CN101027735A - 陶瓷电容器及其制造方法 - Google Patents

陶瓷电容器及其制造方法 Download PDF

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CN101027735A
CN101027735A CN200580032267.8A CN200580032267A CN101027735A CN 101027735 A CN101027735 A CN 101027735A CN 200580032267 A CN200580032267 A CN 200580032267A CN 101027735 A CN101027735 A CN 101027735A
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ceramic capacitor
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森分博纪
平田和希
长井淳夫
小松和博
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Panasonic Holdings Corp
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Abstract

制备具有在1.009到1.011的范围的c轴/a轴比和0.5μm以下的平均粒径、BaTiO3作为主成分并具有四方钙钛矿晶体的晶体结构的原料粉末。通过向该原料粉末混合添加物，获得具有在1.005到1.009的范围的c轴/a轴比和0.5μm以下的平均粒径、BaTiO3作为主成分并具有四方钙钛矿晶体的晶体结构的介电体层。在该介电体层上形成电极从而获得陶瓷电容器。该陶瓷电容器具有大的电容量，并显示小的电容量减少率。

Description

陶瓷电容器及其制造方法
技术领域
本发明涉及陶瓷电容器及其制造方法。
背景技术
日本特开2003-243240号公报公开的现有的陶瓷电容器，包括厚度在1～2μm以下和介电常数在3500以上的介电体层，以及设置在介电体层的两表面上的电极，从而具有大的电容量。
但是，该电容器当在电极间施加直流电压时电容量显著减少。例如，相对于刚制造的电容量，在电极间介电体层的厚度每1μm施加3.15V的直流电压后的电容量的电容量减少率在50％以上。
发明内容
制备具有在1.009到1.011的范围的c轴/a轴比和0.5μm以下的平均粒径、BaTiO3作为主成分并具有四方钙钛矿晶体的晶体结构的原料粉末。通过向该原料粉末混合添加物，获得具有1.005到1.009的范围的c轴/a轴比和0.5μm以下的平均粒径、BaTiO3作为主成分并具有四方钙钛矿晶体的晶体结构的介电体层。在该介电体层上形成电极而获得陶瓷电容器。
该陶瓷电容器具有大的电容量并显示小的电容量减少率。
附图说明
图1为本发明的实施方式中陶瓷电容器的部分被切除的立体图。
图2为实施方式中陶瓷电容器的示意图。
图3所示为实施方式中陶瓷电容器的原料粉末的晶体结构。
图4所示为实施方式中陶瓷电容器的原料粉末的样品的c轴/a轴比。
图5所示为实施方式中陶瓷电容器的介电体层的晶粒的晶体结构。
图6所示为实施方式中陶瓷电容器的介电体层的c轴/a轴比。
附图标记说明
1介电体层
2A电极
2B电极
3A外部电极
3B外部电极
4晶粒
具体实施方式
图1为本发明实施方式的陶瓷电容器101的部分被切除的立体图。陶瓷电容器101包括电容器模块1A、外部电极3A和3B。电容器模块1A具有积层多个介电体层1和介电体层1之间以一定间隔交替设置的电极2A和2B。即介电体层1具有表面1B和与表面1B相对的表面1C，电极2A和2B分别设置在介电体层1的表面1B和1C上。电极2A和2B分别延伸到电容器模块1A的两端，并分别连接到外部电极3A和3B。
图2为陶瓷电容器101的示意图。电极2A和2B之间的介电体层1的厚度(表面1B和1C之间的间隔)T1为1到2μm，并且介电体层1具有高的介电常数，因此陶瓷电容器101具有大的电容量。介电体层1的晶粒4的c轴/a轴之比为从1.005到1.009的范围，从而介电体层1的介电常数可为3500以上。
下面说明陶瓷电容器101的制造方法。
