Facile synthesis of antimony-doped tin oxide nanoparticles by a polymer-pyrolysis method

In this article, antimony-doped tin oxide (ATO) nanoparticles was synthesized by a facile polymer-pyrolysis method. The pyrolysis behaviors of the polymer precursors prepared via in situ polymerization of metal salts and acrylic acid were analyzed by simultaneous thermogravimetric and differential scanning calorimetry (TG-DSC). The structural and morphological characteristics of the products were studied by powder X-ray diffraction (XRD) and transmission electron microscope (TEM). The results reveal that the ATO nanoparticles calcined at 600 °C show good crystallinity with the cassiterite structure and cubic-spherical like morphology. The average particle size of ATO decreases from 200 to 15 nm as the Sb doping content increases from 5 mol% to 15 mol%. Electrical resistivity measurement shows that the resistivity for the 10-13 mol% Sb-doped SnO₂ nanoparticles is reduced by more than three orders compared with the pure SnO₂ nanoparticles. In addition, due to its versatility this polymer-pyrolysis method can be extended to facile synthesis of other doped n-type semiconductor, such as In, Ga, Al doped ZnO, Sn doped In₂O₃.     

Unusual intrinsic luminescence of the host and energy transfer process in YVO4:Er phosphors

YVO₄:Er³⁺ phosphors were prepared by solid state reaction method. The X-ray diffraction results testify the pure tetragonal YVO₄ crystalline phase. The emission spectra of the samples show the obvious intrinsic luminescence of the hosts even though the concentration of the dopants has reached nominal 6 mol%, which is unusual since it is believed that the energy transferring from VO₄³⁻ to rare-earth ions occurs efficiently, thus the intrinsic luminescence of the host disappears when the concentration of the dopants is higher than ∼1 mol%. The comparison of the photoluminescence excited at 320 nm (the absorption of vanadate host) and 380, 490, 525 or 532 nm (the absorption of erbium ions) in visible and infrared range has revealed that energy transfer process has occurred in the system. The study of decay times has revealed that the energy transfer efficiency of the doped YVO₄:Er samples is very low. The low efficiency might be one important reason for the unusual intrinsic emission of the host.     

Structural characterization of 0.5PbMg1/3Nb2/3O3-0.5BaxPb(1−x)TiO3 powders

The present work reports the effects caused by barium on phase formation, morphology and sintering of lead magnesium niobate-lead titanate (PMN-50PT). Ab initio study of 0.5Pb(Mg_1/3Nb_2/3)O₃-0.5(Ba_xPb_(1−x)TiO₃) ceramic powders, with x = 0, 0.20, and 0.40 was proposed, considering that the partial substitution of lead by barium can reestablish the equilibrium of monoclinic-tetragonal phases in the system. It was verified that even for 40 mol% of barium, it was possible to obtain pyrochlore-free PMN-PT powders. The increase of the lattice parameters of PMN-PT doped-powders confirmed dopant incorporation into the perovskite phase. The presence of barium improved the reactivity of the powders, with an average particle size of 120 nm for 40 mol% of barium against 167 nm for the pure sample. Although high barium content (40 mol%) was deleterious for a dense ceramic, contents up to 20 mol% allowed 95% density when sintered at 1100 °C for 4 h.     

Dopant induced variations in microstructure and optical properties of CeO2 nanoparticles

Nanocrystalline CeO₂ particles doped in the range of 0-20% of Ca²⁺, La³⁺, and Zr⁴⁺ have been prepared from hydrothermal synthesis of nitrate solutions at 200 °C and the influences of the dopants on microstructure and optical properties of the nanoparticles have been investigated. The unit cell parameter is found to be modified by −0.39, +0.83 and +0.16% for doping of 20% Zr⁴⁺, La³⁺, and Ca²⁺, respectively. For each batch prepared, nanoparticles with a narrow size distribution of 5-15 nm have been obtained. A high-resolution transmission electron microscopy investigation reveals that these particles are single crystals mostly having hexagonal, square or circular two-dimensional projections. UV-visible spectra of doped powders exhibit shift of the absorption edge and absorption peak with respect to those of the undoped CeO₂ particles and has been attributed to compensation of Ce³⁺ and decreasing crystallite size as result of doping.     

