CN103563024B - 层叠陶瓷电容器 - Google Patents

层叠陶瓷电容器 Download PDF

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CN103563024B
CN103563024B CN201280025957.0A CN201280025957A CN103563024B CN 103563024 B CN103563024 B CN 103563024B CN 201280025957 A CN201280025957 A CN 201280025957A CN 103563024 B CN103563024 B CN 103563024B
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mean diameter
ceramic layer
ceramic capacitor
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CN103563024A (zh
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矢尾刚之
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Murata Manufacturing Co Ltd
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Abstract

本发明提供一种可以抑制耐湿负荷试验后的绝缘电阻降低的层叠陶瓷电容器。陶瓷层3，其特征在于，包含：主相粒子，具有包含Ba和Ti、并选择性地包含Ca、Sr、Zr、Hf的钙钛矿型化合物；和二次相粒子，平均粒径为100nm以上，1个粒子中的Si的含量为50摩尔%以上；（陶瓷层3的平均厚度）/（主相粒子的平均粒径）－1所表示的平均晶界数大于0且为3.0以下，并且，二次相粒子的平均粒径为陶瓷层3的厚度的1/4以上。

Description

层叠陶瓷电容器
技术领域
本发明涉及层叠陶瓷电容器。
背景技术
作为代表性的陶瓷电子部件之一的层叠陶瓷电容器通常具备层叠体和多个外部电极，所述层叠体具有被层叠的多个陶瓷层、和沿着陶瓷层间的界面形成的多个内部电极，所述外部电极形成于层叠体的外表面、并与内部电极电连接。
随着近年来电子技术的发展，对层叠陶瓷电容器要求小型化且大容量化。为了满足这些要求，正不断推进具有高介电常数的陶瓷层的层叠陶瓷电容器的开发。例如，专利文献1中记载了一种层叠陶瓷电容器，其特征在于，陶瓷层含有含钛酸钡的主成分、以及含Mg的氧化物和Si的氧化物的副成分，并且在陶瓷层中主要形成有含Mg和Si的偏析相。
现有技术文献
专利文献
专利文献1：日本特开2006－173352号公报
发明内容
发明所要解决的问题
然而，专利文献1中记载的层叠陶瓷电容器在抑制耐湿负荷试验时的裂纹产生、发展以及IR劣化方面不足。因此，产生了在耐湿负荷试验后绝缘电阻降低的问题。
本发明鉴于该问题而完成，其目的在于，提供一种介电常数高、并且可以抑制耐湿负荷试验后的绝缘电阻的降低的层叠陶瓷电容器。
用于解决问题的方法
本发明的层叠陶瓷电容器，其特征在于，具备层叠体和多个外部电 极，所述层叠体具有被层叠的多个陶瓷层、和沿着陶瓷层间的界面形成的多个内部电极，所述外部电极形成于层叠体的外表面、并与内部电极电连接，陶瓷层包含：主相粒子，具有包含Ba和Ti、并选择性地包含Ca、Sr、Zr、Hf的钙钛矿型化合物；和二次相粒子，平均粒径为100nm以上，1个粒子中的Si的含量为50摩尔％以上；(所述陶瓷层的平均厚度)/(所述主相粒子的平均粒径)－1所表示的平均晶界数大于0且为3.0以下，并且二次相粒子的平均粒径为所述陶瓷层的平均厚度的1/4以上。
