Effect of Ba Nonstoichiometry in Bax(Zr0.8Y0.2)O3−δ on Population of 5‐Coordinated Y

The local environments of Y in the Y‐substituted BaZrO₃ of the starting compositions of Ba_x(Zr_0.8Y_0.2)O_3?δ (x = 0.97, 1.0, 1.03, and 1.06) were analyzed by ⁸⁹Y magic angle spinning NMR spectroscopy. The result showed a strong population dependence of 5‐coordinated Y³⁺ ions mostly at the B site on the Ba contents. The enhancement of Ba contents by 9 at% (from 0.97 to 1.06 in the starting Ba contents) in a nominal composition increased the amount of 5‐coordinated Y³⁺ ions from 35% ± 7% to 49% ± 5%, suggesting the importance of maximizing the Ba contents to populate more oxygen vacancies which is related to the concentration of protons incorporated during the hydration process. The wide variation in the lattice parameter of yttrium‐substituted BaZrO₃ perovskite materials in previous reports was reinterpreted with the variation in the Ba contents resulting from the evaporation of BaO during the sintering processes. Y³⁺ ions were confirmed to replace mainly the Zr⁴⁺ ions, as expected, and a tendency of oxygen vacancy clustering near the Y³⁺ ions was discussed.     

Ba and Gd Doping Effect in (BaxSr1–x)0.95Gd0.05Co0.8Fe0.2O3–δ (x = 0.1–0.9) Cathode on the Phase Structure and Electrochemical Performance

In this study, Ba_xSr_1–xCo_0.8Fe_0.2O_3–δ (BSCF) doped with trace of Gd were studied for phase structures and properties about thermal expansion, electrical conductivity, and electrocatalytic activity. The solution range of barium in Ba_xSr_1–xCo_0.8Fe_0.2O_3–δ can be extended to 0.1 ≤ x ≤ 0.7 after the introduction of small amount of Gd³⁺ ions (only for 5%) into the Ba/Sr‐site. The calculation results of the crystal structure and the crystal lattice energy show that the ratio of Ba/Sr and doping of Gd³⁺ lead to increase the lattice parameter and the Co/Fe ionic average valence state in B‐site. Moreover, the ratio of Ba/Sr and doping of Gd³⁺ were found to have significant impacts on the high‐temperature physical properties and electrochemical characteristics. All oxides exhibited decreases in the thermal expansion coefficient (TEC) and electrical conductivity with increasing Ba/Sr ratio. Barium insertion was found to change the area‐specific resistance (ASR) of porous (not dense) cathodes. An ASR values of 0.048, 0.072, 0.064, 0.121, and 0.059 Ω cm² under air condition were observed at 650 °C for BSGCF with x = 0.1, 0.2, 0.3, 0.5, and 0.7, respectively.     

Variation of crystal structure,magnetization, and dielectric properties of Nd and Ba co-doped BiFeO3 multiferroics

Multiferroics having composition Bi_0.80Nd_0.20-xBa_xFeO₃ were prepared to investigate the effect of doping on crystal structure, magnetic, and dielectric properties. The Rietveld refinement deduces the formation of mixed structural symmetry. With larger content of Nd, crystal structure consisting of major rhombohedral R3c and minor orthorhombic Pnma has been accomplished. The fraction of rhombohedral phase has been found to increase with doping of Ba up to x = 0.10. At composition x = 0.15, the orthorhombic phase Pnma disappears, and there is evolution of triclinic phase P1 in place of it. The mixed structure now accomplished contains ≈61% rhombohedral R3c and rest 39% triclinic P1. In solely Ba-doped sample (ie, at x = 0.20), the fraction of rhombohedral R3c phase again rises and attains ≈92% fraction of the structure along with rest triclinic P1 phase. The M-H loops depict enormous enhancement in magnetic properties with increasing doping of Ba. Dielectric constant (ε′) and dielectric loss (tan δ) both were found to increase with doping of Ba. The anomalies present in the dielectric constant and dielectric loss with temperature may be regarded to the hopping conduction of e⁻ between Fe³⁺ and Fe²⁺ and their interaction with oxygen vacancies.     

