CN101333108A - 电介质陶瓷及使用其的层合陶瓷电容器 - Google Patents
电介质陶瓷及使用其的层合陶瓷电容器 Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 47
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 24
- 238000010030 laminating Methods 0.000 title abstract 3
- 239000003792 electrolyte Substances 0.000 title 1
- 239000010410 layer Substances 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 abstract description 4
- 229910002976 CaZrO3 Inorganic materials 0.000 abstract 2
- 239000010949 copper Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 238000005245 sintering Methods 0.000 description 15
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Abstract
本发明的目的在于改善使用以CaZrO3为主成分的电介质陶瓷、用Cu作为内部电极的层合陶瓷电容器的寿命特性。本发明涉及一种电介质陶瓷，其特征在于，以CaxZrO3+aMn+bLi+cB+dSi表示时，相对于100mol CaxZrO3(其中，1.00≤x≤1.10)，含有0.5mol≤a≤4.0mol、6.0mol≤(b+c+d)≤15.0mol，且0.15≤(b/(c+d))≤0.55、0.20≤(d/c)≤3.30。另外，本发明还涉及一种使用该电介质陶瓷的层合陶瓷电容器。
Description
技术领域
本发明涉及一种以CaZrO3为主要成分的电介质陶瓷及使用该电介质陶瓷的寿命特性优异的层合陶瓷电容器，特别涉及一种在含有由Cu或者Cu合金构成的内部电极的层合陶瓷电容器中使用的电介质陶瓷及使用该电介质陶瓷的层合陶瓷电容器。
背景技术
目前为止，电介质陶瓷被用于电介质共振器、滤光器或层合电容器等中。近年伴随机器运作频率的高频化(100MHz～2GHz左右)，用于上述层合电容器等的电介质陶瓷优选静电电容(介电常数)的温度系数较小。另外，作为高频电路中使用的层合电容器的特性，要求ESR(等效串联电阻)低、高频区域的损耗小(Q值高)。另一方面，从低成本化方面考虑，作为比电阻小的内部电极必须选择贱金属。因此，使用Cu代替Ni、Pd。另外，作为电介质，要求为Q值高、介电常数的温度系数小、且可靠性高的物质。并且，由于内部电极中使用Cu，所以为了能够在1080℃以下的较低温度下烧成，防止Cu氧化，要求电介质为非还原性材料。另外，从环境方面考虑，期望为不含Pb或Bi的电介质。专利文献1及2中公开了满足上述要求的电介质陶瓷组合物的发明，并且公开了将上述电介质陶瓷组合物用于层合陶瓷电容器中。
[专利文献1]特开平5-217426号公报
[专利文献2]特开平11-106259号公报
专利文献1中，公开了一种非还原性电介质陶瓷组合物，所述非还原性电介质陶瓷组合物含有作为主成分的(Ca1-xSrx)m(Zr1-yTiy)O3-zMnO2-wSiO2和作为添加剂的a(LiO1/2-RO)-(1-a)(BO3/2-SiO2)(其中，RO为SrO、BaO及CaO中的至少1种)。此非还原性电介质陶瓷组合物，“可以在约1000℃以下的低温下进行烧成，所以可以使用铜作为电极材料，并且可以得到Q值及介电常数高、且介电常数的温度特性也稳定的电介质陶瓷”(段落[0005])。但是，没有充分地探讨以Cu作为内部电极的层合陶瓷电容器的寿命特性的改善。
专利文献2中公开了一种电介质陶瓷组合物，所述电介质陶瓷组合物含有以(CaO)x(Zr1-y·Tiy)O2表示的复合氧化物、Mn化合物和(aLi2O-bB2O3-cCaO)表示的玻璃成分。此电介质陶瓷组合物，“即使在1000℃以下的还原性气氛中也可以烧结，且介电常数高，并且，介电常数的温度特性稳定，高频区域(GHz带)内的Q值以Qf表示为10000以上，特别是高频区域内的Q值大幅度提高”(段落[0015])。但是，没有充分地探讨以Cu为内部电极的层合陶瓷电容器的寿命特性的改善。
