRD) respectively. Film deposited at 16 mTorr sputtering pressure was porous with rough microstructure and exhibits high sensor response (∼2.9 × 10⁴) towards 50 ppm NO₂ gas at a comparatively low operating temperature (∼100 °C). The sensor response was found to increase linearly from 1.31 × 10² to 2.9 × 10⁴ while the response time decrease from 12.4 to 1.6 min with increase in the concentration of NO₂ gas from 1 to 50 ppm. The reaction kinetics of target NO₂ gas on the surface of SnO₂ thin film at the Sn sites play important role in enhancing the response characteristics at lower operating temperature (∼100 °C). The results obtained in the present study are encouraging for realization of SnO₂ thin film based sensor for efficient detection of NO₂ gas with low power consumption.     

In2O3 + xBaO (x = 0.5-5 at.%) - A novel material for trace level detection of NOx in the ambient

Indium oxide (In₂O₃) doped with 0.5-5 at.% of Ba was examined for their response towards trace levels of NO_x in the ambient. Crystallographic phase studies, electrical conductivity and sensor studies for NO_x with cross interference for hydrogen, petroleum gas (PG) and ammonia were carried out. Bulk compositions with x ≤ 1 at.% of Ba exhibited high response towards NO_x with extremely low cross interference for hydrogen, PG and ammonia, offering high selectivity. Thin films of 0.5 at.% Ba doped In₂O₃ were deposited using pulsed laser deposition technique using an excimer laser (KrF) operating at a wavelength of (λ) 248 nm with a fluence of ∼3 J/cm² and pulsed at 10 Hz. Thin film sensors exhibited better response towards 3 ppm NO_x quite reliably and reproducibly and offer the potential to develop NO_x sensors (Threshold limit value of NO₂ and NO is 3 and 25 ppm, respectively).     

A nitric oxide gas sensor based on Rayleigh surface acoustic wave resonator for room temperature operation

A Rayleigh surface acoustic wave (RSAW) resonator with polyaniline/tungsten oxide nanocomposite thin film is investigated as a gas sensor for detecting the presence of nitric oxide (NO) in air. The sensor developed in this work was sensitive to NO gas at room temperature. It is shown that the sensor had a frequency shift of 1.2 ppm when it was exposed to 138 ppb NO. The negative frequency response increased with NO concentration increasing. The response and recovery times of the NO sensor in this work were about 20-80 s. In addition, this RSAW sensor also exhibited reversibility and repeatability to the presence of NO gas. Especially, the presented sensor showed high selectivity with NO gas to separate from NO₂ and CO₂ gases.     

A route to high sensitivity and rapid response Nb2O5-based gas sensors: TiO2 doping, surface embossing, and voltage optimization

We report a novel route for the fabrication of highly sensitive and rapidly responding Nb₂O₅-based thin film gas sensors. TiO₂ doping of Nb₂O₅ films is carried out by co-sputtering without the formation of secondary phases and the surface area of TiO₂-doped Nb₂O₅ films is increased via the use of colloidal templates composed of sacrificial polystyrene beads. The gas sensitivity of Nb₂O₅ films is enhanced through both the TiO₂ doping and the surface embossing. An additional enhancement on the gas sensitivity is obtained by the optimization of the bias voltage applied between interdigitated electrodes beneath Nb₂O₅-based film. More excitingly, such a voltage optimization leads to a substantial decrease in response time. Upon exposure to 50 ppm CO at 350 °C, a gas sensor based on TiO₂-doped Nb₂O₅ film with embossed surface morphology exhibits a very high sensitivity of 475% change in resistance and a rapid response time of 8 s under 3 V, whereas a sensor based on plain Nb₂O₅ film shows a 70% resistance change and a response time of 65 s under 1 V. Thermal stability tests of our Nb₂O₅-based sensor reveal excellent reliability which is of particular importance for application as resistive sensors for a variety gases.     

