Conduction mechanism of grain oriented Bi3.15Nd0.85Ti3O12 ceramics fabricated by a hot-forging method

We have fabricated ordinary fired (OF) and grain oriented Bi_3.15Nd_0.85Ti₃O₁₂ (HF[⊥], HF[//]) samples by a hot-forging technique. The grain orientation factor F calculated from X-ray diffraction patterns of the c-axis oriented Bi_3.15Nd_0.85Ti₃O₁₂-HF[//] sample is determined to be above 90%. The dielectric and ferroelectric properties of Bi_3.15Nd_0.85Ti₃O₁₂ ceramics with different grain orientation have been investigated as a function of temperature. The a-b axis oriented Bi_3.15Nd_0.85Ti₃O₁₂-HF[⊥] sample had an enhanced dielectric constant (1163 at T _c) and ferroelectric properties (P _r ∼ 32 μC/cm²). The electrical conductivity of BNT ceramic has been studied as a function of temperature in order to investigate the conduction mechanism with different grain orientations.     

Ferroelectric Properties of (Bi, Sm)4Ti3O12 (BST) Thin Films Fabricated by a Metalorganic Solution Deposition Method

Ferroelectric properties of samarium substituted Bi₄Ti₃O₁₂ films, Bi_3.15Sm_0.85Ti₃O₁₂ (BST), were evaluated for use as lead-free thin film ferroelectrics for FeRAM applications. The BST films were fabricated on the Pt/Ti/SiO₂/Si(100) substrates by a metalorganic solution deposition method. The measured XRD patterns revealed that the BST films showed only a Bi₄Ti₃O₁₂-type phase with a random orientation. The BST film capacitors showed excellent ferroelectric properties. For the film capacitor annealed at 700C, 2P_r of 64.2 C/cm² and 2E_c of 101.7 kV/cm at applied electric field of 150 kV/cm were observed. The capacitor did not show any significant fatigue up to 1.5 × 10⁸ read/write switching cycles at a frequency of 1 MHz, which suggests that the samarium should be considered for a promising lanthanide elements to make a good thin ferroelectric film for memory applications.     

Structural and Multiferroic Properties of Bi3.4La0.6Ti3O12/CoFe2O4 Composite Thin Films

Bi_3.4La_0.6Ti₃O₁₂ and CoFe₂O₄ were synthesized by chemical solution route, and Bi_3.4La_0.6Ti₃O₁₂/CoFe₂O₄ multilayers were deposited by spin coating on Pt substrate. X-ray diffraction of multilayer structures reveals composite-like polycrystalline film. Leakage current is less than 10^?5 A at electric field < 90 KV/cm and follows the Ohmic behavior. Dielectric response shows relaxation and the loss (tan δ) is below 3% at 10⁶ Hz. Room temperature ferrroelectric polarization (P_r) = 20.2 μC/cm² and ferromagnetic memory (M_r) = 46.5 emu/cm³ has been obtained. Co-existence of FE and FM response can be attributed to stress and different permeability and permittivity involved in multilayer structures.     

Ferroelectric distortion and electronic structure in Bi4Ti3O12

The ferroelectric phase transition in Bi₄Ti₃O₁₂ has been investigated through Rietveld analysis of high-resolution neutron powder diffraction and electronic structure calculations. The structural and electronic analyses show that the traditional model based on the stereoactive lone-pair 6s electrons of Bi³⁺ is not sufficient to explain the structural distortions in the ferroelectric state. It is strongly suggested that the hybridization of the Bi 6p and the O 2p in the perovskite layers is the trigger of the ferroelectric transition in Bi₄Ti₃O₁₂, and that this orbital interaction is responsible for stabilizing the ferroelectric displacements in the perovskite layers.     

