CN101550002A - 电介质陶瓷组合物、电子部件及其制造方法 - Google Patents

电介质陶瓷组合物、电子部件及其制造方法 Download PDF

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CN101550002A
CN101550002A CNA2009101325226A CN200910132522A CN101550002A CN 101550002 A CN101550002 A CN 101550002A CN A2009101325226 A CNA2009101325226 A CN A2009101325226A CN 200910132522 A CN200910132522 A CN 200910132522A CN 101550002 A CN101550002 A CN 101550002A
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dielectric
dielectric layer
ceramic composition
formula
molar part
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CN101550002B (zh
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野中智明
高石哲男
岩泽健太
佐佐木洋
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TDK Corp
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TDK Corp
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    • H01G4/1236—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates
    • H01G4/1245—Ceramic dielectrics characterised by the ceramic dielectric material based on zirconium oxides or zirconates containing also titanates
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Abstract

本发明涉及电介质陶瓷组合物、电子部件及其制造方法。本发明涉及一种电介质陶瓷组合物，其含有含[(Ca1－xSrx)O]m[(Zr1－y－z－αTiyHfzMnα)O2](其中，0.991≤m≤1.010、0≤x≤1、0≤y≤0.1、0＜z≤0.02、0.002＜α≤0.05)所示组成的电介质氧化物的主要成分，以及相对于主要成分100摩尔份为0.1～0.5摩尔份的Al2O3和0.5～5.0摩尔份的SiO2。本发明的目的在于提供具有[(CaSr)O]m[(ZrTiHfMn)O2]系电介质陶瓷组合物所具有的优异的各种特性，并且即使使电介质层的厚度变薄例如为 2μm以下，也能够防止破裂产生的电介质陶瓷组合物。

Description

电介质陶瓷组合物、电子部件及其制造方法
技术领域
本发明涉及电介质陶瓷组合物、电子部件及其制造方法，更详细地说，涉及适合用于以贱金属为内部电极的层压陶瓷电容器等电子部件的非还原性温度补偿用电介质陶瓷组合物。
背景技术
层压陶瓷电容器作为电子部件被广泛利用，在一台电子设备中使用的个数达到多个。层压陶瓷电容器通常采用片材法或印刷法等将内部电极层用的浆料与电介质层用的浆料层压并同时烧成来制造。
然而，以往的层压陶瓷电容器等中使用的电介质陶瓷材料，具有在还原性气氛下进行烧成时被还原、半导体化的性质。因此，作为内部电极的材料，使用在电介质陶瓷材料烧成温度下不熔融、而且不会使电介质陶瓷材料半导体化的即使在高氧分压下烧成也不被氧化的Pd等贵金属。
然而，由于Pd等贵金属昂贵，因此在谋取层压陶瓷电容器的低价格化方面成为很大的障碍。因此，作为内部电极，使用比较廉价的Ni或Ni合金等贱金属正在成为主流。
