Processing of Bi1.5ZnNb1.5O7 ceramics for LTCC applications: Comparison of synthesis and sintering methods

Bismuth zinc niobate posses a cubic pyrochlore structure and normally is obtained by the conventional solid-state reaction. The great disadvantage of this method is the lack of chemical homogeneity, requiring high synthesis and sintering temperatures (higher than 1000 °C), which is an impeditive for BZN application in LTCC with silver as the internal electrode. The aim of this paper is to compare, from synthesis to sintering, BZN ceramics, derived either from chemically or conventionally synthesized powders, sintered either in both conventional oven for 2 h or microwave oven for 15 min. The results showed that chemically synthesized BZN ceramics sintered in microwave oven at 900 °C for 15 min presented a relative density of 97%, while those obtained by conventional method required 1000 °C to reach the same density. Despite the short period for thermal treatment in microwave oven, the electrical properties of BZN ceramics are compatible with those sintered in conventional oven for 2 h.     

Dielectric properties of Sm, Nd and Fe doped Bi1.5Zn0.92Nb1.5O6.92 pyrochlores

New pyrochlore ceramics have been produced by doping Sm and Nd into the Bi site and Fe into the Nb site in the Bi_1.5Zn_0.92Nb_1.5O_6.92 (BZN) pyrochlore. Doped pyrochlore ceramics were produced by conventional solid state mixing of oxides at different doping levels using the compositions of Bi_1.5−xSm_xZn_0.92Nb_1.5O_6.92, Bi_1.5−xNd_xZn_0.92Nb_1.5O_6.92 and Bi_1.5Zn_0.92Nb_1.5−xFe_xO_6.92−x. The solubility limit of cations was determined as x = 0.13, 0.18 and 0.15 for Sm, Nd and Fe, respectively. While Sm and Nd increased the dielectric constant (?), Fe doping led a decrease in ?. Dielectric constant of Sm and Nd doped BZN increased to 199 at x = 0.13 (Sm) and to 219 at x = 0.18 (Nd). At low Fe dopings (x = 0.05), the dielectric constant of BZN increased to 242 but decreased to 211 at x = 0.15. The dielectric losses were lower for Sm and Nd dopings than Fe but in all cases it was lower than 0.006. The dielectric constant of Sm, Nd and Fe doped BZN ceramics was nearly independent of frequency within the frequency range between 1 kHz and 2 MHz, but decreased considerably with temperature between 20 and 200 °C. Temperature coefficient of Sm doped BZN (−354 ppm/°C) was lower than Nd and Fe doped BZN ceramics at solubility limits (−538 ppm/°C for Nd and −565 ppm/°C for Fe).     

Structural,vibrational, optical,magnetic and dielectric properties of Bi1−xBaxFeO3 nanoparticles

Bi_1−xBa_xFeO₃ (x=0.05, 0.10 and 0.15) nanoparticles were synthesized by the sol–gel method. X-ray diffraction and Raman spectroscopy results showed the presence of distorted rhombohedral structure of Bi_1−xBa_xFeO₃ nanoparticles. Rietveld refinement and Williamson–Hall plot of the x-ray diffraction patterns showed the increase in lattice parameters, unit cell volume and the particle size. Infrared spectroscopy and Raman analysis revealed the shifting of phonon modes towards the higher wavenumber side with increasing Ba concentration. These samples exhibited the optical band gap in the visible region (2.47–2.02 eV) indicating their ability to absorb visible light. Magnetic measurement showed room temperature ferromagnetic behavior, which may be attributed to the antiferromagnetic core and the ferromagnetic surface of the nanoparticles, together with the structural distortion caused by Ba substitution. The magnetoelectric coupling was evidenced by the observation of the dielectric anomaly in the dielectric constant and the dielectric loss near antiferromagnetic Neel temperature in all the samples.     

Synthesis,structural analysis and dielectric properties of Ba8(Mg1−xZnx)Nb6O24 hexagonal perovskites

Ba₈(Mg_1−xZn_x)Nb₆O₂₄ (x=0, 0.2, 0.4, 0.6, 0.8 and 1) ceramics were prepared through the conventional solid-state route. The materials were calcined at 1250 °C and sintered at 1375–1425 °C. The structure of the system was analyzed using X-ray diffraction and vibrational spectroscopic studies. The microstructure of the sintered pellet was analyzed using scanning electron microscopy. The dielectric constant (ε_r), temperature coefficient of resonant frequency (τ_f) and the unloaded quality factor (Q_u) were measured in the microwave frequency region. The τ_f values of the compositions were reduced by varying the value of x from 0 to 1. The dielectric responses to frequency were also studied in the radio frequency region. The compositions have good microwave dielectric properties and hence are suitable for dielectric resonator applications.     