此外，就本发明的层叠陶瓷电容器而言，优选钙钛矿型化合物为钛酸钡或钛酸钡钙。
发明效果
根据本发明，可以提供一种介电常数高、并且可以抑制耐湿负荷试验后的绝缘电阻的降低的层叠陶瓷电容器，可以对层叠陶瓷电容器的小型化·高性能化做出较大的贡献。
附图说明
图1是表示本发明的层叠陶瓷电容器的一个示例的模式图。
图2是表示陶瓷层的平均厚度的测定方法的说明图。
具体实施方式
首先，参照图1，对本发明的层叠陶瓷电容器1进行说明。
陶瓷电容器1，具备层叠体2，所述层叠体2通过具有被层叠的多个陶瓷层3、以及沿着陶瓷层3间的界面形成的多个内部电极4和5而构成。
在层叠体2的外表面上的彼此不同的位置，形成有第1外部电极8和第2外部电极9。在图1所示的层叠陶瓷电容器1中，第1外部电极8和第2外部电极9分别形成于层叠体2的相互对置的各端面6和7上。内部电极4和5具有与第1外部电极8电连接的多个第1内部电极4、以及与第2外部电极9电连接的多个第2内部电极5，这些第1内部电极4和第2内部电极5在层叠方向上交替配置。在外部电极8和9的表面，根据需要形成第1镀层10和11、以及第2镀层12和13。
陶瓷层3包含：主相粒子，具有包含Ba和Ti、并选择性地含有Ca、Sr、 Zr、Hf的钙钛矿型化合物的；以及二次相粒子，平均粒径为100nm以上，1个粒子中的Si的含量为50摩尔％以上。优选钙钛矿型化合物为钛酸钡或钛酸钡钙。这种情况下，本发明的效果显著。
此外，二次相粒子的平均粒径为100nm以上，1个粒子中的Si的含量为50摩尔％以上。
本发明的特征在于，由(陶瓷层的平均厚度)/(主相粒子的平均粒径)－1所表示的平均晶界数大于0且为3.0以下，并且二次相粒子的平均粒径为陶瓷层的平均厚度的1/4以上。这种情况下，能够抑制耐湿负荷试验后的绝缘电阻的降低。
通过控制平均晶界数和二次相粒子的平均粒径、从而可以抑制耐湿负荷试验后的绝缘电阻降低的机理尚不明确，但推测如下。首先，推测通过使平均晶界数大于0且为3.0以下，从而在耐湿负荷试验时，陶瓷层的晶界被水分浸蚀的可能性降低。并且，推测通过使二次相粒子的平均粒径为陶瓷层的平均厚度的1/4以上，从而即使在耐湿负荷试验时产生裂纹，裂纹的发展在二次相粒子部分停止的可能性也提高。
需要说明的是，在不损害本发明目的的范围内，陶瓷层3中还可以包含La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Lu和Y中的至少一种元素。此外，还可以包含Mn、Ni、Fe、Cu、Mg、V和Al中的至少一种元素。
接着，对本发明的层叠陶瓷电容器的制造方法的一个示例进行说明。
首先，作为主成分的起始原料，准备Ba、Ca、Sr、Ti、Zr、Hf的氧化物或碳酸化物粉末。称量这些起始原料的粉末，并在液体中使用介质进行混合粉碎。干燥后，对所得的混合粉末进行热处理，由此得到陶瓷原料粉末。该方法通常被称为固相合成法，而作为其它方法，也可以采用水热合成法、水解法、草酸法等湿式合成法。
接着，将该陶瓷原料粉末在溶剂中根据需要与有机粘合剂混合，制作陶瓷浆料。对该陶瓷浆料进行片成形，由此得到陶瓷生片。
接着，在陶瓷生片上形成可用作内部电极的导体膜。该工序有若干种方法，其中，将包含金属粒子和有机载体的糊剂丝网印刷为所希望图案的方法较为简便。除此以外，还有转印金属箔的方法、通过真空薄膜形成 法一边进行掩蔽一边形成导体膜的方法。
接着，将多层的陶瓷生片和内部电极重叠并进行压合，由此得到烧成前的未加工的层叠体。
接着，在烧成炉中，在规定的气氛、温度下对未加工的层叠体进行烧成，得到层叠体。
接着，对层叠体的内部电极的被引出的部位，形成外部电极。就外部电极的形成方法而言，可以列举涂布含有玻璃料、以及Cu或Ag等金属粒子的糊剂，并进行烘烤的方法等。而且，根据需要，在外部电极的表面形成Ni、Sn等的镀层。如上所述，制作层叠陶瓷电容器。
[实验例1]
在实验例1中，制作陶瓷层的主相粒子为钛酸钡的层叠陶瓷电容器，并对发明效果进行确认。