Gas sensors based on anodic tungsten oxide

Nanostructured porous tungsten oxide materials were synthesized by the means of electrochemical etching (anodization) of tungsten foils in aqueous NaF electrolyte. Formation of the sub-micrometer size mesoporous particles has been achieved by infiltrating the pores with water. The obtained colloidal anodic tungsten oxide dispersions have been used to fabricate resistive WO₃ gas sensors by drop casting the sub-micrometer size mesoporous particles between Pt electrodes on Si/SiO₂ substrate followed by calcination at 400 °C in air for 2 h. The synthesized WO₃ films show slightly nonlinear current-voltage characteristics with strong thermally activated carrier transport behavior measured at temperatures between −20 °C and 280 °C. Gas response measurements carried out in CO, H₂, NO and O₂ analytes (concentration from 1 to 640 ppm) in air as well as in Ar buffers (O₂ only in Ar) exhibited a rapid change of sensor conductance for each gas and showed pronounced response towards H₂ and NO in Ar and air, respectively. The response of the sensors was dependent on temperature and yielded highest values between 170 °C and 220 °C.     

Photoelectrocatalytic regeneration of NADH at poly(4,4′-diaminodiphenyl sulfone)/nano TiO2 composite film modified indium tin oxide electrode

Herein we report the photoelectrocatalytic regeneration of NADH at poly(4,4′-diaminodiphenyl sulfone)/nano TiO₂ (PDDS/TiO₂) composite modified indium tin oxide (ITO) electrode. The PDDS film growth was confirmed through in situ electrochemical quartz crystal microbalance (EQCM) studies. The prepared PDDS/TiO₂ composite was characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD) studies. SEM and AFM results confirmed that TiO₂ nanoparticles size is between 130 and 180 nm. XRD results showed that TiO₂ nanoparticles are crystalline and belong to anatase phase. Electrochemical impedance spectroscopy (EIS) and light induced EIS results substantiate a rapid electron transfer process at PDDS/TiO₂ composite surface. Cyclic voltammetry (CV) results demonstrated that composite film showed excellent response to the photoelectrocatalytic regeneration of NADH. The photoelectrocatalytic oxidation of NADH at composite film surface irradiated for 5 min (optimized irradiation time) produced a notable enhancement in anodic peak current and it was 18-fold higher than that of PDDS film and several folds higher than that of TiO₂ and bare ITO electrodes. Further, composite film showed higher sensitivity of 124.1 μA μM⁻¹ for NADH. From Square wave voltammetry (SWV) results, sensitivity of the irradiated composite film was obtained as 0.252 μA nM⁻¹ of NADH. The linear concentration range was between 23 and 39 nM NADH respectively. Further, the composite film exhibits good selectivity towards NADH and no significant interference effect was observed even when 200-fold excess of ascorbic acid (AA), dopamine (DA) and uric acid (UA) coexist in the same supporting electrolyte solution.     

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.     

Synthesis and enhanced gas sensing properties of crystalline CeO2/TiO2 core/shell nanorods

Crystalline CeO₂/TiO₂ core/shell nanorods were fabricated by a hydrothermal method and a subsequent annealing process under the hydrogen and air atmosphere. The thickness of the outer shell composed of crystal TiO₂ nanoparticles can be tuned in the range of 5-11 nm. The crystal core/shell nanorods exhibited enhanced gas-sensing properties to ethanol vapor in terms of sensor response and selectivity. The calculated sensor response based on the change of the heterojunction barrier formed at the interface between CeO₂ and TiO₂ is agreed with the experimental results, and thus the change of the heterojunction barrier at different gas atmosphere can be used to explain the enhanced ethanol sensing properties.     

H2 sensing properties of diode-type gas sensors fabricated with Ti- and/or Nb-based materials

A thermally oxidized TiO₂ or Nb₂O₅ film equipped with a top Pd film electrode and a bottom Ti or Nb plate electrode (Pd/MO(n)/M, MO: oxide film, M: metal plate, n: annealing temperature (°C)) has been investigated as a diode-type H₂ sensor under air or N₂ atmosphere. Pd/TiO₂(n)/Ti sensors showed relatively poor H₂ sensing properties in air, in comparison with Pd/anodic-TiO₂(n)/Ti sensors constructed with an anodized TiO₂ film equipped with a top Pd film electrode and a bottom Ti plate electrode, which were reported in our previous studies. On the other hand, Pd/Nb₂O₅(n)/Nb sensors showed relatively larger H₂ response with fast response and recovery speeds than Pd/TiO₂(n)/Ti sensors in air under high forward bias conditions. A Pd/Nb₂O₅(450)/Ti sensor, which was fabricated by radio-frequency magnetron sputtering of Nb metal on a Ti substrate followed by thermal oxidation at 450 °C, showed the largest H₂ response and relatively fast response and recovery speeds in air, among the sensors tested. In addition, H₂ response of the Pd/Nb₂O₅(450)/Ti sensor in air was much lower than that in N₂, but the logarithm of H₂ response was almost proportional to the logarithm of H₂ concentration in a wide range of H₂ concentration (10–8000 ppm) in air, and the H₂ sensitivity in air was much higher than that in N₂.     