Properties of Chemical Solution Deposited Polycrystalline Neodymium-Modified Bi4Ti3O12

Thin films of neodymium-modified bismuth titanate Bi_3.44Nd_0.56Ti₃O₁₂ (BNT) were grown on Pt/TiO₂/SiO₂/Si substrates using chemical solution deposition method. The capacitors made by applying top Au electrodes on BNT films showed significantly improved values of the remanent polarization as compared to that using bismuth titanate Bi₄Ti₃O₁₂ (BT) films. The 2P _r value for the BNT capacitors was determined to be equal to 38 C/cm² at an applied voltage of 24 V, whereas, for Bi₄Ti₃O₁₂ (BT) capacitors a value of 20 C/cm² was measured at the same applied voltage. The maximum piezoelectric and pyroelectric coefficients of 22 pm/V and 112 C/m² K respectively, were measured for the BNT thin films.     

Synthesis and properties of ferroelectric Si-doped (Bi, Nd)4Ti3O12 thin films by chemical solution deposition

Ferroelectric Si-doped (Bi,Nd)₄Ti₃O₁₂ thin films have been prepared on Pt/TiO_x/SiO₂/Si substrates through metal-organic compounds by the chemical solution deposition. The Bi_3.25Nd_0.75Ti_2.9Si_0.1O₁₂ (BNTS) precursor films were found to crystallize into the Bi-layered perovskite Bi₄Ti₃O₁₂ single-phase above 600^∘C. The synthesized BNTS films revealed a random orientation having a strong 117 reflection. The BNTS thin films prepared between 600^∘C and 700^∘C showed well-saturated P-E hysteresis loops with P _r of 13–14 μ C/cm² and E _c of 100–110 kV/cm at an applied voltage of 5 V. The surface roughness of the BNTS thin films was improved by Si doping compared with that of undoped Bi_3.35Nd_0.75Ti₃O₁₂ films.     

Laser ablation preparation and property of bismuth-layer-structured SrBi2Ta2Ta2O9 and Bi4Ti3O12 ferroelectric thin films

Abstract

Bismuth-layer-structured ferroelectric thin films, SrBi₂Ta₂O₉ and Bi₄Ti₃O₁₂, have been prepared by laser ablation method on both Pt sheets and Si wafers at low temperatures of 400 ～ 500°C. These thin films have been characterized by XRD, XPS, AFM, C-V, D-E hysteresis and J-V measurement. SrBi₂Ta₂O₉ thin films have a good (105) preferential orientation, and Bi₄Ti₃O₁₂ thin films have (117) and c-axis orientation on these substrates. Ferroelectric film-SiO₂-Si structures show good C-V hysteresis curve owing to Si surface potential controlled by the D-E hysteresis. D-E hysteresis is obtained in Bi₄Ti₃O₁₂ thin film prepared on Pt sheet, and the remnant polarization and the coercive force are 7.5 μC/cm² and 72 kV/cm, respectively.     

EFFECT OF ALKALINE EARTH SUBSTITUTION ON ELECTRICAL PROPERTIES OF SrBi4Ti4O15 CERAMICS

ABSTRACT

Ferroelectric Sr_1–xCa_xBi₄Ti₄O₁₅ (SCBT-x x = 0.00, 0.20, 0.40, 0.50, 0.70, 0.90 and 1.00) ceramic samples were prepared using the conventional solid-state reaction. The Curie temperature (T_c) increases with Ca doping. The temperature dependence of dielectric loss (tan δ) shows two dielectric anomalies at x = 0.20 while only one dielectric loss peak is found in other cases. The remnant polarization (2P_r) and coercive field (E_c) of nondoped SrBi₄Ti₄O₁₅ are about 15.7 μC/cm² and 107 kV/cm, respectively. Small amount of Ca doping increases the 2P_r, the 2P_r reaches a maximum value of 17.6 μC/cm² and E_c is increased to 113 kV/cm when x = 0.20. The piezoelectric coefficient (d₃₃) shows the maximum values of 9.0 pC/N at x = 0 and decreases almost linearly with the increase in x.     

