Dielectric Tunability of BST:MgO Composites Prepared by Using Nano Particles

The dielectric properties of ferroelectric Ba_0.5Sr_0.5TiO₃ and non-ferroelectric MgO composites synthesized by using nano particles are investigated for tunable microwave applications. Dielectric properties are studied in the temperature range of -250°C to 100°C, with and without an electrical field. The dielectric tunability is ∼50% for BST:MgO composites under the field of 80 KV/cm. at around the Curie peak. The use of nano particle sizes of materials considerably reduces dielectric losses and shows comparatively high K-factor values in the resulted composites. The ferroelectric phase is well connected and thus enhances the overall dielectric properties of the composites.     

Structural and Optical Properties of Barium Strontium Titanate (Ba0.5Sr0.5TiO3) Thin Films

Ferroelectric Barium Strontium Titanate (Ba_0.5Sr_0.5TiO₃) or BST thin films on quartz substrates have been prepared by using a modified sol gel processing technique. The starting materials are Barium 2-ethylhexanoate Ba[CH₃(CH₂)₃CH(C₂H₅)CO₂]_2, Strontium 2-ethylhexanoate Sr[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂ and Titanium(IV) isopropoxide [TiOCH(CH₃)₂]₄. The precursors except [TiOCH(CH₃)₂]₄ were synthesized in the laboratory. Transparent and crack-free films were fabricated on quartz substrates by spin coating. The as-fired films were found to be amorphous, which crystallized to cubic phase after annealing at 550°C in air for 1 hr. In this paper we report the structural and optical properties of BST films prepared by the modified sol-gel process.

Communicated by Prof. E. C. Subbarao     

Optical Properties of Barium Strontium Titanate (BST) Ferroelectric Thin Films

Barium strontium titanate (Ba_0.05Sr_0.95TiO₃) ferroelectric thin films have been prepared on single crystal [001] MgO substrates using the pulsed laser deposition method. The X-ray diffraction (XRD) analysis show the films were oriented with the [001] direction perpendicular to the plane of the substrate. The refractive index of Ba_0.05Sr_0.95TiO₃ is determined from model fitting with the calculated data of the reflectivity of Ba_0.05Sr_0.95TiO₃ in the wavelength 1450-1580 nm at the room temperature. The dispersion curve decreases gradually with increasing wavelength. The average value of the refractive index is found to be 1.985 in the wavelength 1450-1580 nm which is important for optoelectronic device applications.     

二氧化硅掺杂钛酸锶钡陶瓷的介电性能与电卡效应

采用传统的固相反应法制备二氧化硅（SiO₂）掺杂钛酸锶钡（Ba_0.65Sr_0.35TiO₃,BST）陶瓷（BST+x%SiO₂）,研究了掺杂二氧化硅对BST陶瓷的物相、微观形貌、介电性能及电卡效应的影响。结果表明：掺杂二氧化硅并未改变BST陶瓷的晶型结构,但有助于提升晶粒的均匀性和材料介电性能频率的稳定性。随着二氧化硅掺杂量增加,BST陶瓷的介电常数呈现单调递减趋势,介电弥散特性逐渐增强。二氧化硅的掺杂有利于提升BST陶瓷的电卡性能,其中BST+3%SiO₂陶瓷具有最优的电卡效应,在30 ℃下可获得最大电卡绝热温变（ΔT_max）,ΔT_max和ΔT_max/ΔE分别为1.6 ℃、8.00×10 ^-7 ℃·m/V,电卡效应半峰宽（T_span）为10 ℃左右。     

Effects of deposition temperature on the crystallinity of Ba0.5Sr0.5TiO3 epitaxial thin films integrated on Si substrates by pulsed laser deposition method

Epitaxial Ba_0.5Sr_0.5TiO₃ (BSTO) thin films were grown on TiN buffered Si (0 0 1) substrates by PLD method and the effects of deposition temperature on their crystallinity and microstructure were studied. BSTO thin films were prepared with substrate temperature ranging from 350 to 650 °C. The BSTO films grown at below 400 °C showed amorphous phase and the film grown at 450 °C showed mixed phase of crystalline and amorphous, where crystalline phase was observed only at the top surface portion of the film. The BSTO films with fully crystalline phase were obtained in the samples deposited at above 500 °C. The (0 0 l) preferred orientation and the crystallinity of the BSTO films were improved with increasing the temperature. The dielectric constant, measured at 100 kHz and at room temperature, of the BSTO film grown at 650 °C was measured to be as high as 1129.     

