改进的sol-gel工艺制备细晶Ba0.6Sr0.4TiO3陶瓷及其介电性能的研究

用改进的sol-gel工艺制备了细晶钛酸锶钡(Ba0.6Sr0.4TiO3,BST)陶瓷块体,研究了BST陶瓷的结晶与介电性能.在这种改进sol-gel的工艺中,用传统的固相反应煅烧形成BST粉体,经高能球磨制备BST纳米陶瓷粉体,再将一定质量的纳米粉体加入到相同化学组成的BST的溶胶液中,经普球球磨12h后,制备成悬浮性好,分散均匀的浆料.浆料可用来制备BST陶瓷,并在1200℃保温2h烧结成瓷,结果显示,BST陶瓷块体结构致密,晶粒尺寸在0.15～2μm之间.分析了样品的介电性能和晶粒尺寸对材料介电性能的影响.介电温谱显示,在0℃,100kHz时,相对介电常数为2500,介电损耗为0.02;并且存在明显的弥散相变.     

钛酸锶钡纳米粒子的低温煅烧法制备与表征

以氢氧化钡、氢氧化锶和钛酸丁酯为原料,采用低温煅烧(300～500℃)法合成了钛酸锶钡(BST)纳米粒子.用XRD、SEM、TEM和IR对产品进行了表征;用TG-DTA对前驱物的热演化过程进行了分析.结果表明,所得钛酸锶钡纳米粒子大小分布均匀,粒径约为13～20nm,粒子形状近似为球形,晶相结构为立方相.该粉体为完全互溶体的固溶体,随Sr含量的增加,晶胞参数a和晶胞体积V减小,a随组成呈线性关系,符合Vegard定律.     

Transitions of barium strontium titanate ferroelectric ceramics for different strontium content

Ceramic based barium strontium titanate (BST) solid solutions with the formula Ba_1 − xSr_xTiO₃ are very important candidates for a wide range of device applications. Several doped (Mn and Mg) and undoped samples were prepared by standard solid-state reaction. Special emphasis was put on compositions with x = 0.35 and 0.60, with high potential for applications. The samples were sintered at temperatures in the 1200 ÷ 1260 °C range. Structural X-ray diffraction analysis preformed confirms the perovskite structure. The dielectric parameters were investigated in a wide temperature range between − 150 and 150 °C. The temperature was cyclically changed in both directions, up and down, at a rate of less than 2 °C/min. Both permittivity and dielectric loss were measured at low frequencies, 1 kHz. The peak values of the permittivity are increasing from 2000 to 4000 with the sintering temperature increase. Moreover the dielectric parameters were measured at room temperature in microwave domain (1 ÷ 2 GHz). The Curie temperature of BST samples with x = 0.35 and x = 0.6 is in agreement with the Curie point dependence on Sr content, as we have previously reported.     

铬掺杂钛酸锶钡陶瓷的介电调谐性能

研究了Cr掺杂对钛酸锶钡(Ba0.6Sr0.4TiO3,BST)陶瓷的介电及其可调性能的影响.结果表明,少量的Cr可进入BST品格形成固溶体,并促进晶粒生长.当Cr掺杂量(摩尔分数)低于1.0%时,陶瓷的介电损耗急剧降低,调谐率明显提高,综合性能显著改善,其中Cr掺杂0.6%的BST陶瓷具有最佳的综合性能,其在1MHz下的介电损耗为0.0005,品质因子(FoM)达到500,而未掺杂样品的FoM值仅为60.Cr掺杂陶瓷损耗的急剧降低可归因于Cr3 离子的还原和Cr3 、Cr2 受主行为中和了氧空位的施主行为.     

Synthesis and characterization of nanocrystalline barium strontium titanate powders prepared by citrate precursor method

Nanocrystalline and well dispersed barium strontium titanate (BST) powders were prepared by a novel and simple citrate precursor method. This method involved direct crystallization of a white precursor from a stable solution in the citric acid (CA)–ethylene glycol (EG)–tetrabutyl titanate–M²⁺ (M = Ba, Sr) system under a specific pH value range. Subsequent heat treatment of the precursor at 850 °C led to a pure phase BST powder. TG/DTA was used to examine the decomposition behaviour of the precursor. The crystalline phase and morphology of the BST powders were investigated by XRD and TEM. It was found that the BST powders synthesized by citrate precursor process were more homogeneous and uniform than that obtained by the citrate gel method.     

