Effect of density and thickness on H2-gas sensing property of sputtered SnO2 films

Undoped and Pd-doped SnO₂ films were deposited under various conditions for the investigation of the effect of Pd doping, porosity, and thickness on their H₂ gas sensing properties. The temperature of the substrate and the pressure of the discharge gas were varied. All films formed were composed of columns with thicknesses between 20 and 30 nm. The film density decreased as the discharge gas pressure increased and the substrate temperature decreased. It showed values between 4.2×10³ and 7.0×10³ kg/m³ depending on the deposition condition. Low film density and Pd doping resulted in high sensitivity and fast response. The largest sensitivity was observed for a Pd-doped film with a low density of 4.7×10³ kg/m³ and a thickness of 20 nm.     

H2S sensing property of porous SnO2 sputtered films coated with various doping films

Pure SnO₂ films and Ag-, Cu-, Pt-, and Pd-doped SnO₂ films were investigated for H₂S sensing properties. SnO₂ films were deposited by DC magnetron sputtering at various substrate temperatures and discharge gas pressures. As the discharge gas pressure increased and the substrate temperature decreased, the film became porous. Doping with Cu or Ag film improved the sensitivity, and the highest sensitivity was obtained in the porous SnO₂ film coated with an Ag film 16 nm thick. According to the X-ray diffraction (XRD) pattern, Ag deposited on SnO₂ film transformed to Ag₂S upon exposure to H₂S. When the Ag-doped film sensor was operated at a low temperature, the sensitivity was extremely high, but the recovery was insufficient. By increasing the operation temperature, the recovery was improved but the sensitivity decreased.     

Influence of effective surface area on gas sensing properties of WO3 sputtered thin films

WO₃ thin films having different effective surface areas were deposited under various discharge gas pressures at room temperature by using reactive magnetron sputtering. The microstructure of WO₃ thin films was investigated by X-ray diffraction, scanning electron microscopy, and by the measurement of physical adsorption isotherms. The effective surface area and pore volume of WO₃ thin films increase with increasing discharge gas pressure from 0.4 to 12 Pa. Gas sensors based on WO₃ thin films show reversible response to NO₂ gas and H₂ gas at an operating temperature of 50-300 °C. The peak sensitivity is found at 200 °C for NO₂ gas and the peak sensitivity appears at 300 °C for H₂ gas. For both kinds of detected gases, the sensor sensitivity increases linearly with an increase of effective surface area of WO₃ thin films. The results demonstrate the importance of achieving high effective surface area on improving the gas sensing performance.     

Fast response detection of H2S by CuO-doped SnO2 films prepared by electrodeposition and oxidization at low temperature

Fast response detection of H₂S by CuO-doped SnO₂ films prepared was prepared by a simple two-step process: electrodeposition from aqueous solutions of SnCl₂ and CuCl₂, and oxidization at 600 °C. The phase constitution and morphology of the CuO-doped SnO₂ films were characterized by X-ray diffraction and scanning electron microscopy. In all cases, a polycrystalline porous film of SnO₂ was the product, with the CuO deposited on the individual SnO₂ particles. Two types of CuO-doped SnO₂ films with different microstructures were obtained via control of oxidation time: nanosized CuO dotted island doped SnO₂ and ultra-uniform, porous, and thin CuO film coated SnO₂. The sensor response of the CuO doped SnO₂ films to H₂S gas at 50–300 ppm was investigated within the temperature range of 25–125 °C. Both of the CuO-doped SnO₂ films show fast response and recovery properties. The response time of the ultra-uniform, porous, and thin CuO coated SnO₂ to H₂S gas at 50 ppm was 34 s at 100 °C, and its corresponding recovery time was about 1/3 of the response time.     

Synthesis and characterization of ferromagnetic cobalt-doped tin dioxide thin films

Co-doped SnO₂ thin films are grown on sapphire (0001) substrates at 600 °C by the technique of dual-beam pulsed laser deposition. The prepared films show preferred orientation in the [100] direction of the rutile structure of SnO₂. Nonequilibrium film growth process results in doping Co into SnO₂ much above the thermal equilibrium limit. A Film with 3% of Co is ferromagnetic at room temperature with a remanent magnetization of ∼ 26% and a coercivity of ∼ 9.0 mT. As Co doping content x increases, the optical band gap absorption edge (E₀) of the Co-doped SnO₂ thin films initially shows a redshift at low x up to x = 0.12 and then increases at the higher x, which are attributed to the sp-d exchange interactions and alloying effects, respectively.     

