Grain Size Effects in Sensor Response of Nanostructured SnO2- and In2O3-Based Conductometric Thin Film Gas Sensor

Based on the experimental results, obtained by studying both structural and gas-sensing properties of the SnO₂ and In₂O₃ films deposited by the spray pyrolysis method, we analyzed the influence of crystallite size on the parameters of the SnO₂- and In₂O₃-based thin film solid-state gas sensors. For comparison, the behavior of ceramic-type gas sensors was considered as well. In particular, we examined the correlation between the grain size and parameters of conductometric-type gas sensors such as the magnitude of sensor signal, the rate of sensor response, thermal stability, and the sensitivity of sensor signal to air humidity. Findings confirmed that that grain size is one of the most important parameters of metal oxides, controlling almost all operating characteristics of the solid state gas sensors fabricated using both the ceramic and thin film technologies. However, it was shown that there is no single universal requirement for the grain size, because changes in grain size could either improve, or worsen of operating characteristics of gas sensors. Therefore, the choice of optimal grain size should be based on the detailed consideration of all possible consequences of their influence on the parameters of sensors designed.     

In2O3/SnO2薄膜的制备及光谱反射性能研究

开展了在伪装网基布上镀In₂O₃/SnO₂薄膜的性能研究,系统分析了薄膜厚度对其光谱反射性能的影响;总结了薄膜厚度对In₂O₃/SnO₂薄膜表面形貌、光谱反射辐射性能的影响规律,为In₂O₃/SnO₂薄膜的红外伪装应用奠定了基础理论和实验依据. 关键词： 2O₃/SnO₂薄膜')" href="#">In₂O₃/SnO₂薄膜 红外反射特性 红外发射率 可见光—近红外透过率     

Response improvement for In2O3-TiO2 thick film gas sensors

In₂O₃ is introduced into TiO₂ by sol-gel method to improve the response/recovery rate and expand the operating temperature, when the In₂O₃-TiO₂ mixed system is exposed to H₂/O₂. The sensor is fabricated by thick film technology. Influence of In₂O₃ on the film phase composition, microstructure and sensing characteristics is discussed. Dynamic response properties show that the operating temperature of the mixed system is at 500-800 °C, which is about 600-800 °C for pure TiO₂. Response time of the sensor is about 200-260 ms (millisecond) while recovery time is in a narrow range of 60-280 ms at 600-800 °C. The promoting mechanism is suggested to arise from the introduction of In₂O₃ and grain size effect of the sensing film. Then In₂O₃-TiO₂ thick films are surface-modified by Pt using chloroplatinic acid. The promoting effect of Pt dispersed on the mixed system is also investigated.     

Study of the In2O3 molecule in the free state and in the crystal

ABSTRACT

The nanomaterials based on the In₂O₃ molecule are widely used as catalysts and sensors among other applications. In the present study, we discuss the possibility of using nanoclusters of In₂O₃ as molecular photomotors. A comparative analysis of the electronic structure of the In₂O₃ molecule in the free state and in the crystal is performed. For the free In₂O₃ molecule the geometry of its lowest structures, V-shape and linear, was optimised at the CCSD(T) level, which is the most precise computational method applied up to date to study In₂O₃. Using experimental crystallographic data, we determined the geometry of In₂O₃ in the crystal. It has a zigzag, not symmetric structure and possesses a dipole moment with magnitude slightly smaller than that of the V-structure of the free molecule (the linear structure due to its symmetry has no dipole moment). According to the Natural Atomic population analysis, the chemical structure of the linear In₂O₃ can be represented as O = In?O?In = O; the V-shaped molecule has the similar double- and single-bond structure. The construction of nanoclusters from ?bricks? of In₂O₃ with geometry extracted from crystal (or nanoclusters extracted directly from crystal) and their use as photo-driven molecular motors are discussed.     

氧氩比对SnO2/Ag/SnO2透明导电膜光电性能的影响

在室温及不同的氧氩比条件下,采用射频磁控溅射Ag层和直流磁控溅射SnO₂层,在载玻片衬底上制备出了SnO₂/Ag/SnO₂多层薄膜.用霍尔效应测试仪、四探针电阻测试仪和紫外-可见-近红外光谱仪等表征了薄膜的电学性质和光学性质.实验结果表明:当氧氩比为1:14时,所制得的薄膜的光电性质优良指数最大,为1.69×10^-2 Ω^-1;此时,薄膜的电阻率为9.8×10^-5 Ω·cm,方电阻为9.68 Ω/sq,在400~800 nm可见光区的平均光学透射率达85%;并且,在氧氩比为1:14时,利用射频磁控溅射Ag层和直流磁控溅射SnO₂层在PET柔性衬底上制备出了光电性质优良的柔性透明导电膜,其在可见光区的平均光学透过率达85%以上,电阻率为1.22×10^-4 Ωcm,方电阻为12.05 Ω/sq.     

