Study on electrical conductivity and phase transition in singly doped BIPBVOX (Bi2V1−xPbxO5.5−x/2) solid electrolyte

Samples of bismuth lead vanadium oxide (BIPBVOX) (Bi₂V_1–xPb_xO_5.5–x/2) singly substituted system in the composition range 0.05 ≤ x ≤ 0.20 were prepared by sol–gel synthesis route. Structural investigations were carried out by using a combination of differential thermal analysis (DTA) and powder X-ray diffraction (PXRD) technique. Energy dispersive X-ray spectroscopy analysis (EDXA) of doped samples was carried out to predict the sample purity and doping concentration. Transitions, α?β, β?γ and γ′?γ were detected by XRD, DTA and variation in the Arrhenius plots of conductivity. The ionic conductivity was measured by AC impedance spectroscopy. The solid solutions with composition x ≤ 0.07 undergo α?β phase transition, at 329 °C and β?γ phase transition at 419 °C. The highly conducting γ′-phase was effectively stabilized at room temperature for compositions with x ≥ 0.17 whose thermal stability increases with Pb content. At 300 °C, the highest value of conductivity 6.234 × 10^?5 S cm^?1 was obtained for composition x = 0.15 and at 600 °C the highest value of conductivity 0.65 S cm^?1 is observed for x = 0.17. AC impedance plots reveal that the conductivity is mainly due to the grain contribution to oxide ion conductivity.     

Effect of Zn substitution on the electrical properties of Bi2Co0.1V0.9O5.35 synthesized by sol-gel method

Samples of Bi₂V_0.9Co_0.1-xZn_xO_5.35, 0.02 ≤ x ≤ 0.08 with layered Aurivillius structure were synthesized successfully by sol-gel citrate method. Structural and electrical characterization of compositions has been investigated by X-ray diffraction, thermogravimetric analysis–differential scanning calorimetric (TGA–DSC) analysis and AC impedance spectroscopy. The tetragonal γ phase has been observed for all investigated samples. The AC impedance response of samples has been measured in the frequency range of 20 Hz to 1 MHz. The impedance for pellets decreases as thermal energy increases. The contribution of grain to the conduction process is more than that of grain boundary. The ionic conductivity and dielectric permittivity are found to be composition-dependent and increase with increasing Zn concentration. The maximum electrical conductivity observed for the composition x = 0.08 is σ = 4.51 × 10^?4 S cm^?1 at 300 °C.     

Influence of calcium substitution on the phase transition and ionic conductivity in BICAVOX oxide ion conductor

Samples of Bi₄Ca _x V_{2? x} O_{11?(3 x /2)?δ} in the composition range 0.07 ≤ x ≤ 0.30 were prepared by conventional solid state reactions. The stability of different phases as a function of composition was analysed by X-ray powder diffraction, FT-IR spectra, differential thermal analysis and AC impedance spectroscopy. For the compositions x ≤ 0.10, monoclinic α-phase structure is retained at room temperature. For x = 0.13, orthorhombic β-phase is observed, whereas for x ≥ 0.17, high O^2?conducting tetragonal γ-phase is stabilised. However, the highest ionic conductivity σ_300°C = 3.27 × 10^?4 S cm^?1 was observed for x = 0.17. This higher value of conductivity of the substituted compound as compared to the parent compound can be attributed to the increased oxygen ion vacancies generated as a result of cation doping. AC impedance spectroscopy reveals the fact that this ionic conductivity is mainly due to the grain contribution.     

