Experimental evidence of enhanced ferroelectricity in Ca doped BiFeO3

Calcium (Ca)-doped bismuth ferrite (BiFeO₃) thin films prepared by using the polymeric precursor method (PPM) were characterized by X-ray diffraction (XRD), field emission gun scanning electron microscopy (FEG-SEM), transmission electron microscopy (TEM), polarization and piezoelectric measurements. Structural studies by XRD and TEM reveal the co-existence of distorted rhombohedral and tetragonal phases in the highest doped BiFeO₃ where enhanced ferroelectric and piezoelectric properties are produced by internal strain. Resistive switching is observed in BFO and Ca-doped BFO which are affected by the barrier contact and work function of multiferroic materials and Pt electrodes. A high coercive field in the hysteresis loop is observed for the BiFeO₃ film. Piezoelectric properties are improved in the highest Ca-doped sample due to changes in the crystal structure of BFO for a primitive cubic perovskite lattice with four-fold symmetry and a large tetragonal distortion within the crystal domain. This observation introduces magnetoelectronics at room temperature by combining electronic conduction with electric and magnetic degrees of freedom which are already present in the multiferroic BiFeO₃.     

Sintering temperature-induced electrical properties of (Ba0.90Ca0.10)(Ti0.85Zr0.15)O3 lead-free ceramics

Effects of the sintering temperature on the microstructure and electrical properties of (Ba_0.90Ca_0.10)(Ti_0.85Zr_0.15)O₃ (BCTZ) lead-free piezoelectric ceramics have been studied, where these ceramics were prepared by the conventional oxide-mixed method at varied sintering temperatures from 1300 °C to 1500 °C. These BCTZ ceramics exhibits a phase transition from a rhombohedral phase to the coexistence of rhombohedral and tetragonal phases with an increase of sintering temperature. With an increase of sintering temperature, their relative density and average grain size gradually increase, and electrical properties are improved greatly. These BCTZ ceramics sintered at ～1440 °C have optimum electrical properties: d₃₃ ～ 442 pC/N and k_p ～ 48.9%, making it a promising material for lead-free piezoelectric ceramics.     

Effects of SrTiO3 on dielectric and piezoelectric properties of K0.48Na0.48Li0.04Nb0.96Ta0.04O3-based piezoceramics

In this study, (100 ? x) K_0.48Na_0.48Li_0.04Nb_0.96Ta_0.04O₃ ? xSrTiO₃ (0 ≤ x ≤ 10) ceramics were fabricated via normal sintering of synthesized powder by using solid state reaction. All ceramics revealed pure perovskite structure, indicating formation of solid solution between KNNLT and ST up to 10%. With increasing x, the crystal structure of ceramics changed from orthorhombic to tetragonal and finally pseudocubic symmetry when x = 10. Ceramic containing 1% ST had orthorhombic and tetragonal symmetries, simultaneously. Investigation of the variation of dielectric constant of ceramics versus temperature revealed that for ceramic with x = 1, polymorphic phase transition (PPT) temperature between orthorhombic and tetragonal is less than room temperature. Thus coexistence of two different structures in this ceramic is due to vicinity of its composition to morphotropic phase boundary (MPB). As a result, the maximum piezoelectric constant was measured for this ceramic. Ceramics containing 5 and 7.5% ST tend to appear relaxor ferroelectric behavior which is because of chemical inhomogeneities in both A- and B-sites of the ABO₃ perovskite structure.     

Beta tricalcium phosphate ceramics with controlled crystal orientation fabricated by application of external magnetic field during the slip casting process

Beta tricalcium phosphate (β-TCP) is a resorbable bioceramic that has hitherto been utilized in the medical field. Since it crystallizes in the anisotropic hexagonal system, properties such as chemical and physical ones are expected to depend on its crystal axis direction and/or on its crystal plane (anisotropy). Control of crystal orientation is thus important when used in polycrystalline form. Meanwhile, application of a strong magnetic field has been found to be a promising technique to control crystal orientation of anisotropic shape or structured crystals. In this work, we attempted to fabricate β-TCP ceramics with controlled crystal orientation by applying an external magnetic field during the slip casting process and subsequently sintering them at 1050 °C, below the β–α transition temperature. Application of a vertical magnetic field increased intensities of planes perpendicular to c-plane on the top surface, while a horizontal one with simultaneous mechanical mold rotation decreased it. These results indicated that crystal orientation of β-TCP ceramics were successfully controlled by the external magnetic field and together that the magnetic susceptibility of β-TCP is χ_c⊥ > χ_c//.     

