Dielectric relaxation, conductivity behaviour and magnetic properties of Mg substituted Ni-Li ferrites

The dielectric properties of Mg substituted Ni-Li spinel ferrites synthesized by sol-gel auto combustion process have been studied using impedance measurements in the frequency range from 10 Hz to 10 MHz and in the temperature range from 310 K to 473 K. The effect of frequency, temperature and composition on dielectric constant (?′), dielectric loss (tan δ) and conductivity (σ) has been discussed in terms of hopping of charge carriers between Fe²⁺ and Fe³⁺ ions. The electrical modulus formulism has been employed to study the relaxation dynamics of charge carriers and the results indicate the presence of non-Debye type of relaxation in the present ferrites. Similar values of activation energies for dc conduction (E_dc) and for conductivity relaxation (E_M″) reveal that the mechanisms of electrical conduction and dielectric polarization are same in these ferrites. A single ‘master curve’ for normalized plots of all the modulus isotherms observed for a given composition indicates the temperature independence of dynamical process for charge carriers. The saturation magnetization and coercivity have been calculated from the hysteresis loop measurements and show striking dependence on the composition.     

Charge compensation, electrical and dielectric behavior of lanthanum doped CaCu3Ti4O12

Mechanism of charge compensation on lanthanum, (La³⁺) substitution on Ca site in calcium copper titanate (CaCu₃Ti₄O₁₂), and its effect on resulting electrical and dielectric properties has been studied in the present investigation. For this purpose samples were prepared according to two stoichiometries viz. La_xCa_(1−3x/2)Cu₃Ti₄O₁₂ (x ≤ 0.09) and La_xCa_(1−x)Cu₃Ti₄O₁₂ (x = 0.03) by solid state ceramic route. The former represents ionic compensation while the later is in accordance with electronic compensation. Nature of charge carriers is identified by measuring Seebeck coefficient which is found to be negative in the entire range of measurement. In order to understand the mechanism of conduction, ac conductivity is measured as a function of temperature and frequency. Space charge polarization is the dominant polarization mechanism phenomenon at low frequency and high temperature while orientation polarization dominates at low temperature and high frequency. Impedance analysis confirms the formation of internal barrier layers which is responsible for high dielectric constant in these samples.     

Dielectric properties of Cu substituted Ni0.5−xZn0.3Mg0.2Fe2O4 ferrites

Dielectric properties of Cu substituted Ni-Zn-Mg ferrite samples having the general formula Ni_0.5−xCu_xZn_0.3Mg_0.2Fe₂O₄ (where x = 0.0, 0.1, 0.2, 0.3, 0.4, and 0.5) synthesized by Pramanik method are reported. The single phase formation of the ferrites was confirmed by XRD technique. The lattice parameter is found to increase with increase in Cu content. Average grain size, obtained from SEM micrographs, is found to increase with increase in Cu content. Dielectric parameters were measured as a function of frequency at room temperature as well as at higher temperatures. The variation in dielectric constant (?′) with temperature at four different fixed frequencies viz. 1 kHz, 10 kHz, 100 kHz, and 1 MHz was also studied. The room temperature dielectric constant (?′) and dielectric loss (tan δ) are found to decrease with increase in frequency. The ac conductivity (σ_ac) is found to increase with increase in the frequency.     

Electrical conduction and dielectric relaxation process in Ce0.8Y0.2O1.9 electrolyte system

In this work, we present the electrical conductivity and dielectric relaxation studies of 20 mol% yttria doped ceria (Ce_0.8Y_0.2O_1.9) electrolyte prepared by mechanical milling technique. The ac conductivity was found to obey the universal dielectric response at low temperatures. At high temperatures, the conductivity value estimated from the high frequency plateau agreed with the bulk conductivity (σ_b) obtained form the impedance spectra and the low frequency plateau value agreed with the grain boundary conductivity (σ_gb). Temperature dependence of σ_b and σ_gb gives the activation energies for conduction in the bulk and grain boundary. Two relaxation peaks were observed in the tan delta spectra; the high frequency relaxation peak is due to the bulk conduction and the low frequency peak result from the grain boundary conduction. The migration energy E_M and the energy required for the creation of free oxygen vacancies assisting oxide ion migration E_O is estimated from the resonant frequency and maxima of the tan delta spectra of these relaxation peaks. The sums of these two values in the low and high frequency peaks are nearly equal to the activation energies obtained from the bulk and grain boundary conductivity plot.     

