Preparation of LixCa1−xTiO3 solid electrolytes by the sol-gel method

Solid electrolytes based on lithium doped CaTiO_3,Li_xCa_1−xTiO₃ (x=0-0.5) were prepared by the sol-gel method in an ethanol and water mixture medium. Phase identification and morphology observation of the products were carried out by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that the Li_xCa_1−xTiO₃ powders sintered above 700 ^°C are of cubic perovskite structure and the mean size of Li_xCa_1−xTiO₃ powders is about 80 nm. A study of ionic conductivity by AC impedance implies that the conductivity of Li_xCa_1−xTiO₃ increases with the increase of substituted Li⁺ ions and reaches a maximum value of 4.53×10⁻⁴ S cm⁻¹ at x=0.1, and then decreases for x>0.1.     

Dielectric properties of valence compensated Ca1−xBixTi1−xCrxO3 perovskite prepared using the sol-gel process

Ca_1−xBi_xNb_1−xCr_xO₃ (x=0.01-0.5) ceramic powders were synthesized using the sol-gel process. The single-phase solids can be presented at x=0.01 and 0.03. The coexistence of orthorhombic perovskite and the secondary phase of BiCrO₃ was verified, as presented for x=0.05-0.5. Grains with a micro-cube topography were obtained for x=0.3-0.5. The average grain size is about 0.4 and 1.1 μm for x=0.3 and 0.5, respectively. The highest dielectric constant peak was measured at around 55 °C for x=0.5 and at 75 °C for x=0.3. The high dielectric constant was caused by the formation of barrier layers at the interface of the bi-phase mixed ceramics. Space charge polarization contributed to the observed behavior.     

The size and strain effects on the Raman spectra of Ce1−xNdxO2−δ (0≤x≤0.25) nanopowders

Ultrafine Ce_1−xNd_xO_2−δ (x=0-0.25) powders were synthesized by self-propagating room temperature synthesis. Raman spectra were measured at room temperature in the 300-700 cm⁻¹ spectral range. The shift and asymmetric broadening of the Raman F_2g mode at about 454 cm⁻¹ in pure and doped ceria samples could be explained with combined size and inhomogenous strain effects. Increased concentration of O²⁻ vacancies with doping is followed by an appearance of new Raman feature at about 545 cm⁻¹.     

Low-temperature synthesis of nanocrystalline Ca1−xHoxMnO3−δ (0?x?0.3) powders

Nanocrystalline Ca_1−xHo_xMnO_3−δ (0?x?0.3) manganites were synthesized as phase-pure by a simple and instantaneous solution autogel combustion method, which is a low temperature initiated synthetic route to obtain fine grain size. All the samples, heated at 800 °C for 18 h, can be produced as phase-pure; the polycrystalline powders are homogeneous and possess ultrafine particle size. The holmium-doped calcium manganites retain the orthorhombic phase of the undoped sample. The scanning electron microscope (SEM) images revealed that the combustion-derived compounds exhibit particle size that decreases with holmium content from 300 to 80 nm. All manganites show two active IR vibrational modes near 400 and 600 cm⁻¹. The high temperature dependence of resistivity was measured using a standard four-probe method in the range 25-600 °C. All the samples exhibit semiconductor behaviour and holmium induces a marked decrease in the electrical resistivity when compared with the parent CaMnO₃. The results can be well attributed to the Mn⁴⁺/Mn³⁺ ratio and to the particle grain size.     

A novel UV-emitting phosphor: Li6CaB3O8.5:Pb

Pure Li₆CaB₃O_8.5 and Li₆Ca_1−xPb_xB₃O_8.5 (0.005≤x≤0.04) materials were prepared by a solution combustion synthesis method. The phase of synthesized materials was determined using the powder XRD and FTIR. The synthesized materials were investigated using spectrofluorometer at room temperature. The emission and excitation bands of the synthesized phosphors were observed at 307 and 268 nm, respectively. The dependence of the emission intensity on the Pb²⁺ concentration for the Li₆Ca_1−xPb_xB₃O_8.5 (0.005≤x≤0.04) was studied and observed that the optimum concentration of Pb²⁺ in phosphor is 0.01 mol. The Stokes shift of the synthesized phosphor was calculated to be 4740 cm^-1.     