Structural,Optical and Multiferroic Properties of (Nd,Zn)-Co-doped BiFeO<Subscript>3</Subscript> Nanoparticles

The pure BiFeO₃ (BFO) and (Nd, Zn)-co-doped BFO nanoparticles were prepared by a sol-gel method. The crystal structure and optical and multiferroic properties of the samples were systematically investigated. Rietveld refinement showed that the samples crystallized in rhombohedral R3c structure. In UV-visible diffuse absorption spectra, an apparent blue shift can be observed after co-doping, which indicates a possible application in photocatalyst and photoconductive devices. Compared with a pure BFO sample, the leakage current density of the x = 0.05 sample decreases about 3 orders of magnitude. The remanent magnetization (M _r) of the x = 0.10 sample reaches 0.105 emu/g while the coercive field (H _c) is as high as 7.0 kOe. The (Nd, Zn) co-doping into BFO nanoparticles has been proved to be an effective way to improve the optical and multiferroic properties.     

Synthesis,structural and magnetic characterization of highly ordered single crystalline BiFeO3 nanotubes

In this work, we report on the fabrication of highly ordered single crystalline BiFeO₃ (BFO) nanotubes by a sol–gel technique using two-step anodic aluminum oxide (AAO) as template. We prepared BFO nanotubes with dimensions of 65 nm in diameter and 3 μm in length, as confirmed by scanning electron microscopy (SEM) measurements. The obtained single crystalline nanotubes present the expected pure phase (BiFeO₃) as confirmed by energy-dispersive X-ray spectroscopy (EDX), selected area electron diffraction (SAED) and high-resolution transmission electron microscopy (HRTEM). In addition to the antiferromagnetic behavior, the magnetization curves of the BFO nanotubes also present a ferromagnetic response, which holds from 2 to 300 K. This desirable behavior is associated to the break of the antiferromagnetic helical spin ordering of the BFO nanotubes. Besides the magnetocrystalline anisotropy, the large length-to-diameter ratio induced an uniaxial shape anisotropy, attested by the applied magnetic field angle measurements.     

Perovskite phase stabilization and dielectric properties of Pb(Zn1/3Ta2/3)O3–BaTiO3 ceramics

The phase structure and dielectric properties of (1 − x)Pb(Zn_1/3Ta_2/3)O₃–xBaTiO₃ (x = 0.00–0.40) ceramics were investigated. Pure perovskite is obtained when x ≥ 0.24. With increasing BT content, the diffuse phase transition and frequency dissipation of the dielectric constant increase and the dielectric maxima temperature decreases. It is related to the existing of Ba(Zn_1/3Ta_2/3)O₃ paraelectric microregions and the incomplete solid solution reaction between Pb(Zn_1/3Ta_2/3)O₃ and BaTiO₃.     

Temperature-dependent multi-k magnetic structure in multiferroic Co3TeO6

A complex magnetic order of the multiferroic compound Co₃TeO₆ has been revealed by neutron powder diffraction studies on ceramics and crushed single crystals. The compound adopts a monoclinic structure (s.g. C2/c) in the studied temperature range 2–300 K but exhibits successive antiferromagnetic transitions at low temperature. Incommensurate antiferromagnetic order with the propagation vector k₁ = (0, 0.485, 0.055) sets in at 26 K. A transition to a second antiferromagnetic structure with k₂ = (0, 0, 0) takes place at 21.1 K. Moreover, a transition to a commensurate antiferromagnetic structure with k₃ = (0, 0.5, 0.25) occurs at 17.4 K. The magnetic structures have been determined by neutron powder diffraction using group theory analysis as a preliminary tool. Different coordinations of the Co²⁺ ions involved in the low-symmetry C2/c structure of Co₃TeO₆ render the exchange-interaction network very complex by itself. The observed magnetic phase transformations are interpreted as an evidence of competing magnetic interactions. The temperature dependent changes in the magnetic structure, derived from refinements of high-resolution neutron data, are discussed and possible mechanisms connected with the spin reorientations are described.     