Site-selective substitution and resulting magnetism in arc-melted perovskite ATiO3-δ (A = Ca,Sr, Ba)

Magnetic properties in perovskite titanates ATiO_3-δ (A = Ca, Sr, Ba) were investigated before and after arc melting. Crystal structure analysis was conducted by powder synchrotron X-ray diffraction with Rietveld refinements. Quantitative chemical element analysis was carried out by X-ray photoelectron spectroscopy. Magnetic measurements were conducted by vibrating sample magnetometer and X-ray magnetic circular dichroism (XMCD). The magnetic properties are found to be affected by impurities of 3d elements such as Fe, Co, and Ni. Depending on the composition and crystal structure, the occupation of the magnetic ions in perovskite titanates is selectively varied, which is interpreted to be the origin of the different magnetic behaviors in arc-melted perovskite titanates ATiO_3-δ (A = Ca, Sr, Ba). In addition, both formation of oxygen vacancies and the reduction of Ti⁴⁺ to Ti³⁺ during arc-melting also play a role as proven by XMCD. Nevertheless, preferential site occupation of magnetic impurities is dominant in the magnetic properties of arc-melted perovskite ATiO_3-δ (A = Ca, Sr, Ba).     

Anisotropic domain structures of Pb(Mg1/3Nb2/3)O3–PbZrO3–PbTiO3 single crystals with high ferroelectric phase transition temperature

The anisotropic domain structures and local piezoresponse of rhombohedral Pb(Mg_1/3Nb_2/3)O₃–PbZrO₃–PbTiO₃ single crystals with high ferroelectric phase transition temperature (T_FE‐FE≥120°C) were systematically investigated by vector piezoresponse force microscopy. The typical size of labyrinthine domain pattern for [001]_C sample was in the range of 100‐200 nm, revealing its relaxor feature. While the [011]_C sample exhibited ordered ribbon‐shaped domain pattern with preferential alignment along <011> direction since the modulation effect of polar nanoregions. For [111]_C sample, it had messy and featureless domain patterns. For as‐grown crystal, the incorporation of Zr⁴⁺ cation in Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ system resulted in that the long‐range coulomb interactions of the charged ions in the short range order regions were weakened, leading to an increased relaxor feature. Concurrently, the incorporation of Zr⁴⁺ cation enhanced the Pb‐B repulsion intensity, resulting in an improved T_FE‐FE. Temperature‐dependent properties of as‐grown crystal exhibited good temperature stability from 30 to 120°C, indicating it is a promising material for actuator and ultrasonic transducer applications.     

Structure,Ferroelectric, Piezoelectric,and Ferromagnetic Properties of BiFeO3‐BaTiO3‐Bi0.5Na0.5TiO3 Lead‐Free Multiferroic Ceramics

Lead‐free multiferroic ceramics of BiFeO₃‐BaTiO₃‐Bi_0.5Na_0.5TiO₃ have been prepared by a conventional ceramic technique. The microstructure, multiferroic, and piezoelectric properties of the ceramics have been studied. The ceramics sintered at 1000°C for 2 h possess a pure perovskite structure and a morphotropic phase boundary of rhombohedral and tetragonal phases is formed at x = 0.02. After the addition of Bi_0.5Na_0.5TiO₃, two dielectric anomalies are observed at high temperatures (T_m ~ 510°C–570°C and T₂ ~ 720°C). The phase transition around T_m becomes wider gradually with increasing x. The ferroelectricity, piezoelectricity, and ferromagnetism of the ceramics are significantly improved after the addition of Bi_0.5Na_0.5TiO₃. High resistivity (~1.3 × 10⁹ Ω·cm), strong ferroelectricity (P_r = 27.4 μC/cm²), good piezoelectricity (d₃₃ =140 pC/N, k_p = 31.4%), and weak magnetic properties (M_r =0.19 emu/g) are observed.     

Structural,Raman, and Dielectric Studies on Multiferroic Mn‐doped Bi1−xLaxFeO3 Ceramics