Low dielectric loss and enhanced tunability of Ba(Zr0.3Ti0.7)O3-based thin film by sol–gel method

In this work, dopants and buffer layers were employed to simultaneously lower the dielectric loss and enhance the dielectric tunability of Ba(Zr_0.3Ti_0.7)O₃ (BZT) thin films. The BZT, 1 mol% La doping BZT (BZTL) with and without La_0.5Sr_0.5CoO₃ (LSCO) buffer layers were prepared by sol–gel technique. The dielectric properties of the thin films were investigated as a function of frequency and current bias field. As a result, the BZTL thin film with LSCO buffer layer showed lower dielectric loss and higher tunability simultaneously, which can be a promising candidate for tunable microwave device applications.     

(1-x)(Mg0.95Mn0.05)_2TiO_4-xCaTiO_3陶瓷的微波介电性能研究

采用传统固相法制备了(1-x)(Mg_0.95Mn_0.05)_2TiO_4-xCaTiO_3微波介质陶瓷,研究CaTiO_3添加量对陶瓷体系物相组成、显微结构以及微波介电性能的影响。XRD分析结果表明,陶瓷样品以(Mg_0.95Mn_0.05)_2TiO_4为主晶相,以CaTiO_3和MgTiO_3作为次晶相存在陶瓷样品中。另外发现添加CaTiO_3能增加陶瓷的致密度,并在1325~1400℃下都能促进陶瓷的烧结。当CaTiO_3的添加量为x=0.12时,复合陶瓷在1375℃烧结4 h时具有最佳的微波介电性能:介电常数ε_r=20.26,品质因数Q×f=35125.9 GHz,τ_f=+2.7×10~(-6)/℃。     

Effect of various dopants on the tunable and dielectric properties of Ba0.6Sr0.4TiO3 ceramics

Acceptor (Mn-, Co-) doped and donor Y-doped Ba_0.6Sr_0.4TiO₃ have been prepared by traditional ceramic processing and their structural, surface morphological, dielectric and tunable properties were investigated. The results show all dopants to have a strong effect on the average grain size. The curie temperature of all doped specimens decreases and their temperature spectrum broadens. Loss tangent at 15 °C and low frequency (10 kHz) increases for all doped specimens whereas the loss tangent at high frequency (100 MHz) is not affected. The tunability of all the doped specimens is lower than the undoped one.     

Effect of pre-sintering temperature on the structural and dielectric properties of (Ba0.5Sr0.5)TiO3 thin films deposited by sol–gel technique

(Ba_0.5Sr_0.5)TiO₃ thin films have been deposited by sol–gel technique and the effect of pre-sintering temperature on the structural and dielectric properties has been studied. The sol was prepared from barium acetate and strontium acetate powders by dissolving them in acetic acid; while titanium isopropoxide was used as titanium source. Acetyl acetone, 2-methoxyethanol, and formamide were used as chelating agent, diluting reagent, and for getting crack free films, respectively. Two sets of films were prepared; one set pre-sintered at 400 °C while the other one at 600 °C. In all the cases, the final sintering temperature was kept fixed at 700 °C for 2 h. These films were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), dielectric constant, and loss measurements and AC conductivity studies. It has been found that with an increase in the pre-sintering temperature from 400 to 600 °C, the dielectric constant increases from 225 to 383 (measured at 100 kHz); whereas, the loss tangent remains nearly constant at 0.03–0.05. The XRD results show better crystallinity and enhanced grain growth in case of films pre-sintered at 600 °C. The FTIR spectra reveals that there is significant removal of organic materials in films with higher pre-sintering temperature as compared to that with lower pre-sintering temperature. The AC conductivity studies show a decrease in the frequency exponent ‘s’ with an increase in the pre-sintering temperature which has been correlated with the reduction in oxygen vacancy densities in the sample with higher pre-sintering temperature.     