发明内容
本发明的目的在于解决上述技术中没有充分探讨的课题，本发明的课题在于使用以CaZrO3为主成分的电介质陶瓷，改善使用Cu作为内部电极的层合陶瓷电容器的寿命特性。
本发明为了解决上述课题，采用以下手段。
(1)一种电介质陶瓷，以CaxZrO3+aMn+bLi+cB+dSi表示，相对于100mol CaxZrO3(其中，1.00≤x≤1.10)，含有0.5mol≤a≤4.0mol、6.0mol≤b+c+d≤15.0mol，且0.15≤b/(c+d)≤0.55、0.20≤d/c≤3.30。
(2)如上述(1)所述的电介质陶瓷，其特征在于，用Sr取代上述CaxZrO3中的部分Ca。
(3)如上述(1)或(2)所述的电介质陶瓷，其特征在于，用Ti取代上述CaxZrO3中的部分Zr。
(4)如上述(1)～(3)中任一项所述的电介质陶瓷，其特征在于，还含有Mg及/或Al。
(5)一种层合陶瓷电容器，所述层合陶瓷电容器配备多层电介质陶瓷层、和形成于上述电介质陶瓷层间的由Cu或者Cu合金构成的内部电极、和与上述内部电极电连接的外部电极，其中，上述电介质陶瓷层由上述(1)～(4)中任一项所述的电介质陶瓷构成。
通过使用以CaZrO3为主要成分的组成特定的本发明电介质陶瓷，可以发挥提高使用Cu作为内部电极的层合陶瓷电容器的寿命特性的效果。
具体实施方式
对使用Cu作为内部电极的层合陶瓷电容器的寿命特性的改善进行探讨时，发现CaZrO3类电介质陶瓷的Ca/Zr比、Mn、Li、B及Si的含量是决定寿命的主要原因，从而完成了本发明。另外，还发现即使在为了使用Cu内部电极，而抑制Li及B的含量不使寿命降低的状态下，CaZrO3类电介质陶瓷仍能够在1000℃以下致密化的Ca/Zr比或Li-B-Si组成比的条件。
通过使CaxZrO3类电介质陶瓷的Ca/Zr比在1.00≤x≤1.10的范围内，可以提高寿命特性。x值小于1.00或大于1.10时寿命特性均降低，故优选上述范围。
通过使Mn含量、即a值相对于100mol CaxZrO3在0.5≤a≤4.0mol的范围内，寿命特性提高。a值小于0.5mol或大于4.0mol时寿命特性均降低，故优选上述范围。
通过使Li+B+Si的总含量、即b+c+d相对于100mol CaxZrO3在6.0≤b+c+d≤15.0mol的范围内，可以在1000℃以下烧结(致密化)，另外，寿命特性提高。b+c+d低于6.0时不能在1000℃以下烧结，高于15.0mol时寿命特性降低，故优选上述范围。
通过使Li/(B+Si)比、即b/(c+d)在0.15≤b/(c+d)≤0.55的范围内，可以在1000℃以下烧结(致密化)。b/(c+d)低于0.15或高于0.55时均不能烧结(致密化)，故优选上述范围。
通过使Si/B比、即d/c为0.20≤d/c≤3.30，可以在1000℃以下烧结(致密化)，另外，寿命特性提高。d/c低于0.20时寿命特性降低，高于3.30时不能在1000℃以下烧结，故优选上述范围。
为了任意设计介质特性等，也可以用Sr或Ti等取代作为电介质主要成分的CaxZrO3的一部分，形成(CaySr1-y)x(ZrzTi1-z)O3(其中，1.00≤x≤1.10、0＜y≤1、0＜z≤1)。即，能够以(Ca0.9Sr0.1)xZrO3、Ca(Zr0.9Ti0.1)xO3等为主要成分。另外，为了任意设计介质特性等，也可以与Mn、Li、B及Si一同追加Mg、Al等其他元素。
对于层合陶瓷电容器的制造方法没有限定，可以采用如下所述的方法。作为原料准备CaCO3、ZrO2，进而根据需要准备SrCO3、TiO2等，秤量上述原料使其为规定组成。然后，将上述原料湿式混合，干燥后，在800～1200℃下煅烧，得到CaxZrO3。相对于如上所述合成的CaxZrO3，秤量Mn原料(氧化物、碳酸盐等)、Li原料(Li2CO3等)、B原料(B2O3等)、Si原料(SiO2等)，进而根据需要秤量Mg原料(MgO)、Al原料(Al2O3)等，使其为规定的组成。然后，通过将上述原料湿式混合，干燥，得到电介质粉末。向如上所述得到的电介质粉末中适当添加PVB粘合剂(或丙烯酸酯粘合剂)、增塑剂、为溶剂的有机溶剂，制作浆料，制成规定厚度(5～50μm)的印制电路基板。在印制电路基板上印刷内部电极用Cu糊剂，层合·压接后，切成规定的形状。然后，为了使Cu不被氧化，在惰性气氛中于300～600℃下进行脱粘合剂处理，在还原气氛中于900～1050℃下烧成1～5小时。在所得烧结体上涂布Cu终端电极糊剂(termination electrode paste)作为端子电极，然后，在N2气氛中烧结。
