Synthesis of Na0.5Bi0.5TiO3 anisotropic particles with grain orientation by conversion of Na0.5Bi4.5Ti4O15 crystals

Abstract

A novel method for synthesizing Na_0.5Bi_0.5TiO₃ (BNT) anisotropic particles with grain orientation is reported. Anisotropically shaped particles of BNT were prepared by conversion of Na_0.5Bi_4.5Ti₄O₁₅ (NBT15) single crystals. Platelet NBT15 was produced by molten-salt synthesis. They were converted to BNT by second molten-salt synthesis at 800—1200 ?C. NBT15 single-crystal platelets were transformed into platelet particles of polycrystalline BNT. The reaction is topotaxial, those recrystallized BNT were oriented with (h 0 0) plane parallel to the platelet. The use of converted BNT particles as seed was confirmed by performing templated grain growth (TGG) of BNT with 5% grain-oriented, anisotropic particles of BNT.     

Topochemical synthesis of plate-like Na0.5Bi0.5TiO3 templates from Bi4Ti3O12

Plate-like templates for the development of grain oriented microstructures are required for lead-free piezoelectric ceramics with directionality of properties. Plate-like Na_0.5Bi_0.5TiO₃ templates with perovskite structure were synthesized by the Topochemical Microcrystal Conversion (TMC) method from bismuth layer-structured ferroelectric compound Bi₄Ti₃O₁₂. The TMC-derived NBT templates, with diameters of 5-15 µm and an average thickness of 0.7 µm, maintained the morphology of Bi₄Ti₃O₁₂ precursors, showing a high degree of preferred pseudocubic < 001> orientation. The Na_0.5Bi_0.5TiO₃ particles prepared could serve as good templates for the preparation of grain oriented lead-free NBT-based piezoelectric ceramics.     

Properties of La-substituted Na0.5Bi4.5Ti4O15 ferroelectric thin films

Ferroelectric Na_0.5La_0.5Bi₄Ti₄O₁₅ (NaLaBTi) thin films were prepared by a chemical solution deposition method. The NaLaBTi thin films annealed at 750 °C under oxygen atmosphere were randomly oriented polycrystalline. Electrical properties of the NaLaBTi thin films were compared to Na_0.5Bi_4.5Ti₄O₁₅ thin films and better properties were observed in the NaLaBTi thin films. Remnant polarization (2P_r) and coercive electric field (2E_c) were 43 µC/cm² and 204 kV/cm at an applied electric field of 478 kV/cm, respectively. Leakage current density was 1.95 × 10^− 6 A/cm² at 100 kV/cm. Dielectric constant and dielectric loss were 805 and 0.05 at 1 kHz, respectively. Switchable polarization was suppressed by 15% after 1.44 × 10¹⁰ switching cycles.     

Dielectric, ferroelectric and piezoelectric properties of Bi0.5Na0.5TiO3-(Ba0.7Ca0.3)TiO3 ceramics at morphotropic phase boundary composition

(1 − x)Bi_0.5Na_0.5TiO₃-x(Ba_0.7Ca_0.3)TiO₃ (BNT-xBCT, 0 ≤ x ≤ 0.15) solid solutions have been synthesized by a conventional solid state sintering method for obtaining a morphotropic phase boundary (MPB) with good piezoelectric properties. X-ray diffraction patterns reveal that a MPB of rhombohedral and tetragonal phases is formed at compositions 0.09 ≤ x ≤ 0.12. Addition of BCT into BNT greatly lowered coercive field E_c without degrading remanent polarization P_r. The specimen with x = 0.09 has the good piezoelectric properties: d₃₃ = 125 pC/N and k_p = 0.33. A modified Curie-Weiss law was used to fit the dielectric constant of BNT-xBCT ceramics, and a frequency dispersion was observed during the phase transitions from antiferroelectric to paraelectric in specimens with x exceeding 0.06.     

