Structural and ac electrical properties of a newly synthesized single phase rare earth double perovskite oxide: Ba2CeNbO6

A single phase rare earth double perovskite oxide Ba₂CeNbO₆ (BCN) is synthesized by solid-state reaction technique for the first time. The X-ray diffraction pattern of the sample at room temperature shows monoclinic structure, with the lattice parameters, a=5.9763 Å, b=5.975 Å and c=8.48 Å and β=90.04°. Impedance spectroscopy is used to study the ac electrical behavior of this material as a function of frequency (10²-10⁶ Hz) at various temperatures (30-450 °C). A relaxation is observed in the entire temperature range. Conduction mechanism is investigated by fitting the complex impedance data to Cole-Cole equation. Complex impedance plane plots show only one semicircular arc, indicating only the grain contribution of dielectric relaxation. The scaling behavior of imaginary part of electric modulus (M″) and imaginary part of electrical impedance (Z″) suggests that the relaxation describes the same mechanism at various temperatures. The frequency dependence of conductivity is interpreted in terms of the jump relaxation model and is fitted to Jonscher's power law. The values of dc conductivities extracted from the Jonscher power law varies from 2.79×10⁻⁷ to 3.5×10⁻⁵ Sm⁻¹ with the increase in temperature from 100 to 450 °C. The activation energies (0.37 eV) extracted from M″(ω) and Z″(ω) peaks are found to follow the Arrhenius law.     

Complex impedance spectroscopic analysis of Mn-modified Pb(Zr0.65Ti0.35)O3 electroceramics

The polycrystalline samples of Pb(Zr_0.65−xMn_xTi_0.35)O₃ (PZMT) (x=0, 0.05, 0.10, 0.15) were prepared by a high-temperature solid-state reaction technique. Detailed studies on the effect of compositional variation of manganese (Mn) on the electrical behavior (complex impedance Z*, complex modulus M*, electrical conductivity and relaxation mechanisms) of the PZMT systems have been carried out by a nondestructive complex impedance spectroscopy (CIS) technique at 400 °C. The Nyquist plots suggest that the grains only are responsible in the conduction mechanism of the materials. The occurrence of single arc in the complex modulus spectrum of all the compositions of Mn confirms the single-phase characteristics of the PZMT compounds, and also confirms the presence of non-Debye type of multiple relaxation in the material.     

Dielectric relaxation and ac conduction in multiferroic TbMnO3 ceramics: Impedance spectroscopy analysis

Polycrystalline samples of Tb_1−xAl_xMnO₃ (x = 0, 0.1, 0.2) have been synthesized by means of standard high-temperature solid-state reaction technique. Detailed studies on the effect of compositional variation of aluminum (Al) on the electrical behavior (complex impedance Z*, complex modulus M*, and relaxation mechanisms) of the parent TbMnO₃ have been performed by using the nondestructive complex impedance spectroscopy technique at temperatures above room temperature. In the temperature range covered, the impedance plots signalize that the grains are the unique responsible for the conduction mechanism of the concerned material. The impedance spectra are well modeled in terms of electrical equivalent circuit with a grain resistance (R_g) and constant phase element impedance (Z_CPE). The conductivity data of the undoped and Al-doped samples are well fitted by the universal Jonscher's power law. The resulting fitting parameters indicate that for the studied samples, the hopping process occurs between neighboring sites. Activation energy values for dc conductivity are calculated for undoped and Al-doped samples and found to decrease when Al is incorporated. In turn, the emergence of single arc in the complex modulus spectrum for all the compositions of Al suggests that for the studied samples only one type of relaxation behavior is present at the selected temperatures. A non-Debye-type relaxation is clearly verified. The relaxation process in the present samples seems to be composition and temperature dependent, particularly at higher frequencies.     