Structural, optical, and electrical properties of tin sulfide thin films grown by spray pyrolysis

Tin sulfide (SnS) thin films have been prepared by spray pyrolysis (SP) technique using tin chloride and N, N-dimethylthiourea as precursor compounds. Thin films prepared at different temperatures have been characterized using several techniques. X-ray diffraction studies have shown that substrate temperature (T_s) affects the crystalline structure of the deposited material as well as the optoelectronic properties. The calculated optical band gap (E_g) value for films deposited at T_s = 320-396 °C was 1.70 eV (SnS). Additional phases of SnS₂ at 455 °C and SnO₂ at 488 °C were formed. The measured electrical resistivity value for SnS films was ∼ 1 × 10⁴ Ω-cm.     

Effects of hydrogen gas on properties of tin-doped indium oxide films deposited by radio frequency magnetron sputtering method

Tin-doped indium oxide (ITO) films were deposited at ∼ 70 °C of substrate temperature by radio frequency magnetron sputtering method using an In₂O₃-10% SnO₂ target. The effect of hydrogen gas ratio [H₂ / (H₂ + Ar)] on the electrical, optical and mechanical properties was investigated. With increasing the amount of hydrogen gas, the resistivity of the samples showed the lowest value of 3.5 × 10^− 4 Ω·cm at the range of 0.8-1.7% of hydrogen gas ratio, while the resistivity increases over than 2.5% of hydrogen gas ratio. Hall effect measurements explained that carrier concentration and its mobility are strongly related with the resistivity of ITO films. The supplement of hydrogen gas also reduced the residual stress of ITO films up to the stress level of 110 MPa. The surface roughness and the crystallinity of the samples were investigated by using atomic force microscopy and x-ray diffraction, respectively.     

High-speed μc-Si films deposition and large-grain poly-Si films deposition by surface wave discharge

Microcrystalline silicon (μc-Si) and polycrystalline silicon (poly-Si) films are deposited by surface wave (SW) discharge at 2.45 GHz in H₂/SiH₄ gas. This high density SW plasma at relatively low pressures (4-60 Pa) enables strong dissociation of feedstock gas. The films deposited on substrate are investigated by X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy (SEM). The SW discharge in 10% SiH₄ at total pressure of ∼ 30 Pa gives μc-Si films on a substrate at 250 °C, at a fairly high deposition rate of 4-20 nm/s, with a crystalline volume fraction of 0.5-0.8 and a grain size of 10-40 nm. Furthermore, poly-Si film with crystalline volume fraction of > 99% is deposited at higher substrate temperature (400 °C) in 2% SiH₄ discharge at lower pressure (4 Pa). X-ray diffraction and SEM results revealed that the grain size of poly-Si films is as large as 600 nm, which is almost 6 times larger than previously reported values.     

Enhanced H2S gas sensing properties of multiple-networked Pd-doped SnO2-core/ZnO-shell nanorod sensors

Pd-doped SnO₂-core/ZnO-shell nanorods were synthesized by using a three-step process: thermal evaporation of Sn powders in an oxygen atmosphere, atomic layer deposition of ZnO, and Pd diffusion followed by annealing. The sensitivity of the multiple networked SnO₂-core/ZnO-shell nanorod sensor to H₂S gas was found to be improved further significantly by Pd doping. The Pd-doped SnO₂-core/ZnO-shell nanorod sensor showed sensitivities of 6.4, 15.4, and 36.2% at H₂S concentrations of 20, 50, and 100 ppm at room temperature. The sensitivity of the nanorods was improved by more than 10 times at a H₂S concentration of 100 ppm. The sensitivity enhancement of the SnO₂-core/ZnO-shell nanorods by Pd doping may be attributed to the spillover effect, active reaction site generation, and the enhancement of chemisorption and dissociation of gas.     

Preparation of SnO2 thin films at low temperatures with H2 gas by the hot-wire CVD method

H₂ additional effect for crystallization of SnO₂ films prepared by the hot-wire CVD method was investigated. The crystallization of SnO₂ films starts at 170 °C. The selectivity enhancement of the solar cell substrate will contribute to reduce the cost of silicon thin film solar cells. The atomic hydrogen assisted nano-crystallization exists for the depositions of SnO₂ films by the hot-wire CVD method. Furthermore, the addition of H₂ gas improved the electrical conductivity up to 5.3 × 10⁰ S/cm. However, these effects are limited in the deposition condition of a small amount of hydrogen. Addition of much higher hydrogen concentration starts an etching effect of oxygen atoms.     

CO sensing with SnO2 thick film sensors: role of oxygen and water vapour

The paper investigates the gas response of nanocrystalline SnO₂ based thick film sensors upon exposure to carbon monoxide (CO) in changing water vapour (H₂O) and oxygen (O₂) backgrounds. The sensing materials were undoped, Pt- and Pd-doped SnO₂. We found that in the absence of oxygen, the sensor signal (defined as the ratio between the resistance in the background gas, R₀ and the resistance in the presence of the target gases, R, namely R₀/R) have the highest values. These values are higher for doped materials than for the undoped ones. The presence of humidity increases dramatically the sensor signal of the doped materials. In the presence of oxygen, the sensor signal decreases significantly for all sensor materials. The results indicate that there is a competitive adsorption between O₂ and H₂O related surface species and, as a result, different sensing mechanisms can be observed for CO.     