A new blue-emitting phosphor, SrZnO2:Pb, synthesized by the adipic acid templated sol-gel route

A new blue-emitting phosphor, Sr_1−xPb_xZnO₂, was prepared by a novel adipic acid templated sol-gel route. Photoluminescence and crystalline properties were investigated as functions of calcination temperatures and the Pb²⁺ doping levels. It was found that under UV excitation with a wavelength of 283 or 317 nm, the phosphors gave emission from 374 to 615 nm with a peak centered at 451 nm. This broad-band was composed of UV and the visible range was attributed to an impurity-trapped exciton-type emission. The maximum emission intensity of the Sr_1−xPb_xZnO₂ phosphors occurred at a Pb concentration of x=0.01. The decay time was observed to be ∼33 ms for the compound doped with 1 mol% Pb prepared at 1000 °C. Diffuse reflectance spectra revealed the characteristic absorption peaks and the bandgap energy of SrZnO₂ was found to be 3.4 eV. SEM analysis indicated that phosphor particles have an irregularly rounded morphology and the average particle size was found to be approximately 1 μm.     

Effect of Mn-site vacancies on the magnetic entropy change and the Curie temperature of La0.67Ca0.33Mn1−xO3 perovskite

Single-phase polycrystalline samples of La_0.67Ca_0.33Mn_1−xO₃ (x=0.00, 0.02, 0.04, 0.06) have been prepared using the sol-gel method. The structure, magnetocaloric properties and the Curie temperature of the samples with different Mn vacancy concentrations have been investigated. The experimental results show that vacancy doping at the Mn-sites has a significant influence on the magnetic properties of La_0.67Ca_0.33Mn_1−xO₃. The Curie temperature decreases monotonically with increasing the Mn-site vacancy concentration x. A remarkable enhancement of the magnetic entropy change has been obtained in the La_0.67Ca_0.33Mn_0.98O₃ sample. The entropy change reaches |ΔS_M|=3.10 J kg⁻¹ K⁻¹ at its Curie temperature (264 K) under an applied magnetic field H=10 kOe, which is almost the same value as that of pure Gd.     

Soft polar modes and phase states of Ca<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript>x</Subscript>TiO<Subscript>3</Subscript> solid solutions

Dielectric spectra ?′(ν) and ?″(ν) of Ca_1?xPb_xTiO₃ ceramic samples (x=0, 0.15, 0.2, 0.4) have been studied in the frequency range ν=7–1000 cm^?1 at temperatures from 5 to 300 K using IR Fourier spectroscopy and submillimeter-range techniques. In the low-frequency range, polar phonons were established to undergo temperature-induced evolution. The results obtained are discussed in terms of the Landau theory of second-order phase transitions for coupled soft modes. The existence of one (or several) phase state(s) in the intermediate concentration region of Ca_1?xPb_xTiO₃ solid solutions is tentatively assumed.     

Effect of 3d metal ion doping on the structure and superconductivity of (Tl0.5Pb0.5)Sr2CaCu2O7

(Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ (M=Co, Ni and Zn) have been synthesized and investigated by means of X-ray diffraction, scanning electron microscope, electrical resistivity and magnetic susceptibility measurements. X-ray diffraction patterns show that all studied samples contain the nearly single ‘1212’ phase. They crystallize in a tetragonal unit cell with a=3.8028-3.8040 Å and c=12.0748-12.1558 Å. In (Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ system (M=Co or Ni), the superconducting critical temperature T_c decreases linearly with both Co and Ni concentrations and the rate of T_c decrease is around −6.5 and −7.0 K/at%, respectively. For (Tl_0.5Pb_0.5)Sr₂Ca (Cu_2−xZn_x)O₇ system, the dependence of T_c on the Zn dopant concentration deviates from a linear behavior and the Zn substitution suppresses T_c much less (−2.5 K/at%) than the Co and Ni substitutions. The suppression in T_c in Co and Ni doped samples are attributed to the magnetic pair-breaking mechanism and the reduction in the carrier concentration. The suppression of T_c in Zn doped samples is not caused by the reduction in carrier concentration which should remain constant, but rather due to nonmagnetic pair-breaking mechanism induced by disorder as well as the filling of the local Cu d_x²−y² state due to the full d band of Zn ions.     