CdTe太阳电池前电极SnO2:F/SnO2复合薄膜性能分析

减薄CdS窗口层是提高CdS/CdTe太阳电池转换效率的有效途径之一,减薄窗口层会对器件造成不利的影响,因此在减薄了的窗口层与前电极之间引入过渡层非常必要.利用反应磁控溅射法在前电极SnO₂:F薄膜衬底上制备未掺杂的SnO₂薄膜形成过渡层,并将其在N₂/O₂=4 ∶1,550 ℃环境进行了30 min热处理,利用原子力显微镜、X射线衍射仪、紫外分光光度计对复合薄膜热处理前后的形貌、结构、光学性能进行了表征,同时分析了复     

Structure and NO2 gas sensing properties of SnO2-core/In2O3-shell nanobelts

SnO₂-core/In₂O₃-shell nanobelts were fabricated by a two-step process comprising thermal evaporation of Sn powders and sputter-deposition of In₂O₃. Transmission electron microscopy and X-ray diffraction analyses revealed that the core of a typical core–shell nanobelt comprised a simple tetragonal-structured single crystal SnO₂ and that the shell comprised an amorphous In₂O₃. Multiple networked SnO₂-core/In₂O₃-shell nanobelt sensors showed the response of 5.35% at a NO₂ concentration of 10 ppm at 300 °C. This response value is more than three times larger than that of bare-SnO₂ nanobelt sensors at the same NO₂ concentration. The enhancement in the sensitivity of SnO₂ nanobelts to NO₂ gas by sheathing the nanobelts with In₂O₃ can be accounted for by the modulation of electron transport by the In₂O₃–In₂O₃ homojunction.     

Characterization of single-crystalline In2O3 films deposited on Y-stabilized ZrO2 (1 0 0) substrates by MOCVD

Epitaxial In₂O₃ films have been deposited on Y-stabilized ZrO₂ (YSZ) (1 0 0) substrates by metalorganic chemical vapor deposition (MOCVD). The films were deposited at different substrate temperatures (450-750 °C). The film deposited at 650 °C has the best crystalline quality, and observation of the interface area shows a clear cube-on-cube epitaxial relationship of In₂O₃(1 0 0)||YSZ(1 0 0) with In₂O₃[0 0 1]||YSZ[0 0 1]. The Hall mobility of the single-crystalline In₂O₃ film deposited at 650 °C is as high as 66.5 cm² V⁻¹ s⁻¹ with carrier concentration of 1.5 × 10¹⁹ cm⁻³ and resistivity of 6.3 × 10⁻³ Ω cm. The absolute average transmittance of the obtained films in the visible range exceeds 95%.     

Synthesis,structural and ellipsometric evaluation of oxygen-deficient and nearly stoichiometric zinc oxide and indium oxide nanowires/nanoparticles

Oxygen-deficient (OD) and nearly stoichiometric (NST) ZnO and In₂O₃ nanowires/nanoparticles were synthesized by chemical vapor deposition on Au-coated silicon substrates. The OD ZnO and OD In₂O₃ nanowires were synthesized at 750 and 950°C, respectively, using Ar flow at ambient pressure. A mixture of flowing Ar and O₂ was used for synthesizing NST ZnO nanowires and NST In₂O₃ nanoparticles. Growth of OD ZnO nanowires and NST In₂O₃ nanoparticles was found to be via a vapor–solid (VS) mechanism and the growth of NST ZnO nanowires was via a vapor–liquid–solid mechanism (VLS). However, it was uncertain whether the growth of OD In₂O₃ nanowires was via a VS or VLS mechanism. The optical constants, thickness and surface roughness of the prepared nanostructured films were determined by spectroscopic ellipsometry measurements. A three-layered model was used to fit the calculated data to the experimental ellipsometric spectra. The refractive index of OD ZnO, NST ZnO nanowires and NST In₂O₃ nanoparticles films displayed normal dispersion behavior. The calculated optical band gap values for OD ZnO, NST ZnO, OD In₂O₃ nanowires and NST In₂O₃ nanoparticles films were 3.03, 3.55, 2.81 and 3.52?eV, respectively.     

