Structure,thermal behavior,and dielectric properties of new cesium hydrogen sulfate arsenate: Cs<Subscript>2</Subscript>(HSO<Subscript>4</Subscript>)(H<Subscript>2</Subscript>AsO<Subscript>4</Subscript>)

Synthesis and structural characterization by single-crystal X-ray diffraction method, thermal behavior, and electrical proprieties are given for a new compound with a superprotonic phase transition Cs₂(HSO₄)(H₂AsO₄). The title compound crystallizes in the monoclinic system with the P2₁/n space group. The structure contains zigzag chains of hydrogen-bonded anion tetrahedra that extend in the [010] direction. Each tetrahedron is additionally linked to a tetrahedron neighboring chain to give a planar structure with hydrogen-bonded sheets lying parallel to (10ī). The existence of O–H and (S/As)–O bonds in the structure at room temperature has been confirmed by IR and Raman spectroscopy in the frequency ranges 4000–400 cm^?1and 1200–50 cm^?1, respectively. Differential scanning calorimetry analysis of the superprotonic transition in Cs₂(HSO₄)(H₂AsO₄) showed that the transformation to high temperature phase occurs at 417 K by one-step process. Thermal decomposition of the product takes place at much higher temperatures, with an onset of approximately 534 K. The superprotonic transition was also studied by impedance and modulus spectroscopy techniques. The conductivity in the high temperature phase at 423 K is 1.58 × 10^?4 Ω^?1 cm^?1, and the activation energy for the proton transport is 0.28 eV. The conductivity relaxation parameters associated with the high disorder protonic conduction have been examined from analysis of the M”/M”_max spectrum measured in a wide temperature range. Transport properties of this material appear to be due to the proton hopping mechanism.     

Li<Superscript>+</Superscript> ion conductivity and transport properties of LiYP<Subscript>2</Subscript>O<Subscript>7</Subscript> compound

A lithium yttrium diphosphate LiYP₂O₇ was prepared by a solid-state reaction method. Rietveld refinement of the X-ray diffraction pattern suggests the formation of the single phase desired compound with monoclinic structure at room temperature. The infrared and Raman spectrum of this compound was interpreted on the basis of P₂O₇ ^4? vibrations. The AC conductivity was measured in the frequency range from 100 to 10⁶ Hz and temperatures between 473 and 673 K using impedance spectroscopy technique. The obtained results were analyzed by fitting the experimental data to the equivalent circuit model. The Cole–Cole diagram determined complex impedance for different temperatures. The angular frequency dependence of the AC conductivity is found to obey Jonscher’s relation. The temperature dependence of σ _AC could be described in terms of Arrhenius relation with two activation energies, 0.87 eV in region I and 1.36 eV in region II. The study of temperature variation of the exponent(s) reveals two conduction models: the AC conduction dependence upon temperature is governed by the correlated barrier hopping (CBH) model in region I (T < 540 K) and non-overlapping small polaron tunneling (NSPT) model in region II (T > 540 K). The near value of activation energies obtained from the equivalent circuit and DC conductivity confirms that the transport is through ion hopping mechanism dominated by the motion of the Li⁺ ion in the structure of the investigated material.     

Effect of deposition temperature on key optoelectronic properties of electrodeposited cuprous oxide thin films

The cuprous oxide (Cu₂O) thin films were electrodeposited with different reaction temperatures. The structural, morphological, optical, photoluminescence and photo response properties of the deposited films were analyzed. XRD analysis reveals cubic crystal structure for the deposited films with polycrystalline nature. The film deposited at room temperature possess high crystallite size of 37 nm. The surface morphology shows that by increasing the deposition temperature pyramid shaped morphology changes. Laser Raman study confirms the peaks 109, 148, 219, 415 and 635 cm^?1 conforms the Cu₂O phase formation. The band gap of the films are 2.02, 2.10 and 2.27 eV for the RT, 40 and 50 °C, respectively. The photoluminescence spectral analysis contains an emission peak at 618 nm confirm the formation of Cu₂O. The photo response study confirms the ohmic nature of the films. The film electrodeposited at room temperature showed good I–V curve at the illumination of 300 W cm^?2.     

