CN103080044A - 电介质陶瓷、层叠陶瓷电容器及其制造方法 - Google Patents

电介质陶瓷、层叠陶瓷电容器及其制造方法 Download PDF

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CN103080044A
CN103080044A CN2011800420021A CN201180042002A CN103080044A CN 103080044 A CN103080044 A CN 103080044A CN 2011800420021 A CN2011800420021 A CN 2011800420021A CN 201180042002 A CN201180042002 A CN 201180042002A CN 103080044 A CN103080044 A CN 103080044A
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dielectric
dielectric ceramics
ceramic capacitor
median size
dielectric layer
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福田惠
矢尾刚之
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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Abstract

本发明提供一种即使将电介质层进一步薄层化，也具有优异的高温负荷试验寿命特性的层叠陶瓷电容器。作为构成电介质陶瓷电容器(1)的电介质层(2)的电介质陶瓷，使用如下的物质：所述物质含有用通式(Ba1-x-yCaxRey)(Ti1-zMz)O3(其中，Re是从La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu以及Y中选择的至少一种以上的元素，M是从Mg、Mn、Al、Cr以及Zn中选择的至少一种以上的元素)表示并且满足0≤x≤0.2、0.002≤y≤0.1、0.001≤z≤0.05的范围的化合物作为主成分。该电介质陶瓷的结晶粒子的平均粒径为20nm以上且150nm以下。