Impedance spectroscopy and relaxation phenomena of (Na,K) excess Na0.5K0.5NbO3 thin films grown by chemical solution deposition

Na_0.5K_0.5NbO₃ (NKN) and 10 mol% (Na,K) excess Na_0.5K_0.5NbO₃ (NKN10) thin films on Pt/Ti/SiO₂/Si substrate were prepared by chemical solution deposition. Crystallization of NKN10 thin films was confirmed by X-ray diffraction. The (Na,K) excess Na_0.5K_0.5NbO₃ thin film shows a ferroelectric P-E hysteresis loop. Dielectric properties and impedance spectroscopy of thin films were investigated in the frequency range from 0.1 Hz to 100 kHz and the temperature range of 25 ~ 500 °C. By analyzing the complex impedance relaxation with Cole-Cole plots, we found impedance relaxations for the thin film. The contribution of electrical conduction is discussed in relation to grain, grain boundary, and interface effects.     

V-doping effects on ferroelectric properties of K0.5Bi4.5Ti4O15 thin films

V-doped K_0.5Bi_4.5Ti₄O₁₅ (K_0.5Bi_{4.5 − x/3}Ti_4 − xV_xO₁₅, KBTiV-x, x = 0.00, 0.01, 0.03, and 0.05) thin films were prepared on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. The thin films were annealed by using a rapid thermal annealing process at 750 °C for 3 min in an oxygen atmosphere. Among them, KBTiV-0.03 thin film exhibited the most outstanding electrical properties. The value of remnant polarization (2P_r) was 75 μC/cm² at an applied electric field of 366 kV/cm. The leakage current density of the thin film capacitor was 5.01 × 10⁻⁸ at 100 kV/cm, which is approximately one order of magnitude lower than that of pure K_0.5Bi_4.5Ti₄O₁₅ thin film capacitor. We found that V doping is an effective method for improving the ferroelectric properties of K_0.5Bi_4.5Ti₄O₁₅ thin film.     

Ferroelectric and pyroelectric properties of (Na0.5Bi0.5)TiO3-BaTiO3 based trilayered thin films

Trilayered Bi_3.25La_0.75Ti₃O₁₂ (25 nm)/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ (300 nm)/Bi_3.25La_0.75Ti₃O₁₂ (25 nm) and Pb(Zr_0.4Ti_0.6)O₃ (25 nm)/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ (300 nm)/Pb(Zr_0.4Ti_0.6)O₃ (25 nm) thin films without undesirable phases have been deposited on Pt/Ti/SiO₂/Si substrates. It was found that the Bi_3.25La_0.75Ti₃O₁₂ and Pb(Zr_0.4Ti_0.6)O₃ layers are very effective to inhibit the charge transport in the trilayered films. Much better insulating properties than those of (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ films have been achieved in the trilayered films. The trilayered films show good dielectric, ferroelectric and pyroelectric properties. Remnant polarizations 2P_r of 16 µC/cm² and 34 µC/cm², pyroelectric coefficients of 4.8 × 10^− 4 C m^− 2 K^− 1 and 7.0 × 10^− 4 C m^− 2 K^− 1 have been obtained for the Bi_3.25La_0.75Ti₃O₁₂/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃/Bi_3.25La_0.75Ti₃O₁₂ and Pb(Zr_0.4Ti_0.6)O₃/(Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃/Pb(Zr_0.4Ti_0.6)O₃ thin films, respectively. The trilayered films are promising candidates for sensor and actuator applications.     

Fabrication of lead-free (Na0.82K0.18)0.5Bi0.5TiO3 piezoelectric nanofiber by electrospinning

(Na_0.82K_0.18)_0.5Bi_0.5TiO₃ nanofibers were synthesized by sol-gel process and electrospinning. Scanning electron microscopy was used to verify that the diameters and lengths are in the range of 150-600 nm and several hundreds of micrometer. Perovskite structure and grain size (20-70 nm) were verified by X-ray diffraction and transmission electron microscopy. The high effective piezoelectric coefficient d₃₃ (96 pm/V) was measured by scanning force microscopy. It may be attributed to easily tilting the polar vector of domain for an electric field and the increase in the number of possible spontaneous polarization direction near the rhombohedral-tetragonal morphotropic phase boundary. The research shows that there are potentional applications for (Na_0.82K_0.18)_0.5Bi_0.5TiO₃ nanofiber in nanoscale lead-free piezoelectric devices.     

