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.     

High permittivity and low dielectric loss of the Ca1−xSrxCu3Ti4O12 ceramics

The Ca_1−xSr_xCu₃Ti₄O₁₂ (CSCTO) giant dielectric ceramics were prepared by conventional solid-state method. X-ray diffraction patterns revealed that a small amount of Sr²⁺ (x < 0.2) had no obvious effect on the phase structure of the CSCTO ceramics, while with increasing the Sr²⁺ content, a second phase of SrTiO₃ appeared. Electrical properties of CSCTO ceramics greatly depended on the Sr²⁺ content. The Ca_0.9Sr_0.1Cu₃Ti₄O₁₂ ceramics exhibited a higher permittivity (71,153) and lower dielectric loss (0.022) when measured at 1 kHz at room temperature. The ceramics also performed good temperature stability in the temperature range from −50 °C to 100 °C at 1 kHz. By impedance spectroscopy analysis, all compounds were found to be electrically heterogeneous, showing semiconducting grains and insulating grain boundaries. The grain resistance was 1.28 Ω and the grain boundary resistance was 1.31 × 10⁵ Ω. All the results indicated that the Ca_0.9Sr_0.1Cu₃Ti₄O₁₂ ceramics were very promising materials with higher permittivity for practical applications.     

Dielectric and magnetic behavior of BaCd2−xSrxFe16O27 W-type hexagonal ferrites

We have prepared BaCd_2−xSr_xFe₁₆O₂₇ (x = 0, 0.5, 1, 1.5 and 2.0) W-type hexagonal ferrites by standard ceramic method. In this work, the structural, dielectric and magnetic properties have been studied of the prepared samples. The XRD analysis of the samples reveals single phase behavior sintered at 1400 °C for 6 h. The saturation magnetization (M_s) shows increasing behavior with the increasing concentration of Sr²⁺. While the coercivity (H_c) decreases rapidly up to 409 G for x = 1.5 and then increases for (x > 1.5) due to the preference of Cd²⁺ for tetrahedral sites and the number of spin-down magnetic ions. The real and imaginary parts of the dielectric constant (?′,?″) and dielectric loss tangent (tan δ) are determined in the frequency range 0.1-10⁷ Hz. It is observed that both the real and imaginary parts of the dielectric constant and tan δ decrease with the increasing concentration of Sr²⁺, which is due to the contribution of Cd²⁺ ions in addition to Fe³⁺ and Fe²⁺ ions to interfacial polarization.     

Effect of Ni substitution on the structural and transport properties of NixMn0.8−xMg0.2Fe2O4; 0.0 ≤ x ≤ 0.40 ferrite

Ni_xMn_0.8−xMg_0.2Fe₂O₄; 0.0≤ x ≤0.40 was prepared by standard ceramic technique, presintering was carried out at 900 °C and final sintering at 1200 °C with heating/cooling rate 4 °C/min. X-ray diffraction analyses assured the formation of the samples in a single phase spinel cubic structure. The calculated crystal size was obtained in the range of 75-130 nm. A slight increase in the theoretical density and decrease in the porosity was obtained with increasing the nickel content. This result was discussed based on the difference in the atomic masses between Ni (58.71) and Mn (54.938). IR spectral analyses show four bands of the spinel ferrite for all the samples. The conductivity and dielectric loss factor give nearly continuous decrease with increasing Ni-content. This was discussed as the result of the significant role of the multivalent cations, such as iron, nickel, manganese, in the conduction mechanism. Anomalous behavior was obtained for the sample with x = 0.20 as highest dielectric constant, highest dielectric loss and highest conductivity. This anomalous behavior was explained due to the existence of two divalent cations on B-sites with the same ratio, namely, Mg²⁺ and Ni²⁺.     

Magnetic and FTIR studies of BixY3−xFe5O12 (x = 0, 1, 2) powders prepared by the metal organic decomposition method

The crystallization process of bismuth substituted yttrium iron garnet (Bi_xY_3−xFe₅O₁₂; x = 0, 1, 2) powder prepared by the metal-organic decomposition method has been studied with various sintering temperatures. The pure garnet phase was observed for the x = 1 powder at 900 °C sintering temperature, whereas the x = 0, 2 powder showed secondary phases. The x = 0 powder showed a similar crystallization process to that of the solid state reaction method. For the x =1, 2 powders, it is proposed that the lowering of the crystallization temperature is due to the lowered stability of the intermediate phase. The infrared spectroscopy and magnetic properties were also investigated. The pure garnet phase showed three absorption bands located at 563, 598, 655 cm⁻¹ that shifted to 555, 588, 639 cm⁻¹ along with an increase of bismuth concentration. The maximum values of saturation and remanence magnetization and the minimum value of coercivity were observed for the x = 1 powder sintered at 900 °C, which were 20.8 emu/g, 2.67 emu/g, and 31.9 Oe, respectively.     

