Studies on gas sensing performance of pure and modified barium strontium titanate thick film resistors

Barium strontium titanate ((Ba_0·87Sr_0·13)TiO₃-BST) ceramic powder was prepared by mechanochemical process. The thick films of different thicknesses of BST were prepared by screen-printing technique and gas-sensing performance of these films was tested for various gases. The films showed highest response and selectivity to ammonia gas. The effect of film thickness on gas response was also studied. As prepared BST thick films were surface modified by dipping them into an aqueous solution of titanium chloride (TiCl₃) for different intervals of time. Surface modification shifted response to H₂S gas suppressing the responses to ammonia and other gases. The surface modification, using dipping process, altered the adsorbate-adsorbent interactions, which gave the unusual sensitivity and selectivity effect. Sensitivity, selectivity, thermal stability, response and recovery time of the sensor were measured and presented.     

Ethanol gas sensing properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-doped ZnO thick film resistors

The characterization and ethanol gas sensing properties of pure and doped ZnO thick films were investigated. Thick films of pure zinc oxide were prepared by the screen printing technique. Pure zinc oxide was almost insensitive to ethanol. Thick films of Al₂O₃ (1 wt%) doped ZnO were observed to be highly sensitive to ethanol vapours at 300°C. Aluminium oxide grains dispersed around ZnO grains would result into the barrier height among the grains. Upon exposure of ethanol vapours, the barrier height would decrease greatly leading to drastic increase in conductance. It is reported that the surface misfits, calcination temperature and operating temperature can affect the microstructure and gas sensing performance of the sensor. The efforts are, therefore, made to create surface misfits by doping Al₂O₃ into zinc oxide and to study the sensing performance. The quick response and fast recovery are the main features of this sensor. The effects of microstructure and additive concentration on the gas response, selectivity, response time and recovery time of the sensor in the presence of ethanol vapours were studied and discussed.     

Gas sensing properties of lead doped tin oxide thick films

The present investigation deals with the fabrication of liquid petroleum gas (LPG) sensor materials based on semiconducting oxide SnO₂. The gas sensor materials have been prepared by conventional solid-state route. The effect of Pb incorporation, operating temperature, morphology, and sensitivity is discussed using the results of X-ray diffraction (XRD), along with sensing performance. Out of various sensor compositions, Pb doped SnO₂ sintered at 1000 °C for 2 h has shown high sensitivity towards LPG at an operating temperature of 150 °C. Different characterization techniques have been employed, such as surface area analyzer, X-ray diffraction (XRD), to study the formation of SnO₂, surface area and crystallite size, respectively. The results suggested the possibility of utilizing the sensor element for the detection of LPG.     

Ethanol vapour sensing properties of screen printed WO<Subscript>3</Subscript> thick films

This paper presents ethanol vapour sensing properties of WO₃ thick films. In this work, the WO₃ thick films were prepared by standard screen-printing method. These films were characterized by X-ray diffraction (XRD) measurements and scanning electron microscopy (SEM). The ethanol vapour sensing properties of these thick films were investigated at different operating temperatures and ethanol vapour concentrations. The WO₃ thick films exhibit excellent ethanol vapour sensing properties with a maximum sensitivity of ∼1424.6% at 400°C in air atmosphere with fast response and recovery time.     

Gas sensing mechanism of TiO2-based thin films

Two classes of thin film gas sensors have been studied: TiO₂ doped with Cr or Nb and TiO₂-SnO₂ mixed systems. Thin films have been prepared by the reactive sputtering from mosaic targets. It is demonstrated that titanium dioxide doped with Nb and Cr should be considered as a bulk sensor. Its performance is governed by the diffusion of point defects, i.e. very slow diffusion of Ti vacancies for TiO₂: 9.5 at% of Nb and fast diffusion of oxygen vacancies in the case of TiO₂: 2.5 at% Cr sensor. The corresponding response times are 55 min for TiO₂: 9.5 at% of Nb and 20 s for TiO₂: 2.5 at% Cr. In turn, sensors based on TiO₂-SnO₂, particularly those of the SnO₂-rich composition, belong to the group of surface sensors.     