首先，作为起始原料，准备BaCO3和TiO2的各粉末，进行称量以使相对于Ti 100摩尔份的Ba含量为100.8摩尔份。然后，在液体中使用介质，将称量物混合粉碎。干燥后，对所得的混合粉末进行热处理，由此得到钛酸钡粉末。
此时，通过对作为起始原料的BaCO3和TiO2的各粉末的粒径进行控制，而改变钛酸钡粉末的合成度。即，如果减小BaCO3和TiO2的各粉末的粒径，则钛酸钡的合成度增高，烧成后的主相粒子的晶粒生长得到抑制。另一方面，如果增大BaCO3和TiO2的粉末的粒径，则钛酸钡的合成度降低，促进了烧成后的主相粒子的晶粒生长。钛酸钡粉末的合成度由c/a轴比进行测定。c/a轴比使用XRD衍射法来测定。
接着，准备Dy2O3、MgCO3、MnCO3、SiO2的各粉末，进行称量以使相对于所述钛酸钡粉末中的Ti 100摩尔份的Dy的含量为1.0摩尔份、Mg的含量为1.0摩尔份、Mn的含量为0.5摩尔份、并且Si的含量为2.0摩尔份。然后，与钛酸钡粉末混合，并在液体中使用介质进行混合粉碎。然后，使所得的浆料蒸发干燥，得到陶瓷原料粉末。
接着，向该陶瓷原料粉末中加入聚乙烯醇缩丁醛系粘合剂和乙醇等有机溶剂，并利用球磨机湿式混合24小时，制作出陶瓷浆料。通过唇式涂布机(lip coater)将该陶瓷浆料成形为片状，得到陶瓷生片。
接着，在陶瓷生片上丝网印刷以Ni为主成分的糊剂，形成可用作内部电极的导体膜。
接着，以使导体膜的被引出侧彼此不同的方式层叠多片形成了导体膜的陶瓷生片，得到未加工的层叠体。
接着，在氮气气氛中，将该未加工的层叠体加热至300℃，使粘合剂燃烧。然后，在氧分压为10－10MPa的含有H2-N2-H2O气体的还原性气氛中，在800℃下保持3小时后，在1200℃下烧成2小时，得到层叠体。
此时，通过控制1200℃时的氧分压，使二次相粒子的粒径发生变化。即，如果氧分压增大，则二次相粒子的粒径变大。另一方面，如果氧分压减小，则二次相粒子的粒径变小。
接着，在内部电极被引出的层叠体的两端面涂布包含B2O3-Li2O-SiO2-BaO玻璃料的铜糊剂。然后，在氮气气氛中，在800℃的温度下烘烤，形成与内部电极电连接的外部电极。
如上制作出的层叠陶瓷电容器的外形尺寸为长度：1mm、宽度：0.5mm、厚度：0.5mm，有效陶瓷层的层数为100层。此外，每1层的对置电极面积为0.3mm2。位于内部电极间的陶瓷层的平均厚度如表1所述。
[陶瓷层的平均厚度的测定]
首先，使各试样立起而垂直，使用树脂将各试样的周围固定。此时，各试样的LT侧面(长度·高度侧面：在研磨时，包括与外部电极的连接部分在内的内部电极露出的侧面)露出。使用研磨机，研磨LT侧面，在层叠体的W方向(宽度方向)的1/2深度处结束研磨，露出LT截面。对该研磨面进行离子研磨，除去因研磨而产生的垂挂(日文：ダレ)。如上操作，得到观察用的截面。
如图2所示，在LT截面的L方向(长度方向)1/2处，引出与内部电极正交的垂线。接着，将试样的层叠有内部电极的区域在T方向(高度方向)上进行3等分，分为上侧部U、中间部M、下侧部D的3个区域。然后，从各区域各自的高度方向中央部选择20层的内部电极(在图2中，将包含该20层的内部电极的区域表示为测定区域R1)，测定这些内部电极在上述垂线上的厚度。但是，将最外层的内部电极和在上述垂线上内部电极发生缺损、夹持该内部电极的陶瓷层发生连接等而导致的不能 测定的区域排除。
根据上述内容，对各试样在60个部位测定内部电极的厚度。基于各条件(试样编号)对各式样进行n＝3次测定，求出它们的平均值。(60个部位×3个＝180点)
[主相粒子的平均粒径]
对于层叠陶瓷电容器的陶瓷层部，使用离子研磨法薄片化至厚度达到40nm以下，得到观察截面。
接着，使用透射型电子显微镜(TEM)，在各试样的粒子中央附近的观察截面中，对于该观察截面选取在垂直方向上多个离子未重叠存在的粒子。即，在本实施例中，使用TEM对各试样的粒子中央附近的截面进行观察，再使用由该TEM得到的电子衍射图案，确认在垂直方向上多个粒子是否重叠存在，并选取未重叠存在的粒子。
