Structure study of Bi4Ti3O12 produced via mechanochemically assisted synthesis

Nanosized bismuth titanate was prepared via high-energy ball milling process through mechanically assisted synthesis directly from their oxide mixture of Bi₂O₃ and TiO₂. Only Bi₄Ti₃O₁₂ phase was formed after 3 h of milling time. The excess of 3 wt% Bi₂O₃ added in the initial mixture before milling does not improve significantly the formation of Bi₄Ti₃O₁₂ phase comparing to stoichiometric mixture. The formed phase was amorphized independently of the milling time. The Rietveld analysis was adopted to determine the crystal structure symmetry, amount of amorphous phase, crystallite size and microstrains. With increasing the milling time from 3 to 12 h, the particle size of formed Bi₄Ti₃O₁₂ did not reduced significantly. That was confirmed by SEM and TEM analysis. The particle size was less than 20 nm and show strong tendency to agglomeration. The electron diffraction pattern indicates that Bi₄Ti₃O₁₂ crystalline powder is embedded in an amorphous phase of bismuth titanate. Phase composition and atom ratio in BIT ceramics were determined by X-ray diffraction and EDS analysis.     

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.     

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.     

The low temperature synthesis and characterization of Bi3.25La0.75Ti3O12 powder by hydroxide coprecipitation in aqueous medium

The fine powders of Bi_3.25La_0.75Ti₃O₁₂ (BLT) were prepared by coprecipitaton method in aqueous medium at low temperature. The differential thermal analysis (DTA), thermo-gravimetric analysis (TG) and X-ray diffraction (XRD) were employed to evaluate the phase formation of BLT and TEM was used to characterize and observe the particle size and morphology of BLT powder obtained. The results show that the bismuth layer perovskite phase of BLT can begin to form at as low as 500 °C by the coprecipitation method. When the precipitates obtained were calcined at 600 °C for 2 h, the mono-phase and perfect BLT powder was synthesized. The BLT powder obtained consists of irregular or plate-like particles which are less than about 100 nm and is nearly aggregate free.     

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.     

Elastic modulus and hardness of CaTiO3, CaCu3Ti4O12 and CaTiO3/CaCu3Ti4O12 mixture

Three ceramic systems, CaTiO₃ (CTO), CaCu₃Ti₄O₁₂ (CCTO) and intermediate nonstoichiometric CaTiO₃/CaCu₃Ti₄O₁₂ mixtures (CTO.CCTO), were investigated and characterized. The ceramics were sintered at 1100 °C for 180 min. The surface morphology and structures were investigated by XRD and SEM. Elastic modulus and hardness of the surfaces were studied by instrumented indentation. It was observed that CCTO presented the higher mechanical properties (E = 256 GPa, hardness = 10.6 GPa), while CTO/CCTO mixture showed intermediate properties between CTO and CCTO.     

Preparation of Lu2Ti2O9 nano-powders from oxides by molten salt method

Nano-sized Lu₂Ti₂O₇ powders have been prepared successfully using TiO₂ and Lu₂O₃ oxides as precursors based on a modified molten salt technique. The results of XRD and SEM analysis show that two-step calcinations retards the grain growth and accelerates the phase transformation of Lu₂Ti₂O₇ more effectively in comparison with single-step calcinations. The spherical Lu₂Ti₂O₇ powders with a particle size of 50 nm are achieved by heating the precursors up to 1100 °C followed by holding at 800 °C for 30 min. Based on the above observations, a possible particle growth mechanism of two-step calcinations under molten salt conditions is also given in this paper, in which it is suggested that a high temperature (T1) can increase nucleation rate and contribute to Lu₂Ti₂O₇ phase transformation while at the same time, the growth process is limited at the lower temperature (T2 ) of the second calcinations step.     

Microwave-assisted synthesis of hierarchical Bi2O3 spheres assembled from nanosheets with pore structure

Hierarchical Bi₂O₃ spheres assembled from nanosheets with nanopore structure have been successfully synthesized by thermal decomposition of the precursor at 400 °C for 3 h in air, which was prepared using Bi(NO₃)₃·5H₂O and poly(vinylpyrrolidone) (PVP) by a microwave-assisted heating method in ethylene glycol (EG) at 150 °C for 10 min. The morphology of Bi₂O₃ is similar to that of the precursor. The products were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectrometry (FT-IR), field-emission scanning electron microscopy (FE-SEM), thermogravimetric analysis (TG) and differential scanning calorimetric analysis (DSC). XRD pattern showed that the product had a high degree of crystallinity. FE-SEM micrograph indicated that hierarchical Bi₂O₃ spheres had sizes around 10 μm.     