Description

电介质陶瓷、层叠陶瓷电容器及其制造方法
技术领域
本发明涉及一种电介质陶瓷及其制造方法。另外还涉及使用该电介质陶瓷构成的层叠陶瓷电容器及其制造方法。
背景技术
随着近年来电子技术的发展，要求层叠陶瓷电容器小型化且大容量。为了满足这种要求，层叠陶瓷电容器的电介质层的薄层化在进展。但是，若将电介质层薄层化，则对每一层施加的电场强度就会相应地变高。因此，对于用于电介质层的电介质陶瓷而言，要求在施加电压时的可靠性，尤其要求提高高温负荷试验的寿命特性。
例如，在专利文献1中，记载了有以下特征的电介质陶瓷。即，以钛酸钡作为主成分，具有含稀土元素、镁及锰的钙钛矿型的晶体结构作为副成分，并以组成式(Ba1-yREy)(Ti1-a-bMgaoMnb)O3(RE：稀土元素)表示，各个范围以0.06≤y≤0.09、0.03≤ao≤0.045。0.012≤b≤0.018表示。
现有技术文献
专利文献
专利文献1：特开2007-145649号公报
发明内容
发明所要解决的课题
然而，在专利文献1中没有记载关于将电介质层薄层化的情况。因此，在专利文献1中记载的电介质陶瓷，没有明确在将电介质层的厚度薄层化到1μm左右时，其在施加电压时的可靠性是否较高。
本发明是鉴于所上述的问题而完成的，其目的在于提供一种即使将电介质层进一步薄层化并施加高电场强度的电压，也具有良好的介电特性，且高温负荷试验的寿命特性优异的层叠陶瓷电容器。
用于解决课题的手段
本发明的电介质陶瓷，其特征在于，含有用通式(Ba1-x-yCaxRey)(Ti1-zMz)O3(其中，Re是从La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu以及Y中选择的至少一种以上的元素，M是从Mg、Mn、Al、Cr以及Zn中选择的至少一种以上的元素)表示并且满足0≤x≤0.2、0.002≤y≤0.1、0.001≤z≤0.05的范围的化合物作为主成分，所述电介质陶瓷的结晶粒子的平均粒径为20nm以上且150nm以下。
另外，本发明所述的电介质陶瓷，优选平均粒径为20nm以上且不足100nm。
另外，本发明还涉及电介质陶瓷电容器，其具有层叠体和多个外部电极；所述层叠体具有被层叠的多个电介质层，和沿着电介质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，其特征在于，电介质层，由上述的电介质陶瓷构成。
另外，本发明还涉及电介质陶瓷的制造方法，其特征在于，具有如下的工序：准备所述陶瓷粉末的工序，所述陶瓷粉末含有用通式(Ba1-x-yCaxRey)(Ti1-zMz)O3(其中，Re是从La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu以及Y中选择的至少一种以上的元素，M是从Mg、Mn、Al、Cr以及Zn中选择的至少一种以上的元素)表示并且满足在0≤x≤0.2、0.002≤y≤0.1、0.001≤z≤0.05范围的化合物作为主成分；对陶瓷粉末进行成形获得所述成形体的工序；对成形体进行烧结，获得结晶粒子的平均粒径为20nm以上且150nm以下的电介质陶瓷的工序。
另外，本发明所述的电介质陶瓷的制造方法，其特征在于，优选平均粒径为20nm以上且不足100nm。
另外，本发明还涉及电介质陶瓷电容器的制造方法，其特征在于，具备上述电介质陶瓷的制造方法。
发明效果
根据本发明所述的电介质陶瓷，通过具有上述的组成，同时规定如上所述的结晶粒子的粒径，可提供一种即使将电介质层进一步薄层化并施加高电场强度的电压，也具有良好的介电特性，且高温负荷试验的寿命特性优异的层叠陶瓷电容器。
附图说明
图1本发明所涉及的层叠陶瓷电容器的剖面图。
具体实施方式
以下，对于用于实施本发明的方式进行说明。
图1是本发明所涉及的层叠陶瓷电容器的剖面图。
层叠陶瓷电容器1具有层叠体5。层叠体5具有被层叠的多个电介质层2，和沿着多个电介质层2之间的界面形成的多个内部电极3和4。作为内部电极3和4的材质，例如可例举出以Ni为主成分的材质。
在层叠体5外表面的互相不同的位置上，形成有外部电极6和7。作为外部电极6和7的材质，例如可例举出以Ag或Cu为主成分的材质。在图1所示的层叠陶瓷电容器中，外部电极6和7被形成在层叠体5相互对置的各端面上。内部电极3和4分别电连接在外部电极6和7上。并且，内部电极3和4，在层叠体5内部隔着电介质层2被交替层叠。
需要说明的是，层叠陶瓷电容器1可以是具有两个外部电极6和7的两端子型的结构，也可以是具有多个外部电极的其它端子型的结构。
电介质层2由含有用通式(Ba1-x-yCaxRey)(Ti1-zMz)O3(其中，Re是从La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu以及Y中选择的至少一种以上的元素，M是从Mg、Mn、Al、Cr以及Zn中选择的至少一种以上的元素)表示并且以满足0≤x≤0.2、0.002≤y≤0.1、0.001≤z≤0.05范围的化合物为主成分的电介质陶瓷构成。并且，电介质陶瓷的结晶粒子的平均粒径设为20nm以上和150nm以下。
另外，在平均粒径为20nm以上且不足100nm的情况下，能够提供比高温负荷试验的寿命特性更为优异的层叠陶瓷电容器。
需要说明的是，可适当地设定(Ba、Ca、Re)和(Ti、M)的摩尔比，最好在0.98～1.05的范围选择。
关于陶瓷粉末，例如可用固相合成法制作。具体来说，首先，将分别含有作为主成分构成元素的Ba、Ca、Re、Ti、M的氧化物、碳酸物、氯化物、金属有机化合物等化合物粉末，以规定的比例混合、煅烧。需要说明的是，除了固相合成法之外，还可以适当地使用水热合成法和水解法等。
关于层叠陶瓷电容器，例如，可按照以下制作。使用按上述所得到的陶瓷粉末来制作陶瓷浆料。然后，用片材成形法等成形陶瓷生片。接着，在将数张陶瓷生片层叠之后压接而得到成形体。然后，烧结成形体。在该烧结工序中，烧结陶瓷粉末，能得到由电介质陶瓷构成的电介质层。此后，在层叠体的端面上用烧焊等形成外部电极。
其次，对根据本发明实施的实验例进行说明。
[实验例1]
(A)陶瓷粉末的制作
