Doping effects of Dy and Mg on BaTiO3 ceramics prepared by hydrothermal method

Fine Dy and Mg-doped barium titanate powders were prepared by hydrothermal method at 240^∘C with BaCl₂⋅ 2H₂O, TiCl₄ and NaOH as the main reactants, Dy₂O₃ and MgCl₂⋅ 6H₂O as additives respectively. The substitution style, microstructure and electrical properties of the two kinds of samples were comparatively studied by X-ray diffractometer (XRD), atomic emission spectrum (AES) and scanning electron microscopy (SEM) characterizations. It is confirmed that Dy or Mg enters into the BaTiO₃ lattice. Ba site is replaced if a little Dy₂O₃ is doped but some more Dy will take up the positions of Ti. Mg always substitutes for Ti site. Dy and Mg are both useful to obtain the microstructure with small grains and high density, and the former results in a better microstructure. Dy has no influence on shifting and depressing Curie peak. When Dy₂O₃ content is 0.6 wt%, the dielectric constant rises up to 4250. However, Mg has evident effect on shifting Curie peak. The value of Δ T _c is −40^∘C in the doping range of 0 to 0.15 wt%. When Mg/Ti atomic ratio is 0.06 in the precursors, the dielectric constant rises up to 4100.     

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.     

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.     

A first principles investigation of new cathode materials for advanced lithium batteries

First principles calculations on the crystal and electronic structure of a layered Li(Ni_1/3Mn_1/3M_1/3)O₂ (M = Al, Ti, Cr, Fe and Mo) were undertaken as part of a search for new positive electrode materials for advanced lithium ion batteries. The formal charge of Ni, Mn and M (Ti and Mo) were estimated to be +2, +3 and +4, respectively, from electronic structures and interatomic distances. In the cases of the Al, Cr and Fe substitution, the compounds had trivalent M and tetravalent Mn ions. The solid-state redox reactions of Li(Ni_1/3Mn_1/3M_1/3)O₂ were calculated assuming a Li deinsertion scheme, and the reactions were shown to be Ni²⁺/Ni³⁺/Ni⁴⁺ and M³⁺/M⁴⁺ for the Cr and Fe substitution. Al substitution will lead to higher voltages, as fixed 3+ valence of Al forces more electron exchange with oxygen. The cases of Ti and Mo substitution, Ti and Ni ions do not participate in the redox reactions over the entire range, respectively. The substitutive cation-oxygen bonding has a more covalent character, when the redox energy of Ni is lowered, resulting in an increase in potential. As described above, the voltage profiles are very different because the types of metals are different and participate in electrochemical reactions according to the substituted.     

Ionic Doping Effects in SrBi2Nb2O9 Ferroelectric Ceramics

Ionic doping effects of various ions in Bi-layered ferroelectric SrBi₂Nb₂O₉ (SBN) ceramics were studied. Un-doped and doped SBN ceramics with Ba²⁺, Pb²⁺, Ca²⁺, Bi³⁺, La³⁺, Ti⁴⁺, Mo⁶⁺, and W⁶⁺ ions were made with solid state reactions. Temperature dependent dielectric constants were measured. Ferroelectric transition temperature (T_C) decreased with Ba²⁺ and Pb²⁺ ions but increased with Ca²⁺ ion which substitutes the 12-coordinated Sr²⁺ site. T_C increased with Ti⁴⁺, Mo⁶⁺, and W⁶⁺ ions which substitute the 6-coordinated Nb⁵⁺ sites. With trivalent Bi³⁺ and La³⁺ ions, T_C increased with Bi³⁺ ion but much decreased with La³⁺ ion. These results showed that the ion size plays an important role in ferroelectricity of SBN ceramics.     

Characterization of Ba(Zr0.05 Ti0.95)O3 thin film prepared by sol-gel process

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin film (∼330 nm) was grown on Pt/Ti/SiO₂/Si(100) substrate by a simple sol-gel process. The microstructure and the surface morphology of BZT thin film were studied by X-ray diffraction and atomic force microscopy. The optical properties of BZT thin film were obtained by spectroscopic ellipsometry. The optical bandgap was found to be 3.74 eV of direct-transition type. Ferroelectric and dielectric properties of BZT thin film were also discussed. The electrical measurements were conducted on BZT films in metal-ferroelectric-metal (MFM) capacitor configuration. The results showed the film exhibited good ferroelectrity with remanent polarization and coercive electric field of 3.54 μC/cm² and 95.5 kV/cm, respectively. At 10 kHz, the dielectric constant and dielectric loss of the film are 201 and 0.029, respectively.     