New substitutions and novel derivatives of the Aurivillius phases, Bi5TiNbWO15 and Bi4Ti3O12

We investigated isomorphous substitution of several metal atoms in the Aurivillius structures, Bi₅TiNbWO₁₅ and Bi₄Ti₃O₁₂, in an effort to understand structure-property correlations. Our investigations have led to the synthesis of new derivatives, Bi₄LnTiMWO₁₅ (Ln = La, Pr; M = Nb, Ta), as well as Bi₄PbNb₂WO₁₅ and Bi₃LaPbNb₂WO₁₅, that largely retain the Aurivillius (n = 1) + (n = 2) intergrowth structure of the parent oxide Bi₅TiNbWO₁₅, but characteristically tend toward a centrosymmetric/tetragonal structure for the Ln-substituted derivatives. On the other hand, coupled substitution, 2Ti^IV → M^V + Fe^III in Bi₄Ti₃O₁₂, yields new Aurivillius phases, Bi₄Ti_3−2xNb_xFe_xO₁₂ (x = 0.25, 0.50) and Bi₄Ti_3−2xTa_xFe_xO₁₂ (x = 0.25) that retain the orthorhombic noncentrosymmetric structure of the parent Bi₄Ti₃O₁₂. Two new members of this family, Bi₂Sr₂Nb₂RuO₁₂ and Bi₂SrNaNb₂RuO₁₂ that are analogous to Bi₂Sr₂Nb₂TiO₁₂, possessing tetragonal (I4/mmm) Aurivillius structure have also been synthesized.     

Ferroelectric properties of epitaxial Bi3.15Nd0.85Ti3O12 films on SiO2/Si using biaxially oriented MgO as templates

High quality epitaxial Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films with thicknesses from 30 to 80 nm have been integrated on SiO₂/Si substrates. MgO templates deposited by ion-beam-assisted deposition and SrRuO₃ (SRO) buffer layers processed by pulsed laser deposition have been used to initiate the epitaxial growth of BNT films on the amorphous SiO₂/Si substrates. The structural and ferroelectric properties were investigated. Microstructural studies by X-ray diffraction and transmission electron microscopy revealed high quality crystalline with an epitaxial relationship of (001)_BNT||(001)_SRO||(001)_MgO and [100]_BNT||[110]_SRO||[110]_MgO. A ferroelectric hysteresis loop with a remanent polarization of 3.1 μC/cm² has been observed for a 30 nm thick film. The polarization exhibits a fatigue-free characteristic up to 1.44 × 10¹⁰ switching cycles.     

Microscale meshes of Ti3O5 nano- and microfibers prepared via annealing of C-doped TiO2 thin films

A new technique to produce microscale Ti₃O₅ nano- and microfiber meshes is proposed. When a 3 wt% carbon-doped TiO₂ film on Si(1 0 0) was annealed at 1000 °C in wet nitrogen (0.8%H₂O), the amorphous TiO₂ phase gave rise to crystalline phases of λ-Ti₃O₅ (75%) and rutile + trace of TiO_2−xC_x (25%). From Raman and FTIR Spectroscopy results, it was concluded that rutile is formed at the inner layer located at the interface between the mesh and the Si that was located away from the surface such that the meshes of nano- and microfibers are predominantly composed of Ti₃O₅ grown from the reaction of rutile with Si to form Ti₃O₅ and SiO₂. On the other hand, it was noteworthy that the microscale mesh of nano- and microfibers showed increased photoluminescence compared with amorphous TiO₂. The PL spectrum which had a broad band in the visible spectrum, fitted as three broad Gaussian distributions centered at 571.6 nm (∼2.2 eV), 623.0 nm (∼2.0 eV) and 661.9 nm (∼1.9 eV).     

Abnormal dielectric behaviors in Mn-doped CaCu3Ti4O12 ceramics and their response mechanism

Mn-doped CaCu₃Ti₄O₁₂ (CCTO) polycrystalline ceramics have been prepared by the conventional solid state sintering. Our results indicate that 10% Mn doping can decrease the dielectric permittivity in CaCu₃Ti₄O₁₂ by about 2 orders of magnitude (from 10⁴ to 10²). The grain and grain boundary activation energies show an obvious increase from 0.054 eV to 0.256 eV, and decrease from 0.724 eV to 0.258 eV with increasing the Mn doping concentration, respectively, which may be caused by the variation of Cu and Ti valence states in the CCTO samples evidenced by the X-ray absorption spectra. The similar grain and grain boundary activation energies result in invalidation of the internal boundary layer capacitance effect for the 10% Mn-doped CCTO sample, and thus result in the dramatic decrease of dielectric permittivity.     

Effects of ZnNb2O6 addition on BaTiO3 ceramics for energy storage

BaTiO₃ ceramics were prepared using solid state reaction with addition of ZnNb₂O₆, to investigate the effects of ZnNb₂O₆ addition on structure and properties. The results show that the ZnNb₂O₆ addition lowers sintering temperature, decreases grain size, while introduces second phase (Ba₂Ti₅O₁₂) for x ≥ 7.26 wt%. The dielectric breakdown strength is enhanced with the increasing doping level of ZnNb₂O₆ and reaches a maximum value at x = 7.26 wt%, exhibiting a maximum energy storage capability.     