Low-temperature hydro/solvothermal synthesis of Ta-modified K0.5Na0.5NbO3 powders and piezoelectric properties of corresponding ceramics

K_0.5Na_0.5Nb_1–xTa_xO₃ (KNNTx, x = 0–0.4) powders were synthesized by a novel hydro/solvothermal method at a low reaction temperature (180 °C) and the corresponding ceramics were obtained by normal sintering. Compared with conventional solid-state reaction technique, the optimal sintering temperatures of these ceramics were reduced at least 150 °C. Crystalline structures and surface morphologies were analyzed by X-ray diffraction and scanning electron microscopy. The excellent piezoelectric properties could be obtained by selecting poling temperature near the orthorhombic–tetragonal polymorphic phase transition temperature region. Ta-modified KNN ceramics exhibited better piezoelectric properties than those of pure KNN, and the piezoelectric coefficient d₃₃ showed the maximum value of 156 pC/N for KNNT0.3 ceramics. In addition, the sintering temperature for maximum d₃₃ value differed from that for maximum density. The present hydro/solvothermal method provides a new potential route for preparing KNN-based materials at relatively low temperature.     

Enhanced luminescence in Er3+-doped chalcogenide glass–ceramics based on selenium

Rare earth doped glass–ceramics transparent in the infrared region up to 16 μm have been prepared and studied. The enhancement of the emission of Er³⁺ ions at 1.54 μm with increasing crystallinity was demonstrated in a selenium-based glass–ceramic having a composition of 80GeSe₂–20Ga₂Se₃ + 1000 ppm Er. The optical transmission, microstructure and luminescence properties of a base glass and glass–ceramics were investigated. Luminescence intensities up to 7 times greater were obtained in glass–ceramics in comparison to the base glass. These materials are promising candidates for the production of new laser sources in the mid-infrared region.     

Influence of V2O5 additions to Ba(Mg1/3Ta2/3)O3 ceramics on sintering behavior and microwave dielectric properties

The microstructures and the microwave dielectric properties of barium magnesium tantalate ceramics prepared by conventional mixed oxide route have been investigated. The prepared Ba(Mg_1/3Ta_2/3)O₃ exhibited a mixture of cubic perovskite and a hexagonal superstructure with Mg and Ta showing 1:2 order in the B-site. It is found that low level doping of V₂O₅ (up to 0.5 wt.%) can significantly improve densification of the specimens and their microwave dielectric properties. The density of doped Ba(Mg_1/3Ta_2/3)O₃ ceramics can be increased beyond 95% of its theoretical value by 1500 °C-sintering, which is caused by the liquid-phase effect of V₂O₅ addition. The detected second phase Ta₂O₅ was mainly the result of V⁵⁺ substitution in the ceramics. Dielectric constant (ε_r) and temperature coefficient of resonant frequency (τ_f) were not significantly affected, while the unloaded quality factors Q were effectively promoted by V₂O₅ addition due to the increase in B-site ordering. The ε_r value of 24.1, Q×f value of 149,000 (at 10 GHz) and τ_f value of 7.2 ppm/°C were obtained for Ba(Mg_1/3Ta_2/3)O₃ ceramics with 0.25 wt.% V₂O₅ addition sintered at 1500 °C for 3 h.     

Ferroelectric and piezoelectric properties of [(Ba1−3x/2Bix)0.85Ca0.15](Ti0.90Zr0.10)O3 lead-free piezoelectric ceramics

Bismuth-modified barium calcium zirconate titanate ceramics [(Ba_1?3x/2Bi_x)_0.85Ca_0.15](Ti_0.90Zr_0.10)O₃ (BBCTZ) have been prepared by the conventional solid-state reaction method, and effects of Bi content on the electrical properties of BBCTZ ceramics were systematically investigated. BBCTZ ceramics endure a phase transition from the coexistence of rhombohedral and tetragonal phases, a tetragonal phase, to a cubic phase with increasing Bi content. The Curie temperature, the remanent polarization, and the dielectric loss of BBCTZ ceramics gradually decrease with increasing the Bi content. The BBCTZ ceramic with x = 0.0075 exhibits an optimum electrical behavior: d₃₃ ～ 361 pC/N and k_p ～ 40.2%.     

Hydrogen-induced degradation in multiferroic BiFeO3 ceramics

Chemical stability of multiferroic BiFeO₃ (BFO) ceramics has been studied through electrochemical hydrogen charging, in which BFO ceramic pellets were placed in 0.01 M NaOH solution with hydrogen deposited on their electrodes from the electrolysis of water. The properties of the samples were greatly degraded after the treatment: The leakage current was increased by orders of magnitude, the capacitance and the dielectric loss were dramatically increased in low frequency region. It was proposed that hydrogen entered into BFO lattice and existed at interstitial sites and the degradation was explained by hydrogen's reduction of some Fe³⁺ to Fe²⁺ in BFO. Hydrogen-induced degradation occurs relatively easily in BFO and much attention should be paid to it for BFO-based devices.     

