高温稳定型MLCC用介质陶瓷材料的制备、结构与性能研究
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摘要
本文以钛酸钡基陶瓷为研究对象，通过掺杂改性成功制备了一系列高温稳定型的多层陶瓷电容器（MLCC）用介质材料，推动了国内该领域尤其是使用温度上限为200℃的MLCC的技术发展，同时对高温稳定型介质材料的成分、结构与性能之间的关系做了大量系统性工作和创新性探究。
选用BaTiO_3_-Nb_2O_5-Co_3O_4作为基本的温度稳定型介质材料体系，通过适量的Re_2O_3和Bi_2O_3共掺杂可获得符合EIA X8R （55~150℃，ΔC/C25≤±15%）特性的空气烧结陶瓷材料，其中Re代表一种小离子半径的稀土元素。重点研究了Re和Bi的掺杂改性机理，证实了Re掺杂具有移峰效应。提出了“芯—壳”界面的内应力模型并指出了具有“芯—壳”结构的BaTiO_3基陶瓷居里温度升高的原因。所开发的瓷料成功应用于X8R型贵金属内电极MLCC的制备。器件的劣化行为、偏压特性及高温阻抗谱分析结果均表明该类MLCC具有良好的可靠性。通过高分辨透射电镜研究了Ag-Pd内电极层与陶瓷介质层界面附近的互扩散行为。
选用BaTiO_3-MgO-Y_2O_3-MnO_2作为基本材料体系，通过适量的CaZrO_3掺杂获得了符合EIA X8R特性的还原气氛烧结陶瓷。研究了CaZrO_3含量对于陶瓷烧结特性、居里温度、介电性能以及劣化行为的影响，揭示了CaZrO_3的改性机理。考察了两性稀土氧化物Y2O3的取代行为对材料各方面特性的影响。制备了平均粒径小于200nm的细晶抗还原X8R陶瓷，发现细晶陶瓷具有优异的电性能及偏压特性并指出了其主要原因。
通过固相法合成了具有高居里点的(1-x)BaTiO_(3–x)(Bi_(0.5)Na_(0.5))TiO_3（x≤0.12）弥散相变型铁电陶瓷。以0.9BaTiO_3–0.1(Bi0.5Na0.5)TiO_3作为基料，通过掺杂Nb_2O_5制备出符合X9R（55~200℃，ΔC/C25≤±15%）标准的空气烧结陶瓷材料。通过两段式烧结、化学包覆等工艺可进一步改善介电性能，获得介电常数为1900~2000，介电损耗为1.7%~2.0%的X9R材料，性能达到国际领先水平。能谱分析的结果表明，Nb元素的微观不均匀分布是材料具有温度稳定特性的根本原因。该类材料显微形貌的演变可以通过“溶解—沉淀”机制加以解释。
This dissertation focuses on the preparation of barium titanate baseddielectric materials for high-temperature-stable multilayer ceramic capacitors(MLCC) application, especially for the MLCCs whose upper temperature limitreaches200oC. The domestic technology in this field is promoted. Therelationship among the composition, microstructures and properties wassystematically studied and the related mechanism was also discussed.
BaTiO_3_-Nb_2O_5-Co_3O_4was chose as the system for air-sinteredtemperature-stable dielectrics. The ceramics which satisfy EIA X8Rspecification (55to150°C, ΔC/C25≤±15%) could be obtained by the co-dopingof Re_2O_3and Bi_2O_3(Re represents a kind of rare-earth element with smallerionic radius). The effects of Re_2O_3and Bi_2O_3on the Curie temperature wereinvestigated and Re was proved to play a major role in Tcshift. A “core-shell”interface model was proposed and the effect of the internal stress on Tcwaselucidated. The above-mentioned X8R material was successfully applied in thefabrication of MLCCs with Ag-Pd inner electrodes. The degradationcharacteristic, the dielectric behavior under a direct current (DC) bias field andthe impedance spectra demonstrated the high reliability of X8R-type MLCCs.The elements interdiffusion in the vicinity of ceramic/electrode interface wasstudied by HRTEM.
With a proper amount of CaZrO_3addtion, the BaTiO_3-MgO-Y_2O_3-MnO_2nonreducible system was found to fulfill EIA X8R specification. The effects ofCaZrO_3content on the sintering process, the Curie temperature, dielectricproperties and degradation behaviors were investigated and the modificationmechanism was discussed. The site occupancy behavior of amphoteric rare-earthoxide Y2O3was also investigated, which had a significant effect on dielectricand electrical properties. Fine-grained X8R materials with an average grain sizeof less than200nm were prepared. Fine-grained ceramics showed much betterperformance under a DC bias field and the explanation was provided.
The solid solutions (1-x)BaTiO_(3–x)(Bi_(0.5)Na_(0.5))TiO_3(x≤0.12) synthesize by solid-state reactions exhibited a high Curie temperature as well as a diffusephase transition (DPT). The temperature coefficient of capacitance (TCC)curves of0.9BaTiO_3–0.1(Bi0.5Na0.5)TiO_3system were largely improved with thedoping of Nb_2O_5. As a result, air-sintered X9R-type (55to200°C,ΔC/C25≤±15%) dielectric materials were successfully obtained. The dielectricproperties were further enhanced via two step sintering and chemical coatingmethod. The newly developed air-sintered X9R materials showed an excellentoverall performance with the dielectric constant of1900~2000and the dielectricloss of1.7%~2.1%, which reached the international leading edge. The energydispersive spectrometry was used to analyse the elements distribution inmicroregions. The results revealed that the temperature stability of permittivityoriginated from the heterogeneous distribution of niobium. The evolution ofmicrostructures could be explained by the “solution-precipitation” mechanism.