Effect of the sintering temperature on the properties of nanocrystalline Ca1−xSmxMnO3 (0 ≤ x ≤ 0.4) powders

Nanocrystalline Ca_1−xSm_xMnO₃ (0 ≤ x ≤ 0.4) manganites were prepared by a soft chemical method (Pechini method) followed by auto-combustion and sintering in air at 1073 or 1473 K. Single-phase powders with general composition Ca_1−xSm_xMnO₃ were obtained after 18 h annealing. The particle and grain sizes of the substituted Sm-manganites did not exhibit variation with samarium content, but increase with increasing the sintering temperature. All manganites show two active IR vibrational modes near 400 and 600 cm⁻¹ characteristic of the BO₆ octahedron vibrations.For the samples sintered at T_s = 1473 K, the partial substitution of calcium by samarium in the CaMnO₃ phase induces a marked decrease in the electrical resistivity, in the temperature range of 300-900 K, and at the same time a metal-to-insulator transition occurs; for T_s = 1073 K all the samples present semiconductor behaviour. With the increase of the annealing temperature the grain size increases and a metal-semiconductor transition appears. The results can be ascribed to the Mn⁴⁺/Mn³⁺ ratio and particle grain size. The effects of particle size on the electrical properties can be attributed to the domain status, changes in the Mn-O-Mn bond angle and Mn-O bond length.     

Polymorphic phase transition-induced electrical behavior of BiCoO3-modified (K0.48Na0.52)NbO3 lead-free piezoelectric ceramics

(1 − x)(K_0.48Na_0.52)NbO₃-xBiCoO₃ [KNN-xBC] lead-free piezoelectric ceramics were prepared by the conventional solid-state sintering method. The effects of the BiCoO₃ addition on the phase structure, dielectric, piezoelectric and ferroelectric properties of KNN-xBC ceramics were systematically investigated. The polymorphic phase transition (PPT) from rhombohedral to orthorhombic phase around room temperature was identified in the composition range of 0.01 ≤ x ≤ 0.02, and the improved electrical properties were induced by this PPT. The KNN-0.01BC ceramics near PPT exhibit optimum electrical properties: d₃₃ ∼ 165 pC/N, k_p ∼ 0.40, P_r ∼ 31.0 μC/cm², and E_c ∼ 12.6 kV/cm. These results indicate that the enhanced piezoelectric properties for alkali niobate can be achieved by forming the coexistence of rhombohedral and orthorhombic phases.     

Microwave dielectric properties of temperature stable Li2ZnxCo1−xTi3O8 ceramics

The Li₂Zn_xCo_1−xTi₃O₈ (x = 0.2-0.8) solid solution system has been synthesized by the conventional solid-state ceramic route and the effect of Zn substitution for Co on microwave dielectric properties of Li₂CoTi₃O₈ ceramics has also been investigated. The microwave dielectric properties of these ceramics show a linear variation between the end members for all compositions. The optimized sintering temperatures of Li₂Zn_xCo_1−xTi₃O₈ ceramics increase with increasing content of Zn. The specimen with x = 0.4 sintered at 1050 °C/2 h exhibits an excellent combination of microwave dielectric properties with ?_r = 27.7, Q_u × f = 57,100 GHz and τ_f = −1.0 ppm/°C.     

Thermoelectric properties of Bi2SexTe3−x prepared by Bridgman method

Bi₂Se_xTe_3−x crystals with various x values were grown by Bridgman method. The electrical conductivity, σ, was found to decrease with increasing Se content. The highest σ of 1.6 × 10⁵ S m⁻¹ at room temperature was reached at x = 0.12 with a growth rate of 0.8 mm h⁻¹. The Seebeck coefficient, S, was less dependent on Se content, all with positive values showing p-type characteristics, and the highest S was measured to be 240 μV K⁻¹ at x = 0.24. The lowest thermal conductivity, κ, was 0.7 W m⁻¹ K⁻¹ at x = 0.36. The electronic part of κ, κ_el, showed a decrease with increasing Se content, which implies that the hole concentration as the main carriers was reduced by the addition of Se. The highest dimensionless figure of merit, ZT, at room temperature was 1.2 at x = 0.36, which is attributed to the combination of a rather high electrical conductivity and Seebeck coefficient and low thermal conductivity.     

