Temperature-dependent characteristics of pulse-laser-deposited (Pb,Sr)TiO<Subscript>3</Subscript> films at low temperatures

Pulsed laser deposition (PLD) of (Pb,Sr)TiO₃ (PSrT) film on Pt/SiO₂/Si at low substrate temperatures (T_s), ranging from 300–450 °C, has been investigated. As T_s increases, the films reveal coarsening clusters, improved crystallization of the perovskite phase, distinct capacitance–electric field (C–E) hysteretic loops and a larger dielectric constant. The 350 °C-deposited film shows strong (100) preferred orientation and optimum dielectric properties with the dielectric constant of ∼620. The current density increases as the measurement temperature and the electric field increase. Moreover, PSrT films exhibit a strong negative temperature coefficient of resistance (NTCR) behavior at temperatures ranging from 100 to 390 °C. PACS 81.15.Fg; 77.22.Ch; 68.60.Dv     

Sonochemical fabrication of morpho-genetic TiO<Subscript>2</Subscript> with hierarchical structures for photocatalyst

Titanium oxides (TiO₂) with hierarchical structures have been successfully replicated from biotemplate using a sonochemical method. The bio-templates, cedarwoods, were irradiated under ultrasonic waves in TiCl₄ solutions and then calcined at temperatures between 450 and 600 °C. The fine replications of the biotemplates in TiO₂ down to nanometer’s level were verified using X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). The photocatalytic activities were assessed by measuring the percentage degradation of methylene blue using UV–vis spectroscopy. The calcination temperature has a strong effect on the structural replication and photocatalytic activity of the replicas. It appears that the calcination temperature of 450 °C results in the best structural replication with the highest surface area of 54.8 m² g⁻¹, and thus has the best photocatalytic properties. This method provides a simple, efficient, and versatile technique for fabricating TiO₂ with hierarchical structures, and it has the potential to be applied to other systems for producing functional hierarchical materials for chemical sensor and nanodevices.     

Structural characterization of the V2O5/TiO2 system obtained by the sol–gel method

The influence of the vanadium load and calcination temperature on the structural characteristics of the V₂O₅/TiO₂ system was studied by X-ray diffraction and X-ray absorption spectroscopy (XAS) techniques. Samples of the V₂O₅/TiO₂ system were prepared by the sol–gel method under acid conditions and calcined at different temperatures. The rutile phase was found to predominate in pure TiO₂ calcined at 450 °C as a result of the reduction of phase transition temperature promoted by the sol–gel method under acid conditions. The anatase phase became predominant at 450 °C as the amount of vanadium increased from 6 to 9 wt%. A structural change in the TiO₂ phase from predominantly anatase to totally rutile with increased calcination temperature was observed in 6 wt% samples. An analysis of the vanadium X-ray Absorption Near Edge Structure (XANES) spectra showed that the oxidation state of vanadium atoms in the samples containing 6 and 9 wt% of vanadium and calcined at 450 °C was predominantly V⁴⁺. However, the presence of V⁵⁺ atoms cannot be ruled out. A qualitative analysis of extended X-ray absorption fine structure (EXAFS) spectra of the samples containing 6 and 9 wt% of vanadium calcined at 450 °C showed that the local structure around vanadium atoms is comparable to that of VO₂ crystalline phase, in which vanadium atoms are fourfold coordinated in a distorted structure. For the sample after calcination at 600 °C, the EXAFS and XANES results showed that a significant portion of vanadium atoms were incorporated in the rutile lattice with a V_xTi_(1−x)O₂ solid solution formation. The conditions of sample preparation used here to prepare V₂O₅/TiO₂ samples associated with different amounts of vanadium and calcination temperatures proved to be useful to modifying the structure of the V₂O₅/TiO₂ system.     