Raman spectroscopy and cathodoluminescence characteristics of order-disorder Ba(Zn1/3Ta2/3)O3 ceramics

The order-disorder transition in Ba(Zn_1/3Ta_2/3)O₃ (BZT) was characterized by using Raman spectroscopy, transmission electron microscopy (TEM), and cathodoluminescence (CL) microscopy. The 1:2 ordered structure of pure BZT ceramics was replaced by a 1:1 ordered structure at 1650 °C and the 1:1 ordered structure of BZT sintered at 1650 °C exhibited a 1:2 ordered structure when it was reannealed at 1500 °C for 12 h. The A_1g lines in the Raman spectrum of the sintered and reannealed samples were shifted to lower and higher wavenumbers, respectively. From the CL analysis, the 1:1 ordered BZT exhibited mainly three emission bands at around 533.2 (2.32 eV), 599.1 (2.07 eV), and 682.1 nm (1.81 eV), whereas the 1:2 ordered BZT exhibited mainly five bands at 346.4 (3.58 eV), 427.5 (2.90 eV), 520.9 (2.38 eV), 593.0 (2.09 eV), and 678.9 nm (1.82 eV). The strongest band originating from 2.32 to 2.38 eV was broadened, and the band center shifted towards a higher and lower wavelength in the 1:1 and 1:2 ordered BZT, respectively. Additional bands at around 346 and 427 nm in the grain interior of the annealed sample were strongly related to the 1:2 ordering of BZT.     

Modification of the physical properties of semiconducting MgAl2O4 by doping with a binary mixture of Co and Zn ions

The effects of doping of MgAl₂O₄ by a binary mixture of Co and Zn ions on the absorbance, electrical resistivity, capacitance, thermal conductivity, heat capacity and thermal diffusivity are reported in this paper. The materials with the nominal composition Mg_1−2x(Co,Zn)_xAl₂O₄ (x = 0.0-0.5) are synthesized by solution combustion synthesis assisted by microwave irradiation. The substituted spinels are produced with a Scherrer crystallite size of 18-23 nm, as opposed to 45 nm for undoped samples, indicated by X-ray diffraction and confirmed by transmission electron microscopy. These materials also show better thermal stability in the temperature range of 298-1773 K. Three strong absorption bands at 536, 577 and 630 nm are observed for the doped samples which are attributed to the three spin allowed (⁴A₂ (F) → ⁴T₁ (P)) electronic transitions of Co²⁺ at tetrahedral lattice sites while pure magnesium aluminate remains transparent in the whole spectral range. The semiconducting behavior of the materials is evident from the temperature dependence of the electrical resistivity. Resistivity and activation energy are higher for the substituted samples. Fitting of the resistivity data is achieved according to the hopping polaron model of solids. Both dielectric constant and loss increase on account of doping. The dielectric data are explained on the basis of space charge polarization. The thermal conductivity and diffusivity are lowered and the heat capacity is increased in the doped materials. Wiedemann-Franz's law is used to compute the electronic and lattice contributions towards the total thermal conductivity.     

Optical properties of MgO doped near-stoichiometric LiTaO3 single crystals

Comparative study of the optical properties of undoped and 1-3 mol% MgO doped near-stoichiometric LiTaO₃ (SLT) crystals were undertaken. It was observed that the red shift in the absorption edge occurred with the increasing MgO doping concentration. The infrared absorption spectrum of the OH-stretch-mode in SLT was measured for crystals of undoped and 1-3 mol% MgO doped compositions. The coercive field for the crystals was measured to be 0.913, 0.610 and 0.735 kV/mm for 1-3 mol% MgO doped SLT, respectively. Photorefractive damage of SLT single crystals with 1-3 mol% MgO doping levels was measured to be 136.29, 180.25 and 222.54 MW/cm².     

Analysis of Er and Ho codoped fluoroindate glasses as wide range temperature sensor

The fluorescence intensity ratio technique for two fluoroindate glass samples has been carried out. The green emissions at 523 nm and at 545 nm in a 0.1 mol% of Er³⁺ doped fluoroindate glass was studied in a wide range of temperature from 125 K to 425 K with a maximum sensitivity of 0.0028 K⁻¹ for 425 K. In a sample doped with 0.1 mol% of Ho³⁺ the emissions at 545 nm and at 750 nm were analyzed as a function of temperature from 20 K to 300 K obtaining a maximum sensitivity of 0.0036 K⁻¹ at 59 K. Using both fluoroindate glass samples a wide temperature range from 20 K to 425 K is easily covered pumping with two low-cost diode laser at 406 nm and 473 nm.     

