Temperature-Stable High-ε Dielectrics Ceramics Based on (1 − x) Ba5NdTi3Ta7O30/xBi4Ti3O12

Modification of Ba₅NdTi₃Ta₇O₃₀ dielectric ceramics was investigated through introducing Bi₄Ti₃O₁₂. With increasing of Bi₄Ti₃O₁₂ content, the dielectric constant increased, and the temperature coefficient of the dielectric constant changed from negative to positive. The small temperature coefficient ( < 50 ppm/°C) combined with high dielectric constant ( = 178) and low dielectric loss (tan = 0.007 at 1 MHz) was achieved in the composition x = 0.6.     

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.     

Textured LaNiO3 Electrode Grown by Spin-Coating Technique

LaNiO₃ thin films were deposited by spin-coating technique on various substrates using metal naphthenates as starting materials. The highly oriented LaNiO₃ films with smooth and crack-free surfaces grown on SrTiO₃(100) and LaNiO₃(012) substrates were observed by X-ray diffraction –2 scans, while the film on sapphire(0001) substrate showed polycrystalline structure. Resistivity vs. temperature curves of the textured LaNiO₃ films showed that the film possessed a good metallic character.     

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.     

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.     

Dielectric Properties of Bi4−x La x Ti3O12 (0 ≤ x ≤ 2) Ceramics

The dielectric properties of the Bi_4–x La _x Ti₃O₁₂ (0 x 2) ceramics were characterized and discussed together with the P-E relation (polarization vs. electric field). With increasing x, the P-E relation changed from normal ferroelectric hysteresis loops to pure linear relation, which indicated that La³⁺ substitution for Bi³⁺ in Bi₄Ti₃O₁₂ induced a phase transition from ferroelectric to paraelectric state at ambient temperature. Low loss dielectric ceramics with temperature stable dielectric constant were obtained for x > 1.2 in Bi_4–x La _x Ti₃O₁₂ at 1 MHz. And the loss increased in all the compositions when the ceramics were measured at microwave frequencies.     

P-Type Partial Conductivity of Donor(La)-Doped BaTiO3

P-type partial conductivity has been determined on donor (La _Ba )-doped BaTiO₃ in full thermodynamic equilibrium state at a fixed temperature of 1200°C: For the nominal compositions of Ba_0.99La_0.01Ti_0.9975O₃, Ba_0.99La_0.01TiO₃ and Ba_0.985La_0.01TiO₃, the p-type conductivity is found to vary with oxygen activity as _p = (_m/2)(a _{O 2}/a _{O 2}*)^+1/4 with _m 0.01 S cm^–1 and a _{O 2}* 32, 120, 310, respectively, in the a _{O 2} region where conventionally the electronic conductivity varies as a_{O 2} ^–1/4 and hence, the doped donors are believed to be compensated by cation vacancies (say, [La_Ba ] 4[VPrime;_Ti]). This experimental fact supports that in the vicinity of the stoichiometric composition of the system which falls approximately at a _{O 2} = a _{O 2}*, while cation vacancy concentration is fixed by the donor concentration, oxygen vacancy concentration in the minority is also essentially fixed, thus, keeping the activity of TiO₂ (or BaO) fixed. It is consequently suggested that donor-doped BaTiO₃ contains a second phase even in its stoichiometric regime.     

Atomic Force Microscopy Examination of the Evolution of the Surface Morphology of Bi4Ti3O12 grown by Molecular Beam Epitaxy

The surface morphology of (0 0 1) Bi₄Ti₃O₁₂ grown on (0 0 1) SrTiO₃ by reactive molecular beam epitaxy (MBE) has been examined using atomic force microscopy (AFM). Initial nucleation of a 1/4 unit cell thick layer is followed by growth of 1/2 unit cell thick layers. Between 9 and 16 layers, a transition to 3-dimensional growth occurs, leading to well-defined mounds. This implies a Stranski-Krastonov growth mode. During growth, the morphology follows a behavior consistent with the dynamic scaling hypothesis and we extract values for the scaling exponents and from the AFM data. A thickness variation in is observed and reflects the strain relief associated with the Stranski-Krastonov growth.     