Electrical conductivity and complex electric modulus of titanium doped nickel-zinc ferrites

The samples Ni_1+x−yZn_yTi_x Fe_2−2xO₄; y=0.1, 0.0≤x≤0.5 were prepared in a single-phase spinel structure as indicated from X-ray analysis. Electrical conductivity and dielectric measurements at different temperatures from 300 K to 600 K in the frequency range from 42 Hz to 5 MHz have been analyzed. The relation of conductivity with temperature revealed a semiconductor to semimetallic behavior as Ti⁴⁺ concentration increases. The conduction mechanism depends mainly on the valence exchange between the different metal ions in the same site or in different sites. The dielectric constant as a function of temperature and frequency showed that there is a strong dependence on the compositional parameter x. The electrical modulus has been employed to study the relaxation dynamics of charge carriers. The result indicates the presence of correlation between motions of mobile ion charges. The activation energies extracted from M′(ω) and M″(ω) peaks are found to follow the Arrhenius law. The electrical conductance of the samples found to be dependent on the temperature and frequency.     

Study of (Bi2O3)(BaxMo1−xO3) polycrystalline ceramic as relaxor ferroelectric

Solid solutions of bismuth layered (Bi₂O₃)(Ba_xMo_1−xO₃) (0.2≤x≤0.8, x is in step of 0.2) ceramics were prepared by conventional solid-state reaction of the constitutive oxides at optimized temperatures with a view to study its electrical properties. Powder X-ray diffraction has been employed for physical characterization and an average grain size of ∼16 to 22 nm was obtained. XRD study reveals the single phase structure of the samples. Dielectric properties such as dielectric constant (ε′), dielectric loss (tanδ) and ac electrical conductivity (σ_ac) of the prepared ceramics sintered at various temperatures in the frequency range 10¹–10⁷ Hz have been studied. A strong dispersion observed in the dielectric properties shows the relaxor type behavior of the ceramic. The presence of maxima in the dielectric permittivity spectra indicates the ferroelectric behavior of the samples. Impedance plots (Cole–Cole plots) at different frequencies and temperatures were used to analyze the electric behavior. The value of grain resistance increases with the increase in Ba ion concentration. The conductivity mechanism shows a frequency dependence, which can be ascribed to the space charge mainly due to the oxygen vacancies. The relaxation observed for the M″ (ω) or Z″ (ω) curves is correlated to both localized and long range conduction. A single ‘master curve’ for the normalized plots of all the modulus isotherms observed for a given composition indicates that the conductivity relaxation is temperature independent.     

Impedance spectroscopy study of BNKLT polycrystalline ceramic

Complex impedance analysis of perovskite structured polycrystalline, [Bi_0.5(Na_1−x−y K _x Li _y )_0.5]TiO₃, at x=0.2, y=0.1 ceramic was synthesized by a mixed oxide method. The formation of single-phase material was confirmed by X-ray studies, and it was found to be rhombohedral structure at room temperature. Under scanning electron microscope, grains separated by well-defined boundaries are visible, which is in good agreement with impedance analysis. The BNKLT ceramic shows excellent piezoelectric properties and the optimum properties measured are: d ₃₃=251 pC/N, g ₃₃=24×10⁻³ mV/N, k _p =30.5% and k _t =28.1%. A complex impedance spectroscopy (CIS) study has been carried out to investigate the electrical properties. Impedance and modulus plots helped to separate the grain and grain boundary to the overall polarization or electrical behavior. CIS analysis suggests the presence of temperature-dependent relaxation process in the material. A possible hopping mechanism for electrical transport processes in the studied material is evident from the modulus analysis. The modulus mechanism indicates the non-Debye type of conductivity relaxation in the materials, which is supported by impedance data. The activation energies have been calculated from impedance (E _τ =0.58 eV) and electric modulus (E _τ =0.40 eV) studies, which suggests that the conduction is ionic in nature. The variation in width of the curves, M"/M"_maxM'/M'_{\max} and Z"/Z"_maxZ'/Z'_{\max} at FWHM, allows to conform that the relaxation process involved is of non-Debye type.     