Study on phase stabilization and electrical performance of BICO0.20−xNIxVOX solid electrolyte

BICO_0.20?xNI_xVOX solid electrolyte in the composition range 0 ≤ x ≤ 0.20 was synthesized by standard solid-state reactions. The influence of Ni substitution for Co on the relationship between the phase stabilization and electrical performance was investigated by means of X-ray powder diffraction (XRPD), differential thermal analysis (DTA) and AC impedance spectroscopy. The highly conductive γ′-phase was effectively stabilized at room temperature for compositions with x ≥ 0.13 whose thermal stability increases with Ni content. On the other hand, complex plane plots of impedance suggested a major contribution of polycrystalline grain interiors to the overall electrical conductivity and the fastest oxygen-vacancy diffusion in the perovskite vanadate layers at x = 0.13. The dielectric permittivity measurements revealed the fact that suppression of the ferroelectric transition is compositionally dependent. However, a maximum ionic conductivity at lower temperatures (～2.56 × 10^?4 S cm^?1 at 300 °C) was observed for the composition with x = 0.13.     

Effect of Cu–Al double substitution on the electrical properties of Bi4V2O11

Bi₂Cu_0.1?xAl_xV_0.9O_5.35?x/2?δ, 0.02 ≤ x ≤ 0.08, were synthesized by standard solid-state reaction route. Structural and electrical properties of samples are characterized by X-ray diffraction (XRD), differential thermal analysis (DTA), Fourier transform infrared (FT-IR) and alternating current (AC) impedance spectroscopy. The tetragonal γ′ phase structure is preserved to room temperature with compound x = 0.02. The stabilization of β orthorhombic phase is observed for compositions 0.04 ≤ x ≤ 0.05. As the Al content increases, the monoclinic α phase is evidenced for materials 0.06 ≤ x ≤ 0.08. The electrical investigation of Bi₂Cu_0.1?xAl_xV_0.9O_5.35?x/2?δ system has been performed in the frequency range from 20 Hz to 1 MHz using AC impedance spectroscopy. The impedance spectra indicate the two semicircle arcs associated with the bulk and grain boundary resistances at temperature below ～450 ^○C. The conductivity generally changes when Al is substituted. The highest conductivity at 300 ^○C (σ = 2.55 × 10^?4 S cm^?1) is shown for x = 0.02.     

Influence of Gd3+ and Dy3+ co-doping and sintering regime on enhancement of electrical conductivity of ceria-based solid electrolyte

In order to improve the conductivity of ceria-based solid electrolytes, effect of co-doped Gd³⁺ and Dy³⁺ was evaluated. For this purpose, nano-crystalline Gd_0.2???x Dy _x Ce_0.8O_1.9 powders with various composition ranges (x?=?0.05, 0.1, 0.15, 0.2) were initially synthesized by high-energy milling method. The effect of micro-structural evolution and co-doping on electrical properties of the dense sintered samples fabricated by two-step sintering and conventional sintering of the synthesized powders were investigated. Electrical conductivity of the samples was discussed based on the results obtained by AC impedance spectroscopy at temperatures in the range of 300–700 °C. The co-doping and sintering regime were found to significantly influence the conductivity of the electrolytes. The electrical conductivity of the co-doped samples depends on Dy³⁺ content and the maximum conductivity obtained by 0.15 mol% Dy and 0.05 mol% Gd. The conductivity of Gd_0.2???x Dy _x Ce_0.8O_1.9 (x?=?0.15) was 0.03 S/cm at 700 °C. A thorough discussion was made, based on the present experimental data.     

Effect of Zn–Ti double substitution on the electrical properties of Bi4V2O11

New samples of the Bi₂Zn_0.1–xTi_xV_0.9O_5.35+x; 0.02 ≤ x ≤ 0.08 system have been synthesized through a standard solid-state reaction route. XRD analysis and differential thermal analysis have been used to characterize the phase structure of samples. The γ′ phase is stabilized to room temperature in all investigated samples. The electrical properties of the BIZNTIVOX system have been studied by using AC impedance spectroscopy. An AC impedance response as a function of frequency (20 Hz–1 MHz) has been used to investigate the electrical conductivity and the dielectric permittivity in the temperature range of 150 °C–700 °C. In this temperature range, the phase transition γ′ to γ has been observed in all the compositions studied. AC impedance spectroscopy indicates that the resistance of samples decreases with increase of temperature. The ionic conductivity of samples appeared as a two-line region in Arrhenius dependence. At 300 °C, the highest ionic conductivity is shown by the composition x = 0.05 (σ₃₀₀ = 1.35 × 10^?4 S cm^?1).     