首先制备具有从1.009到1.011的范围的c轴/a轴比和0.5μm以下的平均粒径、BaTiO3作为主成分并具有四方钙钛矿晶体(tetragonal perovskite)的晶体结构的原料粉末。最初，通过固相反应法合成并制备具有0.1μm到0.5μm的平均粒径、由BaTiO3组成的原始原料粉末。图3所示为该原始原料粉末的晶体结构。原始原料粉末的晶体结构为由Ba原子31、Ti原子32和0原子33构成的，具有a轴34和c轴35的四方钙钛矿晶体。该原始原料粉末的c轴/a轴比通过X射线衍射全谱拟合方法(x-ray diffraction-Rietveld)测定，基于测定的c轴/a轴比，如图4所示选择c轴/a轴比为从1.009到1.011的样品1到样品4的原始原料粉末，从而获得原料粉末。然后，通过现有使用的草酸法(oxalic acid method)，合成具有平均粒径为从0.1μm到0.5μm的四方钙钛矿晶体的晶体结构、主要由BaTiO3组成的原料粉末的比较例1。比较例1通过X射线衍射全谱拟合方法测定的c轴/a轴比为1.008。
然后，通过向原料粉末混合添加物，获得具有c轴/a轴比在从1.005到1.009的范围并且平均粒径在0.5μm以下、BaTiO3作为主成分，并具有四方钙钛矿晶体的晶体结构的介电体层1。图4所示为从样品1到样品4和比较例1的各原始原料粉末中每100摩尔的BaTiO3中分别混入1摩尔以下的MgO作为添加物，并干燥、煅烧、粉碎从而获得研磨粉末。本实施方式中，100摩尔的BaTiO3添加1摩尔以下的MgO，优选的为1摩尔～0.5摩尔，更优选的为1摩尔的MgO。然后，该研磨粉末与粘合剂混合并成形为片状，从而获得多个介电体层1。介电体层1和电极2A、2B积层而形成积层体，该积层体在1200～1300℃烧结。其后，通过削去积层体的两端使得在其两端分别使电极2A和2B露出，从而形成电容器模块1A。在电极2A和2B分别露出的两端分别设置外部电极3A和3B，从而获得陶瓷电容器101的样品。
积层体烧结后，电极2A和2B之间的间隔，即介电体层1的厚度T1，如图2所示约为1μm～2μm。在介电体层1的厚度T1的范围，可积层2、3或4个具有0.5μm以下的平均粒径的晶粒4。图5所示为晶粒4的晶体结构。晶粒4的晶体结构为由Ba原子51、Ti原子52和0原子53构成，并具有a轴54和c轴55的四方钙钛矿晶体。
图6为由图4所示的原料粉末获得的陶瓷电容器101的各样品的介电体层1的c轴/a轴比。使用从样品1到样品4以及比较例1获得的介电体层1的c轴/a轴比，如图6所示在从1.005到1.009的范围。
在使用从样品1到样品4和比较例1的原料粉末的陶瓷电容器101的各样品的电极2A和2B之间，介电体层1的厚度每1μm施加3.15V的直流电压。然后，测定施加直流电压后的样品的电容量相对于刚制造后的样品的电容量的电容量减少率。
图6中显示使用从样品1到样品4和比较例1的原料粉末制备的陶瓷电容器101的各样品的介电体层1的介电常数和测定的电容量减少率。
使用从样品1到样品4作为原料粉末的各样品具有3500以上的介电常数的介电体层1，并且显示40％以下的良好的容量减少率。但是使用比较例1作为原料粉末的样品具有介电常数为3625的介电体层1，却显示53.4％的电容量减少率。
介电常数由完成后的陶瓷电容器101的介电体层1的最终晶体结构所决定，而电容量减少率不仅由介电体层1的最终的晶体结构决定，还依赖于原料粉末的晶体结构。通过将具有比最终的晶体结构的c轴/a轴比大的c轴/a轴比的原料粉末与添加物混合，从而可控制品体结构的微小的应力(fine stress)，同时，可减少微小的缺陷。因此，可以获得3500以上的介电常数和40％以下的良好的电容量减少率。
本实施方式中，向原料粉末混合是使用MgO作为添加物，而MnO2，Dy2O3，V2O5或Ba-Al-Si-O系的玻璃也可以作为添加物使用。
本实施方式中，从通过固相反应法获得的原始原料粉末中使用X射线衍射全谱拟合方法，可高精度的选择c轴/a轴比为从1.009到1.011的样品1到样品4的原料粉末。或者对于原始原料粉末施加规定的热处理，例如，将原始原料粉末在0.2atms以上的氧气分压的雾氛中以600℃～1300℃的温度加热，获得具有在1.009到1.011的范围的c轴/a轴比的原料粉末。本实施方式，原始原料粉末在0.2atms以上的氧气分压的雾氛中加热，也可以在空气中(氧气分压为0.2atms)中加热，优选的在0.2atms～1atms(大气压)的氧气分压中加热。根据热处理装置的成本，也可以在高于1atms的氧气分压中加热原始原料粉末。
工业适用性
根据本发明的方法所制造的陶瓷电容器具有大的电容量并显示小的电容量减少率，对于小型的电子设备是有用的。