Structure and electrical properties of MnO2-doped Sr2−xCaxNaNb5O15 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics Sr_2−xCa_xNaNb₅O₁₅ + y wt% MnO₂have been prepared by the conventional solid state reaction method. Our results reveal that Ca²⁺and Mn ions have entered into the Sr₂NaNb₅O₁₅ lattices to form a solid solution with tungsten-bronze structure. The substitution of Ca²⁺ induces a decrease in piezoelectric coefficient d₃₃, electromechanical coupling factors k_p and k_t, while, the addition of Mn ions decreases the sintering temperature and effectively promotes the densification of the ceramics. The effect of substitution of Ca²⁺and Mn ions on the structure, electrical properties and diffused phase changing were investigated systematically. For the ceramic with x = 0.05 and y = 0.5, the piezoelectric, dielectric and ferroelectric properties become optimum, giving a piezoelectric coefficient d₃₃ = 190 pC/N, electromechanical coupling factors k_p = 13.4% and k_t = 36.5%, ?_r = 2123, loss tangent tan δ = 0.038, remanent polarization P_r = 4.76 μC/cm², coercive field E_c = 12.68 kV/cm, and Curie temperature T_c = 260 °C.     

CuIn1−xAlxS2 thin films prepared by sulfurization of metallic precursors

CuIn_1−xAl_xS₂ thin films (x = 0, 0.09, 0.27, 0.46, 0.64, 0.82 and 1) with thicknesses of approximately 1 μm were formed by the sulfurization of DC sputtered Cu-In-Al precursors. All samples were sulfurized in a graphite container for 90 min at 650 °C in a 150 kPa Ar + S atmosphere. Final films were studied via X-ray diffraction (XRD), scanning electron microscopy (SEM) and micro-Raman spectroscopy. It was found that all samples were polycrystalline in nature and their lattice parameters varied slightly nonlinearly from {a = 5.49 Å, c = 11.02 Å} for CuInS₂ to {a = 5.30 Å, c = 10.36 Å} for CuAlS₂. No unwanted phases such as Cu_2−xS or others were observed. Raman were recorded at a room temperature and the most intensive and dominant A₁ phonon frequency varied nonlinearly from 294 cm⁻¹ (CuInS₂) to 314 cm⁻¹ (CuAlS₂).     

Transparent p-type CuxS thin films

The effect of different mild post-annealing treatments in air, at 270 °C, for 4-6 min, on the optical, electrical, structural and chemical properties of copper sulphide (Cu_xS) thin films deposited at room temperature are investigated. Cu_xS films, 70 nm thick, are deposited on glass substrates by vacuum thermal evaporation from a Cu₂S:S (50:50 wt.%) sulphur rich powder mixture. The as-deposited highly conductive crystalline CuS (covellite) films show high carrier concentration (∼10²² cm⁻³), low electrical resistivity (∼10⁻⁴ Ω cm) and inconclusive p-type conduction. After the mild post-annealing, these films display increasing values of resistivity (∼10⁻³ to ∼10⁻² Ω cm) with annealing time and exhibit conclusive p-type conduction. An increase of copper content in Cu_xS phases towards the semiconductive Cu₂S (chalcocite) compound with annealing time is reported, due to re-evaporation of sulphur from the films. However, the latter stoichiometry was not obtained, which indicates the presence of vacancies in the Cu lattice. In the most resistive films a Cu₂O phase is also observed, diminishing the amount of available copper to combine with sulphur, and therefore the highest values of optical transmittance are reached (65%). The appearance on the surface of amorphous sulphates with annealing time increase is also detected as a consequence of sulphur oxidation and replacement of sulphur with oxygen. All annealed films are copper deficient in regards to the stoichiometric Cu₂S and exhibit stable p-type conductivity.     