Superconducting YBa2Cu3O7-δ thick films on Ba2RETaO6 (RE = Pr5 Nd, Eu, and Dy) substrates

Thick films of YBa₂Cu₃O_7-δ fabricated on polycrystalline Ba₂RETaO₆ (where RE = Pr, Nd. Eu, and Dy) substrates by dip-coating and partial melting techniques are textured and oaxis oriented, showing predominantly (00/) orientation. All the thick films show a superconducting zero resistance transition of 90 K. SEM studies clearly indicate platelike and needlelike grain growth over a wide area of the thick films. The values of the critical current density for these thick films are ∼10⁴ A/cm² at 77 K as determined by the nonresonant R.F. absorption method. Various processing conditions that affect the critical current density of thick films are also discussed.     

Preparation and humidity sensing properties of Ba0.8Sr0.2TiO3 nanofibers via electrospinning

Ba_0.8Sr_0.2TiO₃/Poly (vinylpyrrolidone) (BST/PVP) composite fibers were successfully synthesized via electrospinning. The ceramic nanofibers were obtained after calcining the composite at 800 °C for 2 h. The morphology and structure of the BST fibers were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results reveal that the as-synthesized BST nanofibers show a diameter of 50-150 nm with the length over 0.1 mm, and a well-defined perovskite crystal structure. The electrical properties of the as-synthesized BST nanofibers were investigated through an impedance-type humidity sensor. The nanofibers exhibited excellent humidity sensing properties at room temperature. The possible sensing mechanism was proposed.     

Three-dimensional supercapacitors composed of Ba0.65Sr0.35TiO3 (BST)/NiSi2/silicon microchannel plates

Three-dimensional (3D) supercapacitors consisting of Ba_0.65Sr_0.35TiO₃ (BST)/NiSi₂/silicon microchannel plate (MCP) stacked structure have been fabricated. The silicon MCP produced by electrochemical etching is utilized as a backbone of the 3D structure on which a nickel silicide current collector layer and Ba_0.65Sr_0.35TiO₃ dielectric layer are deposited successively by electroless plating and the sol-gel method, respectively. The morphology and structure of the 3D BST/NiSi₂/Si-MCP structure are characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) and the electrochemical properties are determined by cyclic voltammetry (CV) and chronopotentiometry. The structure exhibits excellent capacitive behavior with a maximum capacitance of 784 F g⁻¹. After 700 charging/discharging cycles, the C_f decreases slightly with only a 5.7% loss and is stable after more than 700 cycles. The BST/NiSi₂/Si-MCP 3D structure is a potential supercapacitor in industrial applications.     

Effects of post-deposition surface treatment on the optical, structural and hydrogen sensing properties of TiO2 thin films

TiO₂ thin films were prepared by DC reactive magnetron sputtering in a mixture of oxygen and argon on glass and oxidized silicon substrates. The effect of post-deposition annealing (300 °C, 500 °C and 700 °C for 8 h in air) on the structural and morphological properties of TiO₂ thin films is presented. In addition, the effect of Pt surface modification (1, 3 and 5 nm) on hydrogen sensing was studied. XRD patterns have shown that in the range of annealing temperatures from 300 °C to 500 °C crystallization starts and the thin film structure changes from amorphous to polycrystalline (anatase phase). In the case of samples on glass substrate, optical transmittance spectra were recorded. TiO₂ thin films were tested as sensors of hydrogen at concentrations 10,000-1000 ppm and operating temperatures within the 180-200 °C range. The samples with 1 nm and in particular with 3 nm of Pt on the surface responded to hydrogen fast and with high sensitivity.     

Sulfo-selenization of metallic thin films of Cu, In and Cu-In

To achieve an optimized adaptation of the semiconductor bandgap to the terrestrial solar spectrum, CIS (CuInSe₂, CuInS₂) based chalcopyrite absorber materials are usually substituted in the cation and anion lattice to yield mixed pentanary crystals with general composition Cu(In,Ga)(Se,S)₂. In the past, in-situ XRD (X-ray diffraction) measurements helped to clarify the phase formation sequences and reaction kinetics while crystallising the ternary chalcopyrites CuInSe₂ and CuInS₂ from metallic precursors in the presence of Se or S atmosphere. To better understand the reaction paths towards pentanary mixed chalcopyrites, the experiments are now extended to a study of the combined sulfo-selenization of metallic precursors. The experimental results of the simultaneous sulfo-selenization of Cu, In and Cu-In precursor thin films are presented and their relevance for the crystallisation of a mixed CuIn(S,Se)₂ phase discussed.The affinity of the metals Cu and In is higher to sulfur. A crystallisation of mixed sulfo-selenides of Cu, In and Cu-In due to exchange reactions between S and Se is observed. Within the Cu-Se-S subsystem a wider solid solution range of S and Se is apparent as compared to the In-Se-S system. The reactions during the chalcopyrite crystallisation for chalcogen ratio [S]:[Se] = 1:1 are similar to those of the pure sulfur system at least within the In-Se-S subsystem.     