Preparation and CO gas-sensing behavior of Au-doped SnO2 sensors

A study on the low-temperature CO gas sensors based on Au/SnO₂ thick film was reported. Au/SnO₂ powders, with different Au loading from 0.36 to 3.57 wt%, were prepared by a deposition-precipitation method. Thick films were fabricated from Au/SnO₂ powders. The Au/SnO₂ thick-film sensors exhibited high sensitivity to CO gas at relatively low operating temperature (83-210 °C). We also reported the effect of the Au loading in Au/SnO₂ on the CO gas sensing behavior. The optimal Au loading in as-prepared Au/SnO₂ was 2.86 wt%.     

Study on inverse spinel zinc stannate, Zn2SnO4, as transparent conductive films deposited by rf magnetron sputtering

Inverse spinel zinc stannate (Zn₂SnO₄, ZTO) films were deposited onto fused quartz glass substrates heated at 800 °C by rf magnetron sputtering using a ceramic ZTO target (Zn:Sn = 2:1). H₂ flow ratios [H₂/(Ar + H₂)] were controlled from 0 to 30% during the depositions. ZTO films deposited at 800 °C possessed a polycrystalline inverse spinel structure. The lowest resistivity of 1.1 × 10^− 2 Ω cm was obtained for a ZTO film deposited at 20% H₂ flow ratio. The transmittance of the ZTO film was approximately 80% in the visible region.     

Atomic layer deposition of ZnS via in situ production of H2S

Atomic layer deposition (ALD) of ZnS films utilizing diethylzinc and in situ generated H₂S was performed over a temperature range of 60 °C-400 °C. This method for generating H₂S in situ was developed to eliminate the need to store high pressure H₂S gas. The H₂S precursor was generated by heating thioacetamide to 150 °C in an inert atmosphere, producing acetonitrile and H₂S as confirmed with mass spectroscopy. ALD behavior was confirmed by investigation of growth behavior and saturation curves. The properties of the films were studied with X-ray diffraction, transmission electron microscopy, ellipsometry, atomic force microscopy, scanning electron microscopy, ultraviolet-visible spectroscopy, and X-ray photoelectron spectroscopy. The results show a growth rate that monotonically decreases with temperature, and films that are stoichiometric in Zn and S. The root mean square roughness of the films increases with temperature above 100 °C. A change in crystal phase begins at ∼ 300 °C. The band gap is dependent on the crystal phase and is estimated to be 3.6-4 eV.     

X-ray absorption near-edge spectroscopy investigation of the oxidation state of Pd species in nanoporous SnO2 gas sensors for methane detection

We report the correlation of the aging of Pd-doped SnO₂ methane sensors with the change of the oxidation state of Pd. Mesoporous SnO₂ doped with palladium species was prepared and exposed to different gas mixtures at high temperature (600 °C) to simulate long term usage. After each exposure step a fraction of the sample was cooled down to “freeze” the current oxidation state of Pd which was then analyzed by X-ray Absorption Near-Edge Spectroscopy (XANES) using the 'white line' (i.e. the absorption peak corresponding to the transition from the 2p_3/2 core level to unoccupied 4 d states) intensity of the L(III) edge as a probe for the oxidation state. The Pd oxidation state correlates with the response of the resistive SnO₂ sensor to methane gas, as determined by measuring the gas response to different concentrations of methane. Samples treated with 5000 ppm methane in air show a significant reduction of Pd(II) to Pd(0), depending clearly on the carrier gas (synthetic air, pure nitrogen) and on the temperature (600 °C vs. 300 °C).     