Electrical analysis of a newly synthesized rare earth double perovskite oxide: Sr2CeNbO6

A polycrystalline rare earth double perovskite oxide, strontium cerium niobate, Sr₂CeNbO₆ (SCN) is synthesized by solid state reaction technique for the first time. Impedance spectroscopy is employed to determine the electrical parameters (resistance (R), capacitance (C) and relaxation time (τ)) of SCN in a temperature range from 303 to 703 K and in a frequency range from 100 Hz to 1 MHz. The spectrum of imaginary part of complex impedance (Z″) at each temperature exhibits one relaxation peak. The modified Cole-Cole equation is used (experimental data is fitted with this model) to describe these relaxation peaks. Scaling behaviour of Z″ suggests that the relaxation describes the same mechanism at the entire temperature range. Impedance data of SCN that have capacitive and resistive components is represented by Nyquist diagram. The experimental impedance data is fitted using equivalent RC circuit at various temperatures. The grain conduction and τ follow an Arrhenius law associated with activation energy 0.87 and 0.88 eV, respectively.     

The impedance spectroscopic study and dielectric relaxation in A(Ni1/3Ta2/3)O3 [A=Ba,Ca and Sr]

We present the results of impedance spectroscopic study with its analytical interpretations in the framework of electric modulus formalism for Barium Nickel Tantalate Ba(Ni_1/3Ta_2/3)O₃ (BNT), Calcium Nickel Tantalate Ca(Ni_1/3Ta_2/3)O₃ (CNT) and Strontium Nickel Tantalate Sr(Ni_1/3Ta_2/3)O₃ (SNT) synthesized by the solid-state reaction technique. The results of powder X-ray diffraction study reveal that BNT and SNT crystallize in cubic structure with lattice parameter a=4.07 Å and 3.98 Å respectively, whereas CNT crystallizes in monoclinic structure having lattice parameters, a=5.71 Å, b=13.45 Å and c=5.47 Å with β=118.3°. The logarithmic angular frequency dependence of the real part of complex dielectric permittivity and loss tangent as a function of temperature indicate significant dielectric relaxation in the samples, which have been explained by the Debye theory. The frequency dependence of the loss peak and the imaginary part of electrical modulus are found to obey the Arrhenius law. The relaxation mechanism of these samples is modeled by the Cole–Cole equation. This confirms that the polarization mechanism in BNT, CNT and SNT is due to the bulk effect arising in semiconductive grains. The scaling behavior of imaginary part of electric modulus M″ suggests that the relaxation describes the same mechanism at various temperatures but relaxation frequency is strongly temperature dependent. The normalized peak positions of tan δ/tan δ_m and M″/M″_m versus log ω for BNT, CNT and SNT do not overlap completely and are very close to each other. These indicate the presence of both long-range and localized relaxation. Due to their high dielectric constant and low loss tangent, these materials may find several technological applications such as in capacitors, resonators, filters and integrated circuits.     

Electrical conductivity of (Er,U)O2+x and (Ce,U)O2+x

The electrical conductivity (σ) of (Er_yU_1−y)O_2+x (y=0.06, 0.20) and (Ce_yU_1−y)O_2+x (y=0.05, 0.15, 0.25) has been measured as a function of oxygen partial pressure in the temperature range of 1100≤T/°C≤1300 by a d.c. 4-probe method. Both of the oxides exhibited Po₂-regions where the electrical conductivity is independent of oxygen partial pressure, which indicates that doped Er and Ce exist as trivalent cations on uranium sites and fix the hole concentration by acting as electron acceptors, i.e. [h]=[Er′_U] and [h]=[Ce′_U], respectively. It is considered that strong oxidization tendency of uranium and reduction tendency of cerium simultaneously render the cerium ions exist exclusively as Ce³⁺ in the uranium dioxide. The electron-hole mobility of (Er_yU_1−y)O_2+x and (Ce_yU_1−y)O_2+x in the Po₂ region where σ is constant has been calculated by the combination of the electrical conductivity and charge carrier concentration; the activation energy (E_H) of each oxide has been obtained from the temperature dependence of the mobility. Small polaron hopping conduction mechanism was confirmed by small magnitude of the mobility (0.018-0.052 cm² V⁻¹ s⁻¹) and the activation energy (0.12-0.22 eV).     