Effect of annealing treatment on the uniformity of CeO2/TiO2 bilayer resistive switching memory devices

Bilayer CeO₂/TiO₂ films with high-k dielectric property were prepared by rf magnetron sputtering technique at room temperature. Effect of annealing treatment on resistive switching (RS) properties of bilayer CeO₂/TiO₂ films in O₂ ambient at different temperature in the range of 350–550 °C was investigated. Our results revealed that the bilayer films had good interfacial property at 500 °C and this annealing temperature is optimum for different RS characteristics. Results showed that bilayer CeO₂/TiO₂ film perform better uniformity and reliability in resistive switching at intermediate temperature (i.e. 450 °C and 500 °C) instead of low and high annealing temperature (i.e. 350 °C and 550 °C) at which it exhibits poor crystalline structure with more amorphous background. Less Gibbs free energy of TiO₂ as compared to CeO₂ results in an easier re-oxidation of the filament through the oxygen exchange with TaN electrode. However, the excellent endurance property (>2500 cycles), data retentions (10⁵ s) and good cycle-to-cycle uniformity is observed only in 500 °C annealed devices. The plots of cumulative probability, essential memory parameter, show a good distribution of Set/Reset voltage.     

Thermostable photocatalytically active TiO<Subscript>2</Subscript> anatase nanoparticles

Anatase is the low-temperature (300–550 °C) crystalline polymorph of TiO₂ and it transforms to rutile upon heating. For applications utilizing the photocatalytic properties of nanoscale anatase at elevated temperatures (over 600 °C) the issue of phase stabilisation is of major interest. In this study, binary TiO₂/SiO₂ particles were synthesized by a flame aerosol process with TiCl₄ and SiCl₄ as precursors. The theoretical Si/Ti ratio was varied in the range of 0.7–1.3 mol/mol. The synthesized TiO₂/SiO₂ samples were heat treated at 900 and 1,000 °C for 3 h to determine the thermostability of anatase. Pyrogenic TiO₂ P25 (from Evonik/Degussa, Germany) widely applied as photocatalyst was used as non-thermostabilized reference material for comparison of photocatalytic activity of powders. Both the non-calcinated and calcinated powders were characterized by means of XRD, TEM and BET. Photocatalytic activity was examined with dichloroacetic acid (DCA) chosen as a model compound. It was found that SiO₂ stabilized the material retarding the collapse of catalyst surface area during calcination. The weighted anatase content of 85% remains completely unchanged even after calcination at 1,000 °C. The presence of SiO₂ layer/bridge as spacer between TiO₂ particles freezes the grain growth: the average crystallite size increased negligibly from 17 to 18 nm even during the calcination at 1,000 °C. Due to the stabilizing effect of SiO₂ the titania nanoparticles calcinated at 900 and 1,000 °C show significant photocatalytic activity. Furthermore, the increase in photocatalytic activity with calcination temperature indicates that the titania surface becomes more accessible either due to intensified cracking of the SiO₂ layer or due to enhanced transport of SiO₂ into the necks thus releasing additional titania surface.     

Synthesis and characterization of nanostructured titania film for photocatalysis

Nanostructured titania film was synthesized using nonionic triblock copolymer P123 as surfactant template removed by ethanol extraction followed by calcination at different temperatures. The results of SAXRD indicate that the mesostructures of the films are not damaged until the calcination temperature as high to 450 °C. The results of TG/DSC, UV–visible and Raman spectra analyses provide the evidences for anatase phase to occur at 400 °C and above. The results of TEM and N₂ adsorption and desorption measures indicate that, with temperature increasing from 350 to 500 °C, anatase nanocrystal sizes and pore diameter increase, while the calculated BET surface area decreases. The photocatalytic activity of the films was characterized by the degradation test of methylene blue, and the results show that it depends on both the specific surface area and the crystallinity of nanostructured titania film.     