溶胶-沉淀法制备钛酸锶钡粉末及其水热处理

通过溶胶一沉淀法制备出完全钙钛矿结构的Ba0.71Sr0.29TiO3(BST)粉末,粉末的颗粒尺寸约为300nm。但得到的BST粉末不稳定,在乙酸中容易兮解。通过TG-DTA和XRD分析,直接沉淀得到的粉末颗粒失重大,而且由于颗粒所吸附的有机物阻碍了Ba^2 和Sr^2 的扩散,造成了直接沉淀的BST颗粒内部的组分不均匀和结晶不完全。通过对直接沉淀的BST粉末进行150-200℃的水热后处理,其结晶性得到了很大的改善,稳定性也得到了提高。实验表明,水热处理具有与烧结相似的效果,但BST粉末的分散性得到了改善。     

Lamination of magnesium oxide spacers to barium strontium zirconium titanate ceramics

We propose an innovative idea to bond the dielectric barium strontium zirconium titanate (BSTZO) plates with magnesium oxide (MgO) as the spacers to achieve a hermetic module without any air gaps between the dielectric and the spacer. The gold metallization can be applied across the whole assembly to create an integrated electrode. The gold metallization also eliminates pressure contact by external copper plates assemblies, which are required to achieve good contacts between the copper plates and the metallized surfaces of the BSTZO. The MgO spacers are processed using a dry-pressing and pressureless-sintering method. The thermal expansion coefficient (CTE) of BSTZO and MgO spacer was measured. In addition to matching the CTE between BSTZO dielectric and the MgO spacer, it is also critical to develop a good bonding material with CTE matching to BSTZO and MgO spacer. The effect of CTE for various bonding compositions on the dielectric properties was thoroughly studied and reported. The mechanism explaining the high and low dielectric constants for the laminates is proposed and discussed based on the CTE results and their effect on microstructural development.     

Slip casting of sol–gel-synthesized barium strontium zirconium titanate ceramics

The sol–gel method was used to synthesize two different Ba_0.75Sr_0.25Ti_0.95Zr_0.05O₃ powders: one of high purity and the other of low purity. These two sol–gel-synthesized powders show two distinct particle sizes and surface areas. The slip casting method was applied to these two sol–gel powders followed by a pressureless sintering, which shows large differences in sintered density and grain size for the pressureless sintered disks. Neutron powder diffraction shows a transition to the nonpolar cubic Pm–3m space group at higher temperatures for both materials. Pair distribution function analysis was used to examine the local displacements of the Ti⁴⁺ and Zr⁴⁺ cations. The dielectric constant, loss tangent, and bias were measured on these two materials.     

晶粒可控钛酸钡致密陶瓷的制备及表征

采用超重力反应沉淀法制备的纳米钛酸钡粉体和常规陶瓷工艺,通过控制烧结温度在 1200 ~1300℃,分别制备了晶粒尺寸 0.45~2.2μm的致密陶瓷。实验结果表明超重力反应沉淀法制备的粉体具有良好的烧结和介电性能。烧结温度为 1200℃时,相对密度即可达到95%,晶粒尺寸为 0.45μm,随烧结温度的升高,晶粒逐渐长大,未出现晶粒的异常长大现象,到1300℃相对密度和晶粒尺寸分别达到 97.7%和2.2μm。钛酸钡陶瓷介电性能有明显的粒度效应,晶粒在1.2μm左右时,室温介电常数达到最大(4143)。由于晶粒内部立方相成分的出现,包含更细晶粒的陶瓷(d=0.45μm)呈现低的介电常数。     

Atomic-resolution characterization on the structure of strontium doped barium titanate nanoparticles