Dielectric relaxation and conduction mechanism in LaNi3/4M1/4O3 (M = Mo, W) at low temperature

In order to investigate the electrical transport in LaNi_3/4Mo_1/4O₃ and LaNi_3/4W_1/4O₃, the dc conductivity and dielectric properties in these polycrystalline materials are investigated in the temperature range from 163 K to 383 K and frequency range from 50 Hz to 1 MHz. The X-ray diffraction patterns of the samples show monoclinic phase at room temperature. The homogeneity of the samples is determined by energy dispersive analysis of X-ray (EDAX) attached with a scanning electron microscope. The temperature dependence of dc conductivity shows the semiconducting nature of the materials. The complex impedance plane plots show that the relaxation (conduction) mechanism in these materials is purely a bulk effect arising from the semiconductive grains. The frequency-dependent electrical data are also analyzed in the framework of ac conductivity formalism. The ac conductivity spectra follow the universal power law. The activation energies required for bulk conduction is 0.143 and 0.165 eV for LNM and LNW respectively. The scaling behaviour of loss tangent suggests that the relaxation describes the same mechanism at various temperatures.     

Improved dielectric and non-ohmic properties of Ca2Cu2Ti4O12 ceramics prepared by a polymer pyrolysis method

Non-ohmic and dielectric properties of Ca₂Cu₂Ti₄O₁₂ (CaCu₃Ti₄O₁₂/CaTiO₃ composite) ceramics prepared by a polymer pyrolysis method (PP-ceramic samples) are investigated. The PP-ceramics show a highly dense structure and improved non-ohmic and dielectric properties compared to the ceramics obtained by a solid state reaction method (SSR-ceramic samples). ?′ (tan δ) of the PP-ceramic samples is found to be higher (lower) than that of the SSR-ceramic samples. Interestingly, the PP-ceramic sintered at 1050 °C for 10 h exhibits the high ?′ of 2530 with weak frequency dependence below 1 MHz, the low tan δ less than 0.05 in the frequency range of 160 Hz-177 kHz, and the little temperature coefficient, i.e., |Δ?′| ≤ 15 % in the temperature range from −55 to 85 °C. These results indicate that the CaCu₃Ti₄O₁₂/CaTiO₃ composite system prepared by PP method is a promising high-?′ material for practical capacitor application.     

Nd:YAG laser irradiation effects on electrical properties of polycrystalline Li0.5Fe2.5O4

The polycrystalline spinel structured Li_0.5Fe_2.5O₄ ferrite have been prepared by conventional double sintering ceramic method. The samples were palletized and irradiated by Nd:YAG laser with different laser fluencies and characterized by infrared spectroscopy and DC electrical resistivity in order to obtain phase, crystal structure and conduction mechanism in pristine and irradiated samples. The infrared spectroscopy is employed to study the local symmetry and conduction mechanism in crystalline solids before and after irradiation. The DC electrical resistivity measured by two-probe technique from room temperature to beyond Curie temperature with steps of 10 K increases after laser irradiation. Variation of dielectric properties like dielectric constant and dielectric loss tangent is also measured as a function of temperature. A significant reduction in the values of dielectric constant and dielectric loss tangent has been observed with the increase of laser dose.     

Origin of giant dielectric constant in Ba[(Fe1−xCox)1/2Nb1/2]O3

The X-ray diffraction Rietveld refinement of Ba[(Fe_1−xCo_x)_1/2Nb_1/2]O₃ with 0 ≤ X ≤ 1 shows cubic structure formation with space group P_m3_m. No distinct tilting of oxygen octahedron is observed. The dielectric measurement of such a cubic system exhibited giant values (?′ > 10⁴) in the temperature range of 298-483 K and frequency range of 10²-10⁵ Hz. An analysis of the permittivity, electric modulus, and electrical conductivity properties in these systems confirmed the presence of oxygen vacancies induced dipolar relaxation. Our investigations show that the observed extremely high dielectric constant values are predominantly the result of oxygen vacancies induced dipoles produced at the grain boundaries. Additional significant intrinsic contributions to the permittivity comes from the directly doped electrons at the unit cell, as indicated by the enhancement in the observed values of the permittivity on replacement of Fe³⁺ (3d⁵) by Co³⁺ (3d⁶). The contributions of the doped free charges and the oxygen vacancy induced dipoles are separated using the Jump Relaxation Model.     

