Methane sensor based on SnO<Subscript>2</Subscript>/In<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanostructure

Two sets of samples of SnO₂/In₂O₃/TiO₂ system have been fabricated with different concentrations of component materials. In the first set TiO₂ with rutile structure was used, while in the second set it has the structure of anatase. Thin films (up to 50 nm) of obtained mixtures were deposited. Their sensitivity and selectivity with respect to methane (CH4) were studied. Nanostructure on the basis of 70%SnO₂ — 10%In₂O₃ — 20%TiO₂(anatase) exhibits sufficient sensitivity to methane.     

Impedance spectroscopy analysis of Li<Subscript>2</Subscript>SnO<Subscript>3</Subscript>

In this work, Li₂SnO₃ has been synthesized by the sol–gel method using acetates of lithium and tin. Thermogravimetric analysis (TGA) has been applied to the precursor of Li₂SnO₃ to determine the suitable calcination temperature. The formation of the compound calcined at 800 °C for 9 h has been confirmed by X-ray diffraction (XRD) analysis. The Li₂SnO₃ is then pelletized and electrically characterized by using electrochemical impedance spectroscopy (EIS) in the frequency range from 50 Hz to 1 MHz. The complex impedance spectra clearly show the dominating presence of the grain boundary effect on electrical properties whereas the complex modulus plots reveal two semicircles which are due to the grain (bulk) and grain boundary. The spectra of imaginary parts of both impedance and modulus versus frequency show the existence of peaks with the modulus plots exhibiting two peaks that are ascribed to the grain and grain boundary of the material. The peak maximum shifts to higher frequency with an increase in temperature and the broad nature of the peaks indicates the non-Debye nature of Li₂SnO₃. The activation energy associated with the dielectric relaxation obtained from the electrical impedance spectra is 0.67 eV. From the electric modulus spectra, the activation energies related to conductivity relaxation in the grain and grain boundary of Li₂SnO₃ are 0.59 and 0.69 eV, respectively. The conductivity–temperature relationship is thermally assisted and obeys the Arrhenius rule with the activation energy of 0.66 eV. The conduction mechanism of Li₂SnO₃ is via hopping.     

The improvement of gas-sensing properties of SnO<Subscript>2</Subscript>/zeolite-assembled composite

SnO₂-impregnated zeolite composites were used as gas-sensing materials to improve the sensitivity and selectivity of the metal oxide-based resistive-type gas sensors. Nanocrystalline MFI type zeolite (ZSM-5) was prepared by hydrothermal synthesis. Highly dispersive SnO₂ nanoparticles were then successfully assembled on the surface of the ZSM-5 nanoparticles by using the impregnation methods. The SnO₂ nanoparticles are nearly spherical with the particle size of ~?10 nm. An enhanced formaldehyde sensing of as-synthesized SnO₂-ZSM-5-based sensor was observed whereas a suppression on the sensor response to other volatile organic vapors (VOCs) such as acetone, ethanol, and methanol was noticed. The possible reasons for this contrary observation were proposed to be related to the amount of the produced water vapor during the sensing reactions assisted by the ZSM-5 nanoparticles. This provides a possible new strategy to improve the selectivity of the gas sensors. The effect of the humidity on the sensor response to formaldehyde was investigated and it was found the higher humidity would decrease the sensor response. A coating layer of the ZSM-5 nanoparticles on top of the SnO₂-ZSM-5-sensing film was thus applied to further improve the sensitivity and selectivity of the sensor through the strong adsorption ability to polar gases and the “filtering effect” by the pores of ZSM-5.     

Erbium-induced blurring of the fractal surface of SnO<Subscript>2</Subscript> nanocrystals grown in silica

We show here what kind of modification of the interphase morphology of SnO₂ nanoparticles in silica (average nanocrystal radius, in undoped material; in erbium doped material) brings to the passivation of interfacial defects. Surface states, which may preclude the exploitation of UV excitonic emission, are reduced after doping by rare earth ions. We demonstrate, by means of transmission-electron-microscopy and small-angle-neutron-scattering data, that a smooth interphase with a non negligible thickness takes the place of the fractal and discontinuous boundary observed in undoped material.     

Red photoluminescence mechanism in SnO<Subscript>2</Subscript> nanostructures

Tin dioxide nanoribbons were fabricated for clarifying the origin of the red photoluminescence band. It is found that the red band abruptly decreases its intensity after annealing the nanoribbons in O₂. The time-resolved photoluminescence decay curve shows that the red band has a luminescence lifetime of ns. The electron spin resonance spectrum discloses that the red band is related to a kind of combined oxygen-vacancy (V _o⁺ and V _o⁺⁺) centers. Spectral analysis and theoretical calculation confirm that the red band arises from a transition between the combined oxygen-vacancy defect states in the band gap.     