接着，使用能量分散型X射线分析装置(EDX)，对所选取的粒子通过TEM观察进行各粒子的扫描(mapping)分析。然后，由构成各粒子的元素种类，将各粒子分类为主相粒子和主相粒子之外的粒子。
接着，从上述主相粒子中随机选取50个粒子，对TEM图像进行图像分析，求出各粒子的晶界的内侧部分的面积，算出圆等效直径。
对5个视野进行该操作，并由5个视野的圆等效直径的平均值算出主相粒子的平均粒径(50个×5个视野＝250个数据)。
[二次相粒子的平均粒径]
对于按照前述步骤分类为主相粒子之外的粒子，使用TEM－EDX以低倍率进行扫描分析，并特别指定Si含有率为50摩尔％以上的粒子(其中，由比率计算排除氧)。
此外，对上述特别指定的粒子的TEM图像进行图像分析，求出各粒子的晶界的内侧部分的面积，算出圆等效直径。然后将圆等效直径为100nm以上的粒子作为二次相粒子。对1个视野随机抽取10个二次相粒子。对5个视野进行该操作，将5个视野的二次相粒子的圆等效直径的平均值作为二次相粒子的平均粒径(10个×5个视野＝50个数据)。
耐湿负荷试验是在85℃/85％RH的条件下对层叠陶瓷电容器施加4V电压而实施的。试样的n＝50。然后，测定试样的绝缘电阻，并汇总绝缘 电阻劣化了的试样数。
表1中示出试样编号1～10的实验条件和耐湿负荷试验后的绝缘电阻发生劣化的试样数。需要说明的是，表中带有*标记的试样编号表示在本发明的范围之外。
[表1]
由表1可知，就平均晶界数大于0且为3.0以下、并且二次相粒子的平均粒径为陶瓷层的平均厚度的1/4以上的试样编号1～4而言，未产生耐湿负荷试验后绝缘电阻劣化的试样，得到了良好的结果。
(实验例2)
在实验例2中，制作陶瓷层的主相粒子为钛酸钡钙的层叠陶瓷电容器，并确认发明效果。
作为起始原料，准备BaCO3、CaCO3和TiO2的各粉末后，进行称量以使相对于Ti 100摩尔份的Ba、Ca的合计含量为100.5摩尔份、且Ba/(Ba+Ca)的摩尔比为0.9，制作出钛酸钡钙粉末。此外，在准备Y2O3、MgCO3、V2O5、SiO2的各粉末后，进行称量以相对于所述钛酸钡钙粉末中的Ti 100摩尔份而使Y的含量为1.0摩尔份、Mg的含量为1.0摩尔份、V的含量为0.2摩尔份、并且Si的含量为2.0摩尔份，并与钛酸钡钙粉末混合。除此以外，根据和实验例1相同的要领进行制作，得到陶瓷原料粉末。
接着，使用上述陶瓷原料粉末，并根据和实验例1相同的要领，制作出层叠陶瓷电容器。将结果示于表2。
[表2]
由表2可知，就平均晶界数大于0且为3.0以下、并且二次相粒子的平均粒径为陶瓷层的平均厚度的1/4以上的试样编号11～14而言，未产生耐湿负荷试验后绝缘电阻劣化的试样，得到了良好的结果。
符号说明
1 层叠陶瓷电容器
2 层叠体
3 陶瓷层
4、5 内部电极
6、7 端面
8、9 外部电极
10、11 第1镀层
12、13 第2镀层

Claims (2)

1.一种层叠陶瓷电容器，其特征在于，具备层叠体和多个外部电极，所述层叠体具有被层叠的多个陶瓷层、和沿着所述陶瓷层间的界面形成的多个内部电极，所述外部电极形成于所述层叠体的外表面、并与所述内部电极电连接，
所述陶瓷层包含：
主相粒子，具有包含Ba和Ti、且包含或不包含选自Ca、Sr、Zr、Hf中的至少一种的钙钛矿型化合物；和
二次相粒子，平均粒径为100nm以上，1个粒子中的Si的含量为50摩尔百分比以上；
(所述陶瓷层的平均厚度)/(所述主相粒子的平均粒径)-1所表示的平均晶界数大于0且为3.0以下，并且，
所述二次相粒子的平均粒径为所述陶瓷层的平均厚度的1/4以上。
2.根据权利要求1所述的层叠陶瓷电容器，其特征在于，所述钙钛矿型化合物为钛酸钡或钛酸钡钙。
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