Lead-free electrostrictive bismuth perovskite ceramics with thermally stable field-induced strains

Electric field-induced strain (EFIS) properties of Bi_1/2(Na_0.82K_0.18)_1/2TiO₃ (BNKT) ceramics modified with Sr(K_1/4Nb_3/4)O₃ (SKN) have been investigated as functions of composition and temperature. BNKT ceramics near a phase boundary revealed the coexistence of ferroelectric rhombohedral and tetragonal phases, resulting in a typical ferroelectric butterfly-shaped bipolar S–E loop at room temperature, whose normalized strain (S_max/E_max) showed a significant temperature coefficient of 0.38 pm/V/K. However, 5 mol% SKN-modified BNKT ceramics revealed a typical electrostrictive behaviour with a thermally stable electrostrictive coefficient, Q₃₃ = 0.021 m⁴/C², which is almost comparable to that of Pb(Mg_1/3Nb_2/3)O₃ (PMN) ceramics that have been dominantly used as Pb-based electrostrictive materials over the last decades.     

Gd2O3 doped 0.82Bi0.5Na0.5TiO3–0.18Bi0.5K0.5TiO3 lead-free piezoelectric ceramics

Gd₂O₃ (0–0.8 wt.%)-doped 0.82Bi_0.5Na_0.5TiO₃–0.18Bi_0.5K_0.5TiO₃ (BNKT18) lead-free piezoelectric ceramics were synthesized by a conventional solid-state process. The effects of Gd₂O₃ on the microstructure, the dielectric, ferroelectric and piezoelectric properties were investigated. X-ray diffraction (XRD) data shows that Gd₂O₃ in an amount of 0.2–0.8 wt.% can diffuse into the lattice of BNKT18 ceramics and form a pure perovskite phase. Scanning electron microscope (SEM) images indicate that the grain size of BNKT18 ceramics decreases with the increase of Gd₂O₃ content; in addition, all the modified ceramics have a clear grain boundary and a uniformly distributed grain size. At room temperature, the ferroelectric and piezoelectric properties of the BNKT18 ceramics have been improved with the addition of Gd₂O₃, and the BNKT18 ceramics doped with 0.4 wt.% Gd₂O₃ have the highest piezoelectric constant (d₃₃ = 137 pC/N), highest relative dielectric constant (ε_r = 1023) and lower dissipation factor (tan δ = 0.044) at a frequency of 10 kHz. The BNKT18 ceramics doped with 0.2 wt.% Gd₂O₃ have the highest planar coupling factor (k_p = 0.2463).     

Microstructure and properties of porous silicon nitride ceramics prepared by gel-casting and gas pressure sintering

Wave-transparent porous Si₃N₄ ceramics were prepared by gel-casting and gas pressure sintering, and the effects of solid loading on microstructure, mechanical and dielectric properties were investigated. Microstructures with interlocked elongated β-Si₃N₄ grains and uniformly distributed pores were observed, while both the β-Si₃N₄ phase content and grain aspect ratio reduced as the solid loading increased due to the restrained anisotropic growth of β-Si₃N₄ grains. As the solid loading increased from 30 to 45 vol.%, the porosity of ceramics declined from 57.6% to 36.4%. The flexural strength increased linearly from 108.3 to 235.1 MPa, and the dielectric constant and loss tangent of ceramics increased from 2.63 and 2.85 × 10⁻³ to 3.68 and 3.56 × 10⁻³ (10 GHz), respectively.     

Nanocrystalline LaMnO3 preparation and kinetics of crystallization process

Precursor of nanocrystalline LaMnO₃ was synthesized by solid-state reaction at low heat using La(NO₃)₃·6H₂O, MnSO₄·H₂O, and Na₂CO₃·10H₂O as raw materials. XRD analysis showed that precursor was a mixture containing orthorhombic La₂(CO₃)₃·8H₂O and rhombohedral MnCO₃. When the precursor was calcined at 800 ^°C for 2 h, pure phase LaMnO₃ with rhombohedral structure was obtained. Magnetic characterization indicated that rhombohedral LaMnO₃ behaved weak magnetic properties. The thermal process of the precursor experienced four steps, which involved the dehydration of crystallization water at first, and then decomposition of manganese carbonate into MnO₂, and decomposition of La₂(CO₃)₃ and MnO₂ together into La₂O₂CO₃ and Mn₂O₃, and lastly reaction of monoclinic La₂O₂CO₃ with Mn₂O₃ and formation of rhombohedral LaMnO₃. Based on the Kissinger equation, the value of the activation energy associated with the formation of rhombohedral LaMnO₃ was determined to be 260 kJ mol^?1. The value of the Avrami exponent, n, was equal to 1.68, which suggested that crystallization process of LaMnO₃ was the random nucleation and growth of nuclei reaction.     