DC conductivity of silver vanadium tellurite glasses

The mixed electronic-ionic conduction in 0.5[xAg₂O-(1−x)V₂O₅]-0.5TeO₂ glasses with x=0.1-0.8 has been investigated over a wide temperature range (70-425 K). The mechanism of dc conductivity changes from predominantly electronic to ionic within the 30?mol% Ag₂O?40 range; it is correlated with the underlying change in glass structure. The temperature dependence of electronic conductivity has been analyzed quantitatively to determine the applicability of various models of conduction in amorphous semiconducting glasses. At high temperature, T>θ_D/2 (where θ_D is the Debye temperature) the electronic dc conductivity is due to non-adiabatic small polaron hopping of electrons for 0.1?x?0.5. The density of states at Fermi level is estimated to be N(E_F)≈10¹⁹-10²⁰ eV⁻¹ cm⁻³. The carrier density is of the order of 10¹⁹ cm⁻³, with mobility ≈2.3×10⁻⁷-8.6×10⁻⁹ cm² V⁻¹ s⁻¹ at 300 K. The electronic dc conductivity within the whole range of temperature is best described in terms of Triberis-Friedman percolation model. For 0.6?x?0.8, the predominantly ionic dc conductivity is described well by the Anderson-Stuart model.     

Luminescence characteristics of Ca1−xSrxS:Ce nanophosphors

Luminescence characteristics of Ca_1−xSr_xS:Ce (x = 0, 0.25, 0.50, 1) nanophosphors have been investigated. XRD of all the samples show a single cubic phase of Ca_1−xSr_xS:Ce. TEM micrographs exhibit the rod like structure of the samples with a decrease in diameter with decreasing amount of Ca. The results of TEM were found to be in good agreement with the XRD results. The photoluminescence spectrum comprises of a main peak in the range 480-510 nm with a shoulder in the range 530-565 nm, which may be ascribed to transitions from 5d-4f levels of cerium in the mixed host lattice. The red shift in the emission wavelength with increasing Ca content may be correlated with the change in crystal field of mixed host lattice for different Ca and Sr concentrations. We have also investigated TL response of Ca_1−xSr_x:Ce to ⁶⁰Co-γ rays. All the samples with different Sr and Ca contents show different TL response. TL response for the sample with x = 0.75 shows the simplest TL glow curve with the maximum TL intensity, for which we have calculated the activation energy using glow curve deconvolution functions.     

Optical properties of Er/Yb-codoped transparent PLZT ceramic

Optical absorption and emission spectra of Er³⁺/Yb³⁺ ions in PLZT (Pb_1−xLa_xZr_yTi_1−yO₃) ceramic have been studied. Based on the Judd—Ofelt (J-O) theory, the J-O intensity parameters were calculated to be Ω₂=2.021×10⁻²⁰ cm², Ω₄=0.423×10⁻²⁰ cm², Ω₆=0.051×10⁻²⁰ cm² from the absorption spectrum of Er³⁺/Yb³⁺-codoped PLZT. The J-O intensity parameters have been used to calculate the radiative lifetimes and the branching ratios for some excited ⁴I_13/2, ⁴I_11/2, ⁴I_9/2⁴F_9/2, and ⁴S_3/2 levels of Er³⁺ ion. The stimulated emission cross-section (8.24×10⁻²¹ cm²) was evaluated for the ⁴I_13/2→⁴I_15/2 transition of Er³⁺. The upconversion emissions at 538, 564, and 666 nm have been observed in Er³⁺/Yb³⁺-codoped PLZT by exciting at 980 nm, and their origins were identified and analyzed.     

Preparation of five-layered Si/SixGe1−x nano-films by RF helicon magnetron sputtering

Five-layered Si/Si_xGe_1−x films on Si(1 0 0) substrate with single-layer thickness of 30 nm, 10 nm and 5 nm, respectively were prepared by RF helicon magnetron sputtering with dual targets of Si and Ge to investigate the feasibility of an industrial fabrication method on multi-stacked superlattice structure for thin-film thermoelectric applications. The fine periodic structure is confirmed in the samples except for the case of 5 nm in single-layer thickness. Fine crystalline Si_xGe_1−x layer is obtained from 700 °C in substrate temperature, while higher than 700 °C is required for Si good layer. The composition ratio (x) in Si_xGe_1−x is varied depending on the applied power to Si and Ge targets. Typical power ratio to obtain x = 0.83 was 7:3, Hall coefficient, p-type carrier concentration, sheet carrier concentration and mobility measured for the sample composed of five layers of Si (10 nm)/Si_0.82Ge_0.18 (10 nm) are 2.55 × 10⁶ /°C, 2.56 × 10¹² cm⁻³, 1.28 × 10⁷ cm⁻², and 15.8 cm⁻²/(V s), respectively.     