Antimony sulfide thin films in chemically deposited thin film photovoltaic cells

Antimony sulfide thin films of thickness ≈ 500 nm have been deposited on glass slides from chemical baths constituted with SbCl₃ and sodium thiosulfate. Smooth specularly reflective thin films are obtained at deposition temperatures from − 3 to 10 °C. The differences in the film thickness and improvement in the crystallinity and photoconductivity upon annealing the film in nitrogen are presented. These films can be partially converted into a solid solution of the type Sb₂S_xSe_3 − x, detected in X-ray diffraction, through heating them in contact with a chemically deposited selenium thin film. This would decrease the optical band gap of the film from ≈ 1.7 eV (Sb₂S₃) to ≈ 1.3 eV for the films heated at 300 °C. Similarly, heating at 300 °C of sequentially deposited thin film layers of Sb₂S₃-Ag₂Se, the latter also from a chemical bath at 10 °C results in the formation of AgSb(S/Se)₂ with an optical gap of ≈ 1.2 eV. All these thin films have been integrated into photovoltaic structures using a CdS window layer deposited on 3 mm glass sheets with a SnO₂:F coating (TEC-15, Pilkington). Characteristics obtained in these cells under an illumination of 850 W/m² (tungsten halogen) are as follows: SnO₂:F-CdS-Sb₂S₃-Ag(paint) with open circuit voltage (V_oc) 470 mV and short circuit current density (J_sc) 0.02 mA/cm²; SnO₂:F-CdS-Sb₂S₃-CuS-Ag(paint), V_oc ≈ 460 mV and J_sc ≈ 0.4 mA/cm²; SnO₂:F-CdS-Sb₂S_xSe_3 − x-Ag(paint), V_oc ≈ 670 mV and J_sc ≈ 0.05 mA/cm²; SnO₂:F-CdS-Sb₂S₃-AgSb(S/Se)₂-Ag(paint), V_oc ≈ 450 mV and J_sc ≈ 1.4 mA/cm². We consider that the materials and the deposition techniques reported here are promising toward developing ‘all-chemically deposited solar cell technologies.’     

Development of NiO-based thin film structures as efficient H2 gas sensors operating at room temperatures

P-type NiO thin films have been developed on high resistivity Si and SiO₂ substrates by a pulsed laser deposition technique using an ArF^? 193 nm excimer laser at deposition temperature of 300 °C and in 40 Pa partial oxygen pressure. Structures based on such NiO films as host material in the form of Au-NiO Schottky diodes have been subsequently developed under vacuum. In a different procedure, an n-SnO₂ layer has been deposited by a CVD technique on a NiO film to produce a p/n heterojunction. The sensing properties of all above structures have been tested upon exposure to a H₂ flow in air ambient gas at various operating temperature ranging from 30 to 180 °C. For the NiO films, the optimum temperature was about 150 °C exhibiting a sensitivity of 94%. After surface sensitization of NiO by Au the NiO films showed an H₂ response at operating temperature of 30 °C. The sensitivity of p-NiO/n-SnO₂ heterojunction devices was extracted from I-V measurements in air and under H₂ flow mixed in air. In this case a dramatic increase of the sensitivity was achieved at operating temperature of 30 °C for a forward bias of 0,2 V.     

Chemical vapor deposition of phase-rich WC thin films on silicon and carbon substrates

Chemical vapor deposition was used to deposit tungsten carbide from a mixture of WCl₆, H₂ and C₃H₈ at 750-1050 °C on silicon and carbon substrates. The phase composition of the films was correlated with substrate temperature, substrate position in the reactor, and total flow rates. X-ray diffraction and X-ray photoelectron spectroscopy were employed to investigate the surface and bulk properties of the thin films. Thick, adherent films of phase-rich hexagonal WC were deposited using 1.3 × 10³ Pa total pressure, 1050 °C substrate temperature, and reactant flow rates of H₂/C₃H₈/Ar/WCl₆ = 1.8 × 10^− 2/3.6 × 10^− 3/8.9 × 10^− 4/1.8 × 10^− 4 mol/min, where Ar is the carrier gas. The surface composition was oxygen and carbon rich as compared with the bulk.     

The gas sensitivity of nano TiO2-SnO2 film doped with Cd(II) ion

The nanocomposite oxide (0.2TiO₂-0.8SnO₂) doped with Cd²⁺ powder have been prepared and characterized by XRD and their gas-sensing sensitivity were characterized using gas sensing measurement. Experimental results show that, bicomponent nano anatase TiO₂ and rutile SnO₂ particulate thick film doped with Cd²⁺ behaves with good sensitivity to formaldehyde gas of 200 ppm in the air, and the optimum sensing temperature was reduced from 360 °C to 320 °C compared with the undoped Cd²⁺ thick film. The gas sensing thick films doped with Cd²⁺ also show good selectivity to formaldehyde among benzene, toluene, xylene and ammonia as disturbed gas and could be effectively used as an indoor formaldehyde sensor.     

Synthesis and selective gas-sensing properties of hierarchically porous intestine-like SnO2 hollow nanostructures

Hierarchically porous intestine-like SnO₂ hollow nanostructures of different dimension were successfully synthesized via a facile, organic template free, H₂O₂-assisted method at room temperature. The morphology as well as texture (congregated solid sphere, intestine-like solid nanostructure, hollow core–shell one, and intestine-like hollow one) of SnO₂ materials can be controlled by varying H₂O₂ concentration and the size of intestine-like hollow SnO₂ can be tuned in the range of 20–120 nm by changing SnSO₄ concentration. The hierarchically porous intestine-like SnO₂ has high specific surface area (142 m² g⁻¹). The gas-sensing behaviors of the intestine-like SnO₂ material to different gas probes such as ethanol, H₂, CO, methane, and butane have been investigated; among them a high selectivity to ethanol was achieved.