Electrical properties of polycrystalline TiO<Subscript>2</Subscript>: Equilibration kinetics

The equilibration kinetics was determined for high purity polycrystalline TiO₂ in the temperature range of 1,123–1,323 K, within a wide range of oxygen activity, . The equilibration kinetics experiments were performed within narrow p(O₂) ranges. The obtained kinetic data were used for the determination of the chemical diffusion coefficient, D _chem, which exhibits a complex dependence of p(O₂). The D _chem data are considered in terms of the effect of defect disorder on the mass transport kinetics in the chemical potential gradient. The reported diffusion data may be used for prediction of optimized processing conditions required to impose a homogeneous distribution of oxygen activity within the TiO₂ specimen. This project was performed as part of University of New South Wales R&D program on solar hydrogen.     

Modification of the Al<Subscript>2</Subscript>O<Subscript>3</Subscript> surface by high-energy bismuth ions

This paper reports on an atomic-force microscopy study of the surface of α-Al₂O₃ single crystals irradiated by Bi ions with energies of 710, 557, 269, and 151 MeV. The shape of the radiation defects produced by single ions was established to depend on the ionization energy loss. The threshold ionization density above which the surface topography is observed to change lies in the 27–35 keV/nm interval. Possible mechanisms of defect formation in the thermal-spike model, namely, a phase transition and the creation of thermoelastic stresses in the high-energy ion track, are considered.     

Semiconducting SnO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> (S-T) composites for detection of SO<Subscript>2</Subscript> gas

SnO₂-TiO₂ (S-T) composites with different molar ratios were prepared by mechanical mixing followed by sintering at 700 °C for 4 h in air. The structural and microstructural properties of the composites were investigated using powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM). S-T composites were investigated by introducing SO₂ to test their chemical stability using PXRD and SEM coupled with energy dispersive X-ray (EDX) analysis. The sensing performance was measured at different temperatures using various SO₂ concentrations (10–100 ppm). A composite comprising 25 mol% of SnO₂ and 75 mol% TiO₂ (S25-T75) exhibited the highest sensitivity comparing to other S-T composites studied under the presently investigated conditions. t ₉₀ (90 % of response time) was found to be ～5 min for thick pellet (~2 mm in thickness). SO₂ sensing mechanism has been explained through the band structure model.     

Structural and sensing properties of nanocrystalline SnO<Subscript>2</Subscript> films deposited by spray pyrolysis from a SnCl<Subscript>2</Subscript> precursor

We report the fabrication and characterization of tin dioxide gas sensing layers. The tin dioxide layers were synthesized using a convenient, simple and low-cost technique of spray pyrolysis. The formation of stoichiometric SnO₂ layers with fine-grain structure is revealed by Rutherford backscattering spectroscopy. The microstructure, phase, nanoparticle size distribution and surface morphology were studied by transmission electron microscopy, electron diffraction and atomic force microscopy. Most of the grains were of 10–20 nm size; however, some particles were up to 100 nm in size and had a microtwin lamellae structure of SnO₂ phase (cassiterite) with lattice parameters a= 0.474 nm and c= 0.319 nm. The sensitivity of the layers with respect to 1000–10000 ppm CH₄ in air was obtained from both resistivity (S_R) and capacity (S_C) measurements at 330 °C and values of S_R=5–7 and S_C=22–31 were extracted. PACS 68.43.-h; 68.55.-a; 81.05.Hd; 81.07.-b; 81.15.Rs     

Gas-sensing studies on SnO<Subscript>2</Subscript> or NASICON-type composite materials

NASICON powders were prepared by solid-state synthesis, a fraction was ion exchanged by Li or K, verified by X-ray diffraction and energy dispersive X-ray analysis, blended with tin oxide powder, transferred to thick film pastes, and dispensed on a commercial sensor substrate (Heraeus, Germany). Simultaneous gas sensitivity measurements on nine SnO₂/NASICON-type (, x = 0, 2.2, 3, M = Li, Na, K) composites in thermocyclic sensor operation mode by exposure to different concentrations of Ethanol, Toluene, Propylene, CO, and H₂ in humidified synthetic air show a strong correlation of the gas-sensing properties with the mobile ion concentration and type of the solid electrolyte additive.     