Structure, dielectric and electric properties of (Ba0.68−xSr0.308Bi0.006Na0.006Mgx)(Ti0.99Sn0.01)O3 ceramics

(Ba_0.68−xSr_0.308Bi_0.006Na_0.006Mg_x)(Ti_0.99Sn_0.01)O₃ ceramics were synthesized by solid-state reaction process. The samples (X ≤ 0.010) are a mixture of cubic (major) and rhombohedral (minor) phases. The rhombohedral phase causes a large dielectric loss in low temperature regions and plays an important role in diffuse phase transition of ceramics. While X > 0.010, the rhombohedral phase decreases and gradually disappears. The dielectric loss of ceramics in the low temperature regions decreases, and the samples change from the diffuse phase transition to the phase transition of second order, and then to of first order. In the temperature range of 270-370 °C, intrinsic conduction dominates conductivity of ceramics.     

Dielectric properties of polycrystalline Cu-Zn ferrites at microwave frequencies

The real dielectric constant ?′ and complex dielectric constant ?″ of Cu_1−xZn_xFe₂O₄ have been measured at room temperature in the high frequency range 1 MHz to 1.8 GHz. At low frequencies the dielectric loss is found to be constant up to 1.4 GHz and there is a sudden rise at 1.5 GHz. A qualitative explanation is given for the composition, frequency dependence of the dielectric constant and dielectric loss of Cu_1−xZn_x Fe₂O₄. These are correlated with the W-H plot which gives the information about change in the average crystal size and strain of the samples. The micro-morphological features of the samples were obtained by Scanning Electron Microscopy (SEM). The micrograph shows that the increase of the Zn content in Cu ferrite increases the grain size.     

Ferroelectric relaxor behavior and dielectric spectroscopic study of 0.99(Bi0.5Na0.5TiO3)-0.01(SrNb2O6) solid solution

0.99(Bi_0.5Na_0.5TiO₃)-0.01(SrNb₂O₆) was prepared by simple solid state reaction route. Material stabilized in rhombohedral perovskite phase with lattice constants a = 3.9060 Å, α = 89.86° and a_h = 5.4852 Å, c_h = 6.7335 Å for hexagonal unit cells. Density of material was found 5.52 g_m/cm³ (92.9% of theoretical one) in the sample sintered at 950 °C. The temperature dependent dielectric constant exhibits a broad peak at 538 K (?_m = 2270) at 1 kHz that shows frequency dependent shifts toward higher temperature - typical relaxor behavior. Modified Curie-Weiss law was used to fit the dielectric data that exhibits almost complete diffuse phase transition characteristics. The dielectric relaxation obeys the Vogel-Fulcher relationship with the freezing temperature 412.4 K. Significant dielectric dispersion is observed in low frequency regime in both components of dielectric response and a small dielectric relaxation peak is observed. Cole-Cole plots indicate polydispersive nature of the dielectric relaxation; the relaxation distribution increases with increase in temperature.     

Dielectric and ferroelectric properties and electric conductivity of sol-gel derived PBZT ceramics

(Pb_1−xBa_x)(Zr_1−yTi_y)O₃ (PBZT) is a solid solution in which ferroelectric, relaxor or antiferroelectric properties are observed depending on composition. The substitution of Ba²⁺ into A position of the perovskite structure leads to the decrease in phase transition temperature and it gradually leads to relaxor properties. The majority of papers describe PBZT obtained from oxides. We report the results of the investigation of the properties and phase transitions of (Pb_1−xBa_x)(Zr_0.65Ti_0.35)O₃ ceramics with x = 0.09, 0.25 and 0.35 obtained by the sol-gel method with final free sintering (FS) at 1573 K/4 h and by the hot pressing (HP) method at 1473 K/2 h/20 MPa. Unlike pure PZT, the properties of HP-PBZT samples obtained at lower (1473 K) temperature are a little inferior than FS samples. It is probably related to the fact that barium requires higher final sintering temperatures.We present the results of XRD and dielectric measurements vs. temperature for PBZT ceramics. On the basis of dielectric measurements a.c. conductivity and activation energies have been calculated. In agreement with earlier literature data, we note that with the increasing Ba content T_m decreases and the maximum of ?(T) is wider. However, we do not observe a shift of T_m with increasing frequency. The room P(E) hysteresis loops become more narrow and the polarization is smaller. The increase in dielectric losses with increasing temperature makes the measurement of hysteresis loops at low frequencies and high temperatures difficult.     