Diffuse phase transition behavior of dysprosium doped barium titanate ceramic

The effect of dysprosium (Dy) doping on the structural and dielectric properties of barium titanate (BaTiO₃) ceramic has been studied. Dysprosium-doped barium titanate (BT) with general formula Ba_1-xDy_2x/3TiO₃ (x?=?0.0–0.1) is prepared through solid state reaction route. The XRD pattern reports the single phase tetragonal structure up to x?=?0.025 with space group of P4mm and a secondary phase is observed for higher concentration of Dy. The Raman study of Ba_1-xDy_2x/3TiO₃ (x?=?0.00, 0.01, 0.025) also reveals that the ceramic is showing tetragonal symmetry and with an increase in Dy doping the tetragonal phase is moving toward more symmetric phase i.e. cubic pm3m. The surface morphology of the sintered pellets shows a compact and homogeneous grain distribution with a decrease in grain size as the Dy content increases. The temperature and frequency dependency dielectric study of the ceramic compositions (x?=?0.00, 0.01, 0.025) are studied to show the effect of Dy ion on the A site of BaTiO₃ perovskite ceramic. The dielectric constant decreases with increase in Dy content. The dielectric diffusivity increases with increase in doping concentration. The P-E hysteresis loop confirms the ferroelectric behavior of the sample with decrease in remanent polarization and increase in coercive field.     

THE ELECTRICAL AND STRUCTURAL PROPERTIES OF Li2CO3 DOPED 0.7(Ba,Sr)TiO3-0.3MgO CERAMICS

ABSTRACT

We have studied the formation and characterization of Li₂CO₃ doped 0.7(Ba,Sr)TiO₃-0.3MgO ceramics for the low temperature sintering and microwave applications. In this study 1 ～ 5 wt% of Li₂CO₃ was added to the 0.7(Ba,Sr)TiO₃-0.3MgO ceramic materials to reduce the sintering temperature. The MgO contents, which added in this experiment, play a role of improving dielectric permittivity such as low frequency dispersion and low loss tangent.

In this paper, we will discuss the crystalline properties, dielectric properties, and the microstructures of Li₂CO₃ doped 0.7(Ba,Sr)TiO₃- 0.3MgO ceramics. No pyro phase was observed in the X-ray diffraction method. Very weak frequency dispersion of dielectric permittivity was observed from the 1 kHz to 1 MHz range. Different grain sizes of Li₂CO₃ doped 0.7(Ba_0.5Sr_0.5)TiO₃-0.3MgO ceramics were observed through the SEM methods.     

Magnetron sputter-deposited multilayer (BaxSr1x)Ti1+yO3+z thin films for passive and active devices

Abstract

High permittivity (Ba_xSr_1?x)Ti_1+yO_3+z(BST) thin films are being investigated for integration into charge storage dielectrics and electric-field tunable elements for high frequency devices. For the latter application, it is desirable to have BST capacitors with high tunability and low losses. Therefore, we investigated the use of multilayer BST thin films consisting of very low dielectric loss BST/electrode interfacial layers ((Ba+Sr)/Ti = 0.73) sandwiching a high tunability, high permittivity primary BST layer ((Ba+Sr)/Ti = 0.9). BST capacitors with multiple layers of controlled composition can be effectively produced insitu by magnetron sputter deposition, using a single stoichiometric target and controlling the layer composition by changing the total process gas (Ar+O<₂) pressure. The layered BST film capacitors exhibit simultaneous low loss (tan Δ = 0.005), high tunability (76%), high charge storage energy density (34 J/cm³), low leakage, and high dielectric breakdown (>2.8 MV/cm).     

Photoluminescence and photocurrent characteristics of Eu2 + activated MAl2O4 (M = Ba, Ca, Sr) phosphors

Photoluminescence and photocurrent characteristics of Eu^{2 +} activated MAl₂O₄ (M = Ba, Ca, Sr) phosphors during and after Ultraviolet ray and visible light irradiation have been investigated. The photoluminescence (PL) and the photocurrent (PC) of the phosphors, in order to elucidate the relationship between the PL and the PC, were measured simultaneously on the same samples within a specially designed measuring box. Composition effects, such as a presence of Dy^{3 +} as a co-activator and Al-rich composition on the PL and PC characteristics have been investigated. Also, sensing characteristics on UV and visual light have been tested. The simultaneous measurement of PL and PC on the same sample clearly indicated that the presence of co-activator and vacant site, namely Al-rich composition, acted as a hole trap; the introduction of co-activator and vacant site decreased the PC and increased the PL during and after UV and visible light irradiation, whose PC was much lower than that of MAl₂O₄ with only Eu^{2 +} as an activator. The electrical intensity affected on the PL characteristics after UV and visual light irradiation(afterglow); with increasing in the electrical intensity, the afterglow lasted more longer and intensively. The PC of MAl₂O₄ showed a good proportional relationship to UV and visible light intensity. Especially, SrAl₂O₄ showed an excellent linearity within 1–5 mW/cm², but showed somewhat delayed response and hysterisis as seen in CdS photoelectric cell.     