Improved electrochromical properties of sol-gel WO3 thin films by doping gold nanocrystals

In this investigation, the effect of gold nanocrystals on the electrochromical properties of sol-gel Au doped WO₃ thin films has been studied. The Au-WO₃ thin films were dip-coated on both glass and indium tin oxide coated conducting glass substrates with various gold concentrations of 0, 3.2 and 6.4 mol%. Optical properties of the samples were studied by UV-visible spectrophotometry in a range of 300-1100 nm. The optical density spectra of the films showed the formation of gold nanoparticles in the films. The optical bandgap energy of Au-WO₃ films decreased with increasing the Au concentration. Crystalline structure of the doped films was investigated by X-ray diffractometry, which indicated formation of gold nanocrystals in amorphous WO₃ thin films. X-ray photoelectron spectroscopy (XPS) was used to study the surface chemical composition of the samples. XPS analysis indicated the presence of gold in metallic state and the formation of stoichiometric WO₃. The electrochromic properties of the Au-WO₃ samples were also characterized using lithium-based electrolyte. It was found that doping of Au nanocrystals in WO₃ thin films improved the coloration time of the layer. In addition, it was shown that variation of Au concentration led to color change in the colored state of the Au-WO₃ thin films.     

Nitrogen-doped titania photocatalysts induced by shock wave

The nitrogen-doped titania photocatalysts were prepared by shock wave with detonation-driven flyer impact. The samples were shocked at different flyer impact velocities and recovered successfully. The phase composition, light absorption spectra and N doping status of the recovered samples with different flyer velocities and two nitrogen resources containing hexamethylene tetramine (HMT) and dicyandiamide, respectively, were characterized. The absorption edge of the N-doped TiO₂ photocatalysts by shock wave was extended to 450 nm corresponding to visible light region. The photocatalytic degradation to rhodamine B of the samples doped with dicyandiamide increased with increasing flyer velocity due to the higher N doping concentration and wider response to visible light.     

Strong broad green UV-excited photoluminescence in rare earth (RE = Ce, Eu, Dy, Er, Yb) doped barium zirconate

The wet synthesis hydrothermal method at 100 °C was used to elaborate barium zirconate (BaZrO₃) unpurified with 0.5 mol% of different rare earth ions (RE = Yb, Er, Dy, Eu, Ce). Morphological, structural and UV-photoluminescence properties depend on the substituted rare earth ionic radii. While the crystalline structure of RE doped BaZrO₃ remains as a cubic perovskite for all substituted RE ions, its band gap changes between 4.65 and 4.93 eV. Under 267 nm excitation the intrinsic green photoluminescence of the as synthesized BaZrO₃: RE samples is considerably improved by the substitution on RE ions. For 1000 °C annealed samples, under 267 nm, the photoluminescence is dominated by the intrinsic BZO emission. It is interesting to notice that Dy³⁺, Er³⁺ and Yb³⁺ doped samples present whitish emissions that might be useful for white light generation under 267 nm excitation. CIE color coordinates are reported for all samples.     

Texture development in 3 mol% yttria-stabilized tetragonal zirconia

We have developed a method of forming textured tetragonal zirconia. A suspension containing 10 vol% solid loading of monoclinic ZrO₂ mixed with 3 mol% Y₂O₃ was prepared, and then a bead-milling process was performed using 50 μm diameter zirconia beads resulting in a well-dispersed suspension. The mixture suspension of monoclinic zirconia and yttria nanoparticles was slip cast under a magnetic field of 12 T to produce oriented monoclinic zirconia with yttria. The reaction sintering between yttria and the oriented monoclinic zirconia produces a final 3 mol% Y₂O₃ doped tetragonal zirconia that remains oriented.     