然而，使用贱金属作为内部电极层的导电材料时，如果在大气中进行烧成则内部电极层氧化。因此，必需在还原性气氛中进行电介质层和内部电极层的同时烧成。
然而，在还原性气氛中进行烧成时，电介质层被还原，绝缘电阻降低。因此，提出了非还原性的电介质材料。然而，使用非还原性电介质材料的层压陶瓷电容器，若使电介质层变薄(5μm以下)，则在可靠性试验中存在绝缘电阻(IR)降低的问题。
此外，静电电容的温度变化少，也就是说电容温度系数小，而且在-150℃～+150ppm/℃的范围内能够任意控制的温度补偿用电介质陶瓷组合物的要求高，可提供能够如此控制的低温度系数的电容器的陶瓷材料成为必须。
应这样的要求，专利文献1(WO2004/063119小册子)公开了“电介质陶瓷组合物，其特征在于，至少含有含[(CaxSr1- x)O]m[(TiyZr1-y-zHfz)O2]所示组成的电介质氧化物的主要成分，以及含有Mn氧化物和/或Al氧化物的第1副成分和玻璃成分，所述主要成分中所含的式中的表示组成摩尔比的符号m、x、y和z具有如下关系，即，0.90≤m≤1.04、0.5≤x＜1、0.01≤y≤0.10、0＜z≤0.20”。进而，根据专利文献1的记载，所述电介质陶瓷组合物中可以添加Mn氧化物，其添加量相对于主要成分100摩尔％，换算成MnO2为0.2～5摩尔％。
根据专利文献1的电介质陶瓷组合物，可以实现高可靠性的非还原性电介质陶瓷组合物，其适合用作以Ni等贱金属为内部电极的层压陶瓷电容器等的电介质层、能够在1300℃以下烧结、静电电容的温度系数小、而且在-15～+150ppm/℃的范围内能够任意控制、在25℃的绝缘电阻在1×1013Ω以上、比介电常数、介质损耗角正切(tanδ)的频率依存性少、即使使电介质层变薄绝缘电阻的加速寿命时间也长、而且绝缘电阻的不良率少。
发明内容
然而，在电子设备的小型化不断发展的现状下，层压陶瓷电容器中电介质层的进一步薄层化备受期待。在上述专利文献1的电介质陶瓷组合物中，虽然在形成厚5μm左右的电介质层时不会特别产生问题，但是如果使电介质层的厚度为2μm以下时，则零散地观察到破裂的发生。
究其其原因，虽然不受限于任何理论，但本发明人等获得了如下的见解。
专利文献1的电介质陶瓷组合物的主要成分是ABO3型的钙钛矿样化合物。其中，明确了A点原子过小(即m值小)且Mn氧化物的添加量多时，B点原子的一部分作为氧化物析出。A点原子减少时，与之相应地B点原子的量也受限。此时，添加Mn氧化物时，Mn取代B点原子。其结果是，过剩的B点原子，特别是Zr作为ZrO2在电介质层析出。电介质层的厚度厚时，电介质层的厚度会吸收(缓冲)因析出的ZrO2导致的体积变动，不会产生破裂。然而，随着电介质层厚度的变薄，电介质层的缓冲作用降低，ZrO2析出所导致的体积变动的结果是，在电介质层产生破裂。
此外，专利文献1的电介质陶瓷组合物添加有玻璃成分作为烧结助剂。玻璃成分在较低的温度就熔解，是用于在低温下进行烧结的有效成分。然而，在特别低温的区域内，容易形成源于玻璃成分的异相。形成异相时，由异相导致的体积变动的结果是，有时在电介质层产生破裂。
因此，在构成主要成分的、Mn在B点固熔的[(CaSr)O]m[(ZrTiHf)O2]、即[(CaSr)O]m[(ZrTiHfMn)O2]中，只要是即使Mn固熔也不会发生ZrO2析出的组成区域，都有能够防止破裂产生的可能性。
此外，如果使用在更高温度下作用、难以形成异相的烧结助剂来代替在较低温度下作用的玻璃系烧结助剂，就有能够防止破裂产生的可能性。基于上述见解，本发明人等想到了下述发明。
为了解决上述课题，本发明包括如下要点。
[1]电介质陶瓷组合物，含有含(2)式所示组成的电介质氧化物的主要成分，以及相对于主要成分100摩尔份为0.1～0.5摩尔份的Al2O3和0.5～5.0摩尔份的SiO2，
[(Ca1-xSrx)O]m[(Zr1-y-z-αTiyHfzMnα)O2]...(2)
其中，(2)式中，m、x、y、z和α满足：
0.991≤m≤1.010
0≤x≤1
0≤y≤0.1
0＜z≤0.02
0.002＜α≤0.05。
[2]电介质陶瓷组合物的制造方法，包括如下工序：
以总组成满足(1)式的比例混合CaCO3、SrCO3、ZrO2、TiO2、HfO2，准备第1混合粉末的工序；