Characterization and Photocatalytic Performance of Rb+-Doped TiO2 Photocatalysts

ABSTRACT

Rb⁺-doped TiO₂ nanoparticles with higher photocatalytic activity were prepared by sol–gel method. The prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive analysis of X-rays (EDAX), and surface area (BET) measurements. The photocatalytic activity for the degradation of rhodamine B (RhB) was evaluated. The effects of calcination temperature, Rb⁺-doping amount, and the dosage of catalyst in the reaction liquid were investigated. The results showed that Rb⁺ doping can inhibit phase transformation from anatase to rutile, increase surface area of TiO₂ crystals, and reduce crystallite size. TiO₂ doped with 1% Rb⁺ and calcined at 650°C shows much higher photoactivity than the others when the doping level of Rb⁺ and calcination temperature are 0–5% and 350–850°C, respectively. The kinetics of the degradation of RhB was also analyzed. The kinetics of this reaction fits the pseudo first-order kinetics model well, and the reaction rate constants for pure TiO₂ and Rb1-650 are 0.086 min^?1 and 0.226 min^?1 respectively. Doping with Rb⁺ improves the photocatalytic activity of TiO₂ significantly.     

Effects of sintering temperature and atmosphere on magnetism in Mn-doped TiO2 bulk samples

Magnetic properties have been investigated on Mn doped TiO₂(Ti_0.98Mn_0.02O₂) bulk samples prepared by solid state reaction, which were sintered at different temperature ranging from 450 ^°C to 900 ^°C in air and argon atmosphere, respectively. The results show that the magnetic properties were strongly dependent on the sintering temperature and atmosphere. For samples sintered in air, the magnetization initially increase with the increase of sintering temperature up to 600 ^°C and thereafter it decrease. While the magnetization of samples sintered in argon atmosphere decreases monotonically with the increase of sintering temperature. Furthermore, for samples sintered at 600 ^°C in air, the magnetic susceptibility exhibits a dominant Curie-Weiss behaviour and no magnetic transition is observed over the temperature range from 10 to 300 K. In contrast, for samples sintered in argon atmosphere, besides the magnetic transition near 45 K perhaps caused by Mn₃O₄, another magnetic transition appears near room temperature.     

Improved surface‐enhanced Raman scattering properties of TiO2 nanoparticles by Zn dopant

In this paper, pure and Zn‐doped TiO₂ nanoparticles (NPs) with various content of Zn were prepared by a sol–hydrothermal method and were employed as active substrates for surface‐enhanced Raman scattering (SERS). On the 3% Zn‐doped TiO₂ substrate, 4‐mercaptobenzoic acid(4‐MBA) molecules exhibit a higher SERS intensity by a factor of 6, as compared with the native enhancement of 4‐MBA adsorbed on undoped TiO₂ NPs. Moreover, the higher SERS activity was still observed on the 3% Zn‐doped TiO₂ NPs at temperature even up to 125 °C. These results indicate that an appropriate amount of Zn doping can improve the SERS performances of TiO₂ SERS‐active substrates. The introduction of Zn dopant can enrich the surface states (defects) of TiO₂ and improve the separation efficiency of photo‐generated charge carriers (electrons and holes) in TiO₂, according to measurements of X‐ray diffraction, UV‐visible diffuse reflectance spectroscopy, and photoluminescence, which are responsible for the influence of Zn dopant on the improved SERS performances of TiO₂ NPs. Copyright © 2009 John Wiley & Sons, Ltd.     

First-principles study of ground- and metastable-state properties of XO (X = Be,Mg, Ca,Sr, Ba,Zn and Cd)