Ferroelectric Properties of Mo-Doped Bi4-XLaXTi3O12 Films

Mo-doped Bi_3.35La_0.75Ti₃O₁₂ (BLTM) films were deposited on Pt/Ti bottom electrodes by using a sol-gel method and crystallized at 700°C for 30 min in O₂ atmosphere. The ferroelectric properties were greatly improved by substituting B-site ions with Mo ions and the BLTM films showed strong preferred (117) orientation. Typical remanent polarization (2Pr) and coercive field (2Ec) values were 32.0 μC?cm^?2 and 158 kV?cm^?1, respectively. It was also found that the leakage current densities in the BLTM films were lower than those in Bi_3.35La_0.75Ti₃O₁₂ (BLT) films.     

Structure and ferroelectric property of Nb-doped SrBi4Ti4O15 ceramics

Nb-doped SrBi₄Ti₄O₁₅ (SBT) was produced by conventional method. Structural and ferroelectric properties of SBT were examined as a function of niobium composition. Analyzing the structure futures of SBT by XRD, XPS and Raman spectrum, Nb⁵⁺ substituted Ti⁴⁺ to form NbO₆ octahedron and did not change the structure of SBT. The XRD patterns indicated the formation of the single phase of SBT for x = 0.01and 0.03 and secondary phase of Sr₃Ti₂O₇ appeared when x > 0.1. To compare the effect of Nb doping, the ferroelectric properties (hysteresis loop, piezoelectric coefficient) of Nb-doped SBT were measured. The SBT doped with x = 0.15 was found to exhibit higher remanent polarization with d ₃₃ = 17 pC/N.     

Fatigue Melioration of Neodymium-Modified Bi4Ti3O12 Ceramics

Pure and Nd-modified Bi₄Ti₃O₁₂ ceramics were prepared using the conventional solid state reaction method and their dielectric properties and mechanical properties are investigated. It shows that the activation energy of oxygen vacancies is enhanced whereas the concentration of oxygen vacancies is reduced when Bi³⁺ ions are partially substituted by Nd³⁺ ions. The Cole-Cole fitting to the dielectric loss reveals a strong correlation among oxygen vacancies. The strong correlation reduces the activation energy of oxygen vacancies efficiently. Therefore, we conclude that the diluted oxygen vacancies concentration is the origin of the excellent fatigue resistance of Nd-modified Bi₄Ti₃O₁₂ materials.     

Flux-mediated epitaxy for ferroelectric Bi4Ti3O12 single crystal film growth

We propose the “Flux-mediated epitaxy” as a novel concept for the growth of single crystalline films of incongruent, volatile, and high-temperature-melting compounds. In flux-mediated eptitaxy, by supplying materials precursors from the gas phase through the liquid flux films pre-deposited on the substrate, a quasi-thermodynamic equilibrium condition is obtained at the interface between the growing films and the flux films. This process has been demonstrated in this paper by fabricating ferroelectric Bi₄Ti₃O₁₂ films, which has volatile Bi oxide. The most important step in this process is the selection of the right flux material, which is hard to predict due to the lack of an appropriate phase diagram. In order to overcome this problem, we have selected the combinatorial approach. A series of ternary flux libraries composed of two self-fluxes (Bi₂O₃ and Bi₄Ti₃O₁₂) and a third impurity flux were fabricated on SrTiO₃ (001) substrates. After that, stoichiometric Bi₄Ti₃O₁₂ films were grown on each of these flux libraries at a temperature presumed to melt the flux. High-throughput characterization with the concurrent X-ray diffraction method resulted in the identification of CuO containing Bi₂O₃ as the flux material for the growth of single crystalline Bi₄Ti₃O₁₂ films. Stoichiometric Bi₄Ti₃O₁₂ films fabricated by using a novel CuO containing Bi₂O₃ are qualified to be single crystalline judging from their large grain size and the electrical properties equivalent to bulk single crystal’s.     