Swift heavy ion irradiation-induced modifications in structural and electrical properties of Y3+-substituted yttrium iron garnet

The consequences of 50 MeV Li³⁺ ion irradiation (fluence: 5×10¹³ ions/cm²) on the structural and electrical properties of the Y_3+xFe_5?xO₁₂ (x=0.0, 0.2, 0.4 and 0.6) garnet system have been investigated over the temperature range of 300–673 K. It is found that the percentage formation of an additional yttrium orthoferrite phase observed along with the bcc garnet phase considerably reduces for x=0.4 and 0.6 compositions after swift heavy ion (SHI) irradiation. The nature of thermal variation of DC resistivity curves for x=0.0 and 0.2 compositions is different from that for x=0.4 and 0.6 compositions. The SHI irradiation influences the magnitude of DC resistivity and conduction mechanism for the single-phase compositions while for mixed-phase compositions they remain unaffected. The results have been explained in the light of replacement of magnetic (5μ_B), smaller (0.64 Å), Fe³⁺ ion by nonmagnetic (0μ_B), larger (0.89 Å), Y³⁺ ion, the presence of the yttrium orthoferrite phase and swift heavy ion irradiation-induced paramagnetic centers in the system.     

How Far can the Anisotropy Deviate from Uniaxiality in a Dy-Based Single-Molecule Magnet? Dinuclear Dy(III) Complex Study

The Dy^III ions in the dimer [Dy₂(H₂tea)₂(O₂CPh)₄]·2H₂O (1) (H₃tea = triethanolamine) have the 9-coordinate monocapped square-antiprismatic ligand field environment. Compound 1 shows slow relaxation of magnetization which is observable only with applied magnetic fields. This is consistent with the idea that low-symmetry ligand fields allow for the quantum tunneling of magnetization. This is reflected by the fact that there are no observable maxima in the out-of-phase ac susceptibility above 1.8 K. The {g}-tensor of the Dy^III ions {g _x = 11, g _y = 8.2, g _z = 1} further underlying the reduced uniaxiality in this system was determined in electron paramagnetic resonance (X- and Q-band) studies of 1 at temperatures down to 4 K.     

Thermophysical properties of Cu–In–Sn liquid Pb-free alloys: viscosity and surface tension

The viscosity of a few Cu–In–Sn liquid alloys has been investigated by a number of geometric (Muggianu, Kohler, Toop) and physical thermodynamic models (Kozlov–Romanov–Petrov, Budai–Benko–Kaptay, Schick et al.) and GSM for the cross section (z/y = 1/3) in Pb-free liquid alloy Cu_x–In_y–Sn_z at 1073 K. Moreover, the surface tensions of the same liquid alloys have been investigated by a number of geometric models and the Butler model for the cross section Cu_x–In_y–Sn_z (z/(y + z) = 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1) at the same temperature. The best agreement of the surface tensions was obtained in the Kohler model for x_Cu = 10 at % and the Butler model for x_Cu = 20 at % and x_Cu = 30 at.%, respectively. The best agreement among chosen geometric and physical models and experiment for these selected sections Cu₈₀In₁₅Sn₅, Cu₇₅In₁₅Sn₁₀, Cu₅₅In₇Sn₃₈, Cu₃₃In₅₀Sn₁₇ and Cu₂₆In₅₅Sn₁₉ at 1073 K was obtained for the Budai–Benkö–Kaptay model.     

