Effect of annealing atmosphere on the structural and electrical properties of BiFeO3 multiferroic ceramics prepared by sol–gel and spark plasma sintering techniques

Phase-pure BiFeO₃ powders were synthesized by sol–gel technique. Based on these powders, high-density BiFeO₃ ceramics were prepared by spark plasma sintering (SPS) at 700 °C along with annealing for 2 and 4 h, respectively, at 650 °C under atmospheres of air and oxygen. X-ray diffraction analysis revealed that the 4 h-oxygen-annealed sample contained a single rhombohedral perovskite phase while the samples annealed in the other conditions contained small quantities of impurity phases besides the rhombohedral perovskite phase. The relative density of the 4 h-oxygen-annealed sample was about 96%, being apparently higher than that of the other samples. In comparison with the 4 h-air-annealed sample, the dielectric constant of the 4 h-oxygen-annealed sample was relatively higher. The activation energy for electrical conduction was about 1.17 eV for the 4 h-oxygen-annealed sample while it was about 0.98 eV for the 4 h-air-annealed sample, showing that the former would have a lower room-temperature conductivity (~2.6×10⁻¹⁴ S cm⁻¹) than the latter (~2.1×10⁻¹³ S cm⁻¹). It is therefore anticipated that the oxygen-annealed sample could possess better ferroelectric properties as compared to the air-annealed sample.     

Ferroelectric and magnetic properties of magnetoelectric (Na0.5Bi0.5)TiO3–BiFeO3 synthesized by acetic acid assisted sol–gel method

The perovskite solid solution system resulting from the combination of Na_0.5Bi_0.5TiO₃ (NBT) and BiFeO₃ (BFO) has been studied for its magnetoelectric properties in BFO-rich phases of the series, using magnetometry and piezoresponse force microscopy (PFM). Raman spectroscopy results confirmed the successful formation of solid solutions having spectral features that are combination of two parent compounds. The solid solutions displayed a variable bandgap in the range 2.12–2.39 eV with composition. The results of PFM suggest an improved spontaneous polarization with the progressive replacement of (Na,Bi)²⁺ and Ti⁴⁺ ions at A- and B-sites of BFO lattice. At the same time room temperature weak ferromagnetic response was seen in mixed compositions. A systematic shift in magnetic transition temperatures from 650 K to 410 K was observed with the increase of NBT content. Magnetoelectric (ME) coefficient of 9 mV/cm-Oe was obtained for 40NBT–60BFO composition. Our studies indicate that NBT–BFO solid solution system is a potentially useful candidate for lead-free single phase ME applications.     

Effects of annealing temperature on the microstructure,optical, ferroelectric and photovoltaic properties of BiFeO3 thin films prepared by sol–gel method

Bismuth ferrite thin films were prepared via sol–gel spin-coating method and the effects of annealing temperature on microstructure, optical, ferroelectric and photovoltaic properties have been investigated. The results show that the bismuth ferrite thin films annealed at 550 °C is single phase and the grain size increases with the rise of annealing temperature. The band gap of bismuth ferrite thin films annealed at 550–650 °C is between 2.306 eV and 2.453 eV. With the rise of the annealing temperature, the remnant polarization gradually decreases and the coercive electric field increases. The short circuit photocurrent density decreases with the rise of annealing temperature, and the open circuit photovoltage and the power conversion efficiency of bismuth ferrite thin films annealed at 550 °C are higher than the thin films annealed at higher temperature.     

Structural,dielectric and piezoelectric properties of (Bi0.5Na0.5)TiO3–(Bi0.5K0.5)TiO3–Bi(Zn0.5Ti0.5)O3 thin films prepared by sol–gel method

Lead free (1−x)(0.8Bi_0.5Na_0.5Ti_0.5O₃–0.2Bi_0.5K_0.5TiO₃)–xBiZn_0.5Ti_0.5O₃ (x=0–0.06) (BNT–BKT–BZT) thin films were deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by a sol–gel processing technique. The effects of BZT content on the structural, dielectric, ferroelectric and piezoelectric properties of the BNT–BKT–BZT thin films were investigated systematically. The BNT–BKT–BZT thin films undergo a transition from ferroelectric to relaxor phase with increasing temperature. The phase transition temperature decreases with the increase of BZT content. The BNT–BKT–BZT thin film with x=0.04 exhibits the best ferroelectric properties (P_max=40 µC/cm² and P_r=10 µC/cm²), largest dielectric constant (ε=560) and piezoelectric constant (d₃₃=40 pm/V). This finding demonstrates that the BNT–BKT–BZT thin film has an excellent potential for demanding high piezoelectric properties in lead free films.     