Characterization of Fe states in dilute 57 Mn implanted SnO 2 film

States of dilute Fe in SnO₂ have been monitored using ⁵⁷Fe emission Mössbauer spectroscopy following implantation of ⁵⁷Mn (T _1/2 = 85.4 s) in the temperature range from 143 K to 711 K. A sharp annealing stage is observed at ~330 K where the Fe^3?+?/Fe^2?+? ratio shows a marked increase. It is suggested that this annealing stage is due to the dissociation of Mn-V_O pairs during the lifetime of ⁵⁷Mn; the activation energy for this dissociation is estimated to be 0.9(1) eV. Fe^3?+? is found in a paramagnetic state showing spin-lattice relaxation rates consistent with an expected T ² dependence derived for a Raman process. In addition, a sharp lined doublet in the Mössbauer spectra is interpreted as due to recoil produced interstitial Fe.     

Origin of dielectric relaxations in KHSeO4 above room temperature

The dispersion curves of the dielectric response for KHSeO₄ were obtained in the radio frequency range at several isotherms below the fast proton conducting phase (T?<?415 K). The results reveal a distinct dielectric relaxation at low frequency, which is about 682 Hz at 320 K, and then, it shifts to higher frequencies (～10 kHz) as the temperature increases. The f _max vs. reciprocal T shows an activated relaxation process with an activation energy of 0.5 eV, which is in close agreement with that associated with transport of charge carriers. We suggest that the observed dielectric relaxation could be attributed to polarization induced by the proton jump and selenate tetrahedral reorientations. The displacement of mobile H⁺ proton accompanied by SeO ₄ ^??2 tetrahedra reorientations creates structural distortion in both sublattices which induce localized dipoles like HSeO ₄ ^? .     

Microwave-assisted rapid synthesis of tetragonal Cu2SnS3 nanoparticles for solar photovoltaics

A simple and rapid process for the synthesis of Cu₂SnS₃ (CTS) nanoparticles by microwave heating of metal–organic precursor solution is described. X-ray diffraction and Raman spectroscopy confirm the formation of tetragonal CTS. X-ray photoelectron spectroscopy indicates the presence of Cu, Sn, S in +1, +4, ?2 oxidation states, respectively. Transmission electron microscopy divulges the formation of crystalline tetragonal CTS nanoparticles with sizes ranging 2–25 nm. Diffuse reflectance spectroscopy in the 300–2,400 nm wavelength range suggests a band gap of 1.1 eV. Pellets of CTS nanoparticles show p-type conduction and the carrier transport in temperature range of 250–425 K is thermally activated with activation energy of 0.16 eV. Thin film solar cell (TFSC) with architecture: graphite/Cu₂SnS₃/ZnO/ITO/SLG is fabricated by drop-casting dispersion of CTS nanoparticles which delivered a power conversion efficiency of 0.135 % with open circuit voltage, short circuit current and fill factor of 220 mV, 1.54 mA cm^?2, 0.40, respectively.     

Synthesis and characterization of Ce-doped Sm<Subscript>2</Subscript>CuO<Subscript>4 + <Emphasis Type="Italic">δ</Emphasis></Subscript> cathode for IT-SOFC applications

Single-phase solid solutions of Sm_2 ? x Ce _x CuO_4 + δ (0.05 ≤ x ≤ 0.20) with tetragonal structure are synthesized using acetate combustion followed by sintering at 1373 K for 10 h. X-ray powder diffraction and transmission electron microscopy studies confirmed the formation of solid solution in a single phase. Maximum conductivity (σ = 96.0 ± 0.5 S cm^?1 at 973 K) giving composition Sm_1.90Ce_0.10CuO₄ offers the minimum activation energy (E _a = 0.32 ± 0.004 eV) among all prepared compositions. Lowest cathode polarization resistance (R _p = 3.92 ± 0.07 Ω cm² at 973 K) and activation energy (E _a = 1.12 ± 0.03 eV) values across the measured temperature range are obtained for Sm_1.90Ce_0.10CuO₄. The impedance data fitted well to the Gerischer model indicates that a chemical-electrochemical-chemical-type reaction occurred at the mixed electronic-ionic conducting cathode.     

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.     