Effect of post-annealing treatment in oxygen on dielectric properties of K0.5Na0.5NbO3 thin films prepared by chemical solution deposition

K_0.5Na_0.5NbO₃ thin films were prepared on Pt/Ti/SiO₂/Si substrates by chemical solution deposition method with different annealing temperatures of 550 °C, 600 °C, 700 °C. The post-annealing treatment was introduced at 550 °C for 3 min in oxygen ambient. It is found that the films were composed of pure provskite phase, and the post-annealing treatment promoted the crystallization and improved the quality of the films, which resulted in the enhancement of the dielectric property of the films. The effect of the post-annealing on the dielectric properties of the films was also discussed.     

Synthesis and characterization of (Na0.85K0.15)0.5Bi0.5TiO3 ceramics by different methods

The (Na_0.85K_0.15)_0.5Bi_0.5TiO₃ (BNKT) powders were synthesized by solid-state method, sol-gel method and stearic acid method. Microstructure, piezoelectric and dielectric properties of the ceramics were investigated. Attempts had been made to understand the reaction processes by using thermo gravimetric (TG) and differential scanning calorimetry (DSC). The BNKT powders have a perovskite structure with average crystallite sizes of 168 nm, 85 nm and 79 nm, corresponding to the solid-state method, the sol-gel method and the stearic acid method, respectively. The ceramics derived from the powder synthesized by sol-gel method presents the most homogeneous microstructure and largest grain size (5-7 μm). The effects of average crystallite size on microstructures and electric properties of the BNKT ceramics were investigated. Both the piezoelectric properties and dielectric properties were enhanced with the increase of grain size.     

Synthesis of the intermetallic clathrate Na2Ba6Si46 by oxidation of Na2BaSi4 with HCl

A new preparation route to the intermetallic clathrate-I compound Na₂Ba₆Si₄₆ is introduced, which allows one to make large amounts of product with standard laboratory equipment. The precursor Na₂BaSi₄ is oxidized with gaseous HCl at 673 K to Na₂Ba₆Si₄₆, NaCl and BaCl₂. Full-profile refinement of the crystal structure from the X-ray powder diffraction data revealed a composition close to Na₂Ba₆Si₄₆ (Na_1.94(1)Ba_6.06(1)Si₄₆, space group , a=10.281(1) Å). Differential scanning calorimetry showed an exothermic effect at 874 K, indicating that Na₂Ba₆Si₄₆ is metastable. The product was additionally characterized by scanning electron microscopy. The electronic structure of Na₂Ba₆Si₄₆ was investigated by a first-principles, all-electron full-potential method, predicting metallic conductivity. Na₂Ba₆Si₄₆ obtained by oxidation with HCl shows Pauli paramagnetism; no bulk superconductivity was found down to 1.8 K in a magnetic field of 20 Oe.     

Variations of microstructures and electrical properties of Bi4Ti3O12/SrTiO3/(La0.5, Sr0.5)CoO3/MgO epitaxial thin films by annealing

Epitaxial thin films of a heterostructure with Bi₄Ti₃O₁₂(BIT)/SrTiO₃(ST) were successfully grown with a bottom electrode consisting of La_0.5Sr_0.5CoO₃(LSCO) on MgO(001) substrates using pulsed laser deposition. The grown BIT and ST (001) planes were parallel to the growth surface with the orientation relationship of BIT <110>//ST <010>. In the as-deposited film, the BIT (001) plane appeared to expand to relieve a lattice mismatch with the ST (001) plane. However, annealing for 20-40 min induced the BIT (001) plane to contract horizontally with its c-axis expanding, which was associated with a local perturbation in the layer stacking of the BIT structure. This structural distortion was reduced in the film annealed for 1 h, with restoration of the periodicity of the layer stacking. Correspondingly, the dielectric constant of the as-deposited film was increased from 292 to 411 by annealing for 1 h. In parallel, the film was paraelectric but became more ferroelectric, with the remanent polarization and the coercive field changing from 0.1 μC/cm² and 14 kV/cm to 1.7 μC/cm² and 69 kV/cm, respectively.     

