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.     

Relaxation Motion and Possible Memory of Domain Structures in Barium Titanate Ceramics Studied by Mechanical and Dielectric Losses

The relaxation motion and memory effect of domain structures have been investigated using mechanical and dielectric loss measurements in BaTiO₃ ceramics with grains sizes varied from 1 m to 50 m. The measurements of mechanical loss, elastic modulus, dielectric loss and permittivity show that each phase transition induces a loss peak and an anomaly in the dielectric constants and elastic modulus, furthermore, a number of relaxation loss peaks due to ferroelectric domains in the samples with large grain have been observed. All the relaxation peaks can be analysed by Arrhenius relationship for a wide range of frequency from 10^–2 to 10⁶ Hz. The activation energies of relaxation peaks have been determined as 0.92 eV, 0.68 eV, 0.47 eV, and 0.29 eV for the peaks located in the tetragonal, orthorhombic, and rhombohedral phase, with Arrhenius perfactor in the order of 10^–13 s. Moreover, one relaxation process is insensitive to ferroelectric phase transitions, and it can exist in all the ferroelectric phases. This implies a possible memory effect of ferroelectric domain structures. Such a motion of domain wall is limited in fine-grained materials. Effect of vacuum annealing on the relaxation peak in the tetragonal phase is also studied to clarify the mechanisms of the peak. These relaxation peaks could be explained by the interaction between different domain walls and the diffusion of oxygen vacancy in the domains.     

Dielectric Characteristics and Tunability of Barium Stannate Titanate Ceramics

Ba(Ti_{1 –x} Sn _x )O₃ solid solutions were prepared by a solid state reaction method, and their dielectric and tunable characteristics were investigated together with the microstructures and diffused phase transition behaviors. The dielectric relaxation behaviors were observed and became stronger with increasing x.The obvious field dependence of the present system was observed with high dielectric constant and low loss at relatively lower DC electric field. The excellent tunable dielectric characteristics were achieved for x= 0.15 at room temperature: tunability 56%, tan 0.003 at 10 kHz under 7.6 kV/cm, indicating that it is a promising candidate for electric-field tunable dielectrics working at room temperature.     

Copper Cofire X7R Dielectrics and Multilayer Capacitors Based on Zinc Borate Fluxed Barium Titanate Ceramic

Copper cofired dielectrics may give new opportunities for high temperature capacitors. To demonstrate feasibility, BaTiO₃ has been formulated into X7R dielectrics with copper inner electrodes. This requires the development of a formulation that permits sintering at temperatures below 1000°C, and then firing in a reducing environment in atmospheres pO₂ 10^–8 atms. ZnO—B₂O₃ chemistries were explored with additional dopants to modify densification and the temperature coefficient of capacitance of the BaTiO₃ dielectric anomaly. X7R characteristics with relative dielectric permittivities 2750 and tan 0.01 at 1 kHz were obtained at room temperature. Multilayer capacitors were fabricated in 3.2 mm × 1.6 mm size multilayers with an acrylic binder system and oxidation resistive copper inner electrodes.     

Formation of BaTiO3 from Barium Oxalate and TiO2

Barium titanate powder has been prepared via a semi-oxalate method that uses barium oxalate and TiO₂ precursors, instead of titanyl oxalate. Barium oxalate was precipitated from nitrate solution onto the surface of TiO₂ powders. Crystallization of BaTiO₃ from the precursors was investigated by TGA, DTA and XRD analysis. It is evident that an intermediate barium oxycarbonate along with BaCO₃, forms between 450–500°C and that decomposes to BaCO₃ again at high temperature. Decomposition of BaCO₃ occurs at much lower temperature, from 600°C onwards, due to the presence of TiO₂. The precursor completely transforms into BaTiO₃ at 900°C. Nanometer size BaTiO₃ crystallites are produced during this synthesis due to the lower calcination temperature. The crystalline morphology of BaTiO₃ is controlled mainly by the morphology of BaCO₃, which formed in the intermediate stage.     