Microwave-sintered Pr<Superscript>3+</Superscript>, Sm<Superscript>3+</Superscript>, and Gd<Superscript>3+</Superscript> triple-doped ceria electrolyte material for IT-SOFC applications

The Pr³⁺, Sm³⁺, and Gd³⁺ triple-doped ceria Ce_0.76Pr_0.08Sm_0.08Gd_0.08O_2-δ material as solid electrolyte for IT-SOFC has been successfully synthesized by sol–gel auto-combustion route. The effect of microwave sintering (1300 °C for 15, 30, and 60 min, named as PSG-MS15, PSG-MS30, and PSG-MS60, respectively) on structural, electrical, and thermal properties of prepared electrolyte material has been studied. Powder X-ray diffraction, scanning electron microscope, energy dispersive spectroscopy, and Raman analysis revealed the single phase, microstructure, elemental confirmation, and structural oxygen vacancy formation of all the samples. Impedance spectroscopy analysis revealed the highest total ionic conductivity, i.e., 3.47 × 10^?2 S cm^?1 at 600 °C with minimum activation energy of 0.69 eV, in PSG-MS30 sample when compared to PSG-MS15 and PSG-MS60. The thermal expansion measurements have been carried out for PSG-MS30 specimen. The highest total ionic conductivity with minimum activation energy and moderate thermal expansion coefficient of PSG-MS30 sample makes the possibility of its use as solid electrolyte in IT-SOFC applications.     

Growth and Characterization of CdSe1 − y S y Nanofilms Obtained by Chemical Bath Deposition

In this work, the growth and characterization of cadmium selenide sulphur (CdSe_1???y S _y ) deposited by chemical bath deposition (CBD) technique at the reservoir temperature of 20?±?2 °C are presented, varying the thiourea volume added to the growth solution in the range of 0–30 ml. The films chemical stoichiometry was determined by energy-dispersive X-ray spectroscopy (EDS). The X-ray diffraction (XRD) analysis and Raman scattering reveal that CdSe_1???y S _y -deposited films showed hexagonal wurtzite crystalline phase. The average size of the crystalline grain in relation to the sulphur volume varies in the range of 1.48–9.2 nm that was determined by using the Debye-Scherrer equation for the direction (100), which is confirmed by analyzing the grain average diameter by high-resolution transmission electron microscopy (HRTEM). Raman scattering shows that the lattice dynamics is characteristic of bimodal behaviour and the multipeak adjust of the first optical longitudinal mode for the CdSeS denotes, in all cases, the Raman shift of the characteristic peak in the range of 177–181 cm^?1 of the CdSe crystals associated with the sulphur incorporation. CdSe_1???y S _y band gap energy can be varied from 1.86 to 2.11 eV by varying the thiourea volume added in the growth solution measured by transmittance at room temperature.     

Superionic phase transition in (NH4)2SeO4·2NH4HSeO4 single crystal at 378 K

Abstract

DTA, structural and electric conductivity investigations were made for (NH₄)₄H₂(SeO₄)₃ single crystals. A high-temperature phase transition at 378 K to a superionic phase was found. The phase is characterized by a high electrical conductivity (～4.10^?3 Ω^?1 cm^?1) and a low activation energy (0.11 eV).     

Oxygen diffusion in uranium dioxide in the temperature range of phase transitions

The structure of and oxygen diffusion in UO₂ are studied by the molecular dynamics method in the range of transition to the superionic state (melting of the oxygen sublattice) and near the melting point of UO₂. The temperature dependence of the diffusion coefficient of a doubly charged oxygen ion in UO₂ is constructed. In the crystalline state at temperatures between 1800 and 2600 K, this dependence is described by an exponential dependence with a diffusion activation energy of 2.6±0.2 eV. In the superionic state (2600–3100 K), the activation energy of diffusion of an oxygen anion decreases to 1.88±0.13 eV. In melt (3100–3600 K), the exponential dependence of the diffusion coefficient of O^2- persists but the activation energy of diffusion decreases still further, to 0.8±0.2 eV. Our experimental results agree (within the limits of experimental error) with data on oxygen diffusion in the crystalline phase obtained by other researchers.     

Synthesis,structural characterization and ionic conductivity of NASICON-type Ba<Subscript>x/2</Subscript>Li<Subscript>1-x</Subscript>Ti<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> (0.4 ≤ x ≤ 1) materials

The NASICON series, with formula Ba_x/2Li_1-xTi₂(PO₄)₃ (0.4 ≤ x ≤ 1), has been prepared by solid-state reaction and characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), Raman, nuclear magnetic resonance (NMR) and impedance spectroscopy (IS). XRD patterns of samples indicated the formation of single phases with rhombohedral structure (space group R-3c). The Rietveld analysis of XRD patterns was performed to deduce location of Li and Ba ions. FTIR, Raman, and NMR techniques showed the only presence of isolated PO₄ groups in analyzed phosphates. ³¹P MAS-NMR spectra were used to investigate Li and Ba distribution and ⁷Li MAS-NMR spectra to discriminated Li ions with different mobility in conduction paths. A maximum total conductivity of 2.5 × 10^?7 S cm^?1 and a minimum activation energy of 0.47 eV were obtained at room temperature for Ba_0.3Li_0.4Ti₂(PO₄)₃ (x = 0.6).     