Electrical properties of MWCNT-composite (Se80Te20)100−xAgx (0 ≤ x ≤ 4) chalcogenide glasses

This article describes the preparation of multi-walled carbon nanotube (MWCNT) chalcogenide glass composite by the melt-quenching technique. MWCNT composite (Se₈₀Te₂₀)_100?xAg_x (0 ≤ x ≤ 4) bulk samples are characterized by the XRD, SEM and EDX. The electrical measurements were carried out in the temperature range of the 308-388 K. Cole–Cole plot has been used to determine the electrical conductivity at room temperature. It has been observed that MWCNT chalcogenide composite have higher value of electrical conductivity than pure glass. The results have been discussed on the basis of increased ionic conductivity (Ag⁺ ions) in MWCNT doped (Se₈₀Te₂₀)_100?xAg_x (0 ≤ x ≤ 4) bulk samples.     

Optical properties of polyvinyl alcohol doped (Se80Te20)100–xAgx (0 ≤ x ≤ 4) composites

Polyvinyl alcohol (PVA) doped (Se₈₀Te₂₀)_100–xAg_x (0 ≤ x ≤ 4) thin films were prepared by the spin-coating technique on a quartz substrate. The optical parameters of PVA-doped (Se₈₀Te₂₀)_100–xAg_x (0 ≤ x ≤ 4) composites at the same chalcogen concentration (S₀ = 0.1 mg ml^?1) and PVA/(Se₈₀Te₂₀)₉₆Ag₄ composites at three different chalcogen concentrations viz. S₁ = 0.3 mg ml^?1, S₂ = 0.6 mg ml^?1 and S₃ = 1 mg ml^?1 have been studied. The semi-crystalline nature of the as-deposited thin filmsisdetermined by X-ray diffraction. The transmission and reflection spectra of PVA-doped Se–Te–Ag thin films were obtained in a 350–650 nm spectral region. The optical-band gap has been calculated from the transmission and reflection data. The refractive index has been calculated by the measured reflection data. It has been found that the optical-band gap increases, but the refractive index, extinction coefficient, and the real and imaginary parts of the dielectric constant decrease, with increase in Agcontent in PVA-doped (Se₈₀Te₂₀)_100–xAg_x (0 ≤ x ≤ 4) thin films. Such type of behavior is explained on the basis of decrease in density of the defect states. However, the optical-band gap has been found to be decreased and all other optical parameters show increase in their values with increase in concentration of (Se₈₀Te₂₀)₉₆Ag₄ glass in PVA-doped composites. The results have been explained on the basis of cluster-size formation at the time of dissolution. This study shows that the optical properties of new composites are affected by the change in silver and chalcogen concentration.     

Infrared and auger spectra of dysprosium silicate films

Dysprosium silicate films, Dy _x Si _y O _z , have been investigated using infrared (IR) and Auger spectroscopy. The films have been formed by oxidizing dysprosium metal films on 5.2-nm-thick silicon dioxide films at a temperature of 600°C. It is shown that the composition of the Dy _x Si _y O _z dysprosium silicate films is close to that of dysprosium pyrosilicate, Dy₂Si₂O₇, and irregular in thickness. On going from the film outer surface to the silicon substrate, the amount of dysprosium decreases and that of silicon bound to oxygen increases. Silicon dioxide, SiO₂, predominates in the layer composition near the silicon substrate. The dielectric leakage current density in the accumulation mode is one order of magnitude lower in the Dy _x Si _y O _z films than in the SiO₂ films of the same equivalent thickness due to the larger physical thickness of the former.     

A novel Dy3+-doped Gd(PO3)3 white-light phosphors under VUV excitation for Hg-free lamps application

Novel Dy³⁺-doped Gd(PO₃)₃ white light phosphors each with an orthorhombic system are successfully synthesized by solid-state reaction. The luminescence properties of white-light Gd_1-x(PO₃)₃:xDy³⁺ (0<x≤ 0.25) under vacuum ultraviolet (VUV) excitation are investigated. The strong absorption at around 147 nm in excitation spectrum energy can be transferred to the energy levels of Dy³⁺ ion from the host absorption. Additionally, the white light phosphor is activated by a single Dy³⁺ ion. Therefore, the luminescence of Gd_1-x(PO₃)₃:xDy (0<x≤ 0.25) under VUV excitation is effective, and it has the promise of being applied to mercury-free lamp.     

