Effect of partially oxidized Ti powders on the microstructure and PTCR characteristics of (Ba,Sr)TiO3

Rutile TiO₂ (a=4.594 å and c=2.958 å) phase was formed on the outer region of Ti powders after oxidation at 600 °C for 1–300 h. Porous (Ba,Sr)TiO₃ ceramics were fabricated by adding partially oxidized Ti powders (4–8 vol %) into (Ba,Sr)TiO₃ powders, and showed excellent positive temperature coefficient of resistivity (PTCR) characteristics after paste-baking treatment at 580 °C in air. The PTCR characteristics of the porous ceramics were mainly attributed to the adsorption of oxygen at the grain boundaries. The microstructure and electrical properties of the porous (Ba,Sr)TiO₃ ceramics containing the partially oxidized Ti powders oxidized at 600 °C for different oxidation times (1–300 h) were investigated.     

PTCR properties of Sb2O3-doped (Ba,Sr)TiO3

Perovskite barium–strontium titanate, (Ba,Sr)TiO₃ was prepared and effects of Sb₂O₃ additives on its PTCR properties were investigated. The (Ba,Sr)TiO₃ with 0.05∼0.25 mol% Sb₂O₃ showed semiconducting PTCR behavior and anomalous grain growth was also observed when sintered at 1360 °C. It was considered that charge compensation by doping Sb₂O₃ as well as anomalous grain growth by sintering leads to resistivity reduction from insulating to semiconducting transition.     

不同掺杂对Yb半导的（Ba,Sr）TiO3系PTCR材料性能的影响

研究了不同掺杂方式对ＰＴＣＲ材料电学性能的影响,结果表明,Ｙｂ一次掺杂ＢａＴｉＯ３电阻变化“Ｕ”型曲线,低阻区为０．１ｍｏｌ％～０．３ｍｏｌ％,其移峰效率为３～５℃／ｍｏｌ。二次单一掺杂Ｙｂ提高电阻率,降低对升阻比,二次单一掺杂Ｍｎ提高电阻率与升阻经,二次Ｙｂ,Ｍｎ共掺杂可降低电阻率,提高升阻比,并探讨了二者配合作用的机理,Ｙｂ：Ｍｎ＝１：１效果最佳。     

Sintering condition and PTCR characteristics of porous (Ba,Sr)(Ti,Sb)O3

We fabricated porous (Ba,Sr)(Ti,Sb)O₃ ceramics by adding potato-starch (1–20 wt %) and investigated the effects of sintering temperature (1300–1450 °C) and time (0.5–10 h) on the positive temperature coefficient of resistivity characteristics of the porous ceramics. The room-temperature electrical resistivity of the (Ba,Sr)(Ti,Sb)O₃ ceramics decreased with increasing sintering temperature, while that of the ceramics increased with increasing sintering time. For example, the room-temperature electrical resistivity of the (Ba,Sr)(Ti,Sb)O₃ ceramics for the samples sintered at 1300 °C and 1450 °C for 1 h is 6.8×10³ and 5.7×10² cm, respectively, while that of the ceramics is 6.5×10² and 1.3×10⁷ cm, respectively, for the samples sintered at 1350 °C for 0.5 h and 10 h. In order to investigate the reason for the decrease and increase of room-temperature electrical resistivity of the samples with increasing sintering temperature and time, the average grain size, porosity, donor concentration of grains (N _d), and electrical barrier height of grain boundaries () of the samples are discussed.     

纳米(Ba,Sr)TiO_3粉体材料的制备

采用溶胶 -凝胶工艺制备了 (Ba ,Sr)TiO3凝胶 ,并利用微波烧结技术对凝胶进行合成和烧结。结果表明 ,获得的 (Ba ,Sr)TiO3粉体颗粒较细 ,与传统固相反应合成法相比 ,其钙钛矿相的合成温度由 110 0℃降至 90 0℃ ;粉体的颗粒尺寸在 5 0nm附近     

Electrical properties of (Ba,Sr)TiO3 on (Sr,Ca)RuO3 electrode

A perovskite (Sr,Ca)RuO₃ [SCR] electrode has been explored in order to utilize its advantages in structural match with (Ba,Sr)TiO₃ [BST] films, which may enhance the electrical properties of BST films. The SCR electrode led to the leakage current density (10^–7 A/cm²) of BST films an order lower than that on RuO₂. The leakage current was not sensitive to the composition of the SCR electrodes, while the dielectric constant of the BST thin film capacitor ranged from 160 to 280 depending on the Sr/Ca ratio in SCR electrodes. The BST/SCR (Sr/Ca = 7/3) system resulted in a 5–nm thick interfacial layer. Furthermore, the interfacial layer turned out to be partially crystallized according to the lattice image taken by an HRTEM. It is believed that such enhancement in electrical properties of BST films could be induced by the improvement of interfacial characteristics through structural matching.     