Structural, electrical and dielectric properties of Bi1.5Zn0.92Nb1.5−xTaxO6.92 pyrochlore ceramics

The micro-structural, compositional, temperature dependent dielectric and electrical properties of the Bi_1.5Zn_0.92Nb_1.5−xTa_xO_6.92 solid solution has been investigated. The increasing Ta content from 0.2 to 1.5 caused; single phase formation, a pronounced grain size reduction from ∼7.0 to 2.5 μm, sharp decrease in the dielectric constant from 198 to 88 and an increase in the electrical conductivity from 3.16 × 10⁻¹⁰ to 5.0 × 10⁻⁹ (Ω cm)⁻¹, respectively. The temperature dependent dielectric constant which is found to be frequency invariant in the frequency range of (0.0-2.0 MHz) exhibited a sharp change in the temperature coefficient of dielectric constant at a (doping independent) critical temperature of 395 K. The analysis of the measured data reflects a promising future for this type of pyrochlore to be used in high voltage passive device applications.     

Structural and dielectric properties of Bi1−xSrxMnO3 (0.40≤x≤0.55)

In order to study the effect of Sr substitution on structural and dielectric properties of Bi_1−xSr_xMnO₃ (0.40≤x≤0.55) compounds were synthesized by the solid state reaction method. The as-prepared samples were characterized by X- ray diffraction (XRD) and dielectric measurements to correlate structural changes with dielectric properties. The XRD data were further analyzed by the Rietveld refinement. The highest dielectric constant was observed in Bi_0.55Sr_0.45MnO₃ and Bi_0.5Sr_0.5MnO₃ systems (∼10⁶) mainly because of orientation polarization. The charge ordering temperature decreases with increasing Sr concentration in Bi_1−xSr_xMnO₃ systems.     

Adjustable dielectric properties of Li2CuxZn1−xTi3O8 (x=0 to 1) ceramics with low sintering temperature

Single-phase dielectric ceramics Li₂Cu_xZn_1−xTi₃O₈ (x=0–1) were synthesized by the conventional solid-state ceramic route. All the solid solutions adopted Li₂MTi₃O₈ cubic spinel structure in which Li/M and Ti show 1:3 order in octahedral sites whereas Li and M are distributed randomly in tetrahedral sites with the degree of Li/M cation mixing varying from 0.5 to 0.3. The substitution of Cu for Zn effectively lowered the sintering temperatures of the ceramics from 1050 to 850 °C and significantly affected the dielectric properties. As x increased from 0 to 0.5, τ_f gradually increased while the dielectric constant (ε_r) and quality factor value (Q×f) gradually decreased, and a near-zero τ_f of 1.6 ppm/°C with ε_r of 25.2, Q×f of 32,100 GHz could be achieved for Li₂Cu_0.1Zn_0.9Ti₃O₈ ceramic sintered at 950 °C, which make it become an attractive promising candidate for LTCC application. As x increases from 0.5 to 1, the dielectric loss significantly increases with AC conductivity increasing up to 2.3×10⁻⁴ S/cm (at 1 MHz).     

Fabrication and characterisation of Cr and Co doped Bi1.5Zn0.92Nb1.5O6.92 pyrochlores

Cr and Co doped Bi_1.5Zn_0.92Nb_1.5O_6.92 pyrochlore ceramics were produced by solid state mixing of oxides. Cr and Co were doped into the Nb and Nb-Zn sites considering the compositions of Bi_1.5Zn_0.92Nb_1.5−xCr_xO_6.92−x, (Bi_1.5Zn_0.46)(Zn_0.46−3x/6Nb_1.5−3x/5Cr_x)O_6.92−x/2 for Cr doping and Bi_1.5Zn_0.92Nb_1.5−3x/5Co_xO_6.92, (Bi_1.5Zn_0.46)(Zn_0.46−3x/6Nb_1.5−3x/5Co_x)O_6.92−x/2 for Co doping. The solubility limit of Cr in BZN was higher than that of Co and the solubility limit increased when doping was made both into Nb and Zn sites. The second phases appeared when x > 0.2 for Cr and x > 0.15 for Co doping into the Nb-Zn sites. Simultaneous Cr doping into the Nb- and Zn-sites of BZN pyrochlore gave higher dielectric constant than doping into the Nb-site of pyrochlore. However, Co doping into the Nb- and Zn-sites and only into the Nb-site of BZN gave identical dielectric results in the range of 202-218. The temperature coefficient of dielectric constant decreased with Cr doping and increased with Co doping.     