[(Ca1-xSrx)O]m[(Zr1-y-zTiyHfz)O2]...(1)
其中，(1)式中，m、x、y和z满足：
0.993≤m≤1.055
0≤x≤1
0≤y≤0.1
0＜z≤0.02，
将第1混合粉末在1100～1300℃进行热处理，得到第1烧成物的第1热处理工序；
以总组成满足(2)式所示的电介质氧化物组成的比例准备锰化合物，并且准备相对于(2)式所示的电介质氧化物100摩尔份为0.1～0.5摩尔份的Al2O3和0.5～5.0摩尔份的SiO2，将它们与所得的第1烧成物混合，准备第2混合粉末的工序；
[(Ca1-xSrx)O]m[(Zr1-y-z-αTiyHfzMnα)O2]...(2)
其中，(2)式中，m、x、y、z和α满足：
0.991≤m≤1.010
0≤x≤1
0≤y≤0.1
0＜z≤0.02
0.002＜α≤0.05，
将第2混合粉末在1150～1300℃进行热处理的第2热处理工序。
[3]电子部件，其具有电介质层，其特征在于，所述电介质层由[1]所述的电介质陶瓷组合物构成。
[4]电子部件，内部电极与电介质层交替地层压，其特征在于，所述电介质层由[1]所述的电介质陶瓷组合物构成。
[5]如[4]所述的电子部件，所述内部电极至少含有镍。
根据本发明，提供具有[(CaSr)O]m[(ZrTiHfMn)O2]系电介质陶瓷组合物所具有的优异的各种特性，并且即使使电介质层的厚度变薄例如为2μm以下，也能够防止破裂产生的电介质陶瓷组合物。
附图说明
图1是本发明一种实施方式所述层压陶瓷电容器的剖面图。
具体实施方式
以下，参照包括其最佳方式的附图所示的实施方式详细说明本发明。
层压陶瓷电容器
如图1所示，作为本发明一种实施方式的电子部件的层压陶瓷电容器1，具有交替地层压有电介质层2和内部电极层3的构成的电容器元件本体10。在该电容器元件本体10的两端部，形成有与在元件本体10的内部交替配置的内部电极层3分别导通的一对外部电极4。电容器元件本体10的形状没有特别限制，通常为长方体状。此外，其尺寸也没有特别限制，根据用途设为适当的尺寸即可，但通常为(0.4～5.6mm)×(0.2～5.0mm)×(0.2～1.9mm)左右。
内部电极层3以各端面在电容器元件本体10的相对两端部的表面交替地露出的方式层压。一对外部电极4形成于电容器元件本体10的两端部，与交替配置的内部电极层3的露出端面连接，从而构成电容器电路。
电介质层2
(电介质陶瓷组合物)
电介质层2含有本发明的电介质陶瓷组合物。
本发明的电介质陶瓷组合物含有含(2)式([(Ca1-xSrx)O]m[(Zr1-y-z-αTiyHfzMnα)O2])所示组成的电介质氧化物的主要成分、以及Al2O3和SiO2。
其中，(2)式中，表示组成摩尔比的符号m、x、y、z和α具有如下关系：
0.991≤m≤1.010，优选0.995≤m≤1.005，
0≤x≤1，优选0≤x≤0.5，
0≤y≤0.1，优选0≤y≤0.05，
0＜z≤0.02，优选0＜z≤0.01，
0.002＜α≤0.05，优选0.005＜α≤0.03。
主要成分的组成式中的m值过小时，存在静电电容和tanδ的频率依存性变大且ZrO2析出的倾向，过大时，存在在1300℃的烧成温度下难以烧成的倾向。
主要成分的组成式中的x值没有特别限定，随着其变大，存在静电电容和tanδ的频率依存性变大的倾向，随着其变小，存在烧结性降低的倾向。因此，考虑目标电介质特性和烧结性后，优选选择上述的优选范围。
此外，组成式中的y的下限没有特别限定，随着其变小，存在烧结性降低的倾向，过大时，存在静电电容和tanδ的频率依存性变大且异相析出从而诱发破裂的倾向。
进而，组成式中的z的值过小时，存在烧结性降低的倾向且存在静电电容和tanδ的频率依存性变大的倾向，过大时，存在异相析出从而诱发破裂的倾向。
此外，组成式中的α的值过小时，存在烧结性降低的倾向，过大时，存在ZrO2析出从而诱发破裂的倾向。
本发明的电介质陶瓷组合物，含有所述主要成分以及Al2O3和SiO2。以相对于所述主要成分100摩尔份为0.1～0.5摩尔份、优选0.1～0.3摩尔份的比例含有Al2O3。以相对于所述主要成分100摩尔份为0.5～5.0摩尔份、优选1.0～2.0摩尔份的比例含有SiO2。