[实施例]
(实施例1)
作为原料准备CaCO3、ZrO2。秤量上述原料，如表1所示使Ca/Zr比、即x值在0.98～1.12的范围内变化。然后，用球磨机将上述原料湿式混合，干燥后，在1000℃下煅烧，得到CaxZrO3(0.98≤x≤1.12)。相对于上述CaxZrO3(以下，简称“CaZrO3”)，秤量MnCO3、Li2CO3、B2O3、SiO2，如表1所示相对于100mol CaZrO3，使Mn含量、即a值在0～5.0mol范围内变化，使Li/(B+Si)比、即b/(c+d)值为0.21～0.50、使Si/B比、及d/c值为0.24～2.35，使Li+B+Si的总含量b+c+d在3.0～18.0mol范围内变化。然后，通过用球磨机将上述原料湿式混合，干燥，得到电介质粉末。向上述电介质粉末中适当添加PVB粘合剂、增塑剂、作为溶剂的有机溶剂，制作浆料，用金属型涂布机制作厚度12μm的印制电路基板。采用丝网印刷法在印制电路基板上印刷内部电极用Cu糊剂，层合·压接至电极片数为11层(层间10层)后，切成4.0mm×2.0mm。然后，在惰性气氛中，在300～600℃下进行脱粘合剂处理，在还原气氛中(氮-氢混合气体：氢比率1～3％)，于980℃下烧成2hr。然后，涂布Cu糊剂作为端子电极，在N2气氛中烧结。采用上述工序制作10层的层合陶瓷电容器(试料序号101～121)，大小为3.2mm×1.6mm。
使用上述层合陶瓷电容器，对下述特性进行评价。
(1)与上述实施例不同，根据JIS C 2141的测定方法各制作5个试样(10×10×15mm)，测定烧结性(致密化)。在980℃下烧成时吸水率在0.1％以下为◎、其他为×。
(2)在JIS C 5102中，各制作20个试样，在20℃的环境中于1V-1MHz下测定静电电容，根据下式由其测定结果求出介电常数。介电常数＝(电容×电介质层厚度/(电极交叉面积×层合数))/真空的介电常数
需要说明的是，电介质厚度和电极交叉面积通过观察试样剖片的SEM进行测定。
(3)TC(静电电容温度特性)根据JIS C 5101-8(IEC 60384-8)的标准进行测定。以20℃的电容为基准，在-55℃～125℃温度范围内的电容变化率在0±30(ppm/℃)内记为COG。
(4)可靠性：高温加速负荷试验HALT(高加速寿命)试验(条件：30V/μm，150℃)中，MTTF为100hr以上的电容器为◎、低于100hr为×。对于试样序号101～114，电介质的组成和电容器的特性的评价结果如表1所示。
需要说明的是，电特性与背景技术中已说明的专利文献的电介质陶瓷没有很大区别，故省略，只给出作为基本特性的介电常数和静电电容的温度特性。
[表1]
如表1所示，Ca/Zr比即x值为1.00～1.10、相对于100mol CaZrO3、Mn含量、即a值为0.5～4.0mol、Li+B+Si总含量b+c+d为6.0～15.0mol的本发明例的试样序号104～107、109的电容器，能够在1000℃以下烧结(致密化)，且寿命为100hr以上。与此相对，Ca/Zr比低于1.00的试样序号102的电容器、Ca/Zr比超过1.10的试样序号110、111的电容器，寿命低于100hr。不含Mn的试样序号103的电容器、Mn含量超过4.0mol的试样序号108的电容器，寿命均不足100hr。另外，Li+B+Si的总含量b+c+d少于6.0mol的试样序号101的电容器，不能在1000℃以下烧结(致密化)，Li+B+Si的总含量b+c+d超过15.0mol的电容器，寿命低于100hr。
(实施例2)
相对于Ca/Zr比即x值为1.00的CaZrO3 100mol，使Mn含量、即a值为0.5或4.0mol，使Li+B+Si的总含量b+c+d为6.0或15.0mol，使Li/(B+Si)比即b/(c+d)、Si/B比即d/c如表2所示变化，进行混合，除此之外，与实施例1相同地得到电介质粉末。然后，与实施例1相同地，制作大小为3.2mm×1.6mm的10层的层合陶瓷电容器，试样序号为201～217，对特性进行评价。试样序号201～217的电介质组成和电容器各特性的评价结果如表2所示。