Structural,magnetic and dielectric behavior of Mg1−xCaxNiyFe2−yO4 nano-ferrites synthesized by the micro-emulsion method

Ca–Ni co-substituted samples of nanocrystalline spinel ferrites with chemical formula Mg_1−xCa_xNi_yFe_2−y O₄ (x=0.0–0.6, y=0.0–1.2) were synthesized by the micro-emulsion method and were annealed at 700 °C for 7 h. The synthesized samples were characterized by x-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, vibrating sample magnetometry (VSM) and dielectric measurements. The XRD and FTIR analysis reveals that single phase samples can be achieved by substituting Ca and Ni ions at Mg and Fe sites respectively in cubic spinel nano-ferrites. The crystallite size of the synthesized samples was found in the range 29–45 nm. The saturation magnetization (M_s) increases from 9.84 to 24.99 emu/g up to x=0.2, y=0.4 and then decreases, while the coercivity (H_c) increases continuously from 94 to 153 Oe with the increase in dopants concentration. The dielectric properties of these nano materials were also studied at room temperature in the frequency range 100 MHz to 3 GHz. The dielectric parameters were found to decrease with the increased Ca–Ni concentration. Further the peaking behavior was observed beyond 1.5 GHz. The frequency dependent dielectric properties of all the samples have been explained qualitatively on the basis of the Maxwell–Wagner two-layer model according to Koop's phenomenological theory. The enhanced magnetic parameters and reduced dielectric properties make the synthesized materials suitable for switching and high frequency applications, respectively.     

Enhanced ferroelectric properties in (Ba1−xCax)(Ti0.94Sn0.06)O3 lead-free ceramics

Lead-free (Ba_1−xCa_x)(Ti_0.94Sn_0.06)O₃ (BCST) (x = 0.01-0.04) ceramics were prepared using a solid-state reaction technique. The effects of Ca content on the phase structure and electrical properties of the BCST ceramics were investigated. High piezoelectric coefficient of d₃₃ = 440 pC/N, planar electromechanical coupling factor of k_p = 45% and dielectric constant ?_r = 6900 were obtained for the samples at x = 0.03. At room temperature, a polymorphic phase transition (PPT) from orthorhombic phase to tetragonal phase was identified in the composition range of 0.02 < x < 0.04.     

Effect of La substitution on the structural and electrical properties of BaBi4−xLaxTi4O15

Pure and lanthanum doped barium bismuth titanate BaBi_4−xLa_xTi₄O₁₅ (BBLT, x=0, 0.05, 0.15, 0.30) ceramics were prepared utilizing solid state method. The X-ray diffraction (XRD) data confirmed formation of single-phase Aurivillius compounds while SEM micrographs did not show evident grain size change of doped ceramics. Dielectric properties were investigated in 1.21 kHz to 1 MHz frequency range and in the temperature range of 20 to 727 °C. When Bi³⁺ is substituted with La³⁺, a significant disorder was induced and the material exhibited broadening of the phase transition. Impedance analysis confirmed the presence of two semicircular arcs in doped samples suggesting the existence of grain and grain-boundary conduction. The dc-conductivity and activation energies were evaluated for all compositions.     

Ionic conductivity in Bi2Sn2O7 ceramics

Impedance spectroscopy measurements, in the temperature range from room temperature to 600 K, were performed in order to investigate the dielectric and ionic properties of Bi₂Sn₂O₇ ceramics. The results show that the conductivity in this pyrochlore is associated with the hopping of ions. An activation energy of 1.26 eV was observed and the dielectric constant exhibits a strong contribution from ionic conduction.     