BiFeO3 ceramic matrix with Bi2O3 or PbO added: Mössbauer, Raman and dielectric spectroscopy studies

In this paper Mössbauer, Raman and dielectric spectroscopy studies of BiFeO₃ (BFO) ceramic matrix with 3 or 10 wt% of Bi₂O₃ or PbO added, obtained through a new procedure based on the solid-state method, are presented. Mössbauer spectroscopy shows the presence of a single magnetically ordered phase with a hyperfine magnetic field of 50 T. Raman spectra of BFO over the frequency range of 100-900 cm⁻¹ have been investigated, at room temperature, under the excitation of 632.8 nm wavelength in order to evaluate the effect of additives on the structure of the ceramic matrix. Detailed studies of the dielectric properties of BiFeO₃ ceramic matrix like capacitance (C), dielectric permittivity (ε) and dielectric loss (tan δ), were investigated in a wide frequency range (1 Hz-1 MHz), and in a temperature range (303-373 K). The complex impedance spectroscopy (CIS) technique, showed that these properties are strongly dependent on frequency, temperature and on the added level of impurity. The temperature coefficient of capacitance (TCC) of the samples was also evaluated. The study of the imaginary impedance (−Z″) and imaginary electric modulus (M″) as functions of frequency and temperature leads to the measurement of the activation energy (E_ac), which is directly linked to the relaxation process associated with the interfacial polarization effect in these samples.     

Theoretical studies of structural, elastic, electronic and lattice dynamic properties of AlxYyB1−x−yN quaternary alloys

A theoretical study on the structural, elastic, electronic and lattice dynamic properties of Al_xY_yB_1−x−yN quaternary alloys in zinc-blend phase has been carried out with first-principles methods. Information on the lattice parameter, the lattice matching to available substrates and energy band-gaps is a prerequisite for many practical applications. The dependence of the lattice parameter a, bulk modulus B, elastic constants C₁₁, C₁₂ and C₄₄, band-gaps, optical phonon frequencies (ω_TO and ω_LO), the static and high-frequency dielectric coefficients ε (0) and ε (∞) and the dynamic effective charge Z^? were analyzed for y=0, 0.121, 0.241, 0.362 and 0.483. A significant deviation of the bulk modulus from linear concentration dependence was observed. A set of isotropic elastic parameters and related properties, namely bulk and shear moduli, Young's modulus, Poisson's ratio are numerically estimated in the frame work of the Voigt-Reuss-Hill approximation. The resistance to changes in bond length and lateral expansion in Al_xY_yB_1−x−yN increase with increasing y concentration. We observe that at y concentration about 0.035 and 0.063, Al_xY_yB_1−x−yN changes from brittle to ductile and Γ-X indirect fundamental gap becomes Γ-Γ direct fundamental gap. There is good agreement between our results and the available experimental data for the binary compound AlN, which is a support for those of the quaternary alloys that we report for the first time.     

Luminescent properties of HTP AgGd1−xW2O8:Eux and AgGd1−x(W1−yMoy)2O8:Eux phosphor for white LED

Intense red phosphors, AgGd_1−xEu_x(W_1−yMo_y)₂O₈ (x=0.0-1.0, y=0.0-1.0), have been synthesized through traditional solid-state reaction and characterized by X-ray diffraction (XRD) and photoluminescence (PL). XRD results reveal that AgGd_1−xEu_xW₂O₈ synthesized at 1000 °C has a tetragonal crystal structure, which is named as high temperature phase (HTP) AgGdW₂O₈. All phosphors compositions with Eu³⁺ show red and green emission on excitation either in the charge-transfer or Eu³⁺ levels. Analysis of the emission spectra with different Eu³⁺ concentrations reveal that the optimum dopant concentration for Eu³⁺ is x=0.6 in the HTP AgGd_1−xEu_xW₂O₈ (x=0.0-1.0). Studies on the AgGd_0.4Eu_0.6(W_1−yMo_y)₂O₈ (y=0.0-1.0) and AgGd_1−xEu_x(W_0.7Mo_0.3)₂O₈ (x=0.0-1.0) show that the emission intensity is maximum for compositions with y=0.3 and x=0.5, respectively, and a decrease in emission intensity is observed for higher y or x values. The Mo⁶⁺ and Eu³⁺ co-doped AgGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped AgGd(WO₄)₂ in UV region. The intense emission of the tungstate/molybdate phosphors under 394 and 465 nm excitations, respectively, suggests that these materials are promising candidates as red-emitting phosphors for near-UV/blue GaN-based white LED for white light generation.     