The effect of cycle deformation on the AC conductivity of (Bi0.3Sb0.7)2Te3 films

It has been found that the resistance of the (Bi_0.3Sb_0.7)₂Te₃ porous polycrystalline film fabricated by thermal vacuum evaporation at substrate temperature T _s ≤ 363 K drastically decreases near the threshold AC frequency ω₀ ≈ 10⁵ Hz as low as the resistance of dense films with T _s ≈ 423 K. After the action of N ≈ 10⁵ cycles of mechanical deformation with amplitude ε = ±1 × 10^–3 a.u., the film resistance increases by 1.5 times and the threshold frequency decreases in almost 10² times, which can qualitatively be accounted for by the model of microcontacting blocks.

     

Optical and luminescence properties of Dy3+ ions in K–Sr–Al phosphate glasses for yellow laser applications

Trivalent dysprosium (Dy³⁺)-doped K–Sr–Al phosphate glasses have been prepared and investigated for their optical and luminescence properties. Judd–Ofelt theory has been used to derive radiative properties for the ⁴F_9/2 level of Dy³⁺ ions. The luminescence spectrum of 1.0 mol% Dy₂O₃-doped glass shows intense yellow emission around 572 nm ascribed to ⁴F_9/2 → ⁶H_13/2 transition with 78 % branching ratio and emission cross section of the order of 2.48 × 10^?21 cm². Moreover, the quantum efficiency of the ⁴F_9/2 level has been found to be 76 %. The luminescence decay curves for the yellow emission (⁴F_9/2 → ⁶H_13/2) have been measured and analyzed as a function of Dy³⁺ ion concentration. The results revealed that Dy³⁺-doped phosphate glasses could be useful for yellow laser applications.     

PL Properties of Sr<Subscript>2</Subscript>CeO<Subscript>4</Subscript> With Eu<Superscript>3+</Superscript> and Dy<Superscript>3+</Superscript> for Solid State Lighting Prepared by Precipitation Method

Photoluminescence studies of pure and Dy³⁺, Eu³⁺ doped Sr₂CeO₄ compounds are presented by oxalate precipitation method for solid state lighting. The prepared samples also characterized by XRD, SEM (EDS) and FTIR spectroscopy. The pure Sr₂CeO₄ compound displays a broad band in its emission spectrum when excited with 280 nm wavelength, which peaks centered at 488 nm, which is due to the energy transfer between the molecular orbital of the ligand and charge transfer state of the Ce⁴⁺ ions. Emission spectra of Sr₂CeO₄ with different concentration of Dy³⁺ ions under near UV radiation excitation, shows that intensity of luminescence spectra is found to be affected by Dy³⁺ ions, and it increases with adding some percentages of Dy³⁺ ions. The maximum doping concentration for quenching is found to be Dy³⁺?=?0.2 mol % to Sr²⁺ions. The observed broad spectrum from 400 to 560 nm is mainly due to CT transitions in Sr₂CeO₄ matrix and some fractional contribution of transitions between ⁴F_9/2 → ⁶H_15/2 of Dy³⁺ ions. Secondly the effect of Eu³⁺ doping at the Sr²⁺ site in Sr₂CeO₄, have been studied. The results obtained by doping Eu³⁺ concentrations (0.2 mol% to 1.5 mol%), the observed excitation and emission spectra reveal excellent energy transfer between Ce⁴⁺ and Eu³⁺. The phenomena of concentration quenching are explained on the basis of electron phonon coupling and multipolar interaction. This energy transfer generates white light with a color tuning from blue to red, the tuning being dependent on the Eu³⁺ concentration. The results establish that the compound Sr₂CeO₄ with Eu³⁺?=?1 mol% is an efficient “single host lattice” for the generation of white lights under near UV-LED and blue LED irradiation. The commission internationale de I’Eclairage (CIE) coordinates were calculated by Spectrophotometric method using the spectral energy distribution of prepared phosphors.     

