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.     

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.     

A selective room temperature formaldehyde gas sensor using TiO2 nanotube arrays

A new gas sensor using TiO₂ nanotube arrays was fabricated and explored for formaldehyde detection at room temperature. Highly ordered vertically grown TiO₂ nanotube arrays were synthesized by using the conventional electrochemical anodization process. The sensor using the fabricated nanotube arrays as the sensing elements demonstrated a good response to different concentrations of formaldehyde from 10 to 50 ppm and a very good selectivity over other reducing gas species such as ethanol and ammonia at room temperature. While the exact sensing mechanism is unclear, some possibilities are briefly discussed.     

Enhancing performance of FSP SnO2-based gas sensors through Sb-doping and Pd-functionalization

Via flame spray pyrolysis (FSP), SnO₂ gas sensing layers have been doped with 0.01-4 wt% Sb as well as 0.01 wt% Pd in combination with 1 wt% Sb. Characterization of these materials through X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface analysis, and transmission electron microscopy (TEM) revealed particle grain sizes and crystallinity unchanged by the presence of Sb and/or Pd. The addition of Sb to SnO₂ resulted in the significant decrease in baseline resistance; up to two orders of magnitude in dry air at 300 °C and three orders of magnitude in humid air at 300 °C, which is significant for FSP-prepared gas sensors with high porosity and low particle coordination number since they typically suffer from high baseline resistance. While the baseline resistance was improved with Sb-doping, the sensor signal (R₀/R_gas) remained constant over all concentrations explored. Moreover, regarding the surface functionalization of SnO₂ with Pd in combination with Sb-doping, the reduction of baseline resistance was preserved without influencing sensor signal.     

C-doped WO3 microtubes assembled by nanoparticles with ultrahigh sensitivity to toluene at low operating temperature

Novel C-doped WO₃ microtubes (MTs) were successfully synthesized by a facile infiltration and calcination process using the cotton fibers as templates. The prepared MTs were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), N₂ adsorption and desorption measurements and ultraviolet-visible spectroscopy. XPS spectra show the carbon was doped into the lattice of the WO₃ phase, resulting in a decrease of the band gap of the C-doped WO₃ MTs from 2.45 eV to 2.12 eV. Moreover, the WO₃ MTs were assembled by nanoparticles in size of ca. 40 nm and had larger specific surface area (21.3 m²/g) due to existence of meso/macro-pores inside them. At low operating temperature of 90 °C, the gas sensor based on the C-doped WO₃ MTs had a detected limit of 50 ppb to the toluene gas (response of 2.0). The enhancement of toluene sensing performance of C-doped WO₃ MTs was attributed to a larger surface area and higher porosity, which arises from its unique MTs. Furthermore, the band gap reduction and a new intragap band formation for C-doped WO₃ MTs were proposed as the reason for the decrease in optimal operating temperature.     

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.     

Examination of Au/SnO2 core-shell architecture nanoparticle for low temperature gas sensing applications

Au/SnO₂ core-shell structure nanoparticles (NPs) were synthesized using two methods, microwave and conventional precipitation. In both cases, the size of the Au core was 12-18 nm and the thickness of the SnO₂ shell was 8-12 nm. The particle size of SnO₂ synthesized using the microwave and precipitation method was 3-5 nm and 1-2 nm, respectively. Upon heating to 400-600 °C, both particles maintained their core-shell morphology but the smaller SnO₂ particles prepared using the precipitation method were more sintered. The resistance changes in films of these particles were measured as a function of CO concentration. The Au/SnO₂ particles prepared using the microwave method showed higher sensor response than those prepared using the precipitation method, even providing a significant signal at testing temperatures approaching ambient conditions, thereby affording a new class of material for gas sensing. Both sets of core-shell particles showed higher sensor response than the SnO₂ nanoparticles. The role of the Au core as a catalyst in improving the adsorption and oxidation of CO gas is important for improving the low temperature response. In addition, the maintenance of the size of SnO₂ in the microwave method during sintering contributed to the higher response towards CO sensing.     

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.     

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.     

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.     

Structural and properties of nanocrystalline WO3/TiO2-based humidity sensors elements prepared by high energy activation

Nanocrystalline WO₃/TiO₂-based powders have been prepared by the high energy activation method with WO₃ concentration ranging from 1 to 10 mol%. The samples were thermal treated in a microwave oven at 600 °C for 20 min and their structural and micro-structural characteristics were evaluated by X-ray diffraction, Raman spectroscopy, EXAFS measurements at the Ti K-edge, and transmission electron microscopy. Nitrogen adsorption isotherms and H₂ Temperature Programmed Reduction were also carried out for physical characterization. The crystallite and particle mean sizes ranged from 30 to 40 nm and from 100 to 190 nm, respectively. Good sensor response was obtained for samples with at least 5 mol% WO₃ activated for at least 80 min. Ceramics heat-treated in microwave oven for 20 min have shown similar sensor response as those prepared in conventional oven for 120 min, which is highly cost effective. These results indicate that WO₃/TiO₂ ceramics can be used as a humidity sensor element.     