Correlation of dielectric properties,Raman spectra and calorimetric measurements of β-cyclodextrin-polyiodide complexes (β-cyclodextrin)2 ·BaI7 ·11H2O and (β-cyclodextrin)2 ·CdI7·15H2O

The frequency and temperature dependence of real and imaginary parts of the dielectric constant (ε′,?ε″), the phase shift (?) and the ac-conductivity (σ) of polycrystalline complexes (β-CD)₂·BaI₇·11H₂O and (β-CD)₂·CdI₇·15H₂O (β-CD?=?β-cyclodextrin) has been investigated over the frequency and temperature ranges 0–100?kHz and 140–420?K in combination with their Raman spectra, DSC traces and XRD patterns. The ε′(T), ε″(T) and ?(T) values at frequency 300?Hz in the range T<330?K show two sigmoids, two bell-shaped curves and two minima respectively revealing the existence of two kinds of water molecule, the tightly bound and the easily movable. Both complexes show the transition of normal hydrogen bonds to flip-flop type at 201?K. In the β-Ba complex most of the eleven water molecules remain tightly bound and only a small number of them are easily movable. On the contrary, in the β-Cd case the tightly bound water molecules are transformed gradually to easily movable. Their DSC traces show endothermic peaks with onset temperatures 118°C, 128°C for β-Ba and 106°C, 123°C, 131°C for β-Cd. The peaks 118°C, 106°C, 123°C are related to the easily movable and the tightly bound water molecules, while the peaks at 128°C, 131°C are caused by the sublimation of iodine. The activation energy of Ba²⁺ ions is 0.52?eV when all the water molecules exist in the sample and 0.99?eV when the easily movable water molecules have been removed. In the case of β-Cd the corresponding activation energies are 0.57?eV and 0.33?eV. The Raman peaks at 179?cm^?1, 170?cm^?1 and 165–166?cm^?1 are due to the charge transfer interactions in the polyiodide chains.     

Impedance spectroscopy analysis of LiZnVO4 and LiMgVO4

A comparative LiZnVO₄ and LiMgVO₄ conductivity study was done from room temperature to 500 °C and at frequencies from 42 to 1 MHz. The impact of moisture absorption to the materials’ conductivity was investigated. It was shown for LiZnVO₄ that moisture absorption is responsible for the decrease of the compound’s conductivity as the material is heated up to 150 °C. The LiZnVO₄ bulk activation energy value was calculated to be 1.20 eV. Two grain boundary activation energy values were calculated for the LiZnVO₄, 0.59 eV at the lower temperature range and 1.37 eV at the higher temperature range. An explanation for the existence of these two values was given. Both materials’ plots of the loss factor (tanδ) versus frequency at different temperatures were found to display a peak, and the modulus master curves present a scaling behavior that suggests non Debye type conductivity relaxation and ion migration via hopping.     

A Study of the Thermal Hysteresis in AgNO3

The reversible phase transformation of AgNO₃ is studied. Dielectric constant, d.c. resistivity, differential thermal analysis (DTA) and dilatometric measurements show the occurrence of a reversible phase transition II→I at 160°C with heat of transformation H = 0.78 kcal/mol. The thermal hysteresis in this reversible transformation is examined, the magnitude of the temperature hysteresis does not exceed 12°C. An acceptable agreement is observed between the measured values of the transition temperature obtained by three different experimental techniques. The dilatometric analysis shows that this transition is accompanied by thermal shrinkage with relative shrinkage coefficient 8 × 10^?4. Thermal analysis are also used to get thermodynamic and kinetic data of this phase transition. The temperature dependence of the dielectric constant and d.c. resistivity for single crystals as well as polycrystalline samples of AgNO₃ have clearly located and confirm the phase transitions II→I→II with a strong support to its thermal hysteresis character. The conduction mechanism is found to be activated by energy 0.12 eV for phase I and 0.36 eV for phase II. The observed thermal behaviour of the various measured parameters is attributed to orientational disorder of the nitrate group leading to an order-disorder phase transition which is reported here for first time in AgNO₃.     