Effect of the Distribution of Manganese Ions on the Properties of Mn-Doped (Ba,Y)TiO3 PTCR Ceramics

The electrical properties and microstructure of (Ba,Y)TiO₃ PTCR ceramics were studied. The results indicate that the Mn ions increase the intergranular barrier height and produce a high-resistance layer on the grain surface. The temperature-dependent resistances of the grain bulk, surface layer, and grain boundaries, the temperature coefficient of resistance, and the magnitude of the varistor effect were assessed as a function of Mn content.     

快速热处理对(Ba,Sr)TiO3薄膜晶化行为的影响

采用射频溅射法在Si(111)基片上制备了(Ba,Sr)TiO3(BST)薄膜,并对制备的薄膜进行了快速退火热处理.采用X射线衍射和原子力显微镜分析了退火温度、退火时间和加热速度对BST薄膜晶化行为的影响.研究结果表明,BST薄膜的晶化行为强烈依赖于退火温度、退火时间和加热速度.BST薄膜的结晶度随退火温度的升高而提高.适当的热处理可降低BST薄膜的表面粗糙度,BST薄膜的表面粗糙度随退火温度的升高经历了一个先降低后增大的过程,但退火后BST薄膜的表面粗糙度都小于制备态薄膜的表面粗糙度.BST薄膜的晶粒尺寸随退火温度的升高经历了一个先增大后减小的过程.随退火时间的延长,BST薄膜的特征衍射峰越来越强,薄膜的晶化程度越来越高.随退火时问的延长,BST薄膜的晶粒尺寸和表面粗糙度也经历了一个先增大后减小的过程.BST薄膜的晶粒大小主要由退火温度决定.高的升温速率可获得较小的晶粒.     

Effect of Isovalent Ba-Site Substitutions on the Properties of (Ba1 – x – y M y Y x )TiO3(M = Ca, Sr, Pb) PTCR Ceramics

An approach is proposed for fabricating fine-grained, low-resistivity BaTiO₃-based PTCR ceramics via partial isovalent substitutions on the Ba site. The grain size of the ceramics thus prepared is shown to decrease as the ratio of ionic radii r(Ba²⁺)/r(M²⁺) (M = Ca, Sr, Pb) increases. Isovalent substitutions on the Ba site narrow down the range of donor dopant (yttrium) concentrations in which PTCR materials can be prepared. The experimental results agree well with thermodynamic calculations under the assumption that the materials contain the Y³⁺Ti³⁺O₃ phase, as suggested by ESR data, which point to the presence of Y³⁺–Ti³⁺ associates. Partial calcium, strontium, and lead substitutions on the Ba site reduce the average grain size of PTCR ceramics, which is probably due to the lattice strain arising from the isovalent substitution. Partial replacement of Ba²⁺ with mixtures of different isovalent elements (e.g., Sr²⁺ and Pb²⁺) offers the possibility of obtaining fine-grained, low-resistivity PTCR ceramics, without changing the phase transition temperature.     

Ferroelectric (Ba,Sr)TiO3 thin-film 60-GHz phase shifter

The design and microwave characteristics of an integral ferroelectric Ba_0.3Sr_0.7TiO₃ thin-film microwave phase shifter operating in the millimeter wavelength range (f∼60 GHz) are reported. In this frequency range, the device introduces a loss of S ₂₁=−10 dB and allows a continuous phase shift in the interval from zero to 220 deg with a small phase error (not exceeding ±5 deg).     

Nb2O5掺杂高温无铅(Ba,Bi,Na)TiO3基PTCR陶瓷结构与电性能研究

采用固相反应法制备了施主掺杂浓度不同的Nb₂O₅（分别为0.1mol%、 0.3mol%、 0.5mol%、 0.7mol%）掺杂(Ba, Bi,Na)TiO₃基PTCR陶瓷. 对其微观结构及电性能进行研究发现：随着Nb₂O₅掺杂浓度的增加,陶瓷晶粒尺寸先变大后变小,室温电阻率也随之先减小后增大,说明Nb₂O₅的掺杂量存在一个临界施主掺杂浓度. 当Nb₂O₅施主掺杂量为临界施主掺杂浓度0.5mol%时,获得了居里温度T_c为 183℃、室温电阻率ρ为1.06×10³Ω·cm、升阻比ρ_max/ρ_min为1.0×10⁴的高温无铅PTCR陶瓷. 通过交流复阻抗谱分析,探讨了Nb₂O₅施主掺杂在该PTCR陶瓷中的作用机理.     