Multiferroic Bi_1?xLa_xFeO₃ [BLFO (x)] ceramics with x = 0.10–0.50 and Mn‐doped BLFO (x = 0.30) ceramics with different doping contents (0.1–1.0 mol%) were prepared by solid‐state reaction method. They were crystallized in a perovskite phase with rhombohedral symmetry. In the BLFO (x) system, a composition (x)‐driven structural transformation (R3c→C222) was observed at x = 0.30. The formation of Bi₂Fe₄O₉ impure phase was effectively suppressed with increasing the x value, and the rhombohedral distortion in the BLFO ceramics was decreased, leading to some Raman active modes disappeared. A significant red frequency shift (~13 cm^?1) of the Raman mode of 232 cm^?1 in the BLFO ceramics was observed, which strongly perceived a significant destabilization in the octahedral oxygen chains, and in turn affected the local FeO₆ octahedral environment. In the Mn‐doped BLFO (x = 0.30) ceramics, the intensity of the Raman mode near 628 cm^?1 was increased with increasing the Mn‐doping content, which was resulted from an enhanced local Jahn–Teller distortions of the (Mn,Fe)O₆ octahedra. Electron microscopy images revealed some changes in the ceramic grain sizes and their morphologies in the Mn‐doped samples at different contents. Wedge‐shaped 71° ferroelectric domains with domain walls lying on the {110} planes were observed in the BLFO (x = 0.30) ceramics, whereas in the 1.0 mol% Mn‐doped BLFO (x = 0.30) samples, 71° ferroelectric domains exhibited a parallel band‐shaped morphology with average domain width of 95 nm. Dielectric studies revealed that high dielectric loss of the BLFO (x = 0.30) ceramics was drastically reduced from 0.8 to 0.01 (measured @ 10⁴ Hz) via 1.0 mol% Mn‐doping. The underlying mechanisms can be understood by a charge disproportion between the Mn⁴⁺ and Fe²⁺ in the Mn‐doped samples, where a reaction of Mn⁴⁺ + Fe²⁺→Mn³⁺ + Fe³⁺ is taken place, resulting in the reduction in the oxygen vacancies and a suppression of the electron hopping from Fe³⁺ to Fe²⁺ ions effectively.     

Local Structural Rearrangements and Evolution of Relaxor State in the Complex Perovskite (Ba1−xPbx) (In0.50Nb0.50) O3

Local structural rearrangements in lead‐based complex perovskites of the type (Ba_1?xPb_x)(In_0.50Nb_0.50)O₃ responsible for transition from ferroelectric [Ba(In_0.50Nb_0.50)O₃] to relaxor [Pb(In_0.50Nb_0.50)O₃] are examined by careful analysis of their Raman spectra. Subtle changes in the bonding brought about by the differences in the chemical nature of A‐ and B‐site cations have been correlated with the dynamic A–O–B coupling. Deviations in the local structure as a result of such bonding preferences have been confirmed by studying the changes in the Raman spectra when Nb⁵⁺ is substituted by Sn⁴⁺ as the third B‐site cation.     

Investigation of transport behavior in Ba doped BiFeO3

Bi_1?xBa_xFeO₃ (x = 0.00–0.25) samples were prepared by conventional solid state reaction method. X-ray diffraction revealed the rhombohedrally distorted perovskite structure for undoped BiFeO₃ with a phase transition from rhombohedral to pseudo cubic on Ba substitution. The leakage current density of 10% Ba substituted sample is found to be four orders of magnitude less than that of the pure BiFeO₃. Grain boundary limited conduction and space charge limited conduction mechanisms are involved in low and high electric field regions respectively for all the samples except 10% Ba doped BFeO₃ which obeys grain boundary limited conduction mechanism in whole of the electric field range. Dielectric measurements showed that the dielectric constant and dielectric loss attained their minimum values at 10% Ba substitution. Thus 10% Ba is found to be optimum concentration to have better multiferroic properties. Undoped BiFeO₃ and 5% Ba doped samples have very large values of dielectric constants and leakage current densities which can be attributed to a large number of oxygen vacancies in these samples, indicating an extrinsic response of these compositions.     

Tuning of conductive type and magnetic properties of Ca3Co2O6 ceramics through Pb‐doping

The effect of Pb doping on structural, electrical, magnetic, and thermal transport properties of Ca_3?xPb_xCo₂O₆ (x=0‐0.3) ceramics has been investigated systemically. It is found that the substituted Pb‐ions have a mixed valence state of +2 and +4, and a small amount of Co³⁺ ions will transfer into Co²⁺ due to the substitution of Pb⁴⁺ for Ca²⁺. The resistivity decreases monotonically with increasing Pb content, which is related to the variation in carrier concentration and the enhanced grain connectivity. The signs of both Hall coefficient and thermopower changed from positive to negative by a proper Pb doping, indicating the conductive type of Ca₃Co₂O₆ can be effectively tuned from p to n through the doping. The low‐temperature magnetization, the magnetic exchange coupling constant J and Weiss temperature θ decrease monotonically with the increase in Pb‐doping content, indicating the strength of the ferromagnetic interaction between adjacent high spin Co³⁺ ions has been weakened due to the reduced magnetic correlation length in these Pb‐doped samples.     