此外，Al2O3和SiO2的添加量过少时，绝缘电阻和烧结性降低，过多时在电介质层内或层间析出源于铝或硅的异相，有时诱发破裂。
进而，本发明的电介质陶瓷组合物中除了上述成分之外还可以配合各种副成分。优选相对于所述主要成分100摩尔份含有换算成V2O5的V氧化物0～2.5摩尔份(其中，不包括0)，进一步优选0.5～2.5摩尔份。通过添加V氧化物，可以提高IR加速寿命。其添加量过少时，存在难以获得IR加速寿命的提高效果的倾向，过多时，存在烧结性降低的倾向。
此外，优选相对于主要成分100摩尔份含有包括Sc和Y的稀土类元素中的至少一种0.02～1.5摩尔份，进一步优选0.10～1.0摩尔份。另外，稀土类元素种除了Sc和Y以外，还含有由镧系元素构成的17种元素。
此外，优选相对于主要成分100摩尔份含有Nb、Mo、Ta、W和Mg中的至少一种0.02～1.5摩尔份，进一步优选0.10～1.0摩尔份。这些元素可以与所述稀土类元素组合含于电介质陶瓷组合物中。此时，总含量优选相对于所述主要成分100摩尔份为0.02～1.5摩尔份，进一步优选0.10～1.0摩尔份。
通过添加这些元素(包括稀土类元素)的氧化物，可以抑制静电电容的温度系数和tanδ的频率依存性。这些氧化物的添加量过少时，存在难以获得静电电容的温度系数和tanδ的频率依存性的抑制效果的倾向，添加量过多时，存在烧结温度升高的倾向。
另外，图1所示的电介质层2的层压数或厚度等各种条件可以根据目的或用途来适当确定。然而，本发明的电介质陶瓷组合物由于即使在电介质层特别薄的情况下也能够抑制破裂的发生，因此电介质层的厚度优选为1.0～3.0μm左右。此外，电介质层2优选由晶粒和晶界相构成，且电介质层2的晶粒的平均粒径在1.0μm以下。
(电介质陶瓷组合物的制造方法)
本发明的电介质陶瓷组合物，通过将以规定比例含有CaCO3、SrCO3、ZrO2、TiO2、HfO2的第1混合粉末在1100～1300℃进行热处理，得到第1烧成物后，向第1烧成物中以规定比例混合锰化合物、Al2O3和SiO2，得到第2混合粉末，将该第2混合粉末在1150～1300℃进行热处理而得到。
作为第1混合粉末原料的CaCO3、SrCO3、ZrO2、TiO2、HfO2没有特别限定，可使用各种市售原料粉末。从进行均匀混合、提高反应性的观点出发，优选原料粉末的粒子性状为微粒，各原料粉末的平均粒径(D50)优选在0.01～0.5μm，进一步优选0.01～0.2μm，特别优选0.01～0.05μm的范围，且其BET比表面积优选在5m2/g以上，进一步优选10m2/g以上，特别优选20m2/g以上。
为了得到第1混合粉末，以金属原子比满足(1)式的比例混合所述原料粉末。
[(Ca1-xSrx)O]m[(Zr1-y-zTiyHfz)O2]...(1)
其中，(1)式中，m、x、y和z满足：
0.993≤m≤1.055，优选1.009≤m≤1.040，
0≤x≤1，优选0≤x≤0.5，
0≤y≤0.1，优选0≤y≤0.05，
0＜z≤0.02，优选0＜z≤0.01。
第1混合粉末的制备方法没有特别限定，可以采用使用球磨机的湿式法等常规方法。将得到的第1混合粉末干燥后，在规定条件下进行热处理(第1热处理工序)，可得到第1烧成物。
第1热处理工序的热处理温度为1100℃～1300℃，优选1200～1300℃，进一步优选1220～1270℃，上述原料粉末进行反应，使其反应充分的时间以生成上述(1)式所示组成的第1烧成物。因此，热处理时间依赖于热处理温度，虽然没有特别限定，但是1～4小时左右是适当的。热处理气氛没有特别限定，可以是大气气氛，还可以是氮气等气氛或者减压或真空中。
热处理温度过高，或者热处理时间过长时，则原料粉末粒生长，有时生成巨大粒子。这样的巨大粒子生成时，有时最终得到的电介质层的薄层化变难，因此优选采用平均粒径(D50)为0.2～0.5μm左右的第1烧成物生成的条件。
通过如上述的第1热处理工序，得到第1烧成物。
接着，向得到的第1烧成物中以规定比例混合锰化合物、Al2O3和SiO2，得到第2混合粉末。
以与第1烧成物的总金属组成比满足上述(2)式所示的电介质氧化物组成的比例使用锰化合物。作为锰化合物，使用MnCO3、MnO2、MnO3/2、MnO4/3等。