Varistor characteristics in PTCR-type (Ba,Sr)TiO3 ceramics prepared by single-step firing in air

This paper deals with donor, acceptor-codoped (Ba_0.4Sr_.6)TiO₃ ceramics with distinct varistor characteristics at room temperature, which were prepared by single-step firing in air. The materials, with the Curie point at around –90 °C, exhibited a large PTCR (positive temperature coefficient of resistivity) effect of more than seven orders of magnitude in the temperature range –90 °C (the resistivity 10³ · cm) to room temperature ( > 10¹⁰ · cm). An apparent dielectric constant of >20000 and tan < 0.05 (at 100 kHz) were observed for the present materials at room temperature, and moreover, the materials exhibited nonlinear current-voltage characteristics with the nonlinear coefficient, , in the range 7–12 and the varistor field, E_v, in the range 0.3–1.0 kV/cm. The value of in the present materials increased systematically with increasing in their PTCR temperature range. It has been found that there exists a close correlation between and the grain-boundary potential barrier height, e, obtained from the -T characteristic of the materials. An almost linear relationship was also found to exist between and log E_v for the present materials.     

La3+掺杂对(Sr,Ba,Ca)TiO3基压敏陶瓷结构和性能的影响

采用常规固相法制备(Sr,Ba,Ca)TiO3基压敏陶瓷.用Nb5 离子取代Ti4 离子,Mn作受主掺杂元素的前提下,系统研究了稀土离子La3 施主掺杂对压敏陶瓷结构和性能的影响.结果表明,当La2O3=0.4%(摩尔分数)时,(Sr,Ba,Ca)TiO3基压敏陶瓷可获得良好的电性能:其压敏电压V10mA=11.19V,非线性系数α=2.93,电容C=31.16nF,介电损耗tanδ=0.43%,压敏电压温度系数KV10mA=0.1%/℃.     

Effect of atmosphere on the PTCR characteristics of porous Ba(Ti,Sb)O3 ceramics produced by adding corn-starch

Porous Ba(Ti,Sb)O₃ ceramics were fabricated by adding corn-starch at 20 wt %. The effect of atmosphere on the PTCR characteristics of the porous Ba(Ti,Sb)O₃ ceramics and the role of oxygen on the grain boundaries in the PTCR characteristics of the Ba(Ti,Sb)O₃ ceramics were investigated. In air, O₂, N₂, and H₂ atmospheres, the electrical resistivity of Ba(Ti,Sb)O₃ ceramics below 150 °C was independent of atmosphere, while it was strongly dependent on atmosphere above 200 °C. The low electrical resistivity in reducing atmospheres was due to a decrease in potential barrier height, which originated from an increase in the number of electrons owing to the desorption of chemisorbed oxygen atoms at the grain boundaries. In a N₂ atmosphere, the electrical resistivity of Ba(Ti,Sb)O₃ ceramics during the cooling cycle was lower than that during the heating cycle, and then the electrical resistivity of the porous Ba(Ti,Sb)O₃ ceramics during subsequent heating and cooling cycles was increased again by exposure to an O₂ atmosphere.     

Pt–Ru alloy electrode for(Ba,Sr)TiO3 capacitor

The Pt–Ru alloy was evaluated as a bottom electrode material in the (Ba,Sr)TiO₃ (BST) capacitor. Surface oxidation producing the RuO₂ layer for Pt–Ru(50 at %) first occurred and then BST film was deposited in the BST sputtering process. The thickness of RuO₂ formed from oxidation by an oxidant gas for BST formation, was thicker for the higher substrate temperature and the RuO₂ film shows the (1 0 1) orientation. The RuO₂ film between BST and Pt–Ru(50 at %) may block the diffusion of oxygen through the bottom electrode. The BST film deposited on Pt–Ru(50 at %) has a rough surface and a stronger intensity of (1 1 0) than that on Pt.     

CaRuO3电极对(Ba,Sr)TiO3薄膜的介电特性的影响

在Pt(111)/Ti/SiO2/Si(100)衬底上,用脉冲激光沉积工艺分别制备出了(110)外延取向生长的(Ba0.65Sr0.35)TiO3/CaRuO3(BST/CRO)异质结构薄膜;BST/CRO异质结构薄膜由纳米晶团簇组成,最大的团簇晶粒达500 nm,平均晶粒尺寸在60～80 nm,薄膜厚度为650 nm.BST/CRO异质结薄膜均为表面平滑和致密结构.BST/CRO异质结薄膜的介电常数和介电调谐率分别高达851和78.1%.与纯BST薄膜比较,用CRO作电极,增益介电常数与介电调谐率.