Synthesis and morphology of anisotropic NaNbO3 seed crystals

Large platelet NaNbO₃ (NN) seed crystals have been successfully synthesized from bismuth layer-structured ferroelectric Bi_2.5Na_3.5Nb₅O₁₈ (BNN) precursor by topochemical microcrystal conversion method. The effects of synthesis parameters, such as salt/oxide ratio, synthesis temperature and Na₂CO₃/BNN ratio, on the phase structure and morphology of both the BNN precursor and NN particles were investigated. The results show that large platelet BNN precursor with bismuth layer structure was obtained at 1125 °C with a salt-to-oxide weight ratio of 1.50:1. Besides, by optimizing the synthesis parameters, anisotropic NN seed crystals with pure perovskite phase were obtained at 975 °C with a Na₂CO₃/BNN molar ratio of 1.50:1. The obtained NN particles are very promising template for texturing (K, Na) NbO₃-based ceramics by reactive-template grain growth method.     

Processing, dielectric properties and impedance characteristics of Na0.5Bi0.5Cu3Ti4O12 ceramics

Na_0.5Bi_0.5Cu₃Ti₄O₁₂ (NBCTO) ceramics were prepared by conventional solid-state reaction method. The phase structure, microstructure and dielectric properties of NBCTO ceramics sintered at various temperatures with different soaking time were investigated. Pure NBCTO phase could be obtained with increasing the temperature and prolonging the soaking time. High dielectric permittivity (13,495) and low dielectric loss (0.031) could be obtained when the ceramics were sintered at 1000 °C for 7.5 h. The ceramics sintered at 1000 °C for 7.5 h also showed good temperature stability (−4.00 to −0.69%) over a large temperature range from −50 to 150 °C. Complex impedances results revealed that the grain was semiconducting and the grain boundaries was insulating. The grain resistance (R_g) was 12.10 Ω cm and the grain boundary resistance (R_gb) was 2.009 × 10⁵ Ω cm when the ceramics were sintered at 1000 °C for 7.5 h.     

Preparation and characterization of new visible-light-driven BaCo0.5Nb0.5O3 photocatalyst

A new type of visible-light-driven photocatalyst BaCo_0.5Nb_0.5O₃ was successfully synthesized via a sol-gel process in this study. After heating the precursors at 1000 °C, a pure perovskite phase was obtained. The particle size and crystallinity of BaCo_0.5Nb_0.5O₃ powders markedly increased with a rise in the calcination temperature. The band gap of BaCo_0.5Nb_0.5O₃ calculated from the UV-visible spectra was found to be less than that of titania. BaCo_0.5Nb_0.5O₃ was demonstrated to have photocatalytic activity under visible light irradiation and this activity significantly depended on the synthesis temperature. The sol-gel derived powders were found to have better photocatalytic activity than the solid-state derived powders because of the reduced particle size and increased surface area.     

Anisotropic grain growth of Bi4Ti3O12 in molten salt fluxes

Bismuth titanate (Bi₄Ti₃O₁₂) platelets were obtained by the molten salt synthesis method in NaCl-KCl and Na₂SO₄-K₂SO₄ fluxes, using an amorphous Bi₄Ti₃O₁₂ precursor and a mechanically mixed Bi₂O₃-TiO₂ mixture as the starting materials. It was found that the synthesizing temperature, salt species and starting materials could significantly affect the crystallization habit and morphology of Bi₄Ti₃O₁₂ platelets. Under the same processing conditions (i.e. in Na₂SO₄-K₂SO₄ flux at 1000 °C), the Bi₄Ti₃O₁₂ platelets synthesized from the Bi₂O₃-TiO₂ mixture generally showed a smaller particle size than those synthesized using the amorphous Bi₄Ti₃O₁₂ precursor. The Bi₄Ti₃O₁₂ platelets prepared in the chloride flux were faceted along either (0 0 1) or (1 1 2) planes, while those prepared in the sulfate flux were solely (0 0 1) faceted. The former system also had smaller particle size than the latter. Furthermore, the salt content and the addition of plate-like Bi₄Ti₃O₁₂ seeds in the amorphous Bi₄Ti₃O₁₂ precursor showed a strong influence on the particle size of the synthesized Bi₄Ti₃O₁₂ platelets. The particle size of Bi₄Ti₃O₁₂ platelets prepared in the sulfate flux decreased as the mole ratio of the sulfate salts to Bi₄Ti₃O₁₂ was increased from 7.9 to 23.7. And the addition of 10 wt.% plate-like Bi₄Ti₃O₁₂ seeds into the amorphous Bi₄Ti₃O₁₂ precursor led to a significant increase in the particle size of the resulting Bi₄Ti₃O₁₂ platelets.     