Influence of CuO catalyst in the nanoscale range on SnO2 surface for H2S gas sensing applications

The dispersal of CuO catalyst on the surface of the semiconducting SnO₂ film is found to be of vital importance for improving the sensitivity and the response speed of a SnO₂ gas sensor for H₂S gas detection. Ultra-thin CuO islands (8 nm thin and 0.6 mm diameter) prepared by evaporating Cu through a mesh and subsequent oxidation yield a fast response speed and recovery. Ultimately nanoparticles of Cu (average size = 15 nm) prepared by a chemical technique using a reverse micelle method involving the reduction of Cu(NO₃)₂ by NaBH₄ exhibited significant improvement in the gas sensing characteristics of SnO₂ films. A fast response speed of ∼14 s and a recovery time of ∼60 s for trace level ∼20 ppm H₂S gas detection have been recorded. The sensor operating temperature (130° C) is low and the sensitivity (S = 2.06 × 10³) is high. It is found that the spreading over of CuO catalyst in the nanoscale range on the surface of SnO₂ allows effective removal of excess adsorbed oxygen from the uncovered SnO₂ surface due to spill over of hydrogen dissociated from the H₂S-CuO interaction.     

金属有机物化学气相沉积法生长Ga2（1-x）In2xO3薄膜的结构及光电性能研究

采用金属有机物化学气相沉积（MOCVD）法在蓝宝石（0001）衬底上制备出了Ga_2（1-x）In_2xO₃（x=01—09）薄膜,研究了薄膜的结构、电学和光学特性以及退火处理对薄膜性质的影响.测量结果表明：当In组分x=02时,样品为单斜β-Ga₂O₃结构;x=05的样品,薄膜呈现非晶结构,退火处理后薄膜结构得到明显的改善 关键词： 金属有机物化学气相沉积 2（1-x）In_2xO₃薄膜')" href="#">Ga_2（1-x）In_2xO₃薄膜 蓝宝石衬底 退火     

Gd-doped SnO2 nanoparticles: Structure and magnetism

Gd-doped SnO₂ nanoparticles were chemically prepared doping 0-12.5% Gd into SnO₂ and calcined at 600 °C. X-ray diffraction and Fourier transformed infrared spectroscopy measurements show the formation of single phase of Sn_1−xGd_xO₂ up to x=0.0625 while at x=0.125, an additional secondary phase of tetragonal GdO₂ (not cubic Gd₂O₃) is detected. The transmission electron microscopy studies show that the individual particles are single crystalline with an average size in the range of 10-12 nm. Magnetization measurements show the absence of ferromagnetic and antiferromagnetic ordering in all samples; however surface spin effects and enhanced Gd-O-Gd interactions are proposed to account for the observed magnetic properties of the samples.     

Influence of ceramic oxide materials on lithium based potentiometric CO2 sensors

In these potentiometric sensors, a mixed binary carbonate sensing material consisting of 90 mol% Li₂CO₃ and 10 mol% BaCO₃ was modified by adding ceramic oxide materials such as SiO₂, B₂O₃, La₂O₃, Bi₂O₃, CeO₂ and In₂O₃ in different mol% concentrations. Various sensors mixed with these external oxides have shown good performance at operating temperatures below 300 °C. Scanning electron microscopy reveals that a glassy sensing phase is formed in the sensing bi-carbonate by the addition of ceramic oxides and sintered at 600 °C for 1 h. The sensor mixed with SiO₂:B₂O₃:Bi₂O₃ in 1:2:1 mol% showed an excellent response and recovery characteristics and followed a fair Nernstian behavior with a ΔEMF/dec value of −48.18 at as low as 150 °C. The decrease in operating temperature is attributed to the enhanced lithium ion migration through the glassy sensing phase of the sensing electrode.     

Effects of interface between SnO2 thin film and Si substrate on growth time

SnO₂ thin film was grown on Si substrate using the low pressure chemical vapor deposition (LPCVD) method. The SnO₂ thin film was grown in the direction of (110) as deposition time increased. The atomic ratio of O decreased by 62.4, 57.6, and 45.6%, and the thickness of the thin film increased to 0.2, 0.3, and 0.7 ? as the deposition time increased to 10, 20, and 30 min, respectively. The interface of the thin film was examined using high-resolution transmission electron microscope (HRTEM) and energy dispersive spectroscopy (EDS) analysis. The SiO₂ layer was observed at between the SnO₂ thin film and the Si substrate. This layer decreased in thickness as the deposition time increased, which indicates that the deposition time affected the interface of the thin film.     

Low-temperature CO gas sensors based on Au/SnO2 thick film

A study on the low-temperature CO gas sensors based on Au/SnO₂ thick film was reported. Au/SnO₂ powders were prepared by a deposition-precipitation method. Thick films were fabricated from Au/SnO₂ powders. X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) analyses were carried out for investigation of morphology and crystalline structure. 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 calcination temperature of Au/SnO₂ on the CO gas sensing behavior. The optimal calcination temperature of Au/SnO₂ was 300 °C.     