Claims (10)

1.一种陶瓷电容器的制造方法，包括：
制备具有在1.009到1.011的范围的c轴/a轴比和0.5μm以下的平均粒径、BaTiO3作为主成分并具有四方钙钛矿晶体的晶体结构的原料粉末的步骤；
通过向所述原料粉末混合添加物，获得具有在1.005到1.009的范围的c轴/a轴比和0.5μm以下的平均粒径、BaTiO3作为主成分并具有四方钙钛矿晶体的晶体结构的介电体层的步骤；以及
在所述介电体层上形成电极的步骤。
2.根据权利要求1所述的陶瓷电容器的制造方法，其中，
制备所述原料粉末的步骤包括：
制备由BaTiO3组成并具有四方钙钛矿晶体的晶体结构的原始原料粉末的步骤；以及
由所述原始原料粉末获得所述原料粉末的步骤。
3.根据权利要求2所述的陶瓷电容器的制造方法，其中，所述制备原始原料粉末的步骤包括通过固相反应法合成所述原始原料粉末的步骤。
4.根据权利要求2所述的陶瓷电容器的制造方法，其中，由所述原始原料粉末获得所述原料粉末的步骤包括对于所述原始原料粉末施加预定的热处理的步骤。
5.根据权利要求4所述的陶瓷电容器的制造方法，其中，对于所述原始原料粉末施加所述预定的热处理的步骤包括：在0.2atms以上的氧气分压的雾氛中以600℃到1300℃的温度加热所述原始原料粉末的步骤。
6.根据权利要求1所述的陶瓷电容器的制造方法，其中，由所述原始原料粉末获得所述原料粉末的步骤包括：由所述原始原料粉末选择所述原料粉末的步骤。
7.根据权利要求6所述的陶瓷电容器的制造方法，其中，由所述原始原料粉末选择所述原料粉末的步骤包括：
通过X射线衍射全谱拟合方法测定所述原始原料粉末的c轴/a轴比的步骤；以及
基于所述测定的c轴/a轴比，由所述原始原料粉末选择所述原料粉末的步骤。
8.根据权利要求1所述的陶瓷电容器的制造方法，其中，对应于每100摩尔所述原料粉末的BaTiO3，所述添加物是1摩尔以下的MgO。
9.根据权利要求1所述的陶瓷电容器的制造方法，其中，所述介电体层的厚度为2μm以下。
10.一种陶瓷电容器，其通过权利要求1所述的陶瓷电容器的制造方法制造而成。
CN200580032267.8A 2004-09-27 2005-09-07 陶瓷电容器及其制造方法 Pending CN101027735A (zh)

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