Electric quadrupole interaction of Cd in (Ce1−xLax)Ru2 and (Ce1−yCay)Ru2 synthesized at high pressure

Quasibinary Laves systems (Ce_1−xLa_x)Ru₂ and (Ce_1−yCa_y)Ru₂ doped with ¹¹¹In were synthesized at a pressure of 8 GPa, and variations of the electric quadrupole interaction of ¹¹¹Cd at the Ru sites have been studied by the method of time-differential perturbed angular correlation in a wide range of Ce-La and Ce-Ca relative concentrations. In the first case two sites with quadrupole frequencies ν_Q≅220 and 150 MHz persist at x≤0.2, while at x≥0.3 only the higher frequency component remains in the spectra, which are similar to that of pure LaRu₂. In the series (Ce_1−yCa_y)Ru₂, at y≥0.03 the lower frequency component was washed out except in samples with y=0.1 and 0.2, where it was restored.     

Luminescent properties of KGd1−x(WO4)2:Eux and KGd1−x(WO4)2−y(MoO4)y:Eux phosphors in UV-VUV regions

KGd_1−x(WO₄)_2−y(MoO₄)_y:Eu³⁺_x(0.1?x?0.75, y=0 and 0.2) phosphors are synthesized through traditional solid-state reaction and their luminescent properties in ultraviolet (UV) and vacuum ultraviolet (VUV) regions are investigated. Under 147 nm excitation, these phosphors show characteristic red emission with good color purity. In order to improve their emission intensity, the MoO₄²⁻ (20 wt%) is introduced into the anion of KGd_1−x(WO₄):Eu³⁺_x. The Mo⁶⁺ and Eu³⁺ co-doped KGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped KGd(WO₄)₂ in VUV region. The chromaticity coordination of KGd_0.45(WO₄):Eu³⁺_0.55 is (x=0.669, y=0.331), while that of KGd_0.45(WO₄)_1.8(MoO₄)_0.2:Eu³⁺_0.55 is (x=0.666, y=0.334) in VUV region.     

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.     

Theoretical investigation of the conduction and valence band offsets of GaAs1−x Nx/GaAs1−yNy heterointerfaces

Theoretical investigations of the conduction band offset (CBO) and valence band offset (VBO) of the relaxed and pseudo-morphically strained GaAs_1−xN_x/GaAs_1−yN_y heterointerfaces at various nitrogen concentrations (x and y) within the range 0-0.05 and along the [0 0 1] direction are performed by means of the model-solid theory combined with the empirical pseudopotential method under the virtual crystal approximation that takes into account the effects of the compositional disorder. It has been found that for y < x, the CBO and VBO have negative and positive signs, respectively, whereas the reverse is seen when y > x. The band gap of the GaAs_1−xN_x over layer falls completely inside the band gap of the substrate GaAs_1−yN_y and thus the alignment is of type I (straddling) for y < x. When y > x, the alignment remains of type I but in this case it is the band gap of the substrate GaAs_1−yN_y which is fully inside the band gap of the GaAs_1−xN_x over layer. Besides the CBO, the VBO and the relaxed/strained band gap of two particular cases: GaAs_1−xN_x/GaAs and GaAs_1−xN_x/GaAs_0.98N_0.02 heterointerfaces have been determined.     