Co-Doping Effect of Mn and Y on Charge and Mass Transport Properties of BaTiO3

BaTiO₃-based multilayer-ceramic capacitors (MLCC) using base metal (Ni) electrodes normally contains Mn and Y each approximately on the order of 0.5 mol%. It is only empirically known that the co-doping of Y and Mn facilitates sintering with the base-metal electrodes as well as improves the device performance and life time. In order to understand the effect of the co-doping, we have measured the electrical conductivity and chemical diffusivity on polycrystalline BaTiO₃ that is co-doped with Y and Mn each by 0.5 mol% against oxygen partial pressure at elevated temperatures. It is found that while the n-type conductivity in reducing atmospheres (e.g., Po₂ < 10^{– 6} atm at 1000C) remains similar to that of undoped or acceptor-doped BaTiO₃, its p-type conductivity in oxidizing atmospheres (e.g., Po₂ > 10^{– 6}at 1000C) is remarkably suppressed compared to the latter. The chemical diffusivity is also similar to that of the latter in magnitude (e.g., 10^{– 2}–10^{– 5} cm²/s at 1000C), but its trend of variation with oxygen partial pressure is rather opposite. These variations of the conductivity and chemical diffusivity are mainly attributed to Mn ions changing their valence from +2 to +3 to +4 with increasing oxygen partial pressure. It is explained from a defect-chemical view why the codoping of fixed-valent donor (Y) and variable-valent acceptor (Mn) has been practiced in MLCC processing.     

Dysprosium Doped Dielectric Materials for Sintering in Reducing Atmospheres

Substitution of Dy rare earth ions was studied in Ba(Ti,Zr)O₃ dielectric materials, using thermogravimetry, X-ray diffraction and dielectric measurements. Dy³⁺ ions enter both the A- and the B-sites of the perovskite structure, however, the solubility on B-sites is up to 9 mol %, whereas it is only 2.5 mol% on A-sites. Dy can be easily shifted from A- to B-sites and back, using Ba or Ti excess in the material. Dy³⁺ on B-sites is a strong electron acceptor. Dy doped dielectric materials are cofired with Ni electrodes in reducing atmosphere to highly insulating BME multilayer capacitors.     

The Variable Thermal Sensitivity of Strontium-Lead Titanate Semiconducting Ceramics

Strontium-lead titanate semiconducting ceramics with low room temperature resistivity (_RT) and variable NTCR-PTCR composite effects were fabricated at different sintering conditions. Both _RT and the NTCR effect decreased at the higher heating rate or doping excess of PbO. After the heat-treatment at 950°C, the transformations from PTCR to NTCR-PTCR characteristics were observed in excess PbO-doped samples. According to the results, it is assumed that the lead vacancies (V_Pb) in the grain boundary layers degenerate the conductivity of strontium-lead titanate semiconducting ceramics and the NTCR behaviors below the Curie temperature are ascribed to the electron detrapping of acceptor defects with increasing temperature.     

Effect of Cr additions on the microstructural stability of Ni electrodes in ultra-thin BaTiO3 multilayer capacitors

Microstructural control in thin-layer multilayer ceramic capacitors (MLCC) is one of the present day challenges to maintain an increase in capacitive volumetric efficiency. This present paper opens a series of investigations aimed to engineer the stability of ultra-thin Ni electrodes in BaTiO₃-based multilayer capacitors using refractory metal additions to Ni. Here, pure Ni and Ni–1 wt.% Cr alloy powders are used to produce 0805-type BME MLCCs with 300 active layers and with dielectric and electrode layer thickness around 1 μm. To investigate the continuity of Ni electrodes, both MLCC chips with pure and doped electrodes were sintered at different temperatures for 5 h. It is found that the continuity of Ni electrodes is improved most likely due to the effect of Cr on the low-melting point (Ni,Ba,Ti) interfacial alloy layer formation. The interfacial alloy layer is not observed when Cr is segregated at Ni-BaTiO₃ interface in the Cr-doped samples, while it is found in all undoped samples. The interfacial alloy layer is believed to increase mass-transfer along the Ni-BaTiO₃ interfaces facilitating an acceleration of Ni electrodes discontinuities.     