Investigation on the design and synthesis of new systems of BNT-based lead-free piezoelectric ceramics

Three primary differences between BNT- and PZT-based ceramics were analyzed from the composition and the active component of the materials. Based on the analysis the authors’ group developed the new idea of the design of the multiple complex in the A-site ions of BNT compounds. (Bi_0.5Na_0.5)²⁺, Bi³⁺ and Na⁺ in the ABO₃ structure are defined as A-site, A₁-site and A₂-site ions, respectively, and A, A₁ and A₂-site ions can be simultaneously or singly substituted partially by alkaline-earth metal ions, metal ions with +3 valence and metal ions with +1 valence, respectively. Under this consideration, Several new systems of Bi_0.5Na_0.5TiO₃ (abbreviated as BNT)-based lead-free piezoelectric ceramics were proposed. These ceramics can be prepared by conventional ceramic techniques and have excellent piezoelectric performance. Among these materials, Bi_0.5(Na_1−x−y K _x Li _y )_0.5TiO₃ possesses higher piezoelectric constant (d ₃₃ = 230 pC/N), higher electromechanical couple factor (k _p = 0.40), larger remanent polarization (P _r = 38.9 μC/cm²) and a better P-E hysteresis loop until about 200^∘C. This work was supported by the projects of NSFC (50410179), (50572066), and (59972020), and NAMMC (2001-AA325060).     

Effects of Al2O3 on the piezoelectric properties of Pb(Mn1/3Nb2/3)O3-PbZrO3-PbTiO3 ceramics

Piezoelectric properties of Al₂O₃-doped Pb(Mn_1/3Nb_2/3)O₃-PbZrO₃-PbTiO₃ ceramics were investigated. The constituent phases, microstructure, electromechanical coupling factor, dielectric constant, piezoelectric charge and voltage constants were analyzed. Diffraction peaks for (002) and (200) planes were identified by X-ray diffractometer for all the specimens doped with Al₂O₃. The highest sintered density of 7.8 g/cm³ was obtained for 0.2 wt% Al₂O₃-doped specimen. Grain size increased by doping Al₂O₃ up to 0.3 wt%, and it decreased by more doping. Electromechanical coupling factor, dielectric constant, piezoelectric charge and voltage constants increased by doping Al₂O₃ up to 0.2 wt%, and it decreased by more doping. This might result from the formation of oxygen vacancies due to defects in O^{2 −} ion sites and the substitution of Al³⁺ ions.     

Investigation on FTIR spectra of barium calcium titanate ceramics

Barium titanate, which is applied in many fields, is a kind of very important ferroelectric material because it is lead free. Its physical properties are changed by replacement or addition of other ions. Here, barium calcium titanate ((Ba,Ca)TiO₃) ceramics are prepared. The concentration of calcium is up to 20 at.%. The Fourier transformation infrared spectroscopy (FTIR) measurement is carried out in order to reveal the vibration of crystal lattices. The influence of the replacement on the interaction between Ti and O can be observed by investigating the absorption peak of the Ti–O bond. The wavenumber of absorption peak of Ti–O bond becomes larger with increase of the content of Ca, even though the concentration of Ti is not changed. The wavenumber of absorption peak in (Ba_0.95Ca_0.05)TiO₃ is near 525 cm^?1 while that in (Ba_0.80Ca_0.20)TiO₃ is near 550 cm^–1. It is attributed to the decrease of the cell size. The length of Ti–O bond is shortened by replacement of Ca. Then the interaction between Ti and O is enhanced. The similar phenomenon is observed in (Ba,Mg)TiO₃ and alkali doped BaTiO₃ materials as well, supporting the mechanism. Furthermore, the aging effect in (Ba,Ca)TiO₃ and (Ba,Mg)TiO₃ systems is observed. The former exhibits a good stability when the latter shows unstable FTIR spectra. The influence of point defects on the aging effect is discussed. These results indicate that the FTIR measurement is helpful to study the relationship between the structure and physical properties of ferroelectric materials.     