Growth and electrical properties of Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3 lead-free single crystals by the TSSG method

A series of NBT-KBT lead-free crystals with dimensions of Φ 35×10 mm were successfully grown by the TSSG method. The as-grown crystals possess rhombohedral perovskite structure at room temperature. The curves ε(T) for all crystals show two abnormal dielectric peaks. The depolarization temperatures T_d derived from the first peak of curves tan δ(T) vary with the KBT content, which are 130, 150, 140, and 115 °C respectively, for (100−x)NBT−xKBT (x=5, 8, 12, 15) crystals, being well consistent with the T_d obtained from the temperature dependence of k_t. A notable thermal hysteresis, ΔT≈35 °C, for ferroelectric-antiferroelectric phase transition was also disclosed for 92NBT-8KBT crystal. The investigation of orientation dependence for electrical properties disclosed the dielectric parameters show weak anisotropy. The piezoelectric constants (d₃₃) are 147, 175, 205, 238 pC/N and the values of k_t are 38%, 52%, 52%, 54%, respectively for (100−x)NBT−xKBT (x=5, 8, 12, 15) crystals.     

Structural properties of multiferroic 0.5BiFeO3–0.5Pb(Fe0.5Nb0.5)O3 solid solution

Magnetoelectric multiferroics are very promising materials because of their practical applications and fundamental interests. The most widely studied magnetoelectric oxides are ABO₃ perovskites. In the paper structural properties of BiFeO₃ and Pb(Fe_0.5Nb_0.5)O₃ solid solution are described. The material crystallizes in rhombohedral R3c crystal structure which parameters are presented. Mössbauer spectroscopy was used to study local changes in an iron environment due to Fe/Nb substitution and hyperfine interaction parameters of different local surroundings of iron atoms are presented. The random distribution of B-site sublattice cations was confirmed. Ab initio calculations of the studied solid solution were conducted and theoretical crystal structure parameters were compared with the experimental data. The theoretical magnetic and electric properties are discussed. The local iron magnetic moments were estimated and their dependence on the local surrounding changes is shown. The calculated electrons densities and Bader's topological analysis were used to describe chemical bonding properties.     

Optical properties of Nb-doped TiO2 thin films prepared by sol–gel method

In this work, we studied optical properties of pure and Nb-doped TiO₂ synthesized using a sol–gel method and deposited as thin films by spin-coating followed by annealing in air at 500 °C for 1 h. The surface elemental composition was derived from X-ray photoelectron spectra, while structure and surface morphology were investigated using X-ray diffraction and atomic force/scanning electron microscopy. Finally, the optical properties were investigated by means of UV–vis spectrophotometry and spectroscopic ellipsometry.The Nb content was determined from XPS measurements to vary between 1.8 and 4.3 at%. The XRD patterns of the deposited thin films, with a maximum thickness of about 56 nm, showed no diffraction peaks. As proven both by microscopy and spectroscopic ellipsometry studies doping TiO₂ with Nb modified the surface morphology of the samples; the grain size is increasing while the surface roughness decreases with the increase in Nb content. This is accompanied by a decrease in the refractive index and an increase of the extinction coefficient.     

Effect of carbon nanotubes on sintering behavior of alumina prepared by sol–gel method

Alumina (Al2O3)/carbon nanotube (CNT) (99/1 by weight) composite was prepared by mixing CNT dispersion with AlCl₃-based gel, followed by high temperature sintering at a temperature up to 1150 °C in argon. Composite alumina precursor showed phase transition order from amorphous to γ-Al₂O₃ after sintered at 900 °C for 2 h, partially to θ-Al₂O₃ after sintered at 1000 °C for 2 h, and then partially to α-Al₂O₃ after sintered at 1150 °C for 2 h. By comparison, control alumina precursor directly transformed from amorphous to α-Al₂O₃ after sintered at a relatively low temperature of 600 °C for 2 h. Composite alumina showed porous structure with pore diameter ranging from 100 nm to 2 µm, whereas control alumina was relatively pore-free. The elevated alumina-crystal phase transition temperatures and the formation of porous structure were ascribed to the presence of CNTs in alumina precursor. The composite alumina sintered at 900 °C for 2 h containing only γ-Al₂O₃ had a BET surface area of 138 m²/g, which was significantly higher than that of control alumina sintered at 1150 °C for 2 h containing only α-Al₂O₃, ~15 m²/g.     