Ferroelectric Property and Crystal Structure of KNbO3 Based Ceramics

Rietveld refinement analysis was carried out to obtain the knowledge on the solid solution structure of the La and Fe co-doped KNbO₃ ceramics. The diffraction data was well fitted with tetragonal space group P4mm, and showed that La and Fe located at K and Nb sites in KNbO₃ perovskite, respectively. The sum of both occupancy ratios agreed almost well with the doping content. Furthermore, the effects of MnO₂ addition on the ferroelectric properties and crystal structure of the La and Fe co-doped KNbO₃ ceramics were investigated. MnO₂ addition strongly affected the ferroelectric and piezoelectric properties, because the valence of Mn ions changed from Mn^{4 +} to some extents of Mn^{3 +} and Mn²⁺, which were suggested by XAFS analysis.     

Effect of Cr additions on the electrical properties of Ni–BaTiO3 ultra-thin multilayer capacitors

Multilayer ceramic capacitors based on BaTiO₃ dielectric compositions and Ni inner electrodes have complex interfacial reactions that impact the continuity of the inner electrode microstructure. Previously we demonstrated that through the addition of Cr to Ni, a significant improvement in the continuity of ultra-thin Ni electrodes in Ni–BaTiO₃ multilayer capacitors could be achieved. Here, the effect of the Cr addition to the nickel electrode pastes is studied with regard to the electrical properties. Low-field electrical measurements demonstrate no major differences between Cr doped Ni and undoped Ni. However, high-field measurements show a significant decrease to the total capacitor resistance. Under a critical electrical bias the conductivity significantly increases due to a Fowler–Nordheim tunneling conduction though the interfacial Schottky barrier at the dielectric–electrode interface; the onset voltage of this conduction is much lower than with the undoped nickel. Based on these results, we evaluate criteria for the selection of an appropriate refractory metal in order to improve the Ni electrode continuity.     

Defect Chemistry of Y Doped BaTiO3

Defect chemistry of Y doped BaTiO₃ was investigated as a function of the Ba/Ti ratio. When the Ba/Ti ratio was greater than unity, Y^{3 +} was substituted for the normal Ti site and the equilibrium conductivity showed a strong evidence of acceptor-doped behavior. With the Ba/Ti ratio < 1, Y^{3 +} was substituted for the Ba site and the equilibrium conductivity showed donor-doped behavior. In the case excess Y₂O₃ was added to the stoichiometric BaTiO₃(Ba/Ti = 1), the conductivity profile showed a donor-doped behavior at low concentrations (< 1.0 mol%), whereas, at higher donor levels (> 2.0 mol%), the equilibrium conductivity minimum shifted toward lower Po₂, indicating acceptor doped behavior.     

Preparation of (PbxBa1-x)TiO3 thin films by MOCVD using an aerosol-assisted liquid delivery system

Abstract

Thin films of PbTiO₃, BaTiO₃ and (Pb_xBa_1-x)TiO₃ (PBT) have been prepared by metal-organic chemical vapor deposition using a horizontal reactor with an aerosol-assisted liquid delivery system. Structural and electrical properties have been investigated as a function of the lead content x. First results on PBT thin films grown on platinized silicon substrates show, for x < 0.8, an increasing tetragonal distortion of the lattice cell (c/a >1), and accompanying ferroelectric behavior which is similar to the bulk material. For smaller lead content (x < 0.8) no ferroelectric behavior is established and a small tetragonal distortion of opposite type (c/a <1) is observed. This distortion is attributed to a thermally induced tensile film stress and may be responsible for the suppression of the ferroelectric phase transition.     

Electrical Properties of Acceptor Doped BaTiO3

Electrical properties of acceptor (Mn, Mg or Mn+Mg)-doped BaTiO₃ ceramic have been studied in terms of oxygen vacancy concentration, various doping levels and electrical degradation behaviors. The solubility limit of Mn on Ti sites was confirmed to be close to or less than 1.0 mol%. Oxygen vacancy concentration of Ba(Ti_{0.995 –x}Mg_0.005Mn_x)O_{2.995 –y} (x = 0, 0.005, 0.01) was estimated to be 50 times greater than that of the un-doped BaTiO₃. The leakage current of 0.5 mol% Mn-doped BaTiO₃ was stable with time, which was much lower than that of the un-doped BaTiO₃. The BaTiO₃ specimen co-doped with 0.5 mol% Mg and 1.0 mol% Mn showed the lowest leakage current below 10^{– 10}A. It was confirmed that leakage currents of Mg-doped and un-doped BaTiO₃ under dc field are effectively suppressed by Mn co-doping as long as the Mn doping level is greater than Mg contents.     