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.     

Comparison between titania thick films obtained through sol-gel and hydrothermal synthetic processes

Titania films were obtained through two synthetic processes, a traditional sol-gel method and a hydrothermal route. In SG synthesis, thermal decomposition of the precursor in oven at 400 °C for 2 h led to pure anatase TiO₂; in HY synthesis, instead, crystalline anatase grains were obtained in autoclave at 200 °C for 1 h. To investigate the microstructural evolution of SG and HY titania with temperature, each powder was annealed at 650, 750, 850 °C for 1 h and subjected to XRD analysis. Surprisingly, HY titania, contrary to SG, maintained the anatase phase, up to 850 °C, without any introduction of foreign elements. The sensing layers, obtained from as grown powders, were fired at 650, 750 or 850 °C and tested vs. methane and carbon monoxide. Both types of films fired at 850 °C yield insignificant responses to both CO and CH4, demonstrating the lack of influence of the crystalline phase on the gas response. Moreover, as regards the films fired at 650 and 750 °C, the gas responses are higher for SG than for HY samples, despite larger particle size.     

Nanocrystalline chemically modified CdIn2O4 thick films for H2S gas sensor

CdIn₂O₄ sensor with high sensitivity and excellent selectivity for H₂S gas was synthesized by using sol-gel technique. Structural, electrical and gas sensing properties of doped and undoped CdIn₂O₄ thick films were studied. XRD revealed the single-phase polycrystalline nature of the synthesized CdIn₂O₄ nanomaterials. Since the resistance change of a sensing material is the measure of its response, selectivity and sensitivity was found to be enhanced by doping different concentrations of cobalt in CdIn₂O₄ thick films. The sensor exhibits high response and selectivity toward H₂S for 10 wt.% Co doped CdIn₂O₄ thick films. The current-voltage characteristics of 10 wt.% Co doped CdIn₂O₄ calcined at 650 °C shows one order increase in current with change in the bias voltage at an operating temperature of 200 °C for 1000 ppm H₂S gas.     

Blue-violet phosphate phosphor thin films for EL

Photoluminescence (PL) and electroluminescence (EL) in blue-violet emission were observed in newly developed phosphate phosphor thin films such as Ba₃(PO₄)₂:Eu and Ba₃(PO₄)₂:Ti. These phosphate phosphor thin films were first deposited on thick BaTiO₃ ceramic sheets by r.f. magnetron sputtering using powder targets and then post-annealed in various atmospheres. Blue-violet PL and EL emissions were obtained in Ba₃(PO₄)₂:Eu and Ba₃(PO₄)₂:Ti phosphor thin films that were deposited in an Ar + H₂ (10%) gas atmosphere and then post-annealed above about 900 °C in an Ar + H₂ (10%) gas atmosphere. In particular, the EL observed in Ba₃(PO₄)₂:Eu thin films exhibited two peaks, a red emission peaking at about 615 nm and a blue-violet emission peaking at about 420 nm. A luminance of 2.0 cd/m² in blue-violet emission was obtained in a thin-film EL device using a two step post-annealed Ba₃(PO₄)₂:Eu thin-film emitting layer: step 1, post-annealing at 1000 °C in air for 1 h, and step 2, post-annealing at 1000 °C in an Ar + H₂ atmosphere.     

Growth of highT c Bi-Sr-Ca-Cu-O thick films

Thick films of Bi-Sr-Ca-Cu-O were deposited on (100) MgO substrates by screen-printing technique with the starting composition 1112. To attain the superconducting state, the films were subjected to two-step heat-treatment. R-T and XRD have been studied for films annealed at different durations of the second step. InitiallyT _c (R=0) increased from 77 to 103 K as the annealing duration was increased after whichT _c decreased. Kinetics of the growth of highT _c phase is discussed in the light of our results.     