Gas sensing properties of SnO2 nanowires on micro-heater

The SnO₂ nanowires (NWs) network gas sensors were fabricated on a micro-electrode and heater suspended in a cavity. The sensors showed selective detection to C₂H₅OH at a heater power during sensor operation as low as 30-40 mW. The gas response and response speed of the SnO₂ NWs sensor to 100 ppm C₂H₅OH were 4.6- and 4.7-fold greater, respectively, than those of the SnO₂ nanoparticles (NPs) sensor with the same electrode geometry. The reasons for these enhanced gas sensing characteristics are discussed in relation to the sensing materials and sensor structures.     

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.     

Enhanced H2S sensing characteristics of Pt doped SnO2 nanofibers sensors with micro heater

Gas sensors were designed and fabricated using oxide nanofibers as the sensing materials on micro platforms using micromachining technology. Pure and Pt doped SnO₂ nanofibers were prepared by electrospinning and their H₂S gas sensing characteristics were subsequently investigated. The sensing temperatures of 300 and 500 °C could be attained at the heater powers of 36 and 94 mW, respectively, and the sensors showed high and fast responses to H₂S. The responses of 0.08 wt% Pt doped SnO₂ nanofibers to 4-20 ppm H₂S, were 25.9-40.6 times higher than those of pure SnO₂ nanofibers. The gas sensing characteristics were discussed in relation to the catalytic promotion effect of Pt, nano-scale morphology of electrospun nanofibers, and sensor platform using micro heater.     

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.     

Mixed-potential-type zirconia-based NO2 sensor with high-performance three-phase boundary

This paper focuses on the gas sensing properties of the mixed-potential-type NO₂ sensor based on yttria stabilized zirconia (YSZ) and NiO electrode. The sensing performance of the sensor was improved by modifying the three-phase boundary (TPB). Hydrofluoric acid with different concentrations (10%, 20% and 40%) was used to corrode YSZ substrate to obtain large superficial area of TPB. The scanning electron microscope and atomic force microscopic images showed that the 40% HF could form the largest superficial area at the same corroding time (3 h). The sensitivity of the sensor using the YSZ plate corroded with 40% hydrofluoric acid to 20-500 ppm NO₂ was 76 mV/decade at 850 °C, which was the largest among the examined HF concentrations. It was also seen that the sensor showed a good selectivity and speedy response kinetics to NO₂. On the basis of the measurements of anodic and cathodic polarization curves, as well as the complex impedance of the device, the sensing mechanism was confirmed to involve a mixed potential at the oxide sensing electrode.     

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.     

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.     

Composites of carboxylate-capped TiO2 nanoparticles and carbon black as chemiresistive vapor sensors

Titanium (IV) dioxide (TiO₂) nanoparticles (NPs) with a 1-5 nm diameter were synthesized by a sol-gel method, functionalized with carboxylate ligands, and combined with carbon black (CB) to produce chemiresistive chemical vapor sensor films. The TiO₂ acted as an inorganic support phase for the swellable, organic capping groups of the NPs, and the CB imparted electrical conductivity to the film. Such sensor composite films exhibited a reproducible, reversible change in relative differential resistance upon exposure to a series of organic test vapors. The response of such chemiresistive composites was comparable to, but generally somewhat smaller than, that of thiol-capped Au NPs. For a given analyte, the resistance response and signal-to-noise ratio of the capped TiO₂-NP/CB composites varied with the identity of the capping ligand. Hence, an array of TiO₂-NP/CB composites, with each film having a compositionally different carboxylate capping ligand, provided good vapor discrimination and quantification when exposed to a series of organic vapors. Principal components analysis of the relative differential resistance response of the sensor array revealed a clear clustering of the response for each analyte tested. This approach expands the options for composite-based chemiresistive vapor sensing, from use of organic monomeric or polymeric sorbent phases, to use of electrically insulating capped inorganic NPs as the nonconductive phase of chemiresistive composite vapor sensors.     

Formaldehyde sensing properties of electrospun NiO-doped SnO2 nanofibers

Formaldehyde is a kind of hazardous gases dangerous to human health. Hence, gas sensor is an essential device to monitor formaldehyde in air, especially in indoor ambient. Semiconductor metal oxides are studied as gas-sensing material to detect most of key gases for decade years. For the purpose of actual application and meeting a variety of conditions, diverse additives added into host material are expected to improve the performance of gas sensors. The formaldehyde gas-sensing characteristics of undoped and NiO-doped SnO₂ (NSO) nanofibers synthesized via a simple electrospinning method were investigated in this study. It is noticed that the addition of NiO causes the distortion at the surface of SnO₂ nanofibers, which is responsible to adjust activation energy, grain sizes and chemical states of host material. The sensors fabricated from NSO nanofibers exhibited good formaldehyde sensing properties at operating temperature 200 °C, and the minimum-detection-limit was down to 0.08 ppm. The response time and recovery time of the sensors were about 50 s and 80 s to 10 ppm formaldehyde, respectively. The sensor shows a good long-term stability in 90 days. The simple preparation and excellent properties significantly advance the viability of electrospun nanofibers as gas sensing materials. The sensing mechanisms of NSO nanofibers to formaldehyde were discussed. The results indicated that NSO nanofibers could be used as a candidate to fabricate formaldehyde sensors in practice.