可以按相对于上述(2)式所示的电介质氧化物100摩尔份为0.1～0.5摩尔份、优选0.1～0.3摩尔份的比例使用Al2O3。
可以按相对于上述(2)式所示的电介质氧化物100摩尔份为0.5～5.0摩尔份、优选1.0～2.0摩尔份的比例使用SiO2。
作为第2混合粉末原料的锰化合物、Al2O3和SiO2没有特别限定，可使用各种市售原料粉末。从进行均匀混合、提高反应性的观点出发，优选原料粉末的粒子性状为微粒，各原料粉末的平均粒径(D50)优选在0.1～1.5μm，进一步优选0.1～1.0μm，特别优选0.1～0.5μm的范围，且其BET比表面积优选在10m2/g以上，进一步优选20m2/g以上，特别优选30m2/g以上。
第2混合粉末的制备方法没有特别限定，可以采用使用球磨机的湿式法等常规方法。将得到的第2混合粉末干燥后，在规定条件下进行热处理(第2热处理工序)，可得到本发明的电介质陶瓷组合物。
第2热处理工序的热处理温度为1150℃～1300℃，优选1150～1250℃，进一步优选1150～1200℃，上述原料粉末进行反应、使其反应充分的时间以生成上述(2)式所示组成的电介质氧化物为主要成分的电介质陶瓷组合物。因此，热处理时间依赖于热处理温度，虽然没有特别限定，但是1～4小时左右是适当的。热处理气氛没有特别限定，如后所述，形成以Ni等贱金属为电极层的层压陶瓷电容器的电介质层时，优选在还原气氛下烧成。
制造具有包含本发明的电介质陶瓷组合物的电介质层的层压陶瓷电容器时，制备第2混合粉末后，添加粘合剂和载体，进行浆料化。使用所得到的浆料，制造生片材，并在其上形成电极浆料层，然后，在上述第2热处理条件下烧成，由此得到具有包含本发明的电介质陶瓷组合物的电介质层的层压陶瓷电容器。生片材和层压陶瓷电容器的制造的详细内容在后面叙述。
内部电极层3
内部电极层3中含有的导电材料没有特别限定，由于电介质层2的构成材料具有耐还原性，因此可以使用贱金属。作为用作导电材料的贱金属，优选Ni或Ni合金。作为Ni合金，优选选自Mn、Cr、Co和Al中一种以上的元素与Ni的合金，合金中的Ni含量优选为95重量％以上。另外，在Ni或Ni合金中，可以含有P、Fe、Mg等各种微量成分0.1重量％左右以下。
内部电极层的厚度可以根据用途等来适当确定，优选通常优选为0.5～5μm，特别优选为1～2.5μm左右。
外部电极4
外部电极4中含有的导电材料没有特别限定，通常使用Cu或Cu合金或者Ni或Ni合金等。另外，自然也可以使用Ag或Ag-Pd合金等。另外，在本实施方式中，使用廉价的Ni、Cu或它们的合金。外部电极的厚度可以根据用途等来适当确定，通常优选为10～50μm左右。
层压陶瓷电容器的制造方法
使用本发明电介质陶瓷组合物的层压陶瓷电容器，与以往的层压陶瓷电容器同样地通过使用浆料的通常的印刷法或片材法制作生片，对其进行烧成后，将外部电极印刷或转印后进行烧成，由此来制造。以下，对制造方法进行具体说明。
首先，分别制造电介质层用浆料、内部电极用浆料、外部电极用浆料。
电介质层用浆料
电介质层用浆料可以是将电介质原料和有机载体混炼而成的有机系涂料，还可以是水系涂料。
电介质原料中含有上述的第1烧成物、锰化合物、Al2O3和SiO2以及根据需要而添加的副成分。电介质原料中的各化合物的配合比例与上述第2混合粉末相同，而且这些粉末原料可以适当粉碎后使用。
所谓有机载体，是指将粘合剂溶解于有机溶剂中而成的物质，有机载体中使用的粘合剂没有特别限定，可以从乙基纤维素、聚乙烯醇缩丁醛等通常的各种粘合剂中适当选择。此外，此时使用的有机溶剂也没有特别限定，可以根据利用印刷法或片材法等的方法从萜品醇、丁基卡必醇、丙酮、甲苯等有机溶剂中适当选择。
此外，所谓水溶系涂料，是指在水中溶解水溶性粘合剂、分散剂等而成的物质，水溶系粘合剂没有特别限定，可以从聚乙烯醇、纤维素、水溶性丙烯酸树脂、乳液等中适当选择。
内部电极用浆料、外部电极用浆料
内部电极用浆料通过将上述包含各种导电性金属或合金的导电材料或者烧成后成为上述导电材料的各种氧化物、有机金属化合物、树脂酸酯等与上述的有机载体混炼来制备。此外，外部电极用浆料也与该内部电极用浆料同样地制备。
上述各浆料的有机载体的含量没有特别限定，通常的含量例如将粘合剂设为1～5重量％左右、将溶剂设为10～50重量％左右即可。此外，各浆料中根据需要可以含有选自各种分散剂、增塑剂、电介质、绝缘体等的添加物。