Effects of Substrate and Annealing Temperatures on the Characteristics of SrBi4Ti4O15 Thin Films

In this study, radio frequency (RF) sputtering was used as the method and the layer-structured bismuth compound of SrBi₄Ti₄O₁₅ + 4 wt% Bi₂O₃ ferroelectric ceramic was used as the target to deposit the SrBi₄Ti₄O₁₅ (SBT) thin films. The addition of excess Bi₂O₃ content in the target ceramic was used to compensate the vaporization of Bi₂O₃ during the sintering and deposition processes. SBT ferroelectric thin films were deposited on Pt/Ti/SiO₂/Si under optimal RF magnetron sputtering parameters with different substrate temperatures for 2 h. After that the SBT thin films were post-heated using rapid temperature annealing (RTA) method. The dielectric and electrical characteristics of the SBT thin films were measured using metal-ferroelectric-metal (MFM) structure. From the physical and electrical measurements of X-ray diffraction pattern, scanning electronic microscope (SEM), I-V curve, and C-V curve, we had found that the substrate temperature and RTA-treated temperature had large influences on the morphology, the crystalline structure, the leakage current density, and the dielectric constant of the SBT thin films.     

Preparation and Properties of Bi4 − x Nd x Ti3O12 Thin Films by Chemical Solution Deposition

Neodymium-modified Bi₄Ti₃O₁₂, (Bi, Nd)₄Ti₃O₁₂ (BNT) ferroelectric thin films have been prepared on Pt/TiO_x/SiO₂/Si substrates using metal-organic precursor solutions by the chemical solution deposition method. The BNT precursor films crystallized into the Bi layered perovskite Bi₄Ti₃O₁₂ (BIT) as a single-phase above 600C. The synthesized BNT films revealed a random orientation having a strong 117 reflection, whereas non-substituted BIT thin films exhibited a random orientation with strong 00l diffractions. Among Bi_{4 – x}Nd_xTi₃O₁₂ [x = 0.0, 0.5, 0.75, 1.0] thin films, Bi_3.25Nd_0.75Ti₃O₁₂ thin films showed a well-saturated P-E hysteresis loop with the highest P_r (22 C/cm²) and a low E_c (69 kV/cm) at an applied voltage of 5 V. The Nd-substitution with the optimum amount for the Bi site in the BIT structure was effective not only for promoting the 117 preferred orientation but also for improving the microstructure and ferroelectric properties of the resultant films.     

Preparation of Bi4Ti3O12 thin films by electron cyclotron resonance sputtering

Abstract

Ferroelectric Bi₄Ti₃O₁₂ thin films were deposited on Pt-coated oxidized Si substrate by electron cyclotron resonance (ECR) sputtering using ceramic targets. Crystal structure and dielectric properties of the films were investigated as functions of sputtering conditions such as substrate temperature and sputtering gas. Using a target with excess Bi content compared to stoichiometric composition was required to compensate Bi re-evaporation from the substrate and to obtain a perovskite single phase at 600°C. (117)-oriented films exhibited ferroelectric hysteresis loops. The remanent polarization and coercive field of the films were 9.8 μC/cm² and 180 kV/cm, respectively.     

MICROSTRUCTURE AND FERROELECTRIC PROPERTIES OF BaZr0.2Ti0.8O3 FILMS PREPARED BY SOL-GEL

ABSTRACT

BaZr_0.2Ti_0.8O₃ films were prepared using inorganic zirconate and the crystalline microstructure, surface morphology and ferroelectric properties of BZT films were investigated. It is found that the crystal structure of the films belongs to tetragonal phase and is close to cubic phase. The obvious polarization versus electric voltage (P-V) hysteresis loop and butterfly-shaped ?-V curves were observed in BaZr_0.2Ti_0.8O₃ films. The remanent polarization (2P _r) and the coercive field (2E _C) of BaZr_0.2Ti_0.8O₃ films obtained from the hysteresis loop are 0.1669 μC/cm² and 21.53 kV/cm, respectively. The dielectric constant and tunability of the BaZr_0.2Ti_0.8O₃ films are 113 and 10.2%, respectively.     