Comparative dielectric studies of nanostructured BaTiO3, CaCu3Ti4O12 and 0.5BaTiO3⋅ 0.5CaCu3Ti4O12 nano-composites synthesized by modified sol–gel and solid state methods

BaTiO₃ (BTO), CaCu₃Ti₄O₁₂ (CCTO) and 0.5BaTiO₃·0.5CaCu₃Ti₄O₁₂ (BTO–CCTO), as a new nano-composite ceramic, were successfully designed and fabricated by a semi-wet gel route and a modified solid state method. The dielectric properties of the BTO–CCTO ceramic were compared to those of the BTO and CCTO ceramics at lower sintering temperatures and durations. The X-ray diffraction analysis revealed that the BTO and CCTO ceramics form a single crystalline phase and the average crystalline sizes calculated from X-ray diffraction data were in the range of 40–65 nm. The particle sizes of the BTO, CCTO, and BTO–CCTO ceramics obtained from transmission electron microscopy images were in the ranges of 40–65 nm, 80–110 nm, and 70–95 nm, respectively. The phase composition and microstructure were studied by X-ray diffraction and scanning electron microscopy. The energy dispersive X-ray results demonstrated the purity and stoichiometry of the BTO–CCTO nano-composite. The grain sizes of the BTO, CCTO and BTO–CCTO ceramics were found to be in the ranges of 500 nm–1 μm, 4–24 μm, and 250 nm–4 μm, respectively. The AC conductivity as a function of frequency confirmed the semiconducting nature of all of the ceramics and obeyed the Jonscher's power law. The impedance spectrum measurement result showed that the CCTO ceramic possessed an exceptional grain boundary resistance, which supports the internal barrier layer capacitance (IBLC) mechanism present in this ceramic and is responsible for the high ε_r values.     

Structural and pyroelectric properties of sol–gel derived multiferroic BFO thin films

Multiferroic BFO/PZT multilayer films were fabricated by spin-coating method on the (1 1 1)Pt/Ti/SiO₂/Si substrate alternately using PZT(30/70), PZT(70/30) and BFO alkoxide solutions. The structural and ferroelectric properties were investigated for uncooled infrared detector applications. The coating and heating procedure was repeated six times to form BFO/PZT multilayer films. All films showed the typical XRD patterns of the perovskite polycrystalline structure without presence of the second phase such as Bi₂Fe₄O₃. The thickness of BFO/PZT multilayer film was about 200–220 nm. The ferroelectric properties such as dielectric constant, remnant polarization and pyroelectric coefficient were superior to those of single composition BFO film, and those values for BFO/PZT(70/30) multilayer film were 288, 15.7 μC/cm² and 9.1 × 10^?9 C/cm² K at room temperature, respectively. Leakage current density of the BFO/PZT(30/70) multilayer film was 3.3 × 10^?9 A/cm² at 150 kV/cm. The figures of merit, F_V for the voltage responsivity and F_D for the specific detectivity, of the BFO/PZT(70/30) multilayer film were 6.17 × 10^?11 Ccm/J and 6.45 × 10^?9 Ccm/J, respectively.     

Dielectric properties of Sb2O3-doped Ba0.672Sr0.32Y0.008TiO3

Sb₂O₃-doped Ba_0.672Sr_0.32Y_0.008TiO₃ (BSYT) dielectric ceramics were prepared by conventional solid state method, and their dielectric properties were investigated with variation of Sb₂O₃ doping content and sintering temperature. The X-ray diffraction patterns indicated that all the BSYT specimens possessed the perovskite polycrystalline structure. The experimental results reveal that the introduction of Sb₂O₃ into Ba_0.672Sr_0.32Y_0.008TiO₃ can control the grain growth, reduce the relative dielectric constant and dielectric loss, shift the Curie temperature to lower temperature and significantly improve the thermal stability of the BSYT ceramics. The samples doped with 1.6 wt.% Sb₂O₃ sintered at 1320 °C for 2 h exhibited attractive properties, including high relative dielectric constant (> 1500), low dielectric loss (< 40 × 10^− 4), low temperature coefficient of capacitor(< ± 35%) over a wide temperature range from − 25 °C to + 85 °C.