Microstructure Evolution of Pulsed Laser-Deposited (Ba, Sr)TiO3 Films on MgO for Microwave Applications

To develop low-loss tunable microwave circuits, based on the field dependence of dielectric permittivity, phase pure (Ba_0.5, Sr_0.5)TiO₃ doped with 1% W (BST) thin films 0.3-μm thick were deposited on single crystal MgO wafers by pulsed laser deposition. The BST films were characterized by X-ray θ–2θ scans and pole figure analysis, field emission scanning electron microscopy (FESEM), and cross-sectional transmission electron microscopy (TEM), coupled with selected-area electron diffraction (SAED). Although, the X-ray θ–2θ scan indicated an epitaxial nature of BST with an out-of-plane orientation of (100), the pole figure analysis confirmed the presence (4–6%) of (111)-oriented grains in a matrix of (100) textured grains. The columnar grains exhibited an in-plane (i.e., along the plane perpendicular to the growth direction) grain size that was thickness-dependent. The cross-sectional TEM, coupled with SAED in the thickness direction, corroborated the pole figure analysis. Additionally, from X-ray analysis, it was observed that the textured films were under in-plane tension. The deposited film was characterized at microwave frequencies (1–20 GHz) using interdigitated electrodes deposited on top of the film. The film was characterized by a relatively low dielectric Q of 5–7. A 17% change in the capacitance was observed when applying a 40 V bias. From the observed microstructure, a preliminary understanding of its evolution and its relationship with the microwave dielectric properties is discussed, and some ideas to obtain truly epitaxial BST films are presented.     

Dielectric properties of Fe-doped Ba0.65Sr0.35TiO3 thin films fabricated by the sol–gel method

Fe-doped Ba_0.65Sr_0.35TiO₃ (BST) thin films have been fabricated on Pt/Ti/SiO₂/Si substrate using the sol–gel method. The structural and surface morphology, dielectric, and leakage current properties of undoped and 1 mol% and 2 mol% Fe-doped BST thin films have been studied in detail. The results demonstrate that the Fe-doped BST films exhibit improved dielectric loss, tunability, and leakage current characteristics as compared to the undoped BST thin films. The improved figure of merit (FOM) of Fe-doped BST thin film suggests a strong potential for utilization in microwave tunable devices.     

Improvement of Microwave Loss Tangent and Tunability of Ba0.55Sr0.45TiO3/MgO Composites Using the Heterogeneous Precipitation Method

Ba_0.55Sr_0.45TiO₃/MgO composites were successfully prepared by the heterogeneous precipitation method and their structural, surface morphological, tunable properties, and dielectric properties at microwave frequency were systemically investigated. Compared with the sample prepared by the traditional solid-state method, the sample prepared by the heterogeneous precipitation method exhibits a smaller grain size, more uniform microstructure, higher tunability, and lower microwave loss, and these properties are very beneficial to the development of the microwave tunable devices application. Moreover, the effects of La₂O₃ doping on the dielectric and tunable properties of BST/MgO composites are investigated. The result shows that the La³⁺-doped sample has higher tunability and lower microwave loss than the undoped one.     

La-, K- and Nb-doped 0.90(Bi0.5Na0.5TiO3)–0.10PbTiO3

Lanthanum, Potassium and Niobium have been selected as cation dopants to modify the relaxor characteristics of 0.90(Bi_0.5Na_0.5TiO₃)–0.10PbTiO₃. The experimental results show that La lowers the phase transition temperatures and decreases the grain size. In contrast, the grain size of K-doped composition tends to increase. Furthermore, the maximum of dielectric permittivity and the Curie temperature increase as compared to those of La-doped material. La can improve the broadness of dielectric permittivity of 0.90(Bi_0.5Na_0.5TiO₃)–0.10PbTiO₃. However, Nb is a better promising dopant for enhancing the relaxor behavior for this composition.     