Ferromagnetism in Rh-doped SnO<Subscript>2</Subscript> from first-principles calculation

The electronic structures and magnetic properties for Rh-doped SnO₂ crystals have been investigated by density functional theory. The results demonstrate a magnetic moment, which mainly arises from d orbital of Rhodium, of 1.0 μ _B per Rhodium with a little contribution from the Oxygen atoms surrounding it. The Rh-doped SnO₂ system exhibits half-metallic ferromagnetism with high Curie temperature. Several doped configurations calculations show that there are some robust ferromagnetic couplings between these local magnetic moments. The p–d hybridization mechanism is responsible for the predicted ferromagnetism. These results suggest a recipe obtaining promising dilute magnetic semiconductor by doping nonmagnetic elements in SnO₂ matrix.     

Synthesis of nanocrystalline SnO<Subscript>2</Subscript> in supercritical water

Nanocrystalline SnO₂ was synthesized in supercritical water at 385–415°C and 30 MPa (38–106 s residence time) in a tubular flow reactor from an aqueous solution of 0.1–0.4 M SnCl₄. The conversion rate was between 53 and 81%, but increased to 97.8% when 0.1 M NaOH was added. Nanoparticles were analyzed by a series of independent analytical techniques, including TEM, Raman, XRD, SEM, EDX and FT-IR. The initial size of the particles was about 3.7 nm. After calcination at 450°C for 2 h, the particle size increased to 4 nm. The particles were of low crystallinity, as indicated by the weak Raman and XRD signals. All particles were composed of Sn and O, as verified by the EDX spectra. The crystals were tetragonal, as confirmed by the weak XRD spectrum. After calcination at 600°C for 10 h, the particle size increased to 9 nm, while high crystallinity was confirmed by Raman and XRD analyses. All the crystals had the same structure, as indicated by TEM electron diffraction patterns. Using this one-step supercritical water process, nanoparticles of SnO₂ can be conveniently produced continuously in a flow reactor in less than 2 min.     

Antiferromagnetic interactions in Er-doped SnO<Subscript>2</Subscript> DMS nanoparticles

Diluted magnetic semiconductor (DMS) nanoparticles of Sn_1−x Er _x O₂ (x = 0.0, 0.02, 0.04, and 0.1) were prepared by sol–gel method. The X-ray diffraction patterns showed SnO₂ rutile structure for all samples with no impurity peaks. The decrease in crystallite size with Er concentration was confirmed from TEM measurements (from 12 to 4 nm). The UV–Visible absorption spectra of Er-doped SnO₂ nanoparticles showed blue shift in band gap compared to undoped SnO₂. The electron spin resonance analysis of Er-doped SnO₂ nanoparticles indicate Er³⁺ in a rutile lattice and also decrease in intensity with Er concentration above x = 0.02. Temperature-dependent magnetization studies and the inverse susceptibility curves indicated increased antiferromagnetic interaction with Er concentration.     

Electrical properties of polycrystalline TiO<Subscript>2</Subscript>. Prolonged oxidation kinetics

The equilibration kinetics for polycrystalline TiO₂ was monitored during prolonged oxidation at 1,323 K and p(O₂)=75 kPa using the measurements of the electrical conductivity and thermoelectric power. The determined kinetic data indicate the presence of two kinetics regimes; the Regime I (rapid kinetics) and the Regime II (slow kinetics). The prolonged oxidation of TiO₂ is considered in terms of the formation of Ti vacancies at the surface and their subsequent transport into the bulk. This effect, also observed for TiO₂ single crystal, allows to obtain p-type TiO₂ without the incorporation of acceptor-type foreign ions into the TiO₂ lattice. This project was performed as part of the University of New South Wales Research and Development programme on solar-hydrogen.     

Effect of organic dyes on the dielectric properties of KH<Subscript>2</Subscript>PO<Subscript>4</Subscript> crystals

The effect of organic dyes on the dielectric properties of KH₂PO₄ (KDP) crystals is studied over a wide range of temperatures. The dielectric properties of KDP crystals doped with molecules of the Chicago Sky Blue and Amaranth organic dyes are investigated for the first time. The dye molecules can be incorporated into the crystal lattice of KDP and selectively paint the pyramidal growth sectors of the crystal. The influence of dye organic impurities on the domain contribution to the permittivity is analyzed with due regard for the sectoral crystal structure. It is demonstrated that, upon doping of KDP crystals with organic dyes, the blocking effect of background impurities on domain walls is substantially weakened in the prismatic growth sector of the crystal in the polar phase. This leads to a noticeable change in the dielectric properties, specifically to an increase in the domain contribution to the permittivity of the crystal.     