作为起始原料，准备了微粒的BaCO3、CaCO3、TiO2、Re(Re是La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu以及Y)、M(M是Mg、Mn、Al、Cr以及Zn)的各粉末。作为Re的粉末，准备了La2O3、Ce2O3、Pr2O3、Nd2O3，Sm2O3、Eu2O3，Gd2O3，Tb2O3、Dy2O3、Ho2O3、Er2O3、Tm2O3、Yb2O3、Lu2O3以及Y2O3的各粉末。另外，作为M的粉末，准备了MgCO3、MnCO3、A12O3、Cr2O3、ZnO的各粉末。然后，在将这些粉末按(Ba1-x-yCaxRey)(Ti1-zMz)O3在表1中的组成称量之后，用球磨机进行80个小时混合。此后，通过将上述混合粉末在1000℃进行热处理、煅烧合成而得到(Ba1-x-yCaxRey)(Ti1-zMz)O3的主成分粉末。此后，对于主成分粉末100摩尔份，加添1.5摩尔份的BaCO3、2摩尔份的SiO2，可得到陶瓷粉末。
所得到的陶瓷粉末的平均粒径是10nm左右。另外，根据XRD，在陶瓷粉末中的未反应物低于检测水平。即，确认了该陶瓷粉末尽管是极小微粒但也是合成度高的粉末。
[表1]
Figure BDA00002869116600051
(B)层叠陶瓷电容器的制作
首先，形成应成为电介质层的陶瓷生片。具体来说，在上述的陶瓷粉末中添加聚乙烯醇缩丁醛系粘合剂以及乙醇，通过球磨机进行24小时的湿式混合。然后用过滤器进行过滤，制作出将具有规定范围内粒径以外的粒径的粉末除去的浆料。并且，根据模唇方式在片材上成形该浆料而得到陶瓷生片。使陶瓷生片的厚度如后所述，成为在烧结后表2中「电介质层厚度」所示的厚度。
其次，制作成形体。具体来说，在特定的陶瓷生片上，对含有以Ni为主成分的导电性糊剂进行丝网印刷，形成应成为内部电极的导电性糊剂膜。然后，将形成有导电性糊剂膜的陶瓷生片，以导电性糊剂膜被拉出的一侧为交错的方式进行多张层叠并压接，可得到成形体。
其次，对成形体进行烧结。具体来说，首先，在还原气氛下加热至300℃的温度，使粘合剂燃烧。然后，在由氧分压为10-10MPa的H2-N2-H2O气体组成的还原性气氛中，以1200℃的温度烧结1小时。
其次，形成外部电极。具体来说，在层叠体两端面涂覆含有B2O3-Li2O-SiO2-BaO系玻璃料的Cu糊剂。然后，在氮气氛下以800℃的温度加热，烧焊了Cu糊剂。这样形成了与内部电极电连接的外部电极。
如上所述制作出成层叠陶瓷电容器。层叠陶瓷电容器的外形尺寸为长度1.0mm，宽度0.5mm，厚度0.5mm，有效电介质层的层数是100层，每一层电介质层的内部电极的对置面积为0.3mm2。另外，夹在内部电极之间的电介质层的厚度，如表2的“电介质层厚度”中所示。
(C)特性评价
对所得到的层叠陶瓷电容器，评价了各种特性。
[平均粒径]
对平均粒径进行了如下的计算。首先，将各试料的层叠陶瓷电容器进行断裂，并以1000℃的温度进行热腐蚀，使用扫描型显微镜观察断裂面。然后，对此观察进行图像分析，以结晶粒子的圆当量直径作为粒径测定了结晶粒子的粒径。另外，关于各试料，测定300个结晶粒子的粒径，以平均值作为平均粒径计算。
[高温负荷寿命试验]
高温负荷寿命试验如下所述来实施。对各试料的层叠陶瓷电容器，在125℃的温度下，以6.3kV/mm和12.6kV/mm的各电场强度施加DC电压。另外，用100个试样实施高温负荷寿命试验，经过1000个小时，将绝缘电阻值为100kΩ以下的试样判断为不良，求出100个试样中的不良个数。
在表2中出示了平均粒径、电介质层厚度以及高温负荷寿命试验后的不良个数。
[表2]
需要说明的是，在表1及表2中，试样编号带*的是在本发明的范围外的试样。
(D)考察
试样号1、10、14是以(Ba，Re)(Ti，M)O3为主成分，在DC电压为6.3kV/μm、12.6kV/μm时都显示出了良好的可靠性。另外，试样编号2～9、11～13、15～17是以(Ba，Ca，Re)(Ti，M)O3为主成分，在DC电压为6.3kV/μm、12.6kV/μm时都显示出了良好的可靠性。另外，试样号1～3、5、7、8、10～14、16为平均粒径是20nm以上且不足100nm，在DC电压为12.6kV/μm的试验条件下也没有发生不良，显示出了良好的可靠性。
对于这些试样，试样号18是平均粒径不足20nm的试样，其结果是可靠性较低。另外，试样号19是平均粒径大于150nm试样，其可结果是靠性较低。试样号19可以认为是由于平均粒径较大，层叠体中产生局部的电场集中的缘故。
试样号20也是可靠性较低的结果。这可以认为是由于Ca量x大于0.02，不易成为细致化结构，机械强度不好的缘故。
关于试样号21，Re量y小于0.002，其结果可靠性较低。另外，试样号22也是可靠性较低的结果。这可以认为是由于Re量y大于0.1，烧结后产生了偏析的缘故。
关于试样号23，M量z小于0.001，也是可靠性低的结果。另外，试样号24也是可靠性较低的结果。这可以认为是由于M量z大于0.05，烧结后产生了偏析的缘故。
[实验例2]
在实验例2中评价了杂质的影响。在层叠陶瓷电容器的原料制作工序等中，有Sr、Zr、Hf、Zn、Na、Ag、Pd以及Ni等作为杂质混入的可能性。这些杂质可能存在于占据结晶粒子内以及结晶粒子间的晶界中。另外，在层叠陶瓷电容器的烧结工序等中，内部电极成分有可能在占据电介质陶瓷中的晶界以及结晶粒子间的晶界中扩散并存在。实验例2对这些杂质的影响进行了评价。
(A)陶瓷粉末的制作
除了在实验例1的试样号13的组成中加入了表3中示出的杂质成分以外，用与实验例1同样的方法制作了陶瓷粉末。
[表3]
试样编号 杂质成分详情
31 0.4Hf、0.02Zn
32 0.25Sr、0.1Na
33 0.5Zr、0.02Ag、0.01Ni
34 0.05Ni、0.1Na
35 0.2Na、0.02Hf
36 0.4Pd、3.2Ni
37 1.1Ag、1.0Zr
38 0.1Pd、0.05Sr
39 0.03Ag、0.05Pd
40 1.3Ni
(B)层叠陶瓷电容器的制作
使用上述陶瓷粉末，用与实验例1同样的方法制作了层叠陶瓷电容器。
(C)特性评价
对于所得到的层叠陶瓷电容器，用与实验例1同样的方法评价了各种特性。在表4中出示了高温负荷寿命试验的结果。
[表4]
(D)考察
由表4可知，即便在混入了杂质的试样31～40中的任意一个中，在电场强度为6.3kV/mm和12.6kV/mm的两方中，高温负荷寿命试验的不良个数都是0，显示出了较高的可靠性。另外，即便试样31～40中的任意一个都是平均粒径在20nm以上且150nm以下。
符号说明：
1    层叠陶瓷电容器
2    电介质层
3、4  内部电极
5     层叠体
6，7  外部电极