AC conductivity and dielectric properties of GeSexTl0.3 amorphous thin films

AC conductivity and dielectric properties have been studied for amorphous thin films with different thicknesses of glassy system GeSe_xTl_0.3 with X = 3, 4 that prepared with thermal evaporation technique. The measurements are taken at temperature range (303-403 K) and frequency range (10²-10⁵ Hz).AC conductivity σ_ac(ω) is found to be proportional to ω^s where s < 1. The temperature dependence of the ac conductivity and the parameter s can be discussed with the aim of the correlated barrier-hopping (CBH) model.The dielectric constant ?′and the dielectric loss ?″ showed frequency and temperature dependence. The maximum barrier height W_M calculated from the dielectric measurements according to Giuntini equation are in good agreement with that proposed by the theory of hopping of charge carriers over a potential barrier as suggested by Elliott in the case of chalcogenide glasses.     

Spectroscopic and dielectric studies of meso-tetrakis(p-sulfonatophenyl) porphyrin doped hybrid borate glasses

Hybrid borate glasses containing different concentrations of meso-tetrakis(p-sulfonatophenyl) porphyrin sodium salt (TPPS₄) were prepared. The obtained glass samples were found to be transparent and homogeneous. Formation of TPPS₄-J-aggregates in borate glass was investigated by means of optical absorption, steady state and time resolved fluorescence spectroscopy. The hybrid glasses exhibit a strong S₂→S₀ emission at ∼473 nm and J-aggregates show emission at ∼733 nm. Time resolved fluorescence show two exponential decay with lifetime of τ₁ = 65 ± 10 ps (∼80%) and τ₂ = 3.87 ± 0.1 ns (∼20%) respectively. Dielectric properties such as dielectric constant (?′), dielectric loss (tan δ) and ac conductivity (σ_ac) over a range of frequency and temperature of these glasses were studied. The ac conductivity was found to be proportional to ω^s (where s < 1). The observed change in dielectric parameters due to different concentrations of TPPS₄ has been analyzed in light of different polarization mechanisms.     

Effect of Gd doping on magnetic, electric and dielectric properties of MgGdxFe2−xO4 ferrites processed by solid state reaction technique

MgGd_xFe_2−xO₄ (x = 0.0, 0.05, 0.1 and 0.15) ferrites, with improved dc resistivity, initial permeability, saturation magnetization, and extremely low relative loss factor, have been synthesized by solid state reaction technique. The microstructures, electric, dielectric and magnetic properties have been investigated by means of X-ray diffraction, Keithley 2611 system, impedance analyzer and VSM respectively. The addition of Gadolinium in Mg ferrite has been shown to play a crucial role in enhancing the electric, dielectric and magnetic properties. The dc resistivity is increased by two orders of magnitude as compared to Mg ferrite. Saturation magnetization has been increased by two times and remnant magnetization has been increased by more than three times due to the doping of Gd³⁺ ions in Mg ferrite. The relative loss factor was found to have very low values and is of the order of 10⁻⁴-10⁻⁵ in the frequency range 0.1-30 MHz. The variations of electric, dielectric and magnetic properties of the samples have been studied as a function of frequency and Gd³⁺ ions concentration measured at room temperature. High resistivity and improved magnetic properties can be correlated with better compositional stoichiometry and the replacement of Fe³⁺ ions by Gd³⁺ ions. The mechanisms responsible to these results have been discussed in this paper.     

Study of structural, dielectric and electrical behavior of (1 − x)Ba(Fe0.5Nb0.5)O3-xSrTiO3 ceramics

Polycrystalline samples of BaFe_0.5Nb_0.5O₃ and (1 − x)Ba(Fe_0.5Nb_0.5)O₃-xSrTiO₃ [referred as BFN and BFN-ST respectively] (x = 0.00, 0.15 and 0.20) have been synthesized by a high-temperature solid-state reaction technique. The XRD patterns of the BFN and BFN-ST at room temperature show a monoclinic phase. The microstructure of the ceramics was examined by the scanning electron microscopy (SEM) and shows the polycrystalline nature of the samples with different grain sizes, which are inhomogeneously distributed through the sample surface. Detailed studies of dielectric and impedance properties of the materials in a wide range of frequency (100 Hz-5 MHz) and temperatures (30-270 °C) showed that properties are strongly temperature and frequency dependent. Complex Argand plane plot of ?″ against ?′, usually called Cole-Cole plots is used to check the polydispersive nature of relaxation phenomena in above mentioned compounds. Relaxation phenomena of non-Debye type have been observed in the BFN and BFN-ST ceramics, as confirmed by the Cole-Cole plots.     