An aqueous sol-gel synthesis of chromium(III) doped mesoporous titanium dioxide for visible light photocatalysis

Nanoparticles of titanium dioxide doped with Cr³⁺ ions have been prepared through an aqueous sol-gel method. The mesoporous nature of both pure and Cr³⁺ doped TiO₂ powders, with specific surface area of 7.4 and 6.6 m² g⁻¹, respectively, is maintained even at calcination temperature of 800 °C. The transformation of TiO₂ from the anatase to rutile phase is suppressed up to 800 °C by Cr³⁺ ion doping. Even though surface area values are decreased, the doped materials show improved photocatalytic activity, which may be due to increased crystallinity of the anatase phase without the formation of rutile. Doped materials have a red-shift in the band gap energy and hence, photoactivity under visible light. The rate of photodegradation of methylene blue dye for both pure and doped TiO₂ under visible light has been monitored in this study. The 0.25 mol% Cr(III) doped photocatalyst, calcined at 800 °C, shows the highest photocatalytic activity under visible light with a rate constant of ∼15.8 × 10⁻³ min⁻¹, which is nearly three times higher than that of commercially available Degussa P25 titania (5.8 × 10⁻³ min⁻¹).     

Structural and electrical properties of Ce0.75(Gd0.95−xSrxCa0.05)0.25O2−δ thick film electrolyte

The effects of Sr doping on the electrical properties of Ce_0.75(Gd_0.95−xSr_xCa_0.05)_0.25O_2−δ (x = 0, 0.01, 0.02, 0.03, 0.04, 0.05 mol%) electrolytes thick films were investigated. The samples sintered at 1400 °C for 8 h. X-ray diffraction (XRD) showed typical XRD patterns of a cubic fluorite structure, and the ionic conductivity was examined by AC impedance spectroscopy. From the experimental results, it was observed that Ce_0.75(Gd_0.95−xSr_xCa_0.05)_0.25O_2−δ (x = 0.04 mol%) electrolytes thick film have higher conductivity and minimum activation energy at 600 °C. This is explained in terms of the increased in the oxygen vacancy concentration at the grain boundary.     

Preparation and characterization of indium doped CdS0.2Se0.8 thin films by spray pyrolysis

The CdS_0.2Se_0.8 and indium doped CdS_0.2Se_0.8 thin films have been deposited onto the amorphous glass and fluorine doped tin oxide coated glass substrates by spray pyrolysis. The doping concentration of indium has been optimized by photoelectrochemical characterization technique. The structural, surface morphological, optical and electrical properties of CdS_0.2Se_0.8 and indium doped CdS_0.2Se_0.8 thin films have been studied. X-ray diffraction studies reveal that the films are polycrystalline in nature with hexagonal crystal structure. Scanning electron microscopy studies reveal that the grains are uniform with uneven spherically shaped, distributed over the entire substrate surface. The complete surface morphology has been changed after doping. In optical studies, the transition of the deposited films is found to be direct allowed with optical energy gaps decreasing from 1.91 to 1.67 eV with indium doping. Semiconducting behavior has been observed from resistivity measurements. The thermoelectric power measurements reveal that the films exhibit n-type conductivity.     

Growth and characterization of metal ions and dyes doped KDP single crystals for laser applications

The organic dyes (Amaranth, Rhodamine B and Methyl Orange) are doped in Potassium Dihydrogen Phosphate crystals. Influences of supersaturation and dye concentration in the solution, on the color and crystal habit of Potassium Dihydrogen Phosphate, were observed. Amaranth in the solution at low super saturation and high dye concentration colored the pyramidal section (1 0 1) of the crystals. The highly super saturated solutions produce entirely colored crystals. Dyes doped Potassium Dihydrogen Phosphate crystals were also grown by solution growth technique. The concentration of dopants in the mother solution was varied from 0.1 to 10 mol%. The studies on pure and doped Potassium Dihydrogen Phosphate crystals clearly indicate the effect of dopants on the crystal structure, in the absorption of IR frequencies and the non-linear optical property. The frequencies with their relative intensities are obtained in Fourier Transform-Infrared spectra of pure and doped Potassium Dihydrogen Phosphate. The very weak bands for dopants indicate its presence in low concentration. The absence of even such a weak band in the case of Potassium Dihydrogen Phosphate doped with Amaranth indicates the strong interaction with O-H groups. The calculated IR frequency 3333 cm⁻¹ for O-H stretching was in close agreement with the experimentally obtained one for pure Potassium Dihydrogen Phosphate at 3340 cm⁻¹.The doped crystals show good second harmonic generation efficiency. The dopants increase the hardness value of the material, which also depends on the concentration of the dopants. Dye doping improves the Nonlinear Optical properties of the grown crystals. Results of the growth kinetics of Potassium Dihydrogen Phosphate crystals in the presence of impurities are also discussed.     