Electrical property of HfOxNy-HfO2-HfOxNy sandwich-stack films

The effects of HfO_xN_y on the electrical property of HfO_xN_y-HfO₂-HfO_xN_y sandwich-stack (signed as SS) films were investigated. Excellent electrical performances were achieved in SS films, with a high dielectric constant of 16 and a low leakage current of ∼2 × 10⁻⁸ A/cm² at 1 MV/cm. Schottky (SK) emission and Frenkel-Poole (PF) emission are found to be the dominant mechanisms for the current conduction behavior. After a long time stress, the flat-band voltage shift in the SS film is much smaller than that in a pure HfO_xN_y film indicating fewer charge traps existed in the SS film. Based on the experiments, the new SS structure is more favorable for the improvement of electrical performances than a pure HfO_xN_y or HfO₂ structure.     

Synthesis and physical properties of negative thermal expansion materials Zr1−xMxW2O8−y (M=Sc, In, Y) substituted for Zr(IV) sites by M(III) ions

Zr_1−xM_xW₂O_8−y (M=Sc, In and Y) solid solutions substituted up to x=0.04 for Zr(IV) sites by M(III) ions were synthesized by a solid-state reaction. X-ray diffraction experiments from 90 to 560 K revealed that all solid solutions had a cubic crystal structure and showed negative thermal expansion coefficients. The lattice parameters of Zr_1−xM_xW₂O_8−y were smaller than that of ZrW₂O₈ probably due to oxygen defects, though the ionic radii of substituted M³⁺ ions were larger than that of Zr⁴⁺. Order-disorder phase transition temperatures of the substituted samples drastically decreased in the order of Y, In and Sc compared to the percolation theory, and decreased with increasing M content.     

Composition stability limits for the rocksalt-structure phase (Pb1−ySny)1−xTex from lattice parameter measurements

The lattice parameters at 25°C have been measured on powders with a precision of one part in 3(10⁴) for (Pb_1−ySn_y)_1−xTe_x for y = 1·0, 0·90, 0·80,and0·00 and values of x both without and, for the first threey-values, within the composition stability range. For the first threey-values, the composition stability limits for samples metal-saturated at 400°C is 0·5000 ± 0·0002, while those for samples Te-saturated at 356°C is x = 0·5070fory = 1·0, x = 0·5056fory = 0·90,andx = 0·5038fory = 0·80. The fine powders pick up oxygen quickly in air, which reacts with the Pb and Sn upon heating to deplete the telluride solid-solution of metal and consequently reduce its parameter by 2–3(10⁻³)Å. The metals are substantially all returned to the telluride phase upon H₂-reduction at 500–600°C. The present results for SnTe are used to extend the sources of data used in an analysis of SnTe. This analysis shows that the ratio of the number of valence band holes per Sn-vacancy, c, to the 77°K Hall factor, r, is 3·2 ± 0·3 over the entire range of 3(10¹⁹) to 1·8(10²¹) cm⁻³ in the apparent hole concentration. The results for the solid solutions are extrapolated to give the atomic fraction of Te in the 356°C, Te-saturated solid solution for y < 0·8. Comparison with the electrical measurements of others gives c/r equal to about unity for y = 0·27and0·13.     

Modification of dielectric relaxations in sodium bismuth titanate with samarium doping

Na_0.5Bi_(0.5−x) Sm_xTiO₃ (NBST) ceramics with x=0.05, 0.1, and 0.15 are prepared through chemical route. The X-ray diffraction studies confirmed the formation of single phase. Dielectric measurements in the temperature region ranging from room temperature (∼30 °C) to 600 °C at different frequencies (10 kHz-1 MHz) showed anomalies at 130, 306, and 474 °C (at 10 kHz frequency) for x=0.05 sample. Other samples showed only two peaks. To establish the electrical nature of these relaxations, impedance measurements are done at different temperatures and frequencies. The relaxation time, obtained from both impedance and modulus data, is found to decrease with increase in temperature. The relaxations observed are of non-Debye type. Increase in samarium content increases the activation energy for relaxation.