Ferroelectric barium titanate nanoparticles (BTO NPs) may play critical roles in miniaturized passive electronic devices such as multi-layered ceramic capacitors. While increasing experimental and theoretical understandings on the structure of BTO and doped BTO have been developed over the past decade, the majority of the investigation was carried out in thin-film materials; therefore, the doping effect on nanoparticles remains unclear. Especially, doping-induced local composition and structure fluctuation across single nanoparticles have yet to be unveiled. In this work, we use electron microscopy-based techniques including high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), integrated differential phase contrast (iDPC)-STEM, and energy dispersive X-ray spectroscopy (EDX) mapping to reveal atomically resolved chemical and crystal structure of BTO and strontium doped BTO nanoparticles. Powder X-ray diffraction (PXRD) results indicate that the increasing strontium doping causes a structural transition from tetragonal to cubic phase, but the microscopic data validate substantial compositional and microstructural inhomogeneities in strontium doped BTO nanoparticles. Our work provides new insights into the structure of doped BTO NPs and will facilitate the materials design for next-generation high-density nano-dielectric devices.

     

Influence of processing parameters on the structure and properties of barium strontium titanate ceramics

Barium strontium titanate (BST) with the molar formula (Ba_0.8Sr_0.2TiO₃) has been prepared by two different processing methods: mixed-oxide (BST-MO) and reaction-sintering (BST-RS). X-ray powder diffraction study shows differences in grain size and crystal symmetry for both these ceramics. The former shows a tetragonal symmetry while the latter presents a cubic symmetry. The occurrence of polar micro-regions associated with the higher chemical non-homogeneous distribution of ion defects from the influence of the processing parameters is the main reason for the higher peak dielectric constant (K_m), the higher remanent polarization (P_r), the higher coercive field (E_c), the higher peak current density (J_m), and the lower temperature of peak dielectric constant (T_m) in BST-MO ceramics.     

A novel method for preparation of barium strontium titanate nanopowders

Ba_0.6Sr_0.4TiO₃ (BST) nanopowders have been prepared using the modified citrate method with ammonium nitrate as a combustion promoter, and the formation mechanism, phase evolution, and particle size have been investigated using TG/DTA, XRD, and SEM. It is found that the peaks of barium carbonate disappear when the precursor powders are calcined at 650 °C. The fine particles of the nanopowders calcined with the combustion promoter addition are homogeneous and well-dispersed and their narrow size distribution is about 60-90 nm. Comparatively, the particles of the powder calcined without the ammonium nitrate addition are inhomogeneous, with an evident agglomeration. The mechanism for the above results is attributed to that a reaction can generate soft and loose precursor powders by the adoption of ammonium nitrate, and hence a pure BST phase could occur at the low synthesis temperature of 650 °C.     

Preparation of barium titanate by homogeneous precipitation

The barium titanyl oxalate, which was the precursor of barium titanate, was prepared by homogeneous precipitation using the diethyl oxalate as a precipitating agent. The oxalate dried at 80 °C was the crystalline phase, which was converted to amorphous-like phase after drying at 120 °C. The weight loss of oxalate was 47.3 wt%. The chemical formula of the oxalate could correspond to BaTiO(C₂O₄)₂ · 4H₂O. The barium titanate obtained from the calcination of oxalate at 850 °C was a tetragonal phase with a particle size of 0.2 m.     

低掺杂量MgO对钛酸锶钡陶瓷的结构和性能的影响

采用传统的陶瓷工艺制备了MgO掺杂的Ba0.6Sr0.4TiO3(BST)陶瓷样品.系统地研究了MgO掺杂量为0.06%～0.18%的Ba0.5Sr0.4TiO3陶瓷的微结构和介电性能.XRD分析显示,在我们所选取的掺杂范围内,MgO并没有影响到BST陶瓷的主晶相钙钛矿结构,且一定量的Mg离子进入到BST的晶格中.扫描电子显微镜对样品的形貌观察揭示了,随着MgO含量的增加其晶粒尺寸逐渐减小.介电性能和介电偏压测试表明,相对未掺杂BST样品的介电损耗明显降低且居里点逐渐向低温移动,可调性随着MgO掺杂量的增加而减小,MgO的掺杂量为0.18%(质量分数)时居里温度移到-49℃,可调性为16%,且样品的居里温度在外加电场作用下向高温方向移动.微波性能测试表明MgO掺杂BST陶瓷相对未掺杂样品具有较高的Q值.     

