Electrostatic sprayed SnO2 and Cu-doped SnO2 films for H2S detection

This paper presents the ability of electrostatic sprayed tin oxide (SnO₂) and tin oxide doped with copper oxide (1, 2, and 4 at.% Cu) films to detect different pollutant gases, i.e., H₂S, SO₂, and NO₂. The influence of a copper oxide dopant on the SnO₂ morphology is studied using scanning electron microscopy (SEM) technique, which reveals a small decrease in the porosity and particle size when the amount of dopant is increased. The sensing properties of the SnO₂ films are greatly improved by doping, i.e., the Cu-doped SnO₂ films have large response to low concentration (10 ppm) of H₂S at low operating temperature (100 °C). Furthermore, no cross-sensitivity to 1 ppm NO₂ and 20 ppm SO₂ is observed. Among the studied films, the 1 at.% Cu-doped SnO₂ layer is the most sensitive in the detection of all the studied gases.     

Influence of Cs doping in spray deposited SnO2 thin films for LPG sensors

Detection of low concentrations of petroleum gas was achieved using transparent conducting SnO₂ thin films doped with 0–4 wt.% caesium (Cs), deposited by spray pyrolysis technique. The electrical resistance change of the films was evaluated in the presence of LPG upon doping with different concentrations of Cs at different working temperatures in the range 250–400 °C. The investigations showed that the tin oxide thin film doped with 2% Cs with a mean grain size of 18 nm at a deposition temperature of 325 °C showed the maximum sensor response (93.4%). At a deposition temperature of 285 °C, the film doped with 3% Cs with a mean grain size of 20 nm showed a high response of 90.0% consistently. The structural properties of Cs-doped SnO₂ were studied by means of X-ray diffraction (XRD); the preferential orientation of the thin films was found to be along the (3 0 1) directions. The crystallite sizes of the films determined from XRD are found to vary between 15 and 60 nm. The electrical investigations revealed that Cs-doped SnO₂ thin film conductivity in a petroleum gas ambience and subsequently the sensor response depended on the dopant concentration and the deposition temperature of the film. The sensors showed a rapid response at an operating temperature of 345 °C. The long-term stability of the sensors is also reported.     

Room-temperature H2S gas sensing at ppb level by single crystal In2O3 whiskers

In₂O₃ whiskers and bipyramidal nano-crystals were prepared by a carbothermal method. These were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX), photoluminescence and Raman spectroscopy. These were studied for application to sensing of H₂S gas. The single crystal whiskers were found to be sensitive to as low as 200 ppb of H₂S gas at room temperature and showed saturation in response at 10 ppm. On the other hand, the films made of bipyramids were less sensitive to H₂S gas and the response was found to be a nearly linear function of concentration in a concentration range of 10–80 ppm.     

Electrical response of Sm2O3-doped SnO2 to C2H2 and effect of humidity interference

Pure and Sm₂O₃-doped SnO₂ are prepared through a sol–gel method and characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The sensor based on 6 wt% Sm₂O₃-doped SnO₂ displays superior response at an operating temperature of 180 °C, and the response magnitude to 1000 ppm C₂H₂ can reach 63.8, which is 16.8 times larger than that of pure SnO₂. This sensor also shows high sensitivity under various humidity conditions. These results make our product be a good candidate in fabricating C₂H₂ sensors.     

Enhanced H2S sensing characteristics of SnO2 nanowires functionalized with CuO

The CuO-functionalized SnO₂ nanowire (NW) sensors were fabricated by depositing a slurry containing SnO₂ NWs on a polydimethylsiloxane (PDMS)-guided substrate and subsequently dropping Cu nitrate aqueous solution. The CuO coating increased the gas responses to 20 ppm H₂S up to 74-fold. The R_a/R_g value of the CuO-doped SnO₂ NWs to 20 ppm H₂S was as high as 809 at 300 °C, while the cross-gas responses to 5 ppm NO₂, 100 ppm CO, 200 ppm C₂H₅OH, and 100 ppm C₃H₈ were negligibly low (1.5–4.0). Moreover, the 90% response times to H₂S were as short as 1–2 s at 300–400 °C. The selective detection of H₂S and enhancement of the gas response were attributed to the uniform distribution of the sensitizer (CuO) on the surface of the less agglomerated network of the SnO₂ NWs.     