选用BaTiO_3_-Nb_2O_5-Co_3O_4作为基本的温度稳定型介质材料体系，通过适量的Re_2O_3和Bi_2O_3共掺杂可获得符合EIA X8R （55~150℃，ΔC/C25≤±15%）特性的空气烧结陶瓷材料，其中Re代表一种小离子半径的稀土元素。重点研究了Re和Bi的掺杂改性机理，证实了Re掺杂具有移峰效应。提出了“芯—壳”界面的内应力模型并指出了具有“芯—壳”结构的BaTiO_3基陶瓷居里温度升高的原因。所开发的瓷料成功应用于X8R型贵金属内电极MLCC的制备。器件的劣化行为、偏压特性及高温阻抗谱分析结果均表明该类MLCC具有良好的可靠性。通过高分辨透射电镜研究了Ag-Pd内电极层与陶瓷介质层界面附近的互扩散行为。
选用BaTiO_3-MgO-Y_2O_3-MnO_2作为基本材料体系，通过适量的CaZrO_3掺杂获得了符合EIA X8R特性的还原气氛烧结陶瓷。研究了CaZrO_3含量对于陶瓷烧结特性、居里温度、介电性能以及劣化行为的影响，揭示了CaZrO_3的改性机理。考察了两性稀土氧化物Y2O3的取代行为对材料各方面特性的影响。制备了平均粒径小于200nm的细晶抗还原X8R陶瓷，发现细晶陶瓷具有优异的电性能及偏压特性并指出了其主要原因。
通过固相法合成了具有高居里点的(1-x)BaTiO_(3–x)(Bi_(0.5)Na_(0.5))TiO_3（x≤0.12）弥散相变型铁电陶瓷。以0.9BaTiO_3–0.1(Bi0.5Na0.5)TiO_3作为基料，通过掺杂Nb_2O_5制备出符合X9R（55~200℃，ΔC/C25≤±15%）标准的空气烧结陶瓷材料。通过两段式烧结、化学包覆等工艺可进一步改善介电性能，获得介电常数为1900~2000，介电损耗为1.7%~2.0%的X9R材料，性能达到国际领先水平。能谱分析的结果表明，Nb元素的微观不均匀分布是材料具有温度稳定特性的根本原因。该类材料显微形貌的演变可以通过“溶解—沉淀”机制加以解释。
This dissertation focuses on the preparation of barium titanate baseddielectric materials for high-temperature-stable multilayer ceramic capacitors(MLCC) application, especially for the MLCCs whose upper temperature limitreaches200oC. The domestic technology in this field is promoted. Therelationship among the composition, microstructures and properties wassystematically studied and the related mechanism was also discussed.
BaTiO_3_-Nb_2O_5-Co_3O_4was chose as the system for air-sinteredtemperature-stable dielectrics. The ceramics which satisfy EIA X8Rspecification (55to150°C, ΔC/C25≤±15%) could be obtained by the co-dopingof Re_2O_3and Bi_2O_3(Re represents a kind of rare-earth element with smallerionic radius). The effects of Re_2O_3and Bi_2O_3on the Curie temperature wereinvestigated and Re was proved to play a major role in Tcshift. A “core-shell”interface model was proposed and the effect of the internal stress on Tcwaselucidated. The above-mentioned X8R material was successfully applied in thefabrication of MLCCs with Ag-Pd inner electrodes. The degradationcharacteristic, the dielectric behavior under a direct current (DC) bias field andthe impedance spectra demonstrated the high reliability of X8R-type MLCCs.The elements interdiffusion in the vicinity of ceramic/electrode interface wasstudied by HRTEM.
With a proper amount of CaZrO_3addtion, the BaTiO_3-MgO-Y_2O_3-MnO_2nonreducible system was found to fulfill EIA X8R specification. The effects ofCaZrO_3content on the sintering process, the Curie temperature, dielectricproperties and degradation behaviors were investigated and the modificationmechanism was discussed. The site occupancy behavior of amphoteric rare-earthoxide Y2O3was also investigated, which had a significant effect on dielectricand electrical properties. Fine-grained X8R materials with an average grain sizeof less than200nm were prepared. Fine-grained ceramics showed much betterperformance under a DC bias field and the explanation was provided.
The solid solutions (1-x)BaTiO_(3–x)(Bi_(0.5)Na_(0.5))TiO_3(x≤0.12) synthesize by solid-state reactions exhibited a high Curie temperature as well as a diffusephase transition (DPT). The temperature coefficient of capacitance (TCC)curves of0.9BaTiO_3–0.1(Bi0.5Na0.5)TiO_3system were largely improved with thedoping of Nb_2O_5. As a result, air-sintered X9R-type (55to200°C,ΔC/C25≤±15%) dielectric materials were successfully obtained. The dielectricproperties were further enhanced via two step sintering and chemical coatingmethod. The newly developed air-sintered X9R materials showed an excellentoverall performance with the dielectric constant of1900~2000and the dielectricloss of1.7%~2.1%, which reached the international leading edge. The energydispersive spectrometry was used to analyse the elements distribution inmicroregions. The results revealed that the temperature stability of permittivityoriginated from the heterogeneous distribution of niobium. The evolution ofmicrostructures could be explained by the “solution-precipitation” mechanism.
引文
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