The evolution of the local atomic order of an amorphous Ni₄₆Ti₅₄ alloy produced by mechanical alloying as a function of temperature was studied by synchrotron X-ray diffraction (XRD) and differential scanning calorimetry (DSC) techniques. XRD measurements at several temperatures (25 °C, 350 °C, 412 °C, 430 °C, 450 °C and 515 °C) were performed and analyzed using the reverse Monte Carlo (RMC) simulations method or the Rietveld refinement procedure. The experimental total structure factor for samples at 25 °C and 350 °C, which are amorphous in nature, were simulated by using the RMC method, and the local structures of the alloy at both temperatures were determined, indicating a decrease in its density as the temperature increases. At 412 °C, the XRD pattern shows a partially crystalline sample, indicating that the crystallization process is in progress. At 430 °C, 450 °C and 515 °C, the XRD measurements indicate the presence of two crystalline phases, NiTi and NiTi₂, whose structural parameters (lattice parameters, coherently diffracting domains (CDD) sizes, microstrains and relative amount of phases) were determined using the Rietveld refinement procedure. DSC measurements at different heating rates furnished the crystallization temperature, enthalpy and activation energy of the crystallization process, and these values are similar to those found in other amorphous alloys of the Ni-Ti system. They also showed the existence of a second exothermic process, which was related to diffusive processes in the crystalline phases, which could be associated with the changes in the CDD sizes happening from 450 °C to 515 °C.     

Effect of calcinations on the structural and magnetic properties of magnesium ferrite nanoparticles prepared by sol gel method

Magnesium ferrite nanoparticles calcined at 300 °C, 350 °C, 400 °C, 450 °C were synthesized by sol-gel method. The effects of calcinations on the cation distribution, structural and magnetic properties have been investigated. X-ray diffraction (XRD) and vibrating scanning magnetometer (VSM) were used to characterize the structural and magnetic properties. X-ray diffraction analysis revealed the formation of single phase MgFe₂O₄ in all the samples. Lattice constant and crystallite size increased with calcination. X-ray diffraction data were used to estimate the average cationic distribution among A site and B site. Cationic distribution shows that there is migration of cation between tetrahedral A site and octahedral B site. Saturation magnetization increased with particle size. Coercivity decreased with calcination temperature as a result of decrease in pinning effect at the grain boundary. Curie temperature (T_C) decreased slightly due to weakening of A-B exchange interaction. Low temperature magnetic measurement revealed that blocking temperature (T_B) increased due to strong magnetic interaction.     

Improved performances on surface‐enhanced Raman scattering based on electrochemically roughened gold substrates modified with SiO2 nanoparticles

In this work, we use electrochemical oxidation–reduction cycles (ORC) methods to prepare surface‐enhanced Raman scattering (SERS)‐active gold substrates modified with SiO₂ nanoparticles to improve the corresponding SERS performances. Based on the modified substrates, the SERS of Rhodamine 6G (R6G) exhibits a higher intensity by 3‐fold of magnitude, as compared with that of R6G adsorbed on a SERS‐active Au substrate without the modification of SiO₂ nanoparticles. Moreover, the SERS enhancement capabilities of the modified and the unmodified Au substrates are seriously destroyed at temperatures higher than 250 and 200 °C, respectively. These results indicate that the modification of SiO₂ nanoparticles can improve the thermal stability of SERS‐active substrates. The aging in SERS intensity is also depressed on this modified Au substrate due to the contribution of SiO₂ nanoparticles to SERS effects. Copyright © 2009 John Wiley & Sons, Ltd.     

Composition of oxide compounds supported on metal meshes when synthesizing catalysts for the oxidation of hydrocarbons

Samples of a woven mesh of metal wire (fechral) with supported aluminum hydroxide compounds are studied. Aluminum hydroxide is formed in its bayerite modification. Aluminum oxides are produced during calcination: η-Al₂O₃ at 600°C, and θ-Al₂O₃ at 900°C. Subsequent modification with silicon, cerium, lanthanum, tungsten, and calcination at the same temperature results in the formation of their oxides. Interaction between alumina and tungsten at 600°C, and alumina and lanthanum at 900°C, are observed.     