Influence of seed layer on crystal orientation and electrical properties of (Na0.85K0.15)0.5Bi0.5TiO3 thin films prepared by a sol–gel process

Sol–gel derived lead-free (Na_0.85K_0.15)_0.5Bi_0.5TiO₃ (NKBT) thin films, with and without a Pb_0.8La_0.1Ca_0.1Ti_0.975O₃ (PLCT) seed layer, were fabricated on (111)Pt/Ti/SiO₂/Si substrates. The influences of the seed layer on crystal orientation and electrical properties were investigated in detail. XRD indicated that the NKBT thin films fabricated with a seed layer were fully crystallized into a single perovskite structure, while the films fabricated under the same conditions, but without a seed layer, possessed a certain amount of pyrochlore phase. The NKBT film with a 14 nm-thick seed layer showed high (100) orientation, and exhibited enhanced electrical properties, such as a higher remanent polarization (Pr～18 µC/cm²), a lower dielectric loss tangent (tan δ ～0.023) and smaller transient current density (J<10^?5 A/cm²).     

Effect of annealing temperature on ferroelectric electron emission of sol–gel PZT films

In this work, the influence of annealing temperature on the ferroelectric electron emission behaviors of 1.3-μm-thick sol–gel PbZr_0.52Ti_0.48O₃ (PZT) thin film emitters was investigated. The results revealed that the PZT films were crack-free in perovskite structure with columnar-like grains. Increasing annealing temperature led to the growth of the grains with improved ferroelectric and dielectric properties. The remnant polarization increased slightly from 35.3 to 39.6 μC/cm² and the coercive field decreased from the 56.4 to 54.6 kV/cm with increasing annealing temperature from 600 to 700 °C. The PZT film emitters exhibited remarkable ferroelectric electron emission behaviors at the threshold voltage above 95 V. The film annealed at 700 °C showed a relatively lower threshold voltage and higher emission current, which is related to the improved ferroelectric and dielectric properties at higher annealing temperature. The highest emission current achieved in this work was around 25 mA at the trigger voltage of 160 V.     

Impedance spectroscopy studies on PbFe0.5Nb0.5O3 –BiFeO3 multiferroic solid solution

(1-x) PbFe_0.5Nb_0.5O₃ (PFN) – (x) BiFeO₃ (BFO) (PFN – BFO) multiferroic solid solution (x = 0.1, 0.2, 0.3 and 0.4) were synthesized by single step solid state reaction method. Single phase was confirmed in all the samples through room temperature (RT) X-ray Diffraction (XRD) with monoclinic structure (Cm space group). Transmission Electron Microscopy (TEM) studies confirm the high crystallinity of the materials with the average particle size of 100 nm. The temperature (313–528 K) and frequency (100 Hz – 5 MHz) dependent impedance, modulus and DC conductivity of PFN – BFO solid solutions were investigated. An impedance spectroscopy result shows a significant contribution from the grains (bulk) to the conductivity and exhibits non-Debye type of relaxation. The bulk (grain) resistance reduces as the temperature increases corresponds to negative temperature coefficient of resistance (NTCR) behaviour. Electric modulus exhibits thermally dependent relaxation phenomena in the material. The Bergmann modified KWW function fitted to the imaginary modulus with non-Debye type of relaxation. DC conductivity of PFN – BFO solid solutions was found to follow the Arrhenius behaviour.     

Effect of annealing temperature on structural and optoelectronic properties of γ-CuI thin films prepared by the thermal evaporation method

High quality transparent conducting CuI thin films were deposited at room temperature via thermal evaporation technique followed by post deposition annealing at different temperatures. The samples were characterised by X-ray diffraction (XRD), UV–Vis spectrophotometry, Scanning electron microscopy and I-V measurements. The structural, morphological and optical properties were studied as a function of the annealing temperature from room temperature (RT) to 200 °C. XRD results revealed that the films were polycrystalline with zinc blende structure of cubic phase. Increasing the annealing temperature increased the crystallite size from 33 to 49 nm whilst the dislocation density and lattice strain shifted to lower values. High transmittance of about 70–80% was exhibited by all films in the entire visible spectral range. The as deposited film possesed the lowest resistivity of 3.0×10⁻³ Ω cm.     