Eu3+ doped ferroelectric CaBi2Ta2O9 based glass-ceramic nanocomposites: Crystallization kinetics,optical and dielectric properties

We report Eu³⁺ doped transparent glass-ceramics (GCs) containing bismuth layer-structured ferroelectric (BLSF) CaBi₂Ta₂O₉ (CBT) as the major crystal phase. The CBT crystal phase was generated in a silica rich glass matrix of SiO₂-K₂O-CaO-Bi₂O₃-Ta₂O₅ glass system synthesized by melt quenching technique followed by controlled crystallization through ceramming heat-treatment. Non-isothermal DSC study was conducted to analyze crystallization kinetics of the glass in order to understand the crystallization mechanism. The optimum heat-treatment protocol for ceramization of precursor glass that has been determined through crystallization kinetics analysis was employed to fabricate transparent GCs containing CBT nanocrystals, which was otherwise difficult. Structural analysis of the GCs was carried out using XRD, TEM, FESEM and Raman spectroscopy and results confirmed the existence of CBT nanocrystals. The transmittance and optical band gap energies of the GCs were found to be less when compared to the precursor glass. The refractive indices of the GCs were increased monotonically with increase in heat-treatment time, signaling densification of samples upon heat-treatment. The dielectric constants (ε_r) of the GCs were progressively increased with increase in heat-treatment duration indicating evolution of ferroelectric CBT crystals phase upon heat-treatment.     

Effect of Bi2O3 and B2O3 additives on the sintering temperature, microstructure, and microwave dielectric properties for Sm(Mg0.5Ti0.5)O3 ceramics

The microwave dielectric properties of Sm(Mg_0.5Ti_0.5)O₃ incorporated with various amount of Bi₂O₃ and B₂O₃ additives have been investigated systematically. In this study, both Bi₂O₃ and B₂O₃ additives acting as a sintering aid can effectively lower the sintering temperature from 1550 °C to 1300 °C. The ionic radius of Bi³⁺ for a coordination number of 6 is 0.103 nm, whereas the ionic radius of B³⁺ is 0.027 nm. Clearly, the ionic radius of Bi³⁺ is greatly larger than one of B³⁺, which resulted in the specimens incorporated with Bi₂O₃ having larger lattice parameters and cell volume than those incorporated with B₂O₃. The experimental results show that no second phase was observed throughout the entire experiments. Depending on the interfacial tension, the liquid phase may penetrate the grain boundaries completely, in which case the grains will be separated from one another by a thin layer as shown in Sm(Mg_0.5Ti_0.5)O₃ ceramics incorporated with Bi₂O₃. Whereas, in Sm(Mg_0.5Ti_0.5)O₃ ceramics incorporated with B₂O₃, the volume fraction of liquid is high, the grains may dissolve into the liquid phase, and rapidly rearrange, in which case contact points between agglomerates will be dissolved due to their higher solubility in the liquid, leading plate-like shape microstructure.A dielectric constant (?_r) of 29.3, a high Q × f value of 26,335 GHz (at 8.84 GHz), and a τ_f of −32.5 ppm/°C can be obtained for Sm(Mg_0.5Ti_0.5)O₃ ceramics incorporated with 10 mol% Bi₂O₃ sintered at 1300 °C. While Sm(Mg_0.5Ti_0.5)O₃ ceramics incorporated with 5 mol% B₂O₃ can effectively lower temperature coefficient of resonant frequency, which value is −21.6 ppm/°C. The Sm(Mg_0.5Ti_0.5)O₃ ceramic incorporated with heavily Bi₂O₃ and B₂O₃ additives exhibits a substantial reduction in temperature (∼250 °C) and compatible dielectric properties in comparison with that of an un-doped one. This implied that this ceramic is suitable for miniaturization in the application of dielectric resonators and filters by being appropriately incorporated with a sintering aid.     

Raman scattering, electronic structure and microwave dielectric properties of Ba([Mg1−xZnx]1/3Ta2/3)O3 ceramics

Effects of Zn substitution for Mg on the crystal structure, lattice vibrations and microwave dielectric properties of Ba(Mg_1/3,Ta_2/3)O₃ (BMT) ceramics were investigated. Raman scattering spectra for Ba([Mg_1−xZn_x]_1/3Ta_2/3)O₃ (BMZT) ceramics, with x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0, were measured at room temperature. The Raman result shows a dominance of 1:2 ordered structure at all Zn substitution contents. All Raman modes shift to lower frequencies with increasing Zn substitution. Higher Qf value correlates well with narrower width of the breathing Raman mode A_1g(4) and larger relative intensity of 1:2 long-range-ordered mode E_g(2) in BMZT solid solution. First-principle calculation was performed to investigate the electronic structure of 1:2 ordered BMT and Ba(Zn_1/3,Ta_2/3)O₃ (BZT). Covalent bond between Zn and O in BZT is much stronger than that between Mg and O in BMT due to the Zn 3d orbital. Zn substitution for Mg leads to longer and weaker Ta-O bonds, which may be one reason for the variation of Raman spectroscopy and microwave dielectric properties of BMZT system.     