Preparation and photocatalytic activity of novel efficient photocatalyst Sr2Bi2O5

A novel visible-light-driven photocatalyst of Sr₂Bi₂O₅ is prepared by solid-state reaction at 780 °C. The optical band gap of Sr₂Bi₂O₅ is determined to be 2.87 eV by UV-Vis diffuse reflectance spectroscopy. Under both UV and visible-light irradiation, the photocatalytic activity for degrading methyl orange (MO) over Sr₂Bi₂O₅ is higher than those over BiVO₄, and SrBi₂O₄. The relationships between the photocatalytic properties of Sr₂Bi₂O₅, SrBi₂O₄, and BiVO₄ and their crystal structures are discussed. Among Sr₂Bi₂O₅, SrBi₂O₄, and BiVO₄, the higher photocatalytic activity of Sr₂Bi₂O₅ is ascribed to its higher level of distortion of the metal-oxygen polyhedra, and the lower packing factor degree.     

Abnormal electrocaloric effect of Na0.5Bi0.5TiO3–BaTiO3 lead-free ferroelectric ceramics above room temperature

We demonstrate the electrocaloric effect (ECE) of Na_0.5Bi_0.5TiO₃–BaTiO₃ (NBT–BT) lead-free ferroelectric ceramics, which were fabricated by the solid-state reaction method. Based on a Maxwell relation, the ECE was characterized via P–T curves under different electric fields. The polarization of NBT increases monotonically within the temperature range of 25–145 °C. It indicates that the NBT has an abnormal ECE with a negative temperature change (ΔT₁₄₀ = −0.33 K at E = 50 kV/cm) opposite to that of the normal ferroelectrics. The 0.92NBT–0.08BT composition near the morphotropic phase boundary has a normal ECE under low electric fields and an abnormal ECE under high electric fields. The abnormal ECE character originates from the relaxor characteristic between ferroelectric and antiferroelectric phases, while the common ECE is always related to the normal ferroelectric–paraelectric phase transition.     

Effect of BaTiO3 additive on the electrical properties of Na0.50Bi0.50TiO3 lead free ceramics

The near morphotropic phase boundary (MPB) compositions of lead-free piezoelectric ceramics based on sodium bismuth titanate (Na_0.50Bi_0.50TiO₃: NBT) and barium titanate (BaTiO₃: BT) were carefully investigated by conventional high temperature mixed-oxide method. All the ceramics exhibit single phase rhombohedral symmetry. The frequency (100 Hz to 1 MHz) and temperature (Room temperature–500 °C) dependence of impedance spectroscopy of (1 − x)Na_0.50Bi_0.50TiO3–xBaTiO₃ (x = 0.0, 0.06, 0.07 and 0.08) ceramics were investigated by impedance analyzer. The frequency explicit plots of Z″ versus frequency at various temperatures show peaks in the higher temperature range (>400 °C). The compounds show dielectric relaxation, which is found to be of non-Debye type and the relaxation frequency shifted to higher side with increase in temperature. The activation energy values obtained for different BT content suggest that the electrical conduction in NBT is mainly due to the mobility of the ionized oxygen defects.     

Size reduction in crystal grains in LiNb0.5Ta0.5O3 thin films by controlling nucleation density during thermal plasma spray chemical vapor deposition

Two approaches were applied to thermal plasma spray chemical vapor deposition (TPS CVD) in order to reduce crystal grain size or/and surface roughness of LiNb_0.5Ta_0.5O₃ thin films while retaining the advantages of this method, such as high deposition rate. The first method consists of a two-step deposition, where the nucleation density is controlled in the first step and the film with high crystallinity is deposited in the second step. The surface roughness and grain size could be reduced from 1 nm to 7.7 nm, and from 200-350 nm to 120-180 nm, respectively. In the second approach, employing a one-step TPS CVD process, the conventional precursor was substituted by a double-alkoxide precursor and grain size in the deposited films could be reduced to 50-80 nm. Both approaches adopted in this work permitted to reduce the optical propagation loss.