Influence of B2O3/SiO2 Ratio on the Fabrication of Nd:YAG Ceramics

B₂O₃/SiO₂ are used as composite sintering aids to fabricate Nd:YAG ceramics by solid-state reaction and vacuum sintering method at 1750°C for 5h using Nano-Al₂O₃, Y₂O₃, Nd₂O₃ as starting materials. In this article, we focus on the influence of B₂O₃/SiO₂ ratio on grain size, porosity and relative density. Finally, with the increase of B₂O₃/SiO₂ ratio, the density and shrinkage rate of transparent ceramics increase, the grain size becomes uniform and the porosity reduces, for the reason that B³⁺ begins to vaporize at 1300°C and is reduced to trace levels by 1600°C. The best B₂O₃/SiO₂ ratio is 4: 1.     

Growth and electrical properties of (211) BaTiO3 thin films on Pt-coated Si(100) substrates

Abstract

Barium titanate (BaTiO₃) thin films with high (211) orientation have been prepared on Pt(111)/Si(100) substrates by R. F. magnetron sputtering at a substrate temperature between 550°C and 580°C in an Ar/O₂ atmosphere. The I-V curve of a thin film capacitor (Ag-BaTiO_3-Pt) has been measured and the C-V curves are obtained for frequencies between 100Hz and 1MHz. Neither the I-V curve nor the C-V curves are symmetrical and a very large change in the slope of all curves is found to occur at ～+0.5v.     

Electrical characterizations of MgTiO3 thin films grown on Si

Abstract

We have analyzed MgTiO₃ thin films grown on the Si substrate with/without SiO₂ using pulsed laser deposition (PLD). We find that MgTiO₃ thin films start to crystallize at 600°C, causing electrical instabilities in the MIS capacitors above this temperature. Detailed analysis by XRD technique reveals that structural differences of MgTiO₃ thin films were not obvious below 600°C, whereas the electrical characteristics changes as a function of deposition temperature and the presence of thermally grown SiO₂. We observe that the decrease of deposition temperature results in the increase of leakage current and anomalous positive charge (APC) density. These drawbacks were effectively suppressed by growing 100A SiO₂ layer on the Si substrate prior to the deposition of MgTiO₃ thin 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.     

Sintering Behavior and Interfacial Analysis of Ni/Cu Electrode with BaTiO<Subscript>3</Subscript> Particulates

The sintering behavior of Ni electrode alloyed with Cu and the interfacial structure between Ni/Cu to BaTiO₃ (BT) have been investigated. The quantitative properties, which include thermal shrinkage, thermal expansion, wetting behaviors of Ni/Cu alloys on BT sheet, and composition distribution were measured by several thermal analysis techniques (TGA/DTA/TMA) and microstructural techniques (SEM/TEM/ HRTEM) with energy-dispersive spectroscopy (EDS). The shrinkage of the Ni/Cu/ BaTiO₃ composite tested in 5%H₂/N₂ atmosphere showed strong influence by the addition of Cu, and retarded slightly due to the addition of the BT particulates. The Cu alloyed with Ni improves the continuity of the electrode and does not trigger mutual reaction between Ni and BT.     

The Characteristics of Magnesium Titanate Thin Film as Buffer Layer by Electron Beam Evaporation

We have studied the application of magnesium titanate thin films as buffer layer for the improvement of adhesion of Pt films to Si substrate. Magnesium titanate films were successfully prepared on Si(100) substrate by electron beam evaporation. The crystal phase of MgTi₂O₅ and MgTiO₃ films on Si substrate were observed. These films had a very smooth and densely packed surface morphology and showed a good characteristic as the adhesion layer for Pt. Also, AES analysis showed the excellent properties as the reaction barrier layer between Pt and Si.