使用印刷法时，将电介质浆料和内部电极用浆料层压印刷在聚对苯二甲酸乙二醇酯等的基板上，切断成规定形状后从基板剥离，由此制成生片。与此相对，使用片材法时，使用电介质浆料形成生片材，在其上印刷内部电极浆料后将他们层压，由此制成生片。
接着，对该生片进行脱粘合剂处理并进行烧成。
脱粘合剂处理
脱粘合剂处理在通常的条件下进行即可，尤其是使用Ni或Ni合金等贱金属作为内部电极层的导电材料时，在空气氛围中，将升温速度设为5～300℃/小时、更优选10～100℃/小时，将保持温度设为180～400℃、更优选200～300℃，将温度保持时间设为0.5～24小时、更优选5～20小时。
正式烧成(第2热处理工序)
生片的烧成气氛可以根据内部电极层用浆料中的导电材料种类来适当确定，但使用Ni或Ni合金等贱金属作为导电材料时，优选为还原气氛，优选将烧成气氛的氧分压设为10-10～1Pa、更优选设为10-7～1Pa(10-12～10-5atm)。烧成时的氧分压过低时，存在内部电极的导电材料产生异常烧结而中断的倾向，氧分压过高时，存在内部电极被氧化的倾向。
正式烧成(第2热处理工序)的保持温度如上所述，为1150～1300℃，优选为1150～1250℃，进一步优选为1150～1200℃。保持温度过低时，存在致密化变得不充分的倾向，保持温度过高时，由于内部电极的异常烧结所致的电极中断或内部电极材质的扩散，因而存在电容温度特性恶化的倾向。
作为除此之外的烧成条件，优选将升温速度设为50～500℃/小时、更优选200～300℃/小时，将温度保持时间设为0.5～8小时、更优选1～3小时，将冷却速度设为50～500℃/小时、更优选200～300℃/小时，将烧成气氛设为还原性气氛，作为气氛气体，优选例如将氮气和氢气的混合气体加湿后使用。
在还原性气氛下进行烧成时，优选对电容器片的烧结体施行退火(热处理)。
退火(热处理)
退火是用于将电介质层再氧化的处理，由此可以增加绝缘电阻。退火气氛的氧分压优选为10-4Pa以上，更优选1～10-3Pa(10-5～10-8atm)。氧分压过低时，存在电介质层2的再氧化变难的倾向，氧分压过高时，存在内部电极层3被氧化的倾向。
退火时的保持温度在1150℃以下，更优选500～1100℃。保持温度过低时，存在电介质层的再氧化变得不充分，绝缘电阻恶化、其加速寿命也变短的倾向。此外，保持温度过高时，存在不仅内部电极被氧化，电容降低、而且与电介质基质反应、电容温度特性、绝缘电阻及其加速寿命恶化的倾向。另外，退火可以仅由升温过程和降温过程构成。这种情况下，温度保持时间为零，保持温度与最高温度同义。
作为除此之外的退火条件，优选将温度保持时间设为0～20小时、更优选6～10小时，将冷却速度设为50～500℃/小时、更优选100～300℃/小时，作为退火的气氛气体，优选例如将氮气加湿后使用。
另外，与上述烧成相同，在所述脱粘合剂处理和退火工序中，为了加湿氮气或混合气体，可以使用例如加湿器等，此时的水温优选为5～75℃。
此外，这些脱粘合剂处理、烧成和退火可以连续进行，也可以相互独立地进行。将它们连续进行时，更优选在脱粘合剂处理后不是进行冷却，而是变更气氛，接着升温到烧成时的保持温度进行烧成，接着进行冷却，达到退火的保持温度后变更气氛进行退火处理。另一方面，将它们独立地进行时，对于烧成，优选在氮气或经加湿的氮气气氛下升温到脱粘合剂处理时的保持温度，然后变更气氛进一步继续升温，冷却到退火的保持温度后，优选再变更成氮气或经加湿的氮气气氛来继续冷却。此外，对于退火，可以在氮气气氛下升温到保持温度后变更气氛，也可以将整个退火工序设为经加湿的氮气气氛。
在如此得到的电容器烧成体上，采用例如滚筒抛光或喷砂来施行端面抛光，对外部电极用浆料进行印刷或转印并进行烧成，形成外部电极4。外部电极用浆料的烧成条件优选设为例如在经加湿的氮气和氢气的混合气体中在600～800℃进行10分钟～1小时左右。接着，根据需要在外部电极4的表面采用镀敷等形成被覆层(垫层)。
如此制作的本实施方式的陶瓷电容器1通过焊接等实际安装到印刷基板上，用于各种电子设备。
另外，本发明并不限于上述实施方式，可以在本发明的范围内进行各种改变。