Effect of fluoride doping on impedance spectra of barium strontium titanate glass ceramics

A system of barium strontium titanate glass ceramics with different fluoride concentrations were prepared by melt-annealing technique. The effect of fluoride doping on impedance spectra of the barium strontium titanate glass ceramics were investigated. According to the impedance spectroscopy studies, three (low, middle, and high frequency) electrical responses, which corresponds to glass phase, crystal–glass interface and crystal interior were identified. It is shown that with the increase of fluoride concentration, the resistivity of the glass phase passed through a minimum and then increased. In addition, the capacitance of the crystal–glass interface increased and the capacitance of the crystal phase decreased with the increase of the fluoride concentration. Moreover, as a result of ac conductivity calculation and analysis, it is believed that the dc conduction was affected by the glass and crystal–glass interface regions and ac regime was attributed to the crystal phase. Based on the results, a change of the compensation mechanism from electronic to ionic one with variation in fluoride concentration was proposed.     

Low temperature synthesis and characterization of strontium stannate–titanate ceramics

A novel modified chimie douce synthetic approach based on the gel to crystallite conversion (G–C) method has been developed to prepare strontium titanate SrTiO₃, strontium stannate SrSnO₃, and mixed strontium stannate–titanate SrSn_1−xTi_xO₃ (x = 0.05–0.5). The obtained materials were characterized by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). The formation of fully crystalline SrTiO₃ was observed in the temperature range of 800–1000 °C. The formation of monophasic SrSnO₃ occurs in the temperature range of 700–900 °C. At lower and higher temperatures the formation an impurity phases such as SrCO₃ and SnO₂ takes place. The same synthetic approach has been applied for the preparation of mixed strontium stannates–titanates SrSn_1−xTi_xO₃. The SEM images of SrTiO₃ samples indicated that the powder particles are 1–5 μm in size having approximately plate-like shape. Quite different surface morphology was determined for SrSnO₃ samples revealing the size of crystals from 500 nm to 40 μm. For the composition with x = 0.15, it was observed that the grain growth is uniform and the size of the grains is of the order of ∼2–5 μm.     

Switching time of planar ferroelectric capacitors using strontium titanate and barium strontium titanate films

A microstripe cavity was used to make microwave (f∼10 GHz) measurements of the time of variation of the permittivity of SrTiO₃ and (Ba,Sr)TiO₃ films exposed to unipolar video-frequency voltage pulses. It was shown that the permittivity of SrTiO₃ films varies over times less than 30 ns. For (Ba,Sr)TiO₃ films two characteristic times of variation of the permittivity were identified: a fast variation over times less than 30 ns and a slower variation, on the order of 20 μs. Pis’ma Zh. Tekh. Fiz. 24, 19–25 (October 12, 1998)     

Preparation of barium strontium titanate using a modified polymeric precursor method

Barium strontium titanate with Ba/Sr ratio of 50/50 (BST5) was prepared using a modified polymeric precursor method. Unlike other methods, it proved to be cost effective since neither moisture sensitive nor costly starting materials were used for the preparation. The optimum preparation condition was established, and it was found that an annealing temperature of 600 °C with a dwell time of 20 h followed by a heat treatment at 800 °C with dwelling time of 4 h is enough to obtain well crystallized, phase pure fine powder of BST5. The oxide powder thus obtained was single phased, crystalline with cubic structure. The average lattice constant of the polycrystalline oxide was examined using XRD and it was determined to be 0.3950 nm (±0.0003 nm). The average crystallite size of the ceramic was found to be about 25–30 nm. The reaction pathway, temperature of decomposition of the precursor and the temperature of formation of the oxide was found using the data from the EGA-TGA-MS coupled instrument. TGA data showed about 75% of total weight loss over the entire heating process. The SEM studies showed that the grains were in micrometer size range, having high degree of agglomeration and irregular morphology. This process is interesting as it yields phase pure BST5 ceramic at a temperature of 800 °C devoid of secondary phases like (Ba,Sr)₂TiO₄.