Charge ordering analysis by electrical and dielectric measurements in Ca2−xPrxMnO4 (x = 0-0.2) compounds

Ca_2−xPr_xMnO₄ (0 ≤ x ≤ 0.2) polycrystalline ceramic powders were synthesized by sol-gel method. The X-ray diffraction (XRD) profiles were indexed with a tetragonal and orthorhombic structure for Ca₂MnO₄ and Pr-doped compounds, respectively. Electrical properties were investigated by dc and ac electrical measurements. The dc measurements have revealed an insulating state for all compounds in 80-350 K temperature range. Both dc and ac measurements have highlighted a charge ordering (CO) transition at T_CO = 233 and 245 K for x = 0.175 and 0.2, respectively. The CO state was found to be accompanied by a jump of the hopping activation energy and a rapid rise of both dielectric permittivity and imaginary part of ac electrical impedance.     

Relationships between Zr substitution for Ti and microwave dielectric properties in Mg(ZrxTi1−x)O3 ceramics

The influence of Zr substitution for Ti on the microwave dielectric properties and microstructures of the Mg(Zr_xTi_1−x)O₃(MZ_xT) (0.01 ≤ x ≤ 0.3) ceramics was investigated. The quality factors of Mg(Zr_xTi_1−x)O₃ ceramics with x = 0.01-0.05 were improved because the solid solution of a small amount of Zr⁴⁺ substitution in the B-site could increase density and grain size. An excess of Zr⁴⁺ resulted in the formation of a great deal of secondary phase that declined the microwave dielectric properties of MZ_xT ceramics. The temperature coefficient of resonant frequency (τ_f) of Mg(Zr_xTi_1−x)O₃ ceramics slightly increased with increasing Zr content, and the variation in τ_f was attributed to the formation of secondary phases.     

Nanocrystals of a new complex perovskite dielectric Ba2TmSbO6

Nanocrystals of a new complex perovskites ceramic oxide, barium thulium antimony oxide - Ba₂TmSbO₆, were synthesized using a single step auto-ignition combustion process. The combustion product was single phase and composed of aggregates of nanocrystals of sizes in the range 20-50 nm. Ba₂TmSbO₆ crystallized in cubic perovskite structure with lattice parameter, a = 8.4101 Å. The polycrystalline fluffy combustion product was sintered to high density (∼97%) at ∼1450 °C for 4 h. Resistivity of the sintered specimen was ∼5 MΩ/cm. The Ba₂TmSbO₆ has dielectric constant (?′) and dielectric loss (tan δ) of 17 and ∼10⁻⁴ at 5 MHz; the new material would probably be developed as a low-loss dielectric material.     

Structural, optical and electromagnetic properties of Bi1−xHoxFeO3 multiferroic materials

Bi_1−xHo_xFeO₃ (x = 0.00, 0.05, 0.10, 0.15 and 0.20) polycrystalline ceramics were synthesized by a solid-state reaction and their structural, absorption, Raman scattering, impedance and magnetic properties were investigated. The substitution of rare earth Ho for Bi was found to decrease the impurity phase in BiFeO₃ ceramics. There appears an anomalous change in the lattice constants, optical band gap as well as the impedance spectroscopy and magnetization of samples at x = 0.10, suggesting a limit of dissolubility of Ho doped ions in BiFeO₃. Additionally, the Raman measurement performed for the lattice dynamics study of Bi_1−xHo_xFeO₃ samples reveals a band centered at around 1000-1300 cm⁻¹ which is associated with the resonant enhancement of two-phonon Raman scattering in the multiferroic Bi_1−xHo_xFeO₃ samples. Ho-doped BiFeO₃ also showed a ferromagnetic-like behavior with M_r = 1070 × 10⁻⁴ and M_s = 1.60 emu/g for optimum content x = 0.10, which is similar to the solid solution system of BiFeO₃.     

Properties of praseodymium-doped bismuth potassium titanate (Bi0.5K0.5TiO3) synthesised using the soft combustion technique

Bismuth potassium titanate (Bi_0.5K_0.5TiO₃; BKT) and praseodymium-doped BKT (Bi_0.5(1−x)Pr_xK_0.5TiO₃; BPKT) powders were synthesised using the soft combustion technique. Fine particles of 10-100 nm of BKT and BPKT were produced. A single phase BKT was obtained with a minimum of 0.5 mol of glycine. Various compounds of Bi_0.5(1−x)Pr_xK_0.5TiO₃ where x = 0.01, 0.03, 0.05, 0.10, 0.15 and 0.20 were prepared. Pure BKT and BPKT powders were obtained after calcination at 800 °C for 3 h. After sintering at 1050 °C for 5 h, pure BKT and BPKT pellets were obtained for x = 0 and 0.01. However, for BPKT with x = 0.03, 0.05, 0.10, 0.15 and 0.20, a minor amount of Bi₄Ti₃O₁₂ (BIT) secondary phase was present after sintering at 1050 °C for 5 h. The crystallite size and grain size of all the samples followed similar trends, first increasing from x = 0 (undoped BKT) to x = 0.05 and then decreasing above x = 0.05. Among the undoped and doped samples, BPKT with x = 0.05 had the highest dielectric properties (?_r = 713.87) due to its large crystallite size (68.66 nm), large grain size (∼435 nm) and high relative density (93.39%).     