Plastic deformation properties of Zr–Nb–Ti–Ta–Hf high-entropy alloys

We have investigated the plastic deformation properties of single-phase Zr–Nb–Ti–Ta–Hf high-entropy alloys from room temperature (RT) up to 300 °C. Uniaxial deformation tests at a constant strain rate of 10^?4?s^?1 were performed, including incremental tests such as stress relaxations, strain-rate changes, and temperature changes in order to determine the thermodynamic activation parameters of the deformation process. The microstructure of deformed samples was characterized by transmission electron microscopy. The strength of the investigated Zr–Nb–Ti–Ta–Hf phase is not as high as the values frequently reported for high-entropy alloys in other systems. At RT we measure a flow stress of about 850 °C. We find an activation enthalpy of about 1 eV and a stress dependent activation volume between 0.5 and 2 nm³. The measurement of the activation parameters at higher temperatures is affected by structural changes evolving in the material during plastic deformation.     

Fabrication and capacitive characteristics of conjugated polymer composite p-polyaniline/n-WO3 heterojunction

A nanocrystalline and porous p-polyaniline/n-WO₃ dissimilar heterojunction at ambient temperature is reported. The high-quality and well-reproducible conjugated polymer composite films have been fabricated by oxidative polymerization of anilinium ion on predeposited WO₃ thin film by chemical bath deposition followed by thermal annealing at 573 K for 1 h. Atomic force microscopy (AFM) analyses reveal a homogenous but irregular cluster of faceted spherically shaped grains with pores. The scanning electron microscopy confirms the porous network of grains, which is in good agreement with the AFM result. The optical absorption analysis of polyaniline/WO₃ hybrid films showed that direct optical transition exist in the photon energy range 3.50–4.00 eV with bandgap of 3.70 eV. The refractive index developed peak at 445 nm in the dispersion region while the high-frequency dielectric constant, ? _∞, and the carrier concentration to effective mass ratio, N/m^*, was found to be 1.58 and 1.10 × 10³⁹ cm^?3, respectively. The temperature dependence of electrical resistivity of the deposited films follows the semiconductor behavior while the C–V characteristics (Mott–Schottky plots) show that the flat band potential was ?791 and 830 meV/SCE for WO₃ and polyaniline.     

An acoustic study of the mixed-alkali-mixed phase β-aluminas. Part 1: Naβ″/βAl2O3, Kβ″/βAl2O3 and (Na0.6K0.4)β″/βAl2O3

The relative attenuation of compressional sound waves of frequencies 10–60 MHz in mixed alkali (Na/K) mixed phase (β″/β)-aluminas is reported for temperatures 80–550 K. The internal friction peaks shift to higher frequencies at higher temperatures and are attributed to Na⁺ interactions in Naβ″/β alumina and Na⁺ and K⁺ in NaK β″/β alumina. The broad attenuation peaks occuring at low temperatures (< 300 K) and at higher temperatures (> 400 K) suggest multi-relaxation processes giving a distribution of activation energies. The estimated average activation energy for Na⁺ diffusion in Naβ″/βAl₂ O₃ at low temperatures and high temperatures is 0.183 eV and 0.387 eV respectively. In the NaK β″/βAl₂o₃ samples, the Na ⁺ values were 0.239 eV and 0.386 eV, respectively. The estimated average activation energies for K⁺ diffusion at low and high temperatures in the Kβ″/β-alumina samples were 0.269 eV and 0.371 eV and for K⁺ in the NaK β″/β samples, 0252 eV and 0.339 eV, respectively. The low temperature attenuation peaks were interpreted in terms of ionic interaction in the bulk and the high temperature peaks were related to interactions in the grain boundaries. The measured activation energies confirmed these interpretations. A reversal of the temperature appearance of the Na⁺ and K⁺ high temperature peaks in the NaKβ″/βAl₂ O₃ is explained by the disorder at the grain boundaries.     

Pressure and temperature dependence of Raman scattering and optical absorption in crystalline S4N4

Raman scattering and optical absorption in crystalline S₄N₄ have been measured both as a function of pressure at 295 K and low temperatures. Polarized single crystal Raman data were also obtained as an aid in the assignment of the Raman active phonons. The pressure coefficients of the Raman active external and S-S stretching modes show a discontinuity near 7 kbar indicative of a second order phase change. The optical absorption edge at about 2.5 eV of a sublimed film of S₄N₄ shows red shifts of 1.3 × 10^?5 eV bar^?1 and 6.3 × 10^?4 eV K^?1 with pressure and temperature respectively. In the light of these results, the electronic, vibrational and structural properties of the crystal are discussed.