A Highly-Sensitive Ba(Ti1—xSnx)O3 Thin Film Dielectric Bolometer for Uncooled IR Sensor

Ba(Ti_1—xSn_x)O₃ (BTS) ferroelectric thin films have been prepared by metal-organic decomposition method whose final annealing temperature was optimized to 700°C for dielectric bolometer. High temperature coefficient of dielectric constant (TCD) of 1–3%/K and low dielectric loss of 0.04 have been obtained in x = 0.15 and 0.17. Field-induced pyroelectricity of the BTS film was calculated to be an excellent value as high as 750 nC/cm²K. A series of dependence of DB output level were examined on important operation factors. The DB output level was increased when the period of supply voltage waveform is longer than both the electrical and thermal time constant of the DB detector. Finally, a stable infrared detection at temperature lower than 30°C was confirmed.     

White-Light-Emitting Single Component Metal-Organic Frameworks Based on 2,3-Pyridinedicarboxylic Acid

Abstract

Two white-light-emitting MOFs, [Dy(pydc)·(H₂O)₂]·DMF_0.66 (1) and [Gd_1.9Dy_0.1(pydc)_1.5(H₂O)₃]·DMF_1.5?C460 (2), were synthesized by the reaction of a rigid ligands H₂pydc (H₂pydc = 2,3-pyridinedicarboxylic acid) and Dy(III) ions under solvothermal conditions. The emission color of compound 1 is tunable by variation of excitation light to get yellow-to-white photoluminescence. When proportion of Dy³⁺ and H₂pydc is 1:3 could obtain the single component compound 1 with CIE coordinates of (0.2935, 0.3335), which is close to (0.3333, 0.3333) of the pure white light. To investigate the matrixes effect and luminescent dye C460@MOF, Gd(III) ions and C460 were introduced to form MOFs 2 with the mixed metal centers. When concentration of C460 is 10^?3 mol/L, MOFs 2 shows CIE coordinates of (0.3255, 0.3452). This work provides a practical strategy for the development of white-light emitting phosphor based on single component MOFs, which opens a new region for WLEDs.     

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.     

Characteristics of Bi4Ti3O12 thin films on ITO/glass and Pt/Si substrates prepared by R.F. sputtering and rapid thermal annealing

Bi₄Ti₃O₁₂ thin films are deposited on ITO/glass and Pt/Ti/Si(100) substrates by R.F. magnetron sputtering at room temperature. The films are then heated by a rapid thermal annealing (RTA) process conducted in oxygen atmosphere at temperatures ranging from 550–700^∘C. X-ray diffraction examination reveals that the crystalinity of the films grown on Pt/Ti/Si is better than that of the films grown on ITO/glass under the same fabrication conditions. SEM observation shows that the films grown on Pt/Ti/Si are denser than those grown on ITO/glass substrates. Interactive diffusion between the Bi₄Ti₃O₁₂ film and the ITO film increases with the increase of annealing temperature. The optical transmittance of the thin film annealed at 650^∘C is found to be almost 100% when the effect of the ITO film is excluded. The relative dielectric constants, leakage currents and polarization characteristics of the two films are compared and discussed.     

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.     

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.     

Synthesis and characterization of (BaxSr1−x)Ti1+yO3+z thin films and integration into microwave varactors and phase shifters

Abstract

Precise control of composition and microstructure is critical for the production of (Ba_xSr_1?x)Ti_1+yO_3+z (BST) dielectric thin films with the large dependence of permittivity on electric field, low losses, and high electrical breakdown fields that are required for successful integration of BST into tunable high frequency devices. Here we review recent results on composition-microstructure-electrical property relationships of polycrystalline BST films produced by magnetron sputter deposition, that are appropriate for microwave devices such as phase shifters. Films with controlled compositions were grown from a stoichiometric Ba_0.5Sr_0.5TiO₃ target by control of the background processing gas pressure. It was determined that the (Ba+Sr)/Ti ratios of these BST films could be adjusted from 0.73 to 0.98 by changing the total (Ar+O₂) process pressure, while the O₂/Ar ratio did not strongly affect the metal ion composition. Film crystalline structure and dielectric properties as a function of the (Ba+Sr)/Ti ratio are discussed. Optimized BST layers yielded capacitors with low dielectric losses (0.0047), among the best reported for sputtered BST, while still maintaining tunabili-ties suitable for device applications. These BST films were used to produce distributed-cir-cuit phase-shifters, using a discrete periodic loading of a coplanar waveguide with integrated BST varactors on high-resistivity silicon. Phase shifters yielding 30 degrees of phase shift per dB of insertion loss were demonstrated at 20GHz.