High temperature‐insensitive ferro‐/piezoelectric properties and nanodomain structures of Pb(In1/2Nb1/2)O3–PbZrO3–Pb(Mg1/3Nb2/3)O3–PbTiO3 relaxor single crystals

For rhombohedral (R) Pb(In_1/2Nb_1/2)O₃–PbZrO₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PIN–PZ–PMN–PT) relaxor single crystal, high temperature‐insensitive behaviors under different external stimuli were observed (remnant polarization P_r from 30°C to 180°C and piezoelectric strain d₃₃* from 30°C to 116°C). When electric field E ≥ 50 kV/cm in the case of an activation field E_a = 40‐50 kV/cm was applied, it was found that the domain switching was accompanied by a phase transition. The high relaxor nature of the R phase PIN–PZ–PMN–PT was speculated to account for the large E_a and high piezoelectric response. The short‐range correlation lengths extracted from the out‐of‐plane (OP) and in‐plane (IP) nanodomain images, were 64 nm and 89 nm, respectively, which proved the high relaxor nature due to In³⁺ and Zr⁴⁺ ions entering the B‐site in the ABO₃‐lattice and enhancing the disorder of B‐site cations in the R phase PIN–PZ–PMN–PT. The switching process of R nanodomain variants under the step‐increased tip DC voltage was visually revealed. Moreover, the time‐dependent domain evolution confirmed the high relaxor nature of the R phase PIN–PZ–PMN–PT single crystal.     

Effects of Nonstoichiometry and Cocatalyst Loading on the Photocatalytic Hydrogen Production with (Y1.5Bi0.5)1−xTi2O7−3x and (YBi)1−xTi2O7−3x Pyrochlores

By adjusting the Ti/(Y+Bi) ratios during synthesis, nonstoichiometric pyrochlores of (Y_1.5Bi_0.5)_{1 ? x}Ti₂O_{7 ? 3x} and (YBi)_{1 ? x}Ti₂O_{7 ? 3x} were prepared by an aqueous sol–gel method and annealed at different temperatures. The materials were characterized by X‐ray diffraction and UV–vis reflectance spectroscopy. The samples were tested for photocatalytic hydrogen production in the presence of methanol as sacrificial agent after being loaded with nanoparticles of rhodium or platinum acting as cocatalysts. It was found that materials being completely inactive in a stoichiometric composition can be tuned to good photocatalysts by optimizing the Ti/(Y+Bi) ratio. The increase in activity is supposed to derive from an optimization of the TiO₆‐octahedral geometry due to the generation of vacancies inside the structure. Increasing the Bi loading shifts the absorption edge into the visible, but unfortunately, an increase of the bismuth content in the structure also leads to stability issues during photocatalysis, which can be suppressed or at least weakened by a higher cocatalyst loading.     

Structure and Luminescence of New Red‐Emitting Materials‐Eu3+‐Doped Triple Orthovanadates NaALa(VO4)2 (A = Ca,Sr, Ba)

The new red‐emitting phosphors of Eu³⁺‐doped triple orthovanadates NaALa(VO₄)₂ (A = Ca, Sr, Ba) were prepared by the high‐temperature solid‐state reaction. The formation of single phase compound with isostructural structure of Ba₃(VO₄)₂ was verified through X‐ray diffraction (XRD) studies. The photoluminescence excitation and emission spectra, the fluorescence decay curves and the dependence of luminescence intensity on doping level were investigated. The phosphor can be efficiently excited by near UV and blue light to realize an intense red luminescence (613 nm) corresponding to the electric dipole transition ⁵D₀→⁷F₂ of Eu³⁺ ions. Their potential applications as red‐emitting phosphors for solid‐state lighting were evaluated in comparison with the Eu³⁺‐doped lanthanum orthovanadate LaVO₄ and other reported references. The luminescence was discussed in detail on the base of the crystal structures. The luminescence thermal stability on temperature was investigated and the thermal activated energy was calculated. The phosphors can be suggested to be a potential red‐emitting phosphor for the application on white LEDs under irradiation of near‐UV or blue chips.     