Improved crystalline structure and H2S sensing performance of CuO-Au-SnO2 thin film using SiO2 additive concentration

In situ SiO₂-doped SnO₂ thin films were successfully prepared by liquid phase deposition. The influence of SiO₂ additive as an inhibitor on the surface morphology and the grain size for the thin film has been investigated. These results show that the morphology of SnO₂ film changes significantly by increasing the concentration of H₂SiF₆ solution which decreases the grain size of SnO₂. The stoichiometric analysis of Si content in the SnO₂ film prepared from various Si/Sn molar ratios has also been estimated. For the sensing performance of H₂S gas, the SiO₂-doped Cu-Au-SnO₂ sensor presents better sensitivity to H₂S gas compared with Cu-Au-SnO₂ sensor due to the fact that the distribution of SiO₂ particles in grain boundaries of nano-crystallines SnO₂ inhibited the grain growth (<6 nm) and formed a porous film. By increasing the Si/Sn molar ratio, the SiO₂-doped Cu-Au-SnO₂ gas sensors (Si/Sn = 0.5) exhibit a good sensitivity (S = 67), a short response time (t_90% < 3 s) and a good gas concentration characteristic (α = 0.6074). Consequently, the improvement of the nano-crystalline structures and high sensitivity for sensing films can be achieved by introducing SiO₂ additive into the SnO₂ film prepared by LPD method.     

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.     

Microstructure control of TiO2 nanotubular films for improved VOC sensing

Porous gas sensing films composed of TiO₂ nanotubes were fabricated for the detection of volatile organic compounds (VOCs), such as alcohol and toluene. In order to control the microstructure of TiO₂ nanotubular films, ball-milling treatments were used to shorten the length of TiO₂ nanotubes and to improve the particle packing density of the films without destroying their tubular morphology and crystal structure. The ball-milling treatment successfully modified the porosity of the gas sensing films by inducing more intimate contacts between nanotubes, as confirmed by scanning electron microscopy (SEM) and mercury porosimetry. The sensor using nanotubes after the ball-milling treatment for 3 h exhibited an improved sensor response and selectivity to toluene (50 ppm) at the operating temperature of 500 °C. However, an extensive ball-milling treatment did not enhance the original sensor response, probably owing to a decrease in the porosity of the film. The results obtained indicated the importance of the microstructure control of sensing layers in terms of particle packing density and porosity for detecting large sized organic gas molecules.     

Preparation and gas-sensing performance of In2O3 porous nanoplatelets

In₂O₃ porous nanoplatelets were successfully synthesized by solvothermal treatment of indium acetylacetonate, followed by calcination in air. X-ray diffraction and Raman spectrum measurements demonstrate that the products are pure cubic phase In₂O₃. Scanning electron microscopy and transmission electron microscopy analyses reveal that the In₂O₃ nanoplatelets bounded by {1 1 0} planes with thickness less than 6 nm and length about 20-50 nm are single crystalline but with porous structure. The optical absorption property of the In₂O₃ nanoplatelets was investigated by UV-vis spectroscopy, which indicates that the In₂O₃ nanoplatelets are semiconducting with a direct band gap of 3.1 eV. The gas sensing performance of the as-prepared In₂O₃ porous nanoplatelets was investigated towards a series of typical organic solvents and fuels. It was found that the In₂O₃ porous nanoplatelets show structure-induced enhancement of gas sensing performance, and especially possess high sensitivity and rapid response towards ethanol vapor.     