例如，在上述的实施方式中，作为本发明的电子部件例示出层压陶瓷电容器，但是作为本发明的电子部件，并不限于层压陶瓷电容器，只要具有由上述组成的电介质陶瓷组合物构成的电介质层，什么都可以。
以下，基于详细的实施例进一步说明本发明，但本发明并不限于这些实施例。
实施例
首先，作为用于制作第1混合粉末的起始原料，分别准备平均粒径0.1～1.5μm的原料粉末(CaCO3、SrCO3、ZrO2、TiO2、HfO2)。
称量这些原料，使其成为下述表1所示的第1热处理工序后的组成(除Mn以外的主要成分组成)，然后向该原料中加入作为介质的水并用球磨机混合20小时。然后，使该混合物干燥，在1250℃和2小时的条件下对该干燥物(第1混合粉末)进行热处理，得到第1烧成物(第1热处理工序)。然后，用球磨机将得到的第1烧成物湿式粉碎并进行干燥。
接着，称量第1烧成物和平均粒径0.1～1.5μm的原料粉末(MnCO3、Al2O3、SiO2)，使得成为下述表1所示的第2热处理工序后的组成，然后向该原料中加入作为介质的水并用球磨机混合5小时。然后，使该混合物干燥，得到第2混合粉末。
用球磨机将如此得到的干燥后的第2混合粉末100重量份、丙烯酸树脂4.8重量份、二氯甲烷40重量份、乙酸乙酯20重量份、矿油精6重量份和丙酮4重量份混合并浆料化，得到电介质层用浆料。
接着，用三辊磨将Ni粒子100重量份、有机载体(在丁基卡必醇92重量份中溶解乙基纤维素8重量份而成的物质)40重量份和丁基卡必醇10重量份混炼并浆料化，得到内部电极层用浆料。
接着，将Cu粒子100重量份、有机载体(在丁基卡必醇92重量份中溶解乙基纤维素树脂8重量份而成的物质)35重量份和丁基卡必醇7重量份混炼并浆料化，得到外部电极层用浆料。
接着，使用上述电介质层用浆料在PET膜上形成厚2.5μm的生片材，在生片材上印刷内部电极层用浆料后，从PET膜上剥离生片材。接着，将这些生片材和保护用生片材(没有印刷内部电极层用浆料的)层压，压合后得到生坯层压体。具有内部电极的片材的层压数为100层。
此外，另外使用上述电介质层用浆料在PET膜上形成厚6.5μm的生片材，在生片材上印刷内部电极层用浆料后，从PET膜上剥离生片材。接着，将这些生片材和保护用生片材(没有印刷内部电极层用浆料的)层压，压合后得到生坯层压体。具有内部电极的片材的层压数为100层。
接着，将生坯层压体切断成规定尺寸，得到生片，进行脱粘合剂处理、烧成(第2热处理工序)和再氧化处理(退火)，得到层压陶瓷烧成体。脱粘合剂处理在升温时间为30℃/小时、保持温度为260℃、保持时间为8小时、空气气氛的条件下进行。烧成(第2热处理工序)在升温时间为200℃/小时、表2和表3所示的保持温度、保持时间为2小时、冷却速度为300℃/小时、经加湿的N2+H2混合气体气氛(氧分压调节为1×10-8～1×10-6Pa)的条件下进行。再氧化处理在保持温度为750℃、温度保持时间为2小时、冷却速度为300℃/小时、经加湿的N2气体气氛(氧分压为1×10-2～1Pa)的条件下进行。另外，烧成(第2热处理工序)和退火时的气氛气体的加湿使用水温设为35℃的加湿器。
接着，采用喷砂抛光层压陶瓷烧成体的端面后，将外部电极用浆料转印到端面，在经加湿的N2+H2气氛中，在800℃烧成10分钟形成外部电极，得到图1所示构成的层压陶瓷电容器的样品。接着在外部电极表面形成Sn镀膜、Ni镀膜，得到测定用样品。
如此得到的各样品的尺寸是3.2mm×1.6mm×1.6mm，内部电极层夹持的电介质层数为100，内部电极层的厚度为2μm。此外，使用厚2.5μm的生片材时电介质层的厚度为1.5μm，使用厚6.5μm的生片材时电介质层的厚度为5.0μm。对各样品进行下述特性的评价。
比介电常数(εr)、绝缘电阻(IR)
对于电容器样品，在基准温度25℃下使用数码LCR测量计(YHP社制4274A)，在频率1kHz、输入信号水平(测定电压)1Vrms的条件下，测定静电电容。接着，由得到的静电电容、电容器样品的电极尺寸以及电极间距离算出比介电常数(无单位)。
然后，使用绝缘电阻计(ADVANTEST公司制R8340A)，在25℃对电容器样品施加DC50V的电压60秒后，测定绝缘电阻IR。具有厚1.5μm的电介质层的电容器的结果示于表2中。具有厚5.0μm的电介质层的电容器的结果示于表3中。
静电电容的温度系数(τC)