Ferroelectric Properties of Bi3.25Nd0.75Ti3O12 Thin Films Prepared by MOD Process

Ferroelectric Bi_{4 – x}Nd_xTi₃O₁₂(BNdT) thin films with the composition (x = 0.75) were prepared on Pt/Ti/SiO₂/Si(100) substrate by metal-organic deposition. The films were annealed by various temperatures from 550 to 650C and then the electrical and structural characteristics were investigated for the application of FRAM. Electrical properties such as dielectric constant, 2Pr and capacitance were quite dependent on the thermal heat treatment. The measured 2Pr value on the BNdT capacitor annealed at 650C was 56 C/cm² at an applied voltage of 5 V. No fatigue was observed up to 8 × 10¹⁰ read/write switching cycles at a frequency of 1 MHz regardless of annealing temperatures.     

Annealing Effects on Structural and Dielectric Properties of Tunable BZT Thin Films

Ba(Zr, Ti)O₃ thin films have attracted great attention in recent years for their potential use in DRAMs and MCMs due to their high dielectric constant and relatively low leakage current. However, their tunable dielectric properties were rarely investigated and the corresponding potential for tunable microwave applications was seldom reported. In this paper, we present the tunable dielectric behavior of BZT thin films deposited by RF magnetron sputtering from a Ba(Zr_0.3Ti_0.7)O₃ ceramic target on MgO single crystal substrates. The composition, thickness and crystallinity of the thin films were analyzed by Rutherford backscattering (RBS), scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The dielectric constant and loss tangent were measured as a function of electric field (0–7 kV/mm) and temperature (–140 to +160°C) at frequencies up to 1 MHz, using interdigital capacitors (IDC) with Au electrodes on thin films. By optimizing the preparation process, a tunability {defined as = [ (0) – (E_max)]/ (0)} of 76% at E_max = 7 kV/mm and a low loss tangent of 0.0078 can be achieved. In addition, the influence of annealing temperature on the dielectric properties of the thin films is also discussed.     

Phase Formations and Electrical Properties of Various (Bi, La)4Ti3O12 Thin Films by Chemical Solution Deposition

The phase formation and electrical properties of (Bi, La)₄Ti₃O₁₂ (BLT) thin film and V-, Sm-doped BLT thin films prepared by the chemical solution deposition method on Pt/TiO₂/SiO₂/Si substrates have been investigated. It was observed that the microstructure and electrical properties of BLT thin films dramatically varied with V- and Sm-doping. The crystallinity and grain size of BLT thin films were definitely increased by V- and Sm-doping into BLT films, which resulted in the enhancement of remanent polarization in doped BLT films. The remanent polarization (Pr) of Sm-doped BLT films annealed for 3 min by an RTA system was about 9 C/cm². The V- and Sm-doped BLT films also exhibited good fatigue characteristics under bipolar stressing to 10¹⁰ cycles.     

Optical Waveguiding Properties of (Pb,La)TiO3/Al2O3 Planar Structures

Thin films of lead lanthanum titanate (Pb,La)TiO₃ have been grown by radio-frequency magnetron sputtering on (0001) Al₂O₃ substrates. The structure, the microstructure and the optical properties of the films have been investigated as a function of the postdeposition annealing. Films deposited at low temperatures crystallize to a perovskite phase after the annealing treatment from 500°C to 650°C. X-ray (–2) diffraction studies have shown that films are crystallized with a strong (111) orientation and the best crystalline structure is reported at 600°C. The optical properties were both demonstrated by spectrophotometry and prism coupling. PLT thin films with a transparency of 80% in the wavelength range 300–2000nm have exhibited a refractive index of 2.38 @ 632.8nm representing 97% of the bulk corresponding material. Investigation of optical propagation has been accomplished in a 10mm long planar optical waveguide using a butt-coupling configuration.     

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.     

Scaling Effect on the Dielectric Constant in Ba(Ti x Zr1−x )O3 Thin Films

Recent work on PZT and BST thin films reveal a thickness dependence of the dielectric constant for a film thickness below 100 nm. This effect is commonly attributed to an interfacial layer between the electrode and the dielectric film (dead layer). In this contribution we report on the influence of the film thickness on the dielectric constant of Ba(Ti_xZr_{1 – x})O₃ thin films with different Zr-contents (x = 0–30 at.%). The films were prepared by chemical solution deposition (CSD) with thickness between 30 and 350 nm.The electrical characterization was performed in a temperature range between 25 and 200C. Results were interpreted with respect to the formation of a serial dead layer capacitance.     