Ba(Ti1 − xSnx)O3 (x = 0.13) nanomaterials produced by low-temperature aqueous synthesis

BaTi_0.87Sn_0.13O₃ (BTS₁₃) nanopowder was prepared by low-temperature aqueous synthesis (LTAS) method. The evolution of the structure and microstructure of the precursor precipitate, heated at temperatures up to 1000 °C was studied by TGA, FT-IR, SEM and XRD techniques. The dried precipitate showed a microstructure consisting of nano-sized grains (∼40 nm) with great tendency to agglomeration. BaTi_0.87Sn_0.13O₃ single phase was obtained at 800 °C. The ceramics prepared from as-obtained BTS₁₃ powders (60-70 nm) show good dielectric and ferroelectric characteristics. The dielectric constant was about 4800 and the dielectric loss (tan δ) was 0.229 at 1 kHz and at the Curie temperature (31 °C). The remanent polarization (P_r) and the coercive field (E_C) of Ba_0.97Ho_0.03TiO₃ ceramics, at 1 kHz, were P_r = 13 μC/cm² and E_C = 0.89 kV/cm. The ferroelectric parameters E_C and P_r decrease with increasing frequency in the domain 100 Hz to 10 kHz.     

Resistivity, thermopower, and thermal conductivity of nickel doped compounds Cr1−xNixSb2 at low temperatures

Substitutional compounds Cr_1−xNi_xSb₂ (0 ≤ x ≤ 0.1) were synthesized, and the effect of Ni substitution on transport and thermoelectric properties of Cr_1−xNi_xSb₂ were investigated at the temperatures from 7 to 310 K. The results indicated that the magnitudes of the resistivity and thermopower of Cr_1−xNi_xSb₂ decreased greatly with increasing Ni content at low temperatures, owing to an increase in electron concentration caused by Ni substitution for Cr. Experiments also showed that the low-temperature lattice thermal conductivity of Cr_1−xNi_xSb₂ decreased substantially with increasing Ni content due to an enhancement of phonon scattering by the increased number of Ni atoms. As a result, the figure of merit, ZT, of lightly doped Cr_0.99Ni_0.01Sb₂ was improved at T > ∼230 K. Specifically, the ZT of Cr_0.99Ni_0.01Sb₂ at 310 K was approximately ∼29% larger than that of CrSb₂, indicating that thermoelectric properties of CrSb₂ can be improved by an appropriate substitution of Ni for Cr.     

Microstructure, ferroelectric, and piezoelectric properties of (1 − x − y)Bi0.5Na0.5TiO3-xBaTiO3-yBi0.5Ag0.5TiO3 lead-free ceramics

Lead-free (1 − x − y)Bi_0.5Na_0.5TiO₃-xBaTiO₃-yBi_0.5Ag_0.5TiO₃ (BNT-BT-BAT-x/y, x = 0-0.10, y = 0-0.075) piezoelectric ceramics were synthesized by conventional oxide-mixed method. The microstructure, ferroelectric, and piezoelectric properties of the ceramics were investigated. Results show that a morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases of BNT-BT-BAT-x/0.04 ceramics is formed at x = 0.06-0.08. The addition of BAT has no obvious change on the crystal structure of BNT-BT ceramics while it causes the grain size of the ceramics to become more homogenous. Near the MPB, the ceramics with x = 0.06 and y = 0.05-0.06 possess optimum electrical properties: P_r ∼ 42.5 μC/cm², E_c ∼ 32.0 kV/cm, d₃₃ ∼ 172 pC/N, k_p ∼ 32.6%, and k_t ∼ 52.6%. The temperature dependences of k_p and polarization versus electric hysteresis loops reveal that the depolarization temperature (T_d) of BNT-BT-BAT-0.06/y ceramics decreases with increasing y. In addition, the polar and non-polar phases may coexist in the BNT-BT-BAT-x/y ceramics above T_d.