Observation of broadband infrared luminescence in a novel Bi-doped P2O5-B2O3-Al2O3 glass

A novel Bi-doped P₂O₅-B₂O₃-Al₂O₃ glass was investigated, and strong broadband NIR (near infrared) luminescence was observed when the sample was excited by 445 nm, 532 nm, 808 nm and 980 nm lasers, respectively. The max FWHM with 312 nm, the lifetime with 580 μs and the σ_emτ product with 5.3 × 10^− 24 cm² s were obtained which indicates that this glass is a promising material for broadband optical amplifier and tunable laser. The effect of the introduction of B₂O₃ on the glass structure and Bi-ions illuminant mechanism were discussed and analyzed. It is suggested that the introduction of B₂O₃ makes the glass structure closer, and the broadband NIR emission derives from Bi⁰:²D_3/2 → ⁴S_3/2 and Bi⁺:³P₁ → ³P₀ transitions.     

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

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.     

The effect of stress on the dielectric constants of Bi4Ti3O12 films

Both experiment and theory have shown that the stress has a notable impact on the polarization of Nd-doped Bi₄Ti₃O₁₂ films. In this paper, thermodynamic theory is used to study the effect of stress on the dielectric constants of Bi₄Ti₃O₁₂ films at room temperature with a two-dimensional model. Results indicate that the change of the dielectric constant for a-phase induced by the lattice distortion is far greater than that for c-phase. Considering the domain reorientation, the external tensile stress may lead to an obvious decrease in the effective dielectric constant of Bi₄Ti₃O₁₂ films.     

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 of CaCu3Ti4O12 ceramic via a sol-gel method

The novel nano-ultrafine powders for the preparation of CaCu₃Ti₄O₁₂ ceramic were prepared by the sol-gel method and citrate auto-ignition method. The obtained precursor powders were pressed, sintered at 1000 °C to fabricate microcrystal CaCu₃Ti₄O₁₂ ceramic. The microcrystalline phase of CaCu₃Ti₄O₁₂ was confirmed by X-ray powder diffraction (XRD). The morphology and size of the grains of the powders and ceramics under different heat treatments were observed using scanning electron microscopy (SEM). The relative dielectric constant of the ceramic sintered at 1000 °C was measured with a magnitude of more than 10⁴ at room temperature, which was approaching to those of Pb-containing complex perovskite ceramics, and the loss tangent was less than 0.20 in a broad frequency region. The relative dielectric constant and loss tangent were also compared with that of CaCu₃Ti₄O₁₂ ceramic prepared by other reported methods.     

Effect of yttrium doping on the dielectric properties of CaCu3Ti4O12 thin film produced by chemical solution deposition

Pure and yttrium substituted CaCu₃Ti_4 − xY_xO_{12 − x / 2} (x = 0, 0.02, 0.1) thin films were prepared on boron doped silica substrate employing chemical solution deposition, spin coating and rapid thermal annealing. The phase and microstructure of the sintered films were examined using X-ray diffraction and scanning electron microscopy. Dielectric properties of the films were measured at room temperature using electrochemical impedance spectroscopy. Highly ordered polycrystalline CCTO thin film with bimodal grain size distribution was achieved at a sintering temperature of 800 °C. Yttrium doping was found to have beneficial effects on the dielectric properties of CCTO thin film. Dielectric parameters obtained for a CaCu₃Ti_4 − xY_xO_{12 − x / 2} (x = 0.02) film at 1 KHz were k ∼ 2700 and tan δ ∼ 0.07.     

Influence of Ga2O3 addition on transparent conductive oxide films of In2O3-ZnO

Influence of incorporation of Ga in amorphous In-Zn-O transparent conductive oxide films was investigated as a function of Zn/(Zn + In). For In-Zn-O films with no Ga₂O₃, the range of Zn/(Zn + In) ratio where the amorphous phase appears became narrow at a substrate temperature of 250 °C. With increasing Ga₂O₃ quantity, amorphous films were obtained even at a high substrate temperature of 250 °C in a wider range of Zn/(Zn + In) than that of In-Zn-O films with no Ga₂O₃. This means that the trend of crystallization at higher substrate temperature was disturbed with additional Ga incorporation. For the film deposited from ZnO:Ga (Ga₂O₃: 4.5-7.5 wt%) and In₂O₃ targets, we obtained a resistivity of 2.8 × 10⁻⁴ Ω cm, nearly the same value as that for an In-Zn-O film with no Ga₂O₃. The addition of more than 7.5 wt% Ga₂O₃ induced a widening of the optical band gap.