Phase transition effects in polycrystalline Hg<Subscript>2</Subscript>Br<Subscript>2</Subscript> samples

The effects accompanying the ferroelastic phase transition in Hg₂Br₂ polycrystalline samples are compared in an x-ray diffraction study with similar effects observed to occur in Hg₂Br₂ single crystals. In particular, an analysis is made of the “orthorhombic” splitting of the basal plane reflections and the behavior with temperature of the Bragg and diffuse reflections from the X points of the Brillouin zone, which characterize the behavior of the order parameter and its fluctuations, respectively. Polycrystalline samples exhibit strong smearing of the phase transition effects originating from the existence of damaged surface layers and elastic and plastic strain fields which induce order parameter fluctuations over a wide temperature range.     

Electrical properties,equivalent circuit,and dielectric relaxation studies on [(C<Subscript>3</Subscript>H<Subscript>7</Subscript>)<Subscript>4</Subscript>N]<Subscript>2</Subscript>Cd<Subscript>2</Subscript>Cl<Subscript>6</Subscript> polycrystalline

The Ac electrical conductivity and the dielectric relaxation properties of the [(C₃H₇)₄N]₂Cd₂Cl₆ polycrystalline sample have been investigated by means of impedance spectroscopy measurements over a wide range of frequencies and temperatures, 209 Hz–5 MHz and 361–418 K, respectively. The purpose is to make a difference between the electrical and dielectric properties of the polycrystalline sample and single crystal. Besides, a detailed analysis of the impedance spectrum suggests that the electrical properties of the material are strongly temperature-dependent. Plots of (Z" versus Z') are well fitted to an equivalent circuit model consisting of a series combination of grains and grains boundary elements. Moreover, the temperature dependence of the electrical conductivity in the different phases follows the Arrhenius law and the frequency dependence of σ (ω) follows the Jonscher’s universal dynamic law. Furthermore, the modulus plots can be characterized by full width at half height or in terms of a nonexperiential decay function φ(t) = exp(t/t)^β. Finally, the imaginary part of the permittivity constant is analyzed with the Cole–Cole formalism.     

Synthesis and characterization of a polyaniline-modified SnO<Subscript>2</Subscript> nanocomposite

Polyaniline-modified tin oxide and tin oxide nanoparticles were synthesized using a solution route technique. The obtained pristine products were characterized with X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, and optical absorption spectroscopy. Thermogravimetric analysis results showed that the polyaniline-modified SnO₂ nanoparticles exhibit higher thermal stability than the SnO₂ nanoparticles. Scanning electron microscopy analysis on the as-synthesized powders showed spherical particle in the range of 50–100 nm.     

Tuning electronic properties of In<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires by doping control

We present two effective routes to tune the electronic properties of single-crystalline In₂O₃ nanowires by controlling the doping. The first method involves using different O₂ concentrations during the synthesis. Lightly (heavily) doped nanowires were produced by using high (low) O₂ concentrations, respectively, as revealed by the conductances and threshold voltages of nanowire-based field-effect transistors. Our second method exploits post-synthesis baking, as baking heavily doped nanowires in ambient air led to suppressed conduction and a positive shift of the threshold voltage, whereas baking lightly doped nanowires in vacuum displayed the opposite behavior. Our approaches offer viable ways to tune the electronic properties of many nonstoichiometric metal oxide systems such as In₂O₃, SnO₂, and ZnO nanowires for various applications. PACS 85.35.-p     

Synthesis and enhanced acetone gas-sensing performance of ZnSnO<Subscript>3</Subscript>/SnO<Subscript>2</Subscript> hollow urchin nanostructures

A kind of novel ZnSnO₃/SnO₂ hollow urchin nanostructure was synthesized by a facile, eco-friendly two-step liquid-phase process. The structure, morphology, and composition of samples were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption–desorption techniques. The results revealed that many tiny needle-like SnO₂ nanowires with the average diameter of 5 nm uniformly grew on the surface of the ZnSnO₃ hollow microspheres and the ZnSnO₃/SnO₂ hollow urchin nanostructures with different SnO₂ content also were successfully prepared. In order to comprehend the evolution process of the ZnSnO₃/SnO₂ hollow urchin nanostructures, the possible growth mechanism of samples was illustrated via several experiments in different reaction conditions. Moreover, the gas-sensing performance of as-prepared samples was investigated. The results showed that ZnSnO₃/SnO₂ hollow urchin nanostructures with high response to various concentration levels of acetone enhanced selectivity, satisfying repeatability, and good long-term stability for acetone detection. Specially, the 10 wt% ZnSnO₃/SnO₂ hollow urchin nanostructure exhibited the best gas sensitivity (17.03 for 50 ppm acetone) may be a reliable biomarker for the diabetes patients, which could be ascribed to its large specific surface area, complete pore permeability, and increase of chemisorbed oxygen due to the doping of SnO₂.