Enhanced room temperature response of SnO2 thin film sensor loaded with Pt catalyst clusters under UV radiation for LPG

The room temperature response characteristics of SnO₂ thin film sensor loaded with platinum catalyst clusters are investigated for LPG under the exposure of ultraviolet radiation. The SnO₂-Pt cluster sensor structures have been prepared using rf sputtering. Combined effect of UV radiation exposure (λ = 365 nm) and presence of Pt catalyst clusters (10 nm thick) on SnO₂ thin film sensor surface is seen to lead to an enhanced response (4.4 × 10³) for the detection of LPG (200 ppm) at room temperature whereas in the absence of UV illumination a comparable response (∼5 × 10³) could be obtained but only at an elevated temperature of 220 °C. The present study therefore investigates the effect of UV illumination on LPG sensing characteristics of SnO₂ sensors loaded with Pt clusters of varying thickness values. Results indicate the possibility of utilizing the sensor structure with novel dispersal of Pt catalyst clusters on SnO₂ film surface for efficient detection of LPG at room temperature under the illumination of UV radiations.     

Effect of thickness of platinum catalyst clusters on response of SnO2 thin film sensor for LPG

This paper reports the sensing response characteristics of rf-sputtered SnO₂ thin films (90 nm thick) loaded with platinum catalyst cluster of varying thickness (2-20 nm) for LPG detection. The enhanced response (5 × 10³) was obtained for 200 ppm LPG with the presence of 10 nm thin and uniformly distributed Pt catalyst clusters on the surface of SnO₂ thin film at a relatively low operating temperature (220 °C). The high response for LPG is shown to be primarily due to the enhanced catalytic activity for adsorbed oxygen on the surface of SnO₂ thin film besides the spill over mechanism at elevated temperature.     

Laser micro-structuring of magnetron-sputtered SnOx thin films as anode material for lithium ion batteries

SnO_x electrode thin films for lithium ion batteries were deposited by reactive and non-reactive rf magnetron sputtering of a SnO₂ target in an argon–oxygen atmosphere. Amorphous and nano-crystalline SnO_x films could be synthesized, with regard to the O₂:Ar volume ratio in the sputter gas which was adjusted to 0, 3.5 or 10%. Laser micro-structuring using a KrF excimer laser operating at a wavelength of λ = 248 nm was applied to create free-standing microstructures. Thus, the active surface of the anode material was significantly increased. Furthermore, it was expected that the large volume changes during electrochemical cycling of SnO_x could be better compensated by a microstructured surface. The laser parameters were optimized in a way which leads to structures without any defects and little debris. Depending on the laser fluence and pulse number, free-standing conical structures could be formed with a horizontal spacing of <0.5 μm up to 2 μm. The structured and unstructured thin films were cycled in a battery tester against metallic lithium. The structured SnO_x thin films exhibited significantly better battery performance with respect to cycling stability.     

Tetrakis(alkylthio)-substituted lutetium bisphthalocyanines for sensing NO2 and O3

In this study, the nitrogen dioxide (NO₂) and ozone (O₃) sensing properties of a series bis[tetrakis(alkylthio) phthalocyaninato] lutetium(III) complexes [(C_nH_2n+1S)₄Pc]₂Lu(III) (n = 6, 10, 16) are investigated as a function of concentration in the temperature range between 25 °C and 150 °C. The concentration ranges were 1–10 ppm for NO₂, and 50 ppb–1 ppm for O₃. The response time and the sensor response to NO₂ are measured for approximately 1 min and 100% ppm⁻¹, respectively, for compound 1 at room temperature. At room temperature, all compounds are in the solid phase. The response time decreases to a few seconds with increasing operation temperature to 150 °C. At this temperature, all compounds are in the liquid crystal phase. The fastest response to oxidizing gases is observed at the liquid crystal phase of the Pcs. It has also been observed that the response time and the sensor response depend on the alkyl chain lengths of the Pcs. The doping effect of oxygen has been determined under high purity nitrogen N₂ flow, after exposure to dry air, at a different period of time and after annealing. It has been found that the conductivities of [(C_nH_2n+1S)₄Pc]₂Lu(III) thin films increased after exposure to dry air and the conduction mechanism also changed from ohmic behavior to space-charge-limited conduction.     