Synthesis and properties of multiferroic 0.7BiFeO3−0.3BaTiO3 thin films by Mn doping

Multiferroic BiFeO₃?BaTiO₃ thin films that simultaneously exhibit ferroelectricity and ferromagnetism at room temperature were prepared by chemical solution deposition. Perovskite single-phase 0.7BiFeO₃?0.3BaTiO₃ thin films were successfully fabricated in the temperature range 600–700 °C on Pt/TiO_x/SiO₂/Si substrates. As the crystallization temperature was increased, grain growth proceeded, resulting in higher crystallinity at 700 °C. Although the 0.7BiFeO₃?0.3BaTiO₃ thin films exhibited poor polarization (P)?electric field (E) hysteresis loops owing to their low insulating resistance. The leakage current at high applied fields was effectively reduced by Mn doping at the Fe site of the 0.7BiFeO₃?0.3BaTiO₃ thin films, leading to improved ferroelectric properties. The 5 mol% Mn-doped 0.7BiFeO₃?0.3BaTiO₃ thin films simultaneously exhibited ferroelectric polarization and ferromagnetic magnetization hysteresis loops at room temperature.     

Compositional range and electrical properties of the morphotropic phase boundary in the Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3 system

We have investigated the Na_0.5Bi_0.5TiO₃–K_0.5Bi_0.5TiO₃ (NBT–KBT) system, with its complex perovskite structure, as a promising material for piezoelectric applications. The NBT–KBT samples were synthesized using a solid-state reaction method and characterized with XRD and SEM. Room-temperature XRD showed a gradual change in the crystal structure from tetragonal in the KBT to rhombohedral in the NBT, with the presence of an intermediate morphotropic region in the samples with a compositional fraction x between 0.17 and 0.25. The fitted perovskite lattice parameters confirmed an increase in the size of the crystal lattice from NBT towards KBT, which coincides with an increase in the ionic radii. Electrical measurements on the samples showed that the maximum values of the dielectric constant, the remanent polarization and the piezoelectric coefficient are reached at the morphotropic phase boundary (MPB) (? = 1140 at 1 MHz; P_r = 40 μC/cm²; d₃₃ = 134 pC/N).     

Enhanced energy storage properties of BiAlO3 modified Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3 lead-free antiferroelectric ceramics

Lead-free (1−x)(0.75Bi_0.5Na_0.5TiO₃–0.25Bi_0.5K_0.5TiO₃)–xBiAlO₃ (BNT–BKT–100xBA, x=0–0.10) ceramics were prepared by two-step sintering method and their phase structure, micro morphology and electrical properties were systematically investigated. X-ray diffraction analysis indicates a pure perovskite phase for x≤0.06 as well as a structural evolution from a tetragonal toward a pseudocubic phase. Transmission electron microscopy study of the x=0.04 composition reveals the existence of antiferroelectric phase with a⁰a⁰c⁺ oxygen octahedron tilting which is in the form of nano-domains. Polarization-electric field and current-electric field hysteresis loops demonstrate that the increase of BA concentration destroys the ferroelectric order and strengthens antiferroelectric order. A much enhanced energy storage density of 1.15 J/cm³ and efficiency of 73.2% is achieved under 105 kV/cm at x=0.06. In addition, its energy storage property is found to depend weakly on temperature within the measurement range of 25–150 °C.     

Enhancing the dielectric and energy storage properties of lead-free Na0.5Bi0.5TiO3–BaTiO3 ceramics by adding K0.5Na0.5NbO3 ferroelectric

A novel strategy of enhancing the dielectric and energy storage properties of Na_0.5Bi_0.5TiO₃–BaTiO₃ (NBT–BT) ceramics by introducing a K_0.5Na_0.5NbO₃ (KNN) ferroelectric phase is proposed herein, and its underlying mechanism is elucidated. The lead-free KNN ceramic decreases the residual polarisation and increases the electric breakdown strength of the NBT–BT matrix through the simultaneous modification of its A-sites and B-sites. The obtained NBT?BT?x?KNN ceramics have a perovskite structure with unifying grains. A bulk 0.9NBT–BT–0.1KNN ceramic sample with a thickness of 0.2 mm possesses a high energy storage density of 2.81 J/cm³ at an applied electric field of 180 kV/cm. Moreover, it exhibits good insulation properties and undergoes rapid charge and discharge processes. Therefore, the obtained 0.9NBT–BT–0.1KNN ceramic can be potentially used in high-power applications because of its high energy density, good insulation properties, and large discharge rate.     