Influence of Sr2+ on Calcium‐Deficient Hydroxyapatite Formation Kinetics and Morphology in Partially Amorphized α‐TCP

Hydration of partially amorphized α‐TCP powders with Sr²⁺ concentrations ranging from 0 to 10 mol% substitution for Ca²⁺ was analyzed by isothermal calorimetry and quantitative in‐situ XRD. Hydration of both crystalline α‐TCP and amorphous TCP (ATCP) forming CDHA was retarded to an increasing extent with increasing Sr²⁺ content. Sr²⁺ slightly reduced the crystallite size (XRD coherent scattering domains) of the CDHA formed during hydration, while the size of crystals visible under SEM was not noticeably affected. Reaction enthalpies of ΔH_{R(Sr‐α‐TCP→Sr‐CDHA)} = 122 ± 8 J/g_TCP and ΔH_{R(Sr‐ATCP→Sr‐CDHA)} = 257 ± 8 J/g_TCP were determined for the hydration of crystalline α‐TCP and ATCP containing 5 mol% Sr²⁺ substitution for Ca²⁺. This is comparable with the corresponding reaction enthalpies previously obtained for undoped samples, which are 106 ± 7 J/g_TCP for α‐TCP and 250 ± 7 J/g_TCP for ATCP.     

Raman Vibrations,Domain Structures,and Photovoltaic Effects in A‐Site La‐Modified BiFeO3 Multiferroic Ceramics

Micro‐Raman spectroscopy, X‐ray diffraction, high‐resolution transmission electron microscopy (TEM), oxygen vacancies, synchrotron X‐ray absorption spectroscopy, magnetizations, optical band gaps, and photovoltaic (PV) effects have been studied in (Bi_1?xLa_x)FeO₃ (BFO100xL) ceramics for x = 0.0, 0.05, 0.10, and 0.15. XRD, Raman spectra, and TEM confirm a rhombohedral R3c symmetry with the tilted FeO₆ oxygen octahedra in all compounds. The low‐frequency Raman vibrations become broader and shift toward higher frequency as La³⁺ increases. Fe K‐edge synchrotron X‐ray absorptions reveal that Fe³⁺ valence and Fe–O–Fe bond angle are not modified by the La³⁺ substitution. All compounds exhibit a linear antiferromagnetic feature. Optical transmission reveals band gaps in the range of 2.22–2.24 eV. The heterostructures of indium tin oxide (ITO) film/(Bi_1?xLa_x)FeO₃ ceramics/Au film show a p–n junction‐like I–V characteristic behavior. The maximal PV power conversion efficiency can reach 0.19% in ITO/BFO15L/Au under illumination of λ = 405 nm. A junction‐like theoretical model can reasonably describe open‐circuit voltage and short‐circuit current as a function of illumination intensity.     

Theoretical Study of Cubic and Orthorhombic Nd1–xSrxMnO3 as a Potential Solid Oxide Fuel Cell Cathode

In this paper, the atomic and electronic structures of cubic and orthorhombic Nd_1–xSr_xMnO₃ are investigated using the projector augmented‐wave (PAW) methods within the spin‐polarization generalized gradient approximation (GGA+U), where U is on‐site Coulomb interaction correction. The optimized structure parameters of both cubic and orthorhombic bulk phases are obtained. The difference between the AFM and FM structures for NdMnO₃ is very small, indicating a small magneto‐elastic effect. In Nd_1–xSr_xMnO₃, the pseudo‐cubic lattice constant decreases on increasing Sr doping due to the oxidation of Mn³⁺ cations to the smaller Mn⁴⁺ cations. The result of the total density of states shows the majority spin without gap and the minority spin with 4.8 × 10⁻¹⁹ J gap, indicating a half‐metallic ground state for NdMnO₃ in GGA+U treatment. The Bader effective charges in both cubic and orthorhombic phases are analyzed. The oxygen vacancy formation energy of Nd_1–xSr_xMnO₃ becomes smaller as the Sr doping concentration increases. The oxygen vacancies can be formed more easily on Nd_0.5Sr_0.5MnO₃ than other systems. These results suggest that Nd_0.5Sr_0.5MnO₃ could be a promising candidate for application in SOFC.     

Structure Property Relationship in BaTiO3–Na0.5Bi0.5TiO3–Nb2O5–NiO X8R System

A novel BaTiO₃–Na_0.5Bi_0.5TiO₃–Nb₂O₅–NiO (BT‐NBT‐Nb‐Ni) system that meets the X8R specification (?55°C–150°C, ΔC/C≤±15%) of multilayer ceramic capacitors (MLCCs) was fabricated, with a maximum dielectric constant of 2350 at room temperature (25°C). Core–shell microstructure was observed by transmission electron microscopy (TEM), accounting for the good dielectric temperature stability. The role of Ni on the formation of core–shell structure and phase structure, and the subsequent relationship between structure and dielectric/ionic conduction properties were investigated. It was observed that the addition of Ni could adjust the ratio of core/shell, and significantly reduces the dielectric loss over the studied temperature range. A new Ba₁₁(Ni, Ti)₂₈O_66+x phase with a 10‐layer close‐packed structure was identified by X‐ray diffraction (XRD), serving as a source of oxygen vacancies for ionic conduction in addition to Ba(Ni,Ti)O₃. Furthermore, the impedance spectroscopy measurements demonstrated the remarkable impact of these Ni‐induced oxygen vacancies on both the grain and grain‐boundary conductivities.     