Study of glass-nanocomposite and glass–ceramic containing ferroelectric phase

Transparent glass nanocomposite in the pseudo binary system (100 − x) Li₂B₄O₇–xBaTiO₃ with x = 0 and 60 (in mol%) were prepared. Amorphous and glassy characteristics of the as-prepared samples were established via X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC) respectively. The precipitated BaTiO₃ nanocrystal phase embedded in the glass sample at x = 60 mol% was identified by transmission electron microscopic (TEM). The optical transmission bands at 598 and 660 nm were assigned to Ti³⁺ ions in tetragonal distorted octahedral sites. The precipitated Li₂B₄O₇, BaTi(BO₃)₂ and BaTiO₃ nanocrystallites phases with heat-treatment at 923 K for 6 h (HT923) in glass–ceramic were identified by XRD, TEM and infrared absorption spectroscopy. The as-prepared at x = 60 mol% and the HT923 samples exhibit broad dielectric anomalies in the vicinity of the ferroelectric-to-paraelectric transition temperature. The results demonstrate that the method presented may be an effective way to fabricate ferroelectric host and development of multifunctional ferroelectrics.     

Nature of V ions in SnO2: EPR and photoluminescence studies

SnO₂ and 5 at.% V doped SnO₂ samples were prepared by citrate-gel method. From Raman study on vanadium doped SnO₂, the existence of phase separated V₂O₅ clusters has been established. EPR study on the V doped sample clearly revealed the existence of V⁴⁺ ions, which are incorporated in SnO₂ lattice and the existence of conduction electrons with g = 1.993. For vanadium doped SnO₂ sample, there is a decrease in luminescence at 400 nm and an increase in activation energy of electrical conduction compared to undoped SnO₂, and this has been attributed to the decrease in oxygen vacancies brought about by the incorporation of V⁵⁺ in the SnO₂ lattice.     

Microwave-assisted synthesis of ceria nanoparticles

Nanocrystalline ceria (CeO₂) particles have been successfully prepared by microwave-assisted heating technique from an aqueous solution containing ammonium Ce(IV) nitrate and sodium hydroxide. Further thermal treatment of the as-prepared powder at 500 °C resulted in the formation of the well-crystallized CeO₂ nanoparticles with an average crystal size of about 8 nm, varying with the heating temperature. The as-prepared powder and the CeO₂ nanoparticles were examined using X-ray diffraction (XRD) and transmission electron microscope (TEM) techniques. It was found that the morphologies of the synthesized powder show from rod-like for the as-prepared sample to sphere-like for the heat-treated nanoparticles. Mechanism of CeO₂ nanocrystallite growth during annealing is primarily investigated.     

Morphology and crystal structure of CeO2-modified mesoporous ZrO2 powders prepared by sol–gel method

Mesoporous ZrO₂ powder modified by CeO₂ has been prepared by sol–gel method combined with novel heat-treatment without any templates. The morphology and crystal structure were characterized by Fourier transform infrared spectrophotometer (FT-IR), thermal gravimetry/differential thermal analysis (TG/DTA), X-ray diffraction (XRD), Raman spectroscope, N₂ absorption–desorption, scanning electron microscope (SEM) and high-resolution transmission electron microscope (HRTEM). It was demonstrated that the morphologies and crystal structures were varied with the CeO₂ content and calcination temperatures. Some circular grooves with diameter about 300–500 nm and thickness of 150–200 nm were observed for 30 mol% CeO₂ modified samples. Tetragonal ZrO₂ and cubic (Ce,Zr)O₂ solid solution were in turn observed with CeO₂ content increasing. The oxygen storage capacity (OSC) of the mesoporous powders was determined by thermalgravimetry (TG) under cyclic thermal treatments.