Claims (6)

1.一种电介质陶瓷，其含有用通式(Ba1-x-yCaxRey)(Ti1-zMz)O3表示并且满足0≤x≤0.2、0.002≤y≤0.1、0.001≤z≤0.05的范围的化合物作为主成分，所述电介质陶瓷的结晶粒子的平均粒径为20nm以上且150nm以下，
其中，Re是从La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu以及Y中选择的至少一种以上的元素，M是从Mg、Mn、Al、Cr以及Zn中选择的至少一种以上的元素。
2.根据权利要求1所述的电介质陶瓷，其中，所述平均粒径为20nm以上且不足100nm。
3.一种电介质陶瓷电容器，其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电介质层、和沿着所述电介质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，其特征在于，
所述电介质层由权利要求1或2所述的电介质陶瓷形成。
4.一种电介质陶瓷的制造方法，其具备如下的工序：
准备陶瓷粉末的工序，所述陶瓷粉末含有用通式(Ba1-x-yCaxRey)(Ti1-zMz)O3表示并且满足0≤x≤0.2、0.002≤y≤0.1、0.001≤z≤0.05的范围的化合物作为主成分，其中，Re是从La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu以及Y中选择的至少一种以上的元素，M是从Mg、Mn、Al、Cr以及Zn中选择的至少一种以上的元素，
对所述陶瓷粉末进行成形，获得成形体的工序，
对所述成形体进行烧结，获得结晶粒子的平均粒径为20nm以上且150nm以下的电介质陶瓷的工序。
5.根据权利要求4所述的电介质陶瓷的制造方法，其中，所述平均粒径为20nm以上且不足100nm。
6.一种电介质陶瓷电容器的制造方法，其特征在于，具备权利要求4或5所述的电介质陶瓷的制造方法。
CN2011800420021A 2010-09-17 2011-08-23 电介质陶瓷、层叠陶瓷电容器及其制造方法 Pending CN103080044A (zh)

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