Flexible thin‐film transistors application of amorphous tin oxide‐based semiconductors

The structural, optical, and electrical properties of Si‐doped SnO₂ (STO) films were investigated in terms of their potential applications for flexible electronic devices. All STO films were amorphous with an optical transmittance of ~90%. The optical band gap was widened as the Si content increased. The Hall mobility and carrier density were improved in the SnO₂ with 1 wt% Si film, which was attributed to the formation of donor states. Si (1 wt%) doped SnO₂ thin‐film transistor exhibited a good device performance and good stability with a saturation mobility of 6.38 cm²/Vs, a large I_on/I_off of 1.44 × 10⁷, and a SS value of 0.77 V/decade. The device mobility of a‐STO TFTs at different bending radius maintained still at a high level. These results suggest that a‐STO thin films are promising for fabricating flexible TFTs.     

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.     

SnO2 thin films modified by the SnO2–Au nanocomposites: Response to reducing gases

The influence of the SnO₂ surface modification by the SnO₂–Au nanocomposites on conductivity response to such reducing gases as CO and H₂ has been analyzed in the present paper. Both initial SnO₂ films, subjected for surface modification, and SnO₂–Au nanocomposites were deposited by Successive Ionic Layer Deposition (SILD) method. The SnO₂–Au nanocomposites with Au/Sn ratio 1 were synthesized using HAuCl₄ and SnCl₂ precursors. The thickness of the Au-SnO₂ nanolayers varied from 0.7–1.0 nm to 10–15 nm. It was established that the increase in the thickness of the SnO₂–Au nanocomposite layer formed on the surface of the SnO₂ films was accompanied by both the improvement of sensor response and the decrease in response and recovery times. An explanation of the observed effects has been proposed.     

Ultrahigh ethanol response of SnO2 nanorods at low working temperature arising from La2O3 loading

The influences of La₂O₃ loading on the ethanol sensing properties of SnO₂ nanorods were investigated. An obvious enhancement of response was obtained. The response of 5 wt% La₂O₃ loaded SnO₂ nanorods was up to 213 for 100 ppm ethanol at low working temperature of 200 °C, while that of pure SnO₂ nanorods is 45.1. The improvement in response might be attributed to the presence of basic sites, which facilitated the dehydrogenation process. While the working temperature was increased to 300 °C, the sensor response decreased to 16 for 100 ppm ethanol. Additionally, the La₂O₃ loaded SnO₂ nanorods sensors showed good selectivity to ethanol over methane and hydrogen. Our results demonstrated that the La₂O₃ loaded SnO₂ nanorods were promising in fabricating high performance ethanol sensors which could work at low temperature.     

Temperature dependent H2S and Cl2 sensing selectivity of Cr2O3 thin films

The conductometric gas sensing characteristics of Cr₂O₃ thin films - prepared by electron-beam deposition of Cr films on quartz substrate followed by oxygen annealing - have been investigated for a host of gases (CH₄, CO, NO₂, Cl₂, NH₃ and H₂S) as a function of operating temperature (between 30 and 300 °C) and gas concentration (1-30 ppm). We demonstrate that these films are highly selective to H₂S at an operating temperature of 100 °C, while at 220 °C the films become selective to Cl₂. This result has been explained on the basis of depletion of chemisorbed oxygen from the surface of films due to temperature and/or interaction with Cl₂/H₂S, which is supported experimentally by carrying out the work function measurements using Kelvin probe method. The temperature dependent selectivity of Cr₂O₃ thin films provides a flexibility to use same film for the sensing of Cl₂ as well as H₂S.     