Enhancement in dielectric and ferroelectric properties of lead free Bi0.5(Na0.5K0.5)0.5TiO3 ceramics by Sb-doping

Lead free piezoelectric Bi_0.5(Na_0.5K_0.5)_0.5TiO₃ (pure and 1 wt.%, 2 wt.%, 4 wt.% Sb-doped) ceramics were synthesized away from its MPB. The crystalline nature of the BNKT ceramic was studied by XRD and SEM. Depolarization temperature (T_d) and transition temperature (T_c) were observed through phase transitions in dielectric studies which were found to increase after Sb-doping, thus increasing its usable temperature range. In the study of relaxation behavior, the activation energy for relaxation was found to be 0.33, 0.43, 0.57 and 0.56 eV for pure and Sb-doped samples, respectively. All samples were found to exhibit normal Curie-Weiss law above their T_c. Doping of Sb was found to restrain the diffused character of the pure sample. In P-E loop, Sb-doping was found to increase the ferroelectric properties.Pure and Sb-doped BNKT ceramics exhibited high values of piezoelectric charge coefficient (d₃₃) as 115, 121, 129 and 100 pC/N, respectively.     

Moisture sensitivity of YCr(1−x)MnxO3 perovskites

This work deals with the sensitivity to moisture rate in air of perovskite with general formula YCr_(1−x)Mn_xO₃ with x ranging from 0 to 0.8. The combined sensitivity to moisture and temperature let us think the possibility of realizing composite sensors temperature/moisture. This study clearly shows the influence of the Mn content on moisture which affects the working frequency of sensors. Capacitance variation of the most sensitive compositions increases from 100 pF to 1 nF for relative humidity between 20 and 80%. The influence of porosity is also demonstrated.     

Physical properties of new,lead free (Na0.5Bi0.5)(1−x)BaxTi(1−x)(Fe0.5Nb0.5)xO3 ceramics

This study reports on the synthesis of polycrystalline samples of (Na_0.5Bi_0.5)_(1−x)Ba_xTi_(1−x)(Fe_0.5Nb_0.5)_xO₃ with x=0, 0.025, 0.05, 0.075, and 0.1, using the solid-state reaction technique. It investigates the effects of the substitution of sodium and bismuth by barium in the A site and of titanium by iron and niobium in the B site with regard to the free NBT symmetry and dielectric properties were investigated. The crystallographic and dielectric properties were also investigated. The diffractograms showed that all the samples had a single phase character. The increase of ceramic lattice parameters induced an increase in the size of the perovskite lattice. This increase was caused by the increase of the radii of the A and B sites. Room temperature X-ray data revealed that the ceramic structures underwent a gradual distortion with the increase in the composition fraction. Dielectric permittivity was measured in the temperature range of 120–780 K with frequencies ranging from 1 to 10³ KHz. Three anomalies, namely T_d, T₁ and T_m, were detected and noted to coexist at lower T_d and T_m as the rate of substitutions increased. All the samples exhibited a diffuse phase transition and implied better dielectric permittivity maxima values at temperatures approaching room temperature, since the substitution rate values increased more than that of pure NBT. A relaxor behavior with ΔT_m=14 K and ε'_rmax=3876 at 1 kHz was observed for (Na_0.5Bi_0.5)_0.9Ba_0.1Ti_0.9(Fe_0.5Nb_0.5)_0.1O₃ ceramic.     

Effects of Ni doping on structural,optical and dielectric properties of ZnO

Structural, optical and dielectric properties of Ni doped ZnO samples prepared by the solid state route are presented. X-ray diffraction confirmed the substitution of Ni on Zn sites without changing the hexagonal structure of ZnO. NiO phase appeared for 6% Ni doping. Fourier transform infrared measurements were carried out to study phonon modes in Ni doped ZnO. Significant blueshift with Ni doping was observed in UV–visible studies, strongly supported by photoluminescence spectra that show a high intensity UV emission peak followed by the low intensity green emission band corresponding to oxygen vacancies and defects. The photoluminescence analysis suggest that doping of Ni can affect defects and oxygen vacancies in ZnO and give the possibility of band gap tuning for applications in optoelectronic devices. High values of dielectric constant at low frequency and a strong dielectric anomaly around 320 °C were observed.