The preparation and characterization of nanoparticle TiO2/Ti films and their photocatalytic activity

Nanoparticle TiO₂/Ti films were prepared by a sol–gel process using Ti(OBu)₄ as raw material, the as-prepared film samples were also characterized by TG-DTA, XRD, TEM, SEM, XPS, DRS, PL, SPS and EFISPS testing techniques. TiO₂ nanoparticles experienced two processes of phase transition, i.e. amorphous to anatase and anatase to rutile at the calcining temperature range from 450 to 700 °C. TiO₂ nanoparticles calcined at 600 °C had similar composition, structure, morphology and particle size with the internationally commercial P-25 TiO₂ particles. Thus, the conclusion that 600 °C might be the most appropriate calcining temperature during the preparation process of nanoparticle TiO₂/Ti film photocatalysts could be made by considering the main factors such as the properties of TiO₂ nanoparticles, the adhesion of nanoparticle TiO₂ film to Ti substrate, the effects of calcining temperature on Ti substrate and the surface characteristics and morphology of nanoparticle TiO₂/Ti film for the practice view. The Ti element mainly existed on the nanoparticle TiO₂/Ti(3) film calcined at 600 °C as the chemical state of Ti⁴⁺, while O element mainly existed as three kinds of chemical states, i.e. crystal lattice oxygen, hydroxyl oxygen and adsorbed oxygen with increasing band energy. Its photoluminescence (PL) spectra with a peak at about 380 nm could be observed using 260 nm excitation, possibly resulting from the electron transition from the bottom of conduction band to the top of valence band. The PL peak position was nearly the same as the onset of its diffuse reflection spectra (DRS) and surface photovoltage spectroscopy (SPS), demonstrating that the effects of the quantum size on optical property were greater than that of the Coulomb and surface polarization. The PL spectra with two peaks related to the anatase and rutile, respectively, could be observed using the excited wavelength of 310 nm. Weak PL spectra could be observed using the excited wavelength of 450 nm, resulting from surface states. In addition, during the experimental process of the photocatalytic degradation phenol, the photocatalytic activity of nanoparticle TiO₂/Ti film with three layers calcined at 600 °C was the highest.     

Thermally stimulated transformations in brookite-containing TiO<Subscript>2</Subscript> nanopowders produced by the hydrolysis of TiCl<Subscript>4</Subscript>

TiO₂ nanopowder is produced by the low-temperature hydrolysis of TiCl₄. The phase composition of the sample is found to form at a hydrolysis temperature of 30–38°C. Low-temperature annealing (up to 440°C) increases the degree of crystallinity of the phases present in the sample (anatase, brookite) and only weakly affects their ratio. At 500°C, the sample consists of three phases: rutile is detected apart from anatase and brookite. Brookite begins to fail at 600°C; at 700°C, crystalline brookite fails completely.     

Spin‐dependent‐magnetoresistance control by regulation of heat treatment temperature for magnetite nano‐particle sinter

The control of spin‐dependent‐magnetoresistance by regulation of the heat treatment (HT) temperature for magnetite (Fe₃O₃) nano‐particle sinter (MNPS) has been studied. The average nano‐particle size in the MNPS is 30nm and the HT was carried out from 400°C to 800°C. The HT of the MNPS varies the coupling form between adjacent magnetite nano‐particles and the crystallinity of that. The measurements on electrical resistance (ER), magnetoresistance (MR) and magnetization were performed between 4K and 300K. The behavior of the ER and MR considerably changes at the HT temperature of ～600°C. Below ～600°C the ER indicates the variable‐range‐hopping conduction behavior and the MR shows the large intensity in a wide temperature region. Above ～600°C the ER shows the indication of the Verwey transition near 110K like a bulk single crystal and the MR designates the smaller intensity. We consider that below ～600°C the ER and MR are dominated by the grain‐boundary conduction and above ～600°C those are determined by the inter‐grain conduction. The magnetic field application to the grain‐boundary region is inferred to cause the large enhancement of the MR.     