Fabrication of TiO2 nanotubes by anodization of Ti thin films for VOC sensing

Ti thin films were anodized in aqueous HF (0.5 wt.%) and in polar organic (0.5 wt.% NH₄F + ethylene glycol) electrolytes to form TiO₂ nanotube arrays. Ti thin films were deposited on microscope glass substrates and then anodized. Anodization was performed at potentials ranging from 5 V to 20 V for the aqueous HF and from 20 V to 60 V for the polar organic electrolytes over the temperatures range from 0 to 20 °C. The TiO₂ nanotubes were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDX). It has been observed that anodization of the deposited Ti thin films with aqueous HF solution at 0 °C resulted in nanotube-type structures with diameters in the range of 30-80 nm for an applied voltage of 10 V. In addition, the nanotube-type structure is observed for polar organic electrolyte at room temperature at the anodization voltage higher than 40 V. The volatile organic compound (VOC) sensing properties of TiO₂ nanotubes fabricated using different electrolytes were investigated at 200 °C. The maximum sensor response is obtained for carbon tetrachloride. The sensor response is dependent on porosity of TiO₂. The highest sensor response is observed for TiO₂ nanotubes which are synthesized using aqueous HF electrolyte and have very high porosity.     

花状SnO2的制备及其气敏特性的研究

以乙二醇(C2H6O2)为有机溶剂,采用溶剂热法制备了花状SnO2纳米材料,并将制备的SnO2制成旁热式气敏元件.通过XRD,SEM等测试手段对SnO2纳米材料进行了表征,并初步分析了气敏元件对丙酮的敏感机理.制备的SnO2材料是由粒径约为10 nm的颗粒有规则的堆叠而成的直径约为3～4μm的花瓣清晰的多孔分级花状结构.研究发现,气敏元件对丙酮气体有很好的响应灵敏度.在最佳工作温度(350℃)时,检测的丙酮体积分数最低为1×10-6.对100 ppm丙酮的响应及恢复时间分别为40和50 s.且气敏元件对丙酮气体的响应灵敏度远高于对苯、甲苯、甲醇、甲醛、氨等气体的响应灵敏度.     

sol-gel法制备的SnO_2-TiO_2厚膜及其气敏特性研究

采用sol-gel法,以钛酸丁酯、四氯化锡为前驱体制备了不同掺杂量的Sn O2-Ti O2纳米粉末,样品经300,500,700和900℃退火后,利用浸渍提拉法,在Al2O3陶瓷管表面制备了Sn O2-Ti O2厚膜。通过XRD和SEM对制备的纳米粉末的物相、形貌进行表征,静态配气法对其气敏性能进行测试,并结合分子轨道理论探讨了气敏机理。实验结果表明,经700℃退火的4%(原子分数)掺杂的Sn O2-Ti O2气敏元件,对乙醇气体具有很好的选择性,在工作温度为63℃时,对乙醇气体的灵敏度可达1 903,响应-恢复时间分别为1和3 s,所制备的气敏元件有望用于乙醇气体的实用化检测。     

The properties of Ba0.5Sr0.5TiO3 thin film prepared by RF magnetron sputtering from powder target

The Ba_0.5Sr_0.5TiO₃ (BST) thin film with the thickness of 400 nm deposited from powder target is prepared by the radio-frequency magnetron sputtering technique. The deposition rate of BST film is estimated to be 45 nm/min, which is very fast for ferroelectric materials. The dielectric properties of the as-prepared BST thin film are demonstrated. High dielectric tunability up to 42.7% and low dielectric loss small to 0.01 are achieved at a low applied voltage of 5 V. The results demonstrate that the RF magnetron sputtering from powder target is a versatile, novel technique for the deposition of high-quality ferroelectric thin films.     

Evaluation of superconducting ceramic thick films produced from a large bulk specimen of YBa2Cu3Ox

This experimental study concerns the production and evaluation of YBa₂Cu₃O _x superconducting thick films produced by slicing these films from a large bulk specimen. The resistivity/temperature behavior of these films was found to be equivalent to, or better than, the resistivity/temperature behavior of identically prepared bulk specimens made from the same material. Practical applications involving the use of this technique are probably most likely in hybrid microelectronic devices. Applications involving larger-scale electronic circuits and other superconducting devices are also possible.