Structural, ferroelectric and impedance spectroscopy properties of Y modified Pb(Fe0.5Nb0.5)O3 ceramics

Some ceramic samples of Pb_1−xY_x(Fe_0.5Nb_0.5)_1−x/4O₃ (PYFN) (0.00≤x≤0.08) were synthesized by a mixed oxide route. X-ray diffraction patterns of all the above samples confirm the formation of single phase material crystallizing in monoclinic structure. Dielectric properties (ε_r and tan δ) were analyzed in a wide temperature (30-350 °C) and frequency range (100 Hz-1 MHz). Ferroelectric properties of these compounds were confirmed from polarization (P-E hysteresis loop) measurements at room temperature. All the room temperature hysteresis loops of PYFN ceramics were well simulated using the ferroelectric capacitor model. Yttrium substitution resulted in notable enlargement of room temperature remnant polarization (2P_r). The 2P_r of PYFN (x=0.02) reaches to a large value (23 μC/cm²), which is nearly 5 times greater than that of PFN ceramic (4.6 μC/cm²). All the compounds exhibits negative temperature coefficient of resistivity (NTCR) type behavior as that of semiconductors. Dc conductivity (estimated via bulk resistivity) variation with temperature of all the samples follows Arrhenius type of electrical conductivity.     

Optical gain due to the Eu transition in the alloy of Ca1-xEuxGa2S4

Room temperature photoluminescence quantum efficiency of the alloy of Ca_1−xEu_xGa₂S₄ was measured as a function of x, and was found to be nearly unity under excitation at peak wavelength of excitation spectrum (510 nm) in the x range of 0.01≤x≤0.2. At larger x values, it tends to decrease, but still as high as 30% for stoichiometric compound EuGa₂S₄. Taking these backgrounds into account, pump-probe experiments were done with Ca_1−xEu_xGa₂S₄ for searching optical gain at x=0.2. The optical gain of nearly 30 cm⁻¹ was confirmed to exist, though the pumping induced transient absorption which seems to limit the higher gain was found.     

X-ray and IR analysis of Cu-Si ferrite

Polycrystalline soft ferrite, Cu_1+xSi_xFe_2−2xO₄ (x=0.0, 0.05, 0.1, 0.15, 0.2 and 0.3) were prepared by standard ceramic technique. The X-ray analysis confirmed the single phase formation of the samples up to x=0.1 beside a second phase for x?0.15. The lattice parameter was found to decrease with composition(x), which is attributed to ionic size difference of cations involved. The bulk density measurements shows two different behavior for x< >0.15. The IR spectra of Cu-Si ferrite system have been analyzed in the frequency range 200-1200 cm⁻¹. It revealed two prominent bands ν₁ and ν₂ which are assigned to tetrahedral and octahedral metal complexes, respectively. The position of the highest frequency band is around 575 cm⁻¹ while the lower frequency band is around 400 cm⁻¹.     

Raman characterization of Pb2Na1−xLaxNb5−xFexO15 and Pb0.5(5−x)LaxNb5−xFexO15 (0≤x≤1) solid solutions

The ferroelectric compounds Pb₂Na_1−xLa_xNb_5−xFe_xO₁₅ and Pb_0.5(5−x)La_xNb_5−xFe_xO₁₅ (0≤x≤1) with the tungsten bronze type structure have been investigated using Raman spectroscopy. The evolution of the spectra as a function of composition at room temperature is reported. In the frequency range 200-1000 cm⁻¹ three main A₁ phonons around 240 (υ₁), 630 (υ₂) and 816 (υ₃) cm⁻¹ were observed. The broadening of the Raman lines for high values of x originates from a significant structural disorder. This is in good agreement with the relaxor character of these compositions. The lowest-frequency part of the spectra, below 180 cm⁻¹, reveals a structural change in the studied solid solutions. The behaviour of the Raman shift of the υ₁ mode confirms that in Pb₂Na_1−xLa_xNb_5−xFe_xO₁₅, a clear anomaly occurs in the vicinity of x=0.4.     