Investigation of structural and optical properties of 100 MeV F7+ ion irradiated Ga10Se90-xAlx thin films

Present work focuses on the effect of swift heavy ion (SHI) irradiation of 100 MeV F⁷⁺ ions by varying the fluencies in the range of 1 × 10¹² to 1 × 10¹³ ions/cm² on the morphological, structural and optical properties of polycrystalline thin films of Ga₁₀Se_90-xAl_x (x = 0, 5). Thin films of ~300 nm thickness were deposited on cleaned Al₂O₃ substrates by thermal evaporation technique. X-ray diffraction pattern of investigated thin films shows the crystallite growth occurs in hexagonal phase structure for Ga₁₀Se₉₀ and tetragonal phase structure for Ga₁₀Se₈₅Al₅. The further structural analysis carried out by Raman spectroscopy and scanning electron microscopy verifies the defects or disorder of the investigated material increases after SHI irradiation. The optical parameters absorption coefficient (α), extinction coefficient (K), optical band gap (E_g) and Urbach’s energy (E_U) are determined from optical absorption spectra data measured from spectrophotometry in the wavelength range 200–1100 nm. It was found that the values of absorption coefficient and extinction coefficient increase while the value of optical band gap decreases with the increase in ion fluence. This post irradiation change in the optical parameters was interpreted in terms of bond distribution model.     

Synthesis and luminescent properties of BaGd2O4:Dy3+, an novel scintillating phosphor

The BaGd_2?x O₄:xDy³⁺ (0 ≤ x ≤ 0.08) phosphors were synthesized at 1,300 °C in air by the solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction, photoluminescence excitation spectra, photoluminescence (PL) spectra, X-ray excited luminescence (XEL) spectra, and thermoluminescence (TL) spectra. It is found that the quenching concentration of Dy³⁺ ions in BaGd₂O₄ host is dependent on the selected excitation wavelength. The optimal PL intensity for the investigated BaGd_2?x O₄:xDy³⁺ phosphors is found to be x = 0.01, 0.02, and 0.04, upon excitation by 234, 277, and 350 nm ultraviolet light, respectively. The energy transfer among Dy³⁺ ions upon excitation by 350 nm is confirmed to be an electric dipole–dipole interaction mechanism based on the fitting of Huang’s rule. In addition, the intensive XEL from BaGd₂O₄:Dy³⁺ phosphor is observed by the naked eyes at room temperature, and TL properties of the investigated phosphors are analyzed and discussed. All the results imply that the investigated phosphors could be a promising scintillating phosphor.     

Correlation between phase structure and electrical conduction in BISNVOX system for intermediate temperature solid oxide fuel cells (IT-SOFC)

Samples of Sn⁴⁺-substituted bismuth vanadate, formulated as Bi₄Sn _x V_{2? x} O_{11?( x /2)? δ} in the composition range 0.07 ≤ x ≤ 0.30, were prepared by standard solid-state reactions. Sample characterization and the principal phase transitions (α ? β, β ? γ and γ′ ? γ) were investigated by FT-IR spectroscopy, X-ray powder diffraction, differential thermal analysis (DTA) and AC impedance spectroscopy. For composition x = 0.07, the α ? β and β ? γ phase transitions were observed at temperatures of 451 and 536°C, respectively. DTA thermograms and Arrhenius plots of conductivities revealed the γ′ ? γ phase transition at 411 and 423°C for x = 0.20 and 0.30, respectively. AC impedance plots showed that conductivity is mainly due to the grain contribution, which is evident in the enhanced short-range diffusion of oxide ion vacancy in the grains with increasing temperature. The highest ionic conductivity (5.03 × 10^?5 S cm^?1 at 300°C) was observed for the x = 0.17 solid solution with less pronounced thermal hysteresis.