对于电容器样品，使用LCR测量计，在1kHz、1V的电压下测定静电电容，由25℃的静电电容(C25)和125℃的静电电容(C 125)，根据下式算出静电电容的温度系数(τC)。结果示于表2和表3。
τC＝{(C125-C25)/C25}×(1/(125-25))
高温负荷寿命(绝缘电阻的加速寿命)
对于电容器样品，在200℃保持施加70V/μm的直流电压的状态，测定绝缘电阻(LogIR)达到6以下的时间，作为高温负荷寿命。该高温负荷寿命对20个电容器样品进行，通过测定平均寿命时间来进行评价。结果示于表2和表3。
结晶平均粒径
切断电容器样品，抛光其断面，对抛光面实施化学蚀刻或热蚀刻处理后，用扫描型电子显微镜观察断面，采用图像分析处理软件，算出构成电介质层的晶粒的平均粒径。结果示于表2和表3。
发生破裂的个数
观察100个相同组成的样品的外观，计数发生破裂的样品个数。结果示于表2和表3。
表1
Figure A20091013252200191
表2
Figure A20091013252200201
表3
Figure A20091013252200211
另外，在表1～3中，对样品编号的数字加上※的表示超出本发明规定范围之外的样品编号。其他表中也同样。此外，对于样品3，为了使对比容易，在样品11与12之间以及样品16与17之间重新纪录。此外，斜体表示超出本发明规定范围之外的数值。
如表2和表3所示，可以确认，如果采用满足本发明规定的电介质陶瓷组合物，即使电介质层的厚度变薄，破裂产生也得到抑制。
比较例
在上述实施例中，制备第2混合粉末时，以相对于主要成分100摩尔为1.5摩尔份的量添加作为玻璃成分的[(Ba0.6Ca0.4)O]SiO2来代替SiO2，除此之外进行同样的操作。
将主要成分组成和添加成分的添加量示于表4，结果示于表5和表6。
表4
Figure A20091013252200221
表5
Figure A20091013252200222
表6
Figure A20091013252200223
如表5和表6所示，配合玻璃成分来代替SiO2时，虽然电介质层的厚度厚时破裂产生得到抑制，但是电介质层的厚度变薄时零散地观察到破裂。

Claims (5)

1.电介质陶瓷组合物，其含有含(2)式所示组成的电介质氧化物的主要成分，以及相对于主要成分100摩尔份为0.1～0.5摩尔份的Al2O3和0.5～5.0摩尔份的SiO2，
[(Ca1-xSrx)O]m[(Zr1-y-z-αTiyHfzMnα)O2]...(2)
其中，(2)式中，m、x、y、z和α满足：
0.991≤m≤1.010
0≤x≤1
0≤y≤0.1
0＜z≤0.02
0.002＜α≤0.05。
2.电介质陶瓷组合物的制造方法，其包括如下工序：
以总组成满足(1)式的比例混合CaCO3、SrCO3、ZrO2、TiO2、HfO2，准备第1混合粉末的工序；
[(Ca1-xSrx)O]m[(Zr1-y-zTiyHfz)O2]...(1)
其中，(1)式中，m、x、y和z满足：
0.993≤m≤1.055
0≤x≤1
0≤y≤0.1
0＜z≤0.02，
将第1混合粉末在1100～1300℃进行热处理，得到第1烧成物的第1热处理工序；
以总组成满足(2)式所示的电介质氧化物组成的比例准备锰化合物，并且准备相对于(2)式所示的电介质氧化物100摩尔份为0.1～0.5摩尔份的Al2O3和0.5～5.0摩尔份的SiO2，将它们与所得的第1烧成物混合，准备第2混合粉末的工序；
[(Ca1-xSrx)O]m[(Zr1-y-z-αTiyHfzMnα)O2]...(2)
其中，(2)式中，m、x、y、z和α满足：
0.991≤m≤1.010
0≤x≤1
0≤y≤0.1
0＜z≤0.02
0.002＜α≤0.05，
将第2混合粉末在1150～1300℃进行热处理的第2热处理工序。
3.电子部件，其为具有电介质层的电子部件，其特征在于，所述电介质层由权利要求1所述的电介质陶瓷组合物构成。
4.电子部件，其为内部电极与电介质层交替地层压的电子部件，其特征在于，所述电介质层由权利要求1所述的电介质陶瓷组合物构成。
5.如权利要求4所述的电子部件，所述内部电极至少含有镍。
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