Protonic Conduction in SrY0.5Ta0.5O3-Based Ceramics at Elevated Temperatures

The perovskite-type-oxide solid solution SrY_0.5+x Ta_0.5+x O_3– was synthesized and its properties were investigated. The single phase character of the samples was confirmed by X-ray diffraction when 0 x 0.02, while lines from the impurity phase SrY₂O₄ appeared in patterns of x 0.03. The conductivities of SrY_0.52Ta_0.48O_3– were about an order of magnitude higher than those of SrY_0.50Ta_0.50O₃. The results of electrochemical measurements such as emf measurements of gas concentration cells, isotope effect in conductivity, and oxygen partial pressure dependence of conductivity showed that SrY_0.52Ta_0.48O_3– exhibited pure protonic conduction in reducing atmospheres and p-type electronic conduction under high oxygen partial pressure conditions.     

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.     

Microwave Dielectric Properties of Ferroelectric BaTiO3 Thin Film

The dielectric properties of c-axis epitaxial BaTiO₃ thin film on LaAlO₃ are investigated at frequencies of 0.5–30 GHz. For the measurements, interdigital capacitors with the Au/Ti electrode configurations of five fingers pairs that are 15 m wide and spaced 2 m apart are prepared by photolithography and lift-off patterning. Finger length varies from 20 to 80 m. The capacitance of epitaxial BaTiO₃ films exhibited no frequency dependence up to 10 GHz with the exception of slightly upward tendency of capacitance in BaTiO₃ film with a finger length of 80 m due to the self resonant frequency at 20 GHz. The Q-factors of the capacitors, defined as Q = 1/CR, are decreased up to 10 GHz with increased frequency. At 10 GHz, the BaTiO₃ film has a tunability [defined as k(V) = [C(0)–C(V)]C(0)] of 1.5% at 15 V, a loss tangent of 0.2 at room temperature. The small tunability can be interpreted as a result of in-plane compressive stress of BaTiO₃ film exhibiting large dielectric anisotropy. For the improvement of tunability and dielectric loss in the interdigital BaTiO₃ capacitor, the tetragonality (c/a) of epitaxial BaTiO₃ film and design of interdigital capacitor should be modified.     

Crystal Growth and Dielectric Properties of New Ferroelectric Barium Titanate: BaTi2O5

Single crystals of the ferroelectric BaTi₂O₅ and BaTiO₃ were prepared from a solution of 33-mol% BaO and 67-mol% TiO₂ by a rapid cooling method. The dielectric constant () and dielectric loss tangent (tan) were measured in a wide temperature range of 10–860 K and in a frequency range of 0.1–3,000 kHz. The along the b-axis of the BaTi₂O₅ crystal, prepared in air, shows a sharp dielectric anomaly reaching 30,000 at the ferroelectric Curie temperature of T_C = 752 K. By contrast, the crystal prepared in a reducing atmosphere shows a diffuse phase transition near T_C = 703 K. The values of and tan are compared between these three crystals consisting of two kinds of BaTi₂O₅ and one BaTiO₃.     

Coplanar Waveguide Using Ferroelectric Thin Oxide Film: Dielectric Constant

Coplanar waveguide (CPW) transmission lines were fabricated on thin ferroelectric Ba_{1 – x}Sr_xTiO₃ films for tunable microwave applications. The growth of the ferroelectric oxide films was accomplished by a pulsed laser deposition with a partial oxygen background. Microwave properties of the CPW phase shifter were measured using a HP 8510C vector network analyzer from 0.045–20 GHz with –40–40 V of dc bias. A large phase shift angle of 120 at 10 GHz was observed from the CPW (gap = 4m, length = 3 mm) with a 40 V of dc bias change. The dielectric constant of the thin ferroelectric film was extracted from the dimension of the CPW (gap, width, length) and the measured S-parameter by a modified conformal mapping. However, the dielectric constant of the ferroelectric thin film exhibits a gap dependency; dielectric constant (990–830) decreases with increasing gap size (4–19 m, respectively). By adjusting the filling factors of the film, a constant dielectric constant of BST film is found to be 810 ± 5.     

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.