Die Verfestigungserholung von plastisch verformten Steinsalzeinkristallen

Cylindrical rock salt single crystals have been plastically deformed by compression in the [001]-direction at room temperature to shear stresser τ _E of 200 N/cm² and 350 N/cm², respectively. Isochronal annealing experiments reveal, that workhardening recovers at >300° C. The characteristic annealing temperature was found between 400° C and 450° C. At 600° C the residual workhardening still amounts to 15–20%. The isochronal reduction of screw dislocation density between 400 and 600° C shows qualitatively the same behaviour as recovery of workhardening. From the isothermal annealing curves of the samples deformed to 200 N/cm² the activation energy for recovery of workhardening was found to be about 1 eV. Assuming that the kinetics of recovery can be explained by processes distributed in activation energy, an approximate spectrum of activation energies (with a maximum arising at ～1 eV) has been evaluated. The results show that recovery of workhardening after low deformation (stage I of the stress strain curve) is mainly due to the dislocations.     

Biotemplate fabrication of SnO<Subscript>2</Subscript> nanotubular materials by a sonochemical method for gas sensors

A sonochemical method is developed to fabricate SnO₂ nanotubular materials from biological substances (here, it is cotton). The cotton fibers in SnCl₂ solution were first treated with ultrasonic waves in air, followed by calcinations to give nanotubular materials that faithfully retain the initial cotton morphology. The microstructure and morphology of the obtained SnO₂ nanotubules were characterized by the combination of field-emission scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR), X-ray diffraction (XRD), and N₂ adsorption/desorption measurements. The thermal behavior and crystalline properties were examined in the temperature range of 450–700 °C. The nanocrystals composing of SnO₂ nanotubules were estimated about 8.5, 13.2, and 14.2 nm corresponding to calcination temperatures of 450, 550, and 700 °C, respectively. The sensor performance of biomorphic SnO₂ nanotubules calcined at 700 °C was investigated in the atmosphere of ethanol, formaldehyde, carbinol, carbon monoxide, hydrogen, ammonia, and acetone, respectively, which exhibited a good selectivity for acetone at a working temperature of 350 °C. The sensitivity to 20 ppm acetone, S, was 6.4 at 350 °C with rapid response and recovery (around 10–9 s). These behaviors were well explained in relation to the morphology of the nanotubules thus produced.     

Effects of thermally induced anatase-to-rutile phase transition in MOCVD-grown TiO2 films on structural and optical properties

Titanium dioxide (TiO₂) films with a thickness of 550 nm were deposited on quartz glass at 300 °C by metalorganic chemical vapor deposition. The effects of post-annealing between 600 °C and 1000 °C were investigated on the structural and optical properties of the films. X-ray diffraction patterns revealed that the anatase phase of as-grown TiO₂ films began to be transformed into rutile at the annealing temperature of 900 °C. The TiO₂ films were entirely changed to the rutile phase at 1000 °C. From scanning electron spectroscopy and atomic force microscopy images, it was confirmed that the microstructure of as-deposited films changed from narrow columnar grains into wide columnar ones. The surface composition of the TiO₂ films, which was analyzed by X-ray photoelectron spectroscopy data, was nearly constant although the films were annealed at different temperatures. When the annealing temperature increased, the transmittance of the films decreased, whereas the refractive index and the extinction coefficient calculated by the envelope method increased at high temperature. The values of optical band gap decreased from 3.5 eV to 3.25 eV at 900 °C. This abrupt decrease was consistent with the anatase-to-rutile phase transition. Received: 4 October 2000 / Accepted: 4 December 2000 / Published online: 23 May 2001     

Oxidation kinetics of epitaxial Ge-covered Si(100) surfaces

We compared oxidation kinetics on Ge-covered Si(100) surfaces grown at 350 and 600°C for 0.9 and 2.0 ML Ge overlayer thicknesses. The O_KLL intensities showed clear oxidation enhancement on the surfaces grown at 600°C. The oxygen interaction for the surface covered with 2 ML Ge formed at 350°C was weaker than for the Ge(100) surface, indicating that the compressive strain due to the lattice mismatch may suppress the oxygen interaction with surface Ge dimers.