Room temperature hydrogen gas sensor nanocomposite based on Pd-decorated multi-walled carbon nanotubes thin films

Multi-walled carbon nanotubes (MWCNTs) are successfully processed in the form of thin films (buckypapers), and their morphology and electrical behaviour are characterized. The MWCNTs are synthesized by the floating catalyst chemical vapour deposition process. The effects of a sequence of treatments applied for MWCNTs purification on the buckypapers electrical behaviour are also examined. Nanocomposite thin films constituted of pristine and purified MWCNTs and Pd nanoparticles are prepared in order to evaluate their viability as H₂ sensors at room temperature. For this purpose, the electrical resistance of the nanocomposite films in atmospheres with different H₂ concentrations, is determined. Scanning electron microscopy (SEM) images show that the buckypapers and the nanocomposite films are 2D structures constituted by randomly oriented MWCNTs. The buckypapers present a semiconductor-like electrical behaviour as determined by the standard four point method. Room temperature resistivity values of around 10⁻³ Ω m are assessed. Nanocomposite films show different electrical behaviour depending on the purification treatment applied to the MWCNTs employed. Furthermore, the electrical resistance of the nanocomposite films is found to increase when the measurements are performed in H₂ atmosphere. Values of H₂ sensitivity at room temperature of the nanocomposite films up to 2.15% are determined for H₂ average concentration higher than 350 ppm with short recovery time.     

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.     

Structural, optical and electrical properties of CdO/Cd(OH)2 thin films grown by the SILAR method

Successive Ionic Layer Adsorption and Reaction (SILAR) was used to form Cd(OH)₂ thin films from aqueous cadmium–ammonia complex on glass substrates at room temperature and the thermal annealing effect on thin films was studied. The as-deposited films were annealed at 200, 300 and 400 °C for 1 h in an oxygen atmosphere for conversion from Cd(OH)₂ to CdO and change in the structural, optical and electrical properties of the films and the effect of the light on the electrical properties of the films were investigated. The structural and surface morphological properties of the films were studied using X-ray diffraction (XRD) and scanning electron microscopy (SEM). It was found that Cd(OH)₂ phase is converted into the cubic CdO films by annealing. The band gap energy values of films decreased from 3.59 to 2.13 eV through increasing annealing temperature. It was found that the current increased with increasing light intensity and CdO films were more conductive than the as-deposited films.     

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.     

Sensing properties of chemically sprayed TiO2 thin films using Ni, Ir, and Rh as catalysts

The purpose of this work is double, to analyze the influence of (i) the addition of different catalysts and (ii) the implementation of different procedures to introduce them in the titanium dioxide (TiO₂) thin films, in order to improve the film sensitivity for detecting oxygen. For reaching these objectives, TiO₂ thin films were deposited on alumina substrates by the ultrasonic spray pyrolysis (USP) technique employing titanium(IV) oxide acetylacetonate (TiO(acac)₂) as a titanium precursor, and pure methanol as a solvent. Iridium, nickel, and rhodium were the three catalysts used, which were incorporated by impregnation and USP onto the TiO₂ thin films surface. The electrical characterization, consisting in surface resistance measurements of the films, in a mixture of oxygen and zero-grade air, was performed using interdigitated gold electrodes contacted on the alumina substrates. From these, the film response or resistance change of the TiO₂ films was estimated. Single TiO₂ thin films measured at 400 °C displayed a response of the order of 0.02 and 0.18 to oxygen of 1000 and 10,000 ppm, respectively, whereas TiO₂ thin films using impregnated rhodium proved to have the highest response to O₂, with a value in the order of 2.5 to a concentration of 1000 ppm of O₂ diluted in zero-grade air at an optimal operating temperature of 250 °C.     

Water pre-adsorption effect on room temperature SnO2 nanobelt ethanol sensitivity in oxygen-deficient conditions

The water adsorption effects on room temperature ethanol sensitivity of a SnO₂ single crystal nanobelt was studied. SnO₂ nanobelt showed better electrical conductivity in air than in vacuum. The current increased linearly with relative humidity in air and with water concentration in vacuum. In the presence of water vapor, the SnO₂ nanobelt electrical response was quite different, depending on the H₂O and C₂H₅OH molecules adsorption sequence. The current response to ethanol gas increased substantially when water was pre-adsorbed. However, no change was found without water pre-adsorbtion. This interesting behavior is ascribed to competition between the H₂O and C₂H₅OH molecules trying to adsorb on oxygen sites at the tin oxide surface. Dissociated water acts as the surface conduction channel resulting in better conductivity, while ethanol is physisorbed without water pre-adsorption. Based on this sensing mechanism, SnO₂ nanobelt can be used as a highly efficient ethanol detector in humid air.