Effect of Bottom Electrode Materials and Annealing Treatments on the Electrical Characteristics of Ba0.47Sr0.53TiO3 Film Capacitors

The dielectric constant and leakage current density of Ba_0.47Sr_0.53TiO₃ (BST) thin films deposited by radio-frequency magnetron sputtering on various bottom electrode materials (Pt, Ir, IrO₂/Ir, Ru, RuO₂/Ru) before and after annealing in O₂ and N₂ ambient were investigated. Improvement in crystallinity of BST films deposited on various bottom electrodes was observed with annealing. The refractive index, dielectric constant, loss tangent, and leakage current of the films were also strongly dependent on annealing conditions. A BST thin film deposited on an Ir bottom electrode at 500°C, after 700°C annealing in O₂ for 20 min, had a dielectric constant of 593 ± 5%, a loss tangent of 0.019 ± 10% at 100 kHz, a leakage current of (2.1 ± 13%) 10⁻⁸ A/cm² at an electric field of 100 kV/cm with a delay time of 30 s, and a charge storage density of 53 ± 5% fC/μm² at an applied field of 150 kV/cm. Based on the dielectric constant, leakage current, and reliability, the optimum material for the bottom electrode with annealing was Ir. Interdiffusion of Ru and Ti at the interface between the BST film and Ru electrode was observed in 500°-700°C annealed samples. The 10 year lifetime of time-dependent dielectric breakdown (TDDB) studies indicated that BST on Pt, Ir, IrO₂/Ir, Ru, and RuO₂/Ru had long lifetime over 10 years of operation at a voltage bias of 1 V.     

Sr掺杂强化LaCo0.5Cu0.5O3型钙钛矿活化过一硫酸盐的性能

采用溶胶-凝胶法制备A位掺Sr的La_xSr_1-xCo_0.5Cu_0.5O₃钙钛矿增强传统B位掺杂钙钛矿活化过一硫酸盐（PMS）的能力。本文选取效果最好的La_0.7Sr_0.3Co_0.5Cu_0.5O₃型钙钛矿为研究对象,以偶氮染料AO7为目标污染物,考察了钙钛矿投加量、PMS浓度、pH和染料废水中常见Cl^-对La_0.7Sr_0.3Co_0.5Cu_0.5O₃/PMS体系降解AO7的影响,并测试了材料的重复利用性和矿化能力。结果表明,La_0.7Sr_0.3Co_0.5Cu_0.5O₃/PMS降解AO7的速度随着材料投加量和PMS浓度的增加而加快,在中性条件下反应速度最快且矿化率良好。该体系主要活性物种之一为·OH,但Sr掺杂后钙钛矿的O空位增多使得¹O₂也参与到降解过程之中。     

Influence of oxygen supply rates on performances of catalytic membrane reactors: Application to the oxidative coupling of methane

The impact of oxygen permeability using an ionic oxygen conducting membrane reactor with surface catalyst was investigated for the oxidative coupling of methane to higher hydrocarbons. Dense Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCFO), Ba_0.5Sr_0.5Mn_0.8Fe_0.2O_3−δ (BSMFO) and BaBi_0.4Fe_0.6O₃ (BBFO) membrane disks with Pt/MgO catalysts were prepared by sol–gel deposition or wash-coating. It is demonstrated that the oxygen supply by permeation needs to fit to the consumption during the coupling reaction. In case of insufficient oxygen supply comparably poor conversions are observed while higher oxygen fluxes lead to increased methane conversions, especially in the presence of an efficient catalyst. Generally, increasing catalytic activity leads to lower C₂ selectivity, especially for low oxygen permeation fluxes. The concept of a reactor employing dense catalytic membranes is viable, but the present study identifies further potential when the activity of the catalyst for the oxidative coupling is improved, leading to an overall enhanced performance of the membrane reactor.     