Single crystal EPR and optical absorption study of Cr doped l-histidine hydrochloride monohydrate

EPR study of the Cr³⁺ ion doped l-histidine hydrochloride monohydrate single crystal is done at room temperature. Two magnetically inequivalent interstitial sites are observed. The hyperfine structure for Cr⁵³ isotope is also obtained. The zero field and spin Hamiltonian parameters are evaluated from the resonance lines obtained at different angular rotations and the parameters are: D=(300±2)×10⁻⁴ cm⁻¹, E=(96±2)×10⁻⁴ cm⁻¹, g_x=1.9108±0.0002, g_y=1.9791±0.0002, g_z=2.0389±0.0002, A_x=(252±2)×10⁻⁴ cm⁻¹, A_y=(254±2)×10⁻⁴ cm⁻¹, A_z=(304±2)×10⁻⁴ cm⁻¹ for site I and D=(300±2)×10⁻⁴ cm⁻¹, E=(96±2)×10⁻⁴ cm⁻¹, g_x=1.8543±0.0002, g_y=1.9897±0.0002, g_z=2.0793±0.0002, A_x=(251±2)×10⁻⁴ cm⁻¹, A_y=(257±2)×10⁻⁴ cm⁻¹, A_z=(309±2)×10⁻⁴ cm⁻¹ for site II, respectively. The optical absorption studies of single crystals are also carried out at room temperature in the wavelength range 195-925 nm. Using EPR and optical data, different bonding parameters are calculated and the nature of bonding in the crystal is discussed. The values of Racah parameters (B and C), crystal field parameter (Dq) and nephelauxetic parameters (h and k) are: B=636, C=3123, Dq=2039 cm⁻¹, h=1.46 and k=0.21, respectively.     

Temperature dependence of electrical resistivity for Ca-doped perovskite-type Y1−xCaxCoO3 prepared by sol-gel process

The temperature dependences of DC electrical resistivity for perovskite-type oxides Y_1−xCa_xCoO₃ (0?x?0.1), prepared by sol-gel process, were investigated in the temperature range from 20 K up to 305 K. The results indicated that with increase of doping content of Ca the resistivity of Y_1−xCa_xCoO₃ decreased remarkably, which was found to be caused mainly by increase of carrier (hole) concentration. In the whole temperature range investigated the temperature dependence of resistivity ρ(T) for the un-doped (x=0) sample decreased exponentially with decreasing temperature (i.e. ln ρ∝1/T), with a conduction activation energy ; the resisitivity of lightly doped oxide (x=0.01) possessed a similar temperature behavior but has a reduced E_a (0.155 eV). Moreover, experiments showed that the relationship ln ρ∝1/T existed only in high-temperature regime for the heavily doped samples (T?82 and ∼89 K for x=0.05 and 0.1, respectively); at low temperatures Mott's ln ρ∝T^−1/4 law was observed, indicating that heavy doping produced strong random potential, which led to formation of considerable localized states. By fitting of the experimental data to Mott's T^−1/4 law, we estimated the density of localized states N(E_F) at the Fermi level, which was found to increase with increasing doping content.     

The effect of growth ambient on the structural and optical properties of MgxZn1−xO thin films

Mg_xZn_1−xO (x = 0.0-0.20) thin films have been deposited by sol-gel technique on glass substrates and the effect of growth ambient (air and oxygen) on the structural, and optical properties have been investigated. The films synthesized in both ambient have hexagonal wurtzite structure. The c-axis lattice constant decreases linearly with the Mg content (x) up to x = 0.05, and 0.10 respectively for air- and oxygen-treated films, above which up to x = 0.20, the values vary irregularly with x. The change in the optical band gap values and the ultraviolet (UV) peak positions of Mg_xZn_1−xO films show the similar change with x. These results suggest that the formation of solid solution and thus the structural and optical properties of Mg_xZn_1−xO thin films are affected by the growth ambient.