Metastable Ferroelectric Phase Induced by Electric Field in xPb(Zn1/3Nb2/3)O3–(1–x)Pb(Zr0.95Ti0.05)O3 Ceramics

A xPb(Zn_1/3Nb_2/3)O₃–(1–x)Pb(Zr_0.95Ti_0.05)O₃ (xPZN–(1–x) PZT) system close to antiferroelectric–ferroelectric (AFE–FE) morphotropic phase boundary has been prepared and investigated. The XRD results reveal PZN addition induces a phase transition from the orthorhombic (AFE) to rhombohedral (FE) phase through a phase coexistence region (AFE+FE). The polarization–electric field (P–E) measurements indicate that the AFE phase can be induced into a metastable FE (FE_m) phase. And the FE_m can recover to AFE around a critical temperature indicated by temperature‐dependent P–E loops. A composition‐temperature phase diagram was generalized within a certain range of PZN content in which an AFE–FE phase boundary connecting orthorhombic antiferroelectric to rhombohedral ferroelectric phase zones is formed near room temperature.     

Ferroelectric and magnetic properties in (1−x)BiFeO3–x(0.5CaTiO3–0.5SmFeO3) ceramics

Multiferroic ceramics were prepared and characterized in (1?x)BiFeO₃–x(0.5CaTiO₃–0.5SmFeO₃) system by a standard solid‐state reaction process. The structure evolution was investigated by X‐ray diffraction and Raman spectrum analyses. The refinement results confirmed the different phase assemblages with varying amounts of polar rhombohedral R3c and nonpolar orthorhombic Pbnm as a function of the substitution content. In the compositions range of 0.2≤x≤0.5, polar R3c and nonpolar Pbnm coexisted, which was referred to polar‐to‐nonpolar morphotropic phase boundary (MPB). According to the dielectric and DSC analysis results, the ceramics with x≤0.2 changed to diffused ferroelectric, and the ferroelectric properties were enhanced significantly. Two dielectric relaxations were detected in the temperature range of 200‐300 K and 500‐700 K, respectively. The high‐temperature dielectric relaxation was attributed to the grain‐boundary effects. While the low temperature dielectric relaxation obtained in the samples with x=0.3‐0.5 was related to the charge transfer between Fe²⁺ and Fe³⁺. The magnetic hysteresis loops measured at different temperature indicated the enhanced magnetic properties in the present ceramics, which could be attributed to the suppressed cycloidal spin magnetic structure by Ti ions. In addition, the rare‐earth Sm spin moments might also affect the magnetic properties at relatively lower temperature.     

Local Structure Investigation in Multiferroic BiFeO3–BaTiO3 Ceramics by XAS Technique and Their Relevant Properties

The (1?x)BiFeO₃‐xBaTiO₃ (with x = 0.1, 0.2, 0.3, and 0.4) ceramics were fabricated successfully by solid‐state reaction method. Single‐phase perovskite was obtained in all ceramics, as confirmed by XRD technique. It was observed that 0.7BiFeO₃–0.3BaTiO₃ was the morphotropic phase boundary (MPB) between rhombohedral and cubic phases, as also revealed from ferroelectric and magnetic properties. The simulated and experimental X‐Ray Absorption Spectroscopy (XAS) study revealed that BT in 0.75BF‐0.25BT is possibly taken a rhombohedral structure. Furthermore, the rounded ferroelectric hysteresis loops observed for 0.9BiFeO₃–0.1BaTiO₃ and 0.8BiFeO₃–0.2BaTiO₃ compositions could be attributed to their microstructure and surface charge effects and electron transfer between Fe³⁺ and Fe²⁺ ions. It was also found that high dielectric constant of 0.9BiFeO₃–0.1BaTiO₃ composition was a result of grain and grain‐boundary effects, as observed in SEM micrographs. In addition, a strong signature of dielectric relaxation behavior was observed in this ceramic system with the activation energy 0.467 eV obtained from the Arrhenius' law. Finally, the local structure investigation with XAS technique provided additional information to better understand the electric and magnetic properties in the BF‐BT ceramic system.