Surface Chemical and Leakage Current Density Characteristics of Nanocrystalline Ag–Ba0.5Sr0.5TiO3 Thin Films

Nanocrystalline x Ag–(1− x )Ba_0.5Sr_0.5TiO₃ (Ag–BST, 0≤ x ≤0.1, where x is the mole fraction of Ag) thin films have been deposited on Pt/Ti/SiO₂/Si substrates by a sol–gel method. The films have been characterized by X-ray diffraction (XRD), scanning electron microscopy, and X-ray photoelectron spectroscopy (XPS). The core-level XPS of oxygen (O1 s ) of the Ag–BST films indicate that an optimum amount of Ag ( x =0.02 or 2 mol%) enhances the binding energy of oxygen, possibly through a mechanism in which the electrophilic oxygen dissociates from the Ag surface and fills the oxygen vacancies. Similarly, the binding energy of Ag (Ag3 d ) shows a shift toward a higher value with increasing Ag up to 4 mol%, probably because of the chemical shift of Ag in BST along the surface layers, surface relaxation, or changes in the Fermi level of small Ag particles in the solid solution range of Ag in BST films ( x ≤0.04). The leakage current density of 2 mol% Ag-added BST (∼10⁻⁶ A/cm²) is less by about an order of magnitude than pure BST at an electric field of 200 kV/cm. A defect model is proposed to explain the observed leakage current density of Ag–BST films satisfactorily.     

Enhanced Dielectric Properties of Ba0.5Sr0.5TiO3/MgO Composites Prepared by Coprecipitation Derived Core–Shell Powders

Ba_0.5Sr_0.5TiO₃/MgO (BST/MgO) composite ceramics have been prepared in situ by using an oxalate precipitation process. SEM and TEM images show that oleic acid modified BST/MgO nanocomposite exhibits helminth‐like particles consisting of BST core and MgO shell. Results reveal that oleic acid modification is chemisorbed on MgO particles as a carboxylate to form MgO shell, which connects to interparticles. Accordingly, the BST particles are well surrounded naturally by a thin MgO layer in the composite ceramics. As a result, the oleic acid modified BST/MgO composite ceramics shows better dielectric properties, with permittivity of 203, loss tangent of 0.0025 (at 2.4 GHz), and tunability of 10.2%.     

PbTiO3–PbO–SiO2 Glass-Ceramic Thin Film by a Sol–Gel Process

PbTiO₃(PT)-PbO-SiO₂ glass-ceramic thin films were pro-duced by a sol-gel process. The crystallization of PT oc-curred at ∼700°C and was higher than that in PT-PbO-B₂ O₃ sol-gel glass-ceramics. A pinhole-free thin film was obtained by a rapid thermal annealing process when the designed glass-forming phase content in the thin film was >24 vol%. The measured dielectric constants of the films fairly agreed with the predicted values, based on a parallel mixing model. The dielectric constant was 219 and the di-electric loss was 0.04 in the 0.6PT-0.4(PbO-SiO₂) film that was fired at 700°C.     

Dielectric properties of (Ba0.95Ca0.05)(Ti1-yCay)O3-y ceramics

Calcium doped barium titanate ceramics with composition (Ba_0.95Ca_{0. 05}) (Ti_1-yCa_y)O_3-y prepared by a liquid mixing technique were used to measure the dielectric properties. The pure barium titanate and lightly-Ca-doped materials obey a Curie Weiss law when the temperature is above the Curie temperature. It has been found that the average cubic-tetragonal phase transition temperature moves downward when the octahedrally-coordinated Ca concentration increases, and heavily-Ca-doped barium titanate ceramics show relaxor behavior with a diffuse phase transition characteristic (DPT). Above the average transition temperature T_av the dielectric properties for heavily doped materials do not obey the Curie Weiss law, but can be described by a quadratic relation over a wide range of temperature. Experiments have shown that there exists an extra K(T) peak attributable to the existence of separate microregions of Ba_0.95Ca_0.05TiO₃ in a matrix of (Ba_0.95Ca_0.05) (Ti_1-yCa_y)O_3-y (where y ≤ 2%).