Piezoelectric properties and phase transition temperatures of the solid solution of (1 − x)(Bi0.5Na0.5)TiO3–xSrTiO3

The phase diagram of (1 ? x)(Bi_0.5Na_0.5)TiO₃–xSrTiO₃ was completed and investigations on polarization and strain in this system were carried out. (1 ? x)(Bi_0.5Na_0.5)TiO₃–xSrTiO₃-ceramics were prepared by conventional mixed oxide processing. The depolarization temperature (T_d), the temperature of the rhombohedral–tetragonal phase transition (T_r–t) and the Curie temperature (T_m) were determined by measuring the temperature dependence of the relative permittivity. All solid solutions of (1 ? x)(Bi_0.5Na_0.5)TiO₃–xSrTiO₃ show relaxor behavior (A-site relaxor). From XRD-measurements a broad maximum of the lattice parameter can be observed around x = 0.5 but no structural evidence for a morphotropic phase boundary was found. SEM-analysis revealed a decrease of the grain size for increasing SrTiO₃-content. At room temperature a maximum of strain of about 0.29% was found at x = 0.25 which coincides with a transition from a ferroelectric to an antiferroelectric phase. The temperature dependence of the displacement indicates an additional contribution from a structural transition (rhombohedral–tetragonal), which would be of certain relevance for the existence of a morphotropic phase boundary.     

Effect of WO3 doping on dielectric and ferroelectric properties of 0.94(Bi0.5Na0.5)TiO3–0.06BaTiO3 ceramics

WO₃(0–6 mol%)-doped 0.94Bi_0.5Na_0.5TiO₃–0.06BaTiO₃ lead-free ceramics were synthesized by conventional solid-state reaction. The effect of WO₃ addition on the structure and electrical properties were investigated. The result revealed that a small amount of WO₃ (≤1 mol%) can diffuse into the lattice and does not significantly affect the phase structure, however, more addition will result in distortion and enlargement of the unit cells. The maximum permittivity temperature (T_m) is suppressed dramatically as the dopant increasing, while the depolarization temperature (T_d) fall to the minimum with 1 mol% WO₃ additive. The remanent polarization (P_r) was enhanced and coercive field (E_c) was reduced by doping with WO₃. The strain shows the largest value for 1 mol% doped sample, which is due to a field-induced antiferroelectric–ferroelectric phase transition.     

Room temperature multiferroic properties of BiFeO3–MnFe2O4 nanocomposites

The novel functionalities of multiferroic magneto-electric nanocomposites have spawned substantial scope for fast-paced memory devices and sensor applications. Following this, herein we report the development of nanocomposites with soft ferromagnetic MnFe₂O₄ and ferroelectric BiFeO₃ to fabricate a system with engineered multiferroic properties. A modified sol-gel route called Pechini method is demonstrated for the preparation of the (1-x) BiFeO₃-x MnFe₂O₄ (x = 10%, 30%, 50%, 70%) nanocomposites. The crystallographic phase, structure, and morphology are characterized by XRD, FESEM, and HRTEM. The accurate crystallite size and lattice strain are determined by Williamson-Hall plot method and a comparative study with Scherer's equation is carried out. TEM image evidences the interface between BiFeO₃ and MnFe₂O₄ nanoparticles in the composite. The room temperature magnetic response reveals the strong dependence of magnetic saturation, remanent magnetization, and coercivity of the nanocomposites on MnFe₂O₄ addition. The dielectric response and impedance analysis of the prepared nanocomposites are observed. The electrical performance of the composite is affected by grain, grain boundaries, and oxygen vacancies. The unsaturated P-E loops exhibit the leaky ferroelectric behavior for the nanocomposite. The intrinsic magnetoelectric coupling between ferroelectric BiFeO₃ and ferromagnetic MnFe₂O₄ has been determined by varying H_dc/H_ac and its maximum coupling coefficient (α) is found to be 25.39 mV/cmOe for 70% BiFeO₃ -30% MnFe₂O₄ nanocomposite. These distinctive and achievable characteristics of the nanocomposite would enable the designing of magnetic field sensors, spintronic devices, and multiferroic memory devices.     

Systematic investigation of the annealing temperature and composition effects on the dielectric properties of sol–gel BaxSr1−xTiO3 thin films

In this work, Ba_xSr_1?xTiO₃ sol–gel thin films (x = 0.7, 0.5 and 0.3) deposited on Pt/Si substrate and post-annealed at different temperatures have been investigated. A systematic study of the structure, microstructure and dielectric properties has been achieved for each composition. To our knowledge, for the first time, a systematic effect of post-deposition annealing temperature and composition is reported. For each Ba/Sr ratio, higher annealing temperature leads to crystallinity improvement and to grain growth. A shift of the ferroelectric to paraelectric transition toward the bulk Curie temperature with the increase of the annealing temperature is shown. These results are correlated with the increase of the permittivity, tunability and dielectric losses measured on MIM capacitors at low frequency. Moreover, the high frequency results, between 800 MHz and 30 GHz, are in very good agreement with low frequency measurements, and show a huge tunability up to 80% under 600 kV/cm.