Nano particulate SnO2 based resistive films as a hydrogen and acetone vapour sensor

SnCl₂ (solution) was spin coated on soda lime glass and Al₂O₃ substrate to obtain nano-particulate tin oxide film, directly by sintering at 550 °C for 40 minutes (min). The surface morphology and crystal structure of the tin oxide films were analyzed using atomic force microscopy (AFM) and X-ray diffraction (XRD). The size of SnO₂ nanostructure was determined from UV-vis and found to be ?3 nm. These films were tested for sensing H₂ concentration of 0.1-1000 ppm at optimized operating temperature of 265 °C. The results showed that sensitivity (R_air/R_gas per ppm) goes on increasing with decreasing concentration of test gas, giving concentration dependent changes. Special studies carried out at low concentration levels (0.1-1 and 1-10 ppm) of H₂, give high sensitivity (200 × 10⁻³/ppm) for lowest concentration (0.1-1 ppm) of H₂. The selectivity for H₂ against relative humidity (RH), CO₂, CO and LPG gases is also good. The sensor, at operating temperature of 200 °C, is showing nearly zero response to 300 ppm of H₂, and offering response to acetone vapour of 11 ppm. Selectivity for acetone against RH% and CO₂ was also studied. These sensors can be used as H₂ sensor at an operating temperature of 265 °C, and as an acetone sensor at the operating temperature of 200 °C.     

Hydrogen gas sensing properties of Pt/Ta2O5 Schottky diodes based on Si and SiC substrates

We developed Pt/tantalum oxide (Ta₂O₅) Schottky diodes for hydrogen sensing applications. Thin layer (4 nm) of Ta₂O₅ was deposited on silicon (Si) and silicon carbide (SiC) substrates using the radio frequency sputtering technique. We compared the performance of these sensors at different temperatures of 100 °C and 150 °C. At these operating temperatures, the sensor based on SiC exhibited a larger sensitivity, whilst the sensor based on Si exhibited a faster response toward hydrogen gas. We discussed herein, the experimental results obtained for these Pt/Ta₂O₅ based Schottky diodes exhibited that they are promising candidates for hydrogen sensing applications.     

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.     

α-MoO3/TiO2 core/shell nanorods: Controlled-synthesis and low-temperature gas sensing properties

Crystalline α-MoO₃/TiO₂ core/shell nanorods are fabricated by a hydrothermal method and subsequent annealing processes under H₂/Ar flow and in the ambient atmosphere. The shell layer is composed of crystalline TiO₂ particles with a diameter of 2-6 nm, and its thickness can be easily controlled in the range of 15-45 nm. The core/shell nanorods show enhanced sensing properties to ethanol vapor compared to bare α-MoO₃ nanorods. The sensing mechanism is different from that of other one-dimensional metal oxide core/shell nanostructures due to very weak response of TiO₂ nanoparticles to ethanol. The enhanced sensing properties can be explained by the change of type II heterojunction barrier formed at the interface between α-MoO₃ and TiO₂ in the different gas atmosphere. The present results demonstrate a novel sensing mechanism available for gas sensors with high performance.     

Effect of annealing on microstructure and NO2-sensing properties of tungsten oxide nanowires synthesized by solvothermal method

Quasi-orienting W₁₈O₄₉ nanowire bundles were synthesized by solvothermal method. The microstructures and the NO₂-sensing properties of the as-synthesized nanowires annealed at different temperatures were studied. To characterize the morphology and crystalline structure of the annealed tungsten oxide, field emission scanning electron microscope, X-ray diffraction and transmission electron microscope were employed. It was found that with annealing temperature increasing, the nanowire bundles became straighter and slightly thicker, and eventually a nonobelt-like structure was formed via the nanowires coalescence at 450 °C. Meanwhile, the monoclinic W₁₈O₄₉ was transformed to monoclinic WO₃ when annealing temperature rising from 350 to 450 °C. In comparison to the W₁₈O₄₉ nanowire bundles-based sensor, the sensor based on the 450 °C annealing-induced WO₃ nanobelt-like structure exhibited markedly higher response value and gas selectivity, as well as much better response-recovery characteristics to NO₂ gas due to its favorable microstructure feature to gas-sensing.     

Sprayed CdIn2O4 thin films for liquefied petroleum gas (LPG) detection

Nanocrystalline cadmium indium oxide (CdIn₂O₄) thin films of different thicknesses were deposited by chemical spray pyrolysis technique and utilized as a liquefied petroleum gas (LPG) sensors. These CdIn₂O₄ films were characterized for their structural and morphological properties by means of X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. The dependence of the LPG response on the operating temperature, LPG concentration and CdIn₂O₄ film thickness were investigated. The results showed that the phase structure and the LPG sensing properties changes with the different thicknesses. The maximum LPG response of 46% at the operation temperature of 673 K was achieved for the CdIn₂O₄ film of thickness of 695 nm. The CdIn₂O₄ thin films exhibited good response and rapid response/recovery characteristics to LPG.