Enhanced magnetoelectric properties in Bi0.95Ho0.05FeO3 polycrystalline ceramics

Polycrystalline samples of Ho doped BiFeO₃ were prepared by solid state reaction method and effect of partial substitution of Ho on dielectric, magnetic and ferroelectric properties was studied. High temperature dielectric results show two dielectric anomalies both in ? and tan δ, out of which, anomaly at higher temperature (∼400 °C) could be ascribed to antiferromagnetic Néel temperature which, is a signature of magnetoelectric coupling. The magnetic moment is greatly improved and the maximum magnetization was found to be 0.736 emu/g. Saturated ferroelectric hysteresis loops were observed for Bi_0.95Ho_0.05FeO₃ with remnant polarization (P_r) = 1.59 μC/cm², maximum polarization (P_max) = 2.56 μC/cm² and coercivity (E_c) = 5.45 kV/cm. We have conducted comprehensive magnetoelectric and magnetodielectric properties at room temperature. Magnetic field induced ferroelectric hysteresis loop observed in Bi_0.95Ho_0.05FeO₃ is of prime importance.     

High-dielectric-constant and low-loss microwave dielectric in the (1 − x)La(Mg0.5Ti0.5)O3-x(Ca0.8Sr0.2)TiO3 solid solution system

The microwave dielectric properties and microstructures of (1 − x)La(Mg_0.5Ti_0.5)O₃-x(Ca_0.8Sr_0.2)TiO₃ ceramics, prepared by a mixed oxide route, have been investigated. The forming of solid solutions was confirmed by the XRD patterns and the measured lattice parameters for all compositions. A near zero τ_f was achieved for samples with x = 0.5, although the dielectric properties varied with sintering temperature. The Q × f value of 0.5La(Mg_0.5Ti_0.5)O₃-0.5(Ca_0.8Sr_0.2)TiO₃ increased up to 1475 °C, after which it decreased. The decrease in dielectric properties was coincident with the onset of rapid grain growth. The optimum combination of microwave dielectric properties was achieved at 1475 °C for samples where x = 0.5 with a dielectric constant ?_r of 47.12, a Q × f value of 35,000 GHz (measured at 6.2 GHz) and a τ_f value of −4.7 ppm/°C.     

Studies on the magnetic, magnetostrictive and electrical properties of sol-gel synthesized Zn doped nickel ferrite

Zinc doped nickel ferrite i.e., Ni_1−xZn_xFe₂O₄ (0 ≤ x ≤ 0.6) have been prepared by using sol-gel method. X-ray diffraction of these samples shows the presence of single-phase cubic spinel structure. The room temperature magnetic measurements showed that saturation magnetization (M_s) increases with the substitution of Zn²⁺ ions up to x = 0.4 and thereafter it begins to decrease, whereas magnetostriction (λ) value decreases with the addition of Zn²⁺ in the Ni-Zn ferrite. Dielectric permittivity (?′), dielectric loss tangent (tan δ) and AC conductivity (σ_AC) for all the prepared samples have been studied as a function of frequency and composition in the range from 0.05 Hz to 10 MHz at room temperature. It has been observed that initially ?′, tan δ and σ_AC decreases with the substitution of Zn²⁺ up to x = 0.4 and then increases with the further addition of Zn²⁺ ions. Variation in the slope parameter s with zinc contents indicates the presence of different type of conduction mechanism in different compositions. The dielectric loss curves exhibit relaxation peaks which shift with the addition of Zn contents. The results have been explained on the basis of space charge polarization according to Maxwell-Wagner's two-layer model and the hopping of charges between Fe²⁺ and Fe³⁺ as well as between Ni³⁺ and Ni²⁺ ions at the octahedral sites.     

Electric and dielectric behavior of CaCu3Ti4O12-based thin films obtained by soft chemical method

CaCu₃Ti₄O₁₂ (stoichiometric) and Ca_1.1Cu_2.9Ti₄O₁₂ (non-stoichiometric) thin films have been prepared by the soft chemical method on Pt/Ti/SiO₂/Si substrates, and their electrical and dielectric properties have been compared as a function of the annealing temperature. The crystalline structure and the surface morphology of the films were markedly affected by the annealing temperature and excess calcium. The films show frequency-independent dielectric properties at room temperature which is similar to those properties obtained in single-crystal or epitaxial thin films. The room temperature dielectric constant of the 570-nm-thick CCTO thin films annealed at 600 °C at 10 kHz was found to be 124. The best non-ohmic behavior (α = 12.6) presented by the film with excess calcium annealed at 500 °C. Resistive hysteresis on the I-V curves was observed which indicates these films can be used in resistance random access memory (ReRAM).