Towards anode with low indium content as effective anode in organic solar cells

In₂O₃ thin films (100 nm thick) have been deposited by reactive evaporation of indium, in an oxygen partial atmosphere. Conductive (σ = 3.5 × 10³ S/cm) and transparent films are obtained using the following experimental conditions: oxygen partial pressure = 1 × 10⁻¹ Pa, substrate temperature = 300 °C and deposition rate = 0.02 nm/s. Layers of this In₂O₃ thick of 5 nm have been introduced in AZO/In₂O₃ and FTO/In₂O₃ multilayer anode structures. The performances of organic photovoltaic cells, based on the couple CuPc/C₆₀, are studied using the anode as parameter. In addition to these bilayers, other structures have been used as anode: AZO, FTO, AZO/In₂O₃/MoO₃, FTO/In₂O₃/MoO₃ and FTO/MoO₃. It is shown that the use of the In₂O₃ film in the bilayer structures improves significantly the cell performances. However the open circuit voltage is quite small while better efficiencies are achieved when MoO₃ is present. These results are discussed in the light of surface roughness and surface work function of the different anodes.     

Influence of postdeposition annealing on structural properties and electrical characteristics of thin Tm2O3 and Tm2Ti2O7 dielectrics

We describe the structural properties and electrical characteristics of thin thulium oxide (Tm₂O₃) and thulium titanium oxide (Tm₂Ti₂O₇) as gate dielectrics deposited on silicon substrates through reactive sputtering. The structural and morphological features of these films were explored by X-ray diffraction, X-ray photoelectron spectroscopy, secondary ion mass spectrometry, and atomic force microscopy, measurements. It is found that the Tm₂Ti₂O₇ film annealed at 800 °C exhibited a thinner capacitance equivalent thickness of 19.8 Å, a lower interface trap density of 8.37 × 10¹¹ eV⁻¹ cm⁻², and a smaller hysteresis voltage of ∼4 mV than the other conditions. We attribute this behavior to the Ti incorporated into the Tm₂O₃ film improving the interfacial layer and the surface roughness. This film also shows negligible degrees of charge trapping at high electric field stress.     

Investigation of gas sensor based on In2O3:Ga2O3 film

We have fabricated a LPG and butane sensor whose sensitive element is a nanosize In₂O₃:Ga₂O₃ (96:4 weight %) film covered with a thin palladium catalytic layer. Technology of deposition of these films on a glassceramic substrate by the method of rf magnetron sputtering was elaborated. The surfaces of fabricated films were studied with use of a scanning electron microscope and the thickness of films was measured. The sensitivity of sensors based on the glassceramic/In₂O₃:Ga₂O₃ (96:4 weight %)/Pd structure depending on the thickness and sizes of film grains was studied. We revealed technological regimes of sputtering providing fabrication of films with the best parameters.     

Electronic structure analysis of Mn- and Fe-codoped In2O3 by photoemission yield measurements

The valence band electronic structures of Mn- and/or Fe-doped In₂O₃, i.e., In₂O₃:Mn, In₂O₃:Fe, and In₂O₃:(Mn, Fe), are investigated by photoemission yield measurements. Significant changes are observed in the threshold energy of photoemission, depending on the doped magnetic ions, which indicates that an additional occupied band appears above the top of the valence band of In₂O₃ owing to doping with Mn and/or Fe ions. It is confirmed that the order of the threshold energies of photoemission, E_PET, is E_PET(In₂O₃:Mn)<E_PET(In₂O₃:(Mn, Fe))<E_PET(In₂O₃:Fe)<E_PET(In₂O₃). To gain a better understanding of these results, first-principles molecular orbital calculations are also carried out, which successfully explain the observed changes in the photoemission threshold energies.     

Structural, electrical and gas-sensing properties of In2O3 : Ag composite nanoparticle layers

The central objective of this study is to investigate (i) size-dependent properties of In₂O₃ nanoparticles and (ii) the role of metal additives in enhancing the gas sensing response. For this purpose, In₂O₃ : Ag composite nanoparticle layers having welldefined individual nanoparticle size and composition have been grown by a two step synthesis method. Thermogravimetric analysis, X-ray diffraction and transmission electron microscopy have been used to study the effect of post-synthesis heat treatment on the size and structure of the nanoparticles. A first-time unambiguous observation of sizedependent lowering of transformation temperature has been explained in terms of lower cohesive energy of surface atoms and increase in surface-to-volume ratio with decrease in nanoparticle size. The gas sensing studies of In₂O₃ as well as the In₂O₃ : Ag composite nanoparticle layers have been studied as a function of size and composition. In₂O₃: Ag composite nanoparticle layers with 15% silver show a sensitivity of 436 and response time of 6 s for 1000 ppm of ethanol in air. Ag additives form a p-type Ag₂O, which interact with n-type In₂O₃ to produce an electron-deficient space-charge layer. In the presence of ethanol, interfacial Ag₂O reduces to Ag, creating an accumulation layer in In₂O₃ resulting in increased sensitivity