Bilayered Pb(Zr,Ti)O3/(Bi,Nd)4Ti3O12 thin films

Bilayered ferroelectric thin films consisting of Pb(Zr_0.52Ti_0.48)O₃ (PZT) and (Bi_3.15Nd_0.85)Ti₃O₁₂ (BNT) have been successfully synthesized on Pt/Ti/SiO₂/Si substrates, via a combined sol–gel and rf-sputtering route. Their ferroelectric and dielectric properties are critically dependent on the phases present, film texture and in particular layer and film thicknesses. Due to the coupling of PZT and BNT bilayers, there requires an optimized thickness combination of the two ferroelectric layers, in order to give rise to the wanted ferroelectric and dielectric properties, while the phenomenon can not be accounted for by the simple series connection model.     

Ferroelectric properties of (Bi3.15 Nd 0.85 )Ti 3 O 12 with decreasing film thickness

Film texture and ferroelectric behaviors of (Bi_3.15Nd_0.85)Ti₃O₁₂ (BNdT) of layered-perovskite structure deposited on Pt/TiO₂/Si substrate are dependent on the film thickness. When the film thickness is reduced from ∼240 to ∼120 nm, BNdT grains evolve from a rod-like morphology to a spherical morphology, accompanied by a decrease in average grain size. At the same time, P-E hysteresis transforms from a square-shaped hysteresis loop (2Pr ∼24.1 μC/cm² at 240 nm) to a relative slimmer hysteresis loop (with a lower 2Pr = 19.8 μC/cm² at 120 nm). The nonvolatile polarization (Δ P) shows a maximum at the film thickness of 160 nm, where Δ P was measured to be 14.7 μC/cm² and 6.8 μC/cm² at 5 V and 3 V, respectively. A small amount of excess bismuth in the film thickness of 130 nm, introduced by co-sputtering, can lead to a much enhanced remanent polarization (2Pr of 21.3 μC/cm² at 5 V and 15.2 μC/cm²at 3 V), which is promising for low voltage FRAM applications.     

Oriented growth of Bi3.25La0.75Ti3O12 thin films on RuO2/SiO2/Si substrates by using the polymeric precursor method: Structural, microstructural and electrical properties

c-axis oriented Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films were grown on a RuO₂ top electrode deposited on a (100) SiO₂/Si substrate by the polymeric precursor method. X-ray diffraction and atomic force microscope investigations indicate that the films exhibit a dense, well crystallized microstructure having random orientations with a rather smooth surface morphology. The electrical properties of preferred oriented Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films deposited on RuO₂ bottom electrode leaded to a large remnant polarization (P _r ) of 17.2 μC/cm² and (V _c ) of 1.8 V, fatigue free characteristics up to 10¹⁰ switching cycles and a current density of 2.2 μA/cm² at 5 V. We found that the polarization loss is insignificant with nine write/read voltages at a waiting time of 10,000 s. Independently of the applied electric field the retained switchable polarization approached a nearly steady-state value after a retention time of 10 s.     

Formation Mechanism of Plate-like Bi4Ti3O12 Particles in Molten Salt Fluxes

The plate-like Bi₄Ti₃O₁₂ particles were prepared by molten salt synthesis method. The influence of sintering temperature and cooling process on the microstructure of Bi₄Ti₃O₁₂ powders was studied. Much larger particles were formed at higher temperatures. The particles could grow larger in slow cooling process. The formation mechanism of plate-like Bi₄Ti₃O₁₂ particles in Na₂SO₄-K₂SO₄ system could be viewed as four processes: (1) solid reaction and nucleation, (2) plate-like structure formation, (3) diffusion and edge nucleation, (4) diffusion and epitaxial growth.