[表2]
如表2所示，Li/(B+Si)比即b/(c+d)为0.15～0.55、且Si/B比即d/c为0.20～3.30的本发明的试样序号201、202、204、205、211～216的电容器，能够在1000℃以下烧结(致密化)，且寿命在100hr以上。相对于此，不含Li的Li/(B+Si)比即b/(c+d)为0的试样序号203、206的电容器，Li/(B+Si)比即b/(c+d)超过0.55的试样序号208～210的电容器不能在1000℃以下烧结(致密化)。另外，不含Si的Si/B比即d/c为0的试样序号207的电容器，寿命低于100hr，Si/B比即d/c超过3.30的试样序号217的电容器，不能在1000℃以下烧结(致密化)。
(实施例3)
相对于Ca/Zr比即x值为1.05的CaZrO3 100mol，使Mn为2.0mol、Li+B+Si的总含量b+c+d为12.0mol、Li/(B+Si)比即b/(c+d)为0.37、Si/B比即d/c为一定值0.61(Li为3.24mol、B为5.45mol、Si为3.31mol)，再分别混合1.0mol Mg(MgO)、2.0mol Mg(MgO)、0.5mol Al(Al2O3)，除此之外，与实施例1相同地得到电介质粉末。然后，与实施例1相同地制作试样序号301～303的层合陶瓷电容器，对特性进行评价。另外，使用用Sr取代CaZrO3的部分Ca的(Ca0.9Sr0.1)ZrO3或用Ti取代部分Zr的Ca(Zr0.9Ti0.1)O3，相对于(Ca+Sr)/Zr比或Ca/(Zr+Ti)比即A/B比为1.05的(Ca0.9Sr0.1)ZrO3或Ca(Zr0.9Ti0.1)O3100mol，使Mn含量即a值为2.0mol、Li+B+Si的总含量b+c+d为12.0mol、Li/(B+Si)比即b/(c+d)为0.37、Si/B比即d/c为一定值0.61(Li为3.24mol、B为5.45mol、Si为3.31mol)，除此之外，与实施例1相同地得到电介质粉末。然后，与实施例1相同地制作试样序号304、305的层合陶瓷电容器，对特性进行评价。
[表3]
如表3所示，用Sr取代CaZrO3中的部分Ca时或用Ti取代部分Zr时、含有除Mn、Li、B、Si之外的Mg、Al等成分时，均可通过使Ca/Zr比(A/B比)为1.00～1.10，相对于100mol CaZrO3，使Mn含量即a值为0.5～4.0mol、Li+B+Si的总含量b+c+d为6.0～15.0mol、Li/(B+Si)比即b/(c+d)为0.15～0.55、且Si/B比即d/c为0.20～3.30，得到可在1000℃以下烧结(致密化)、且寿命在100hr以上的层合陶瓷电容器。
需要说明的是，本发明的电介质陶瓷的组成并不限定于上述内容，在不脱离本发明宗旨的范围内可以进行多种改变。例如，通常用Ti和Sr两元素同时取代主成分CaxZrO3中的部分Ca，也包括在本发明的目的范围内，是允许的。进而，在取代上述Ca中的一部分的同时，单独添加Mg或Al，或两成分同时添加，也包括在本发明的目的范围内，也是允许的。
Claims (8)
1、一种电介质陶瓷，其特征在于，
以CaxZrO3+aMn+bLi+cB+dSi表示时，
相对于100mol CaxZrO3，
含有0.5mol≤a≤4.0mol、6.0mol≤b+c+d≤15.0mol，
且0.15≤b/(c+d)≤0.55、0.20≤d/c≤3.30，
其中1.00≤x≤1.10。
2、如权利要求1所述的电介质陶瓷，其特征在于，用Sr取代所述CaxZrO3中的部分Ca。
3、如权利要求1所述的电介质陶瓷，其特征在于，用Ti取代所述CaxZrO3中的部分Zr。
4、如权利要求1所述的电介质陶瓷，其特征在于，还含有Mg及/或Al。
5、如权利要求1所述的电介质陶瓷，其特征在于，用Sr取代所述CaxZrO3中的部分Ca，还含有Mg及/或Al。
6、如权利要求1所述的电介质陶瓷，其特征在于，用Ti取代所述CaxZrO3中的部分Zr，还含有Mg及/或Al。
7、如权利要求1所述的电介质陶瓷，其特征在于，用Sr和Ti取代所述CaxZrO3中的部分Ca，还含有Mg及/或Al。
8、一种层合陶瓷电容器，所述层合陶瓷电容器配备多层电介质陶瓷层、和形成于所述电介质陶瓷层间的由Cu或者Cu合金构成的内部电极、和与所述内部电极电连接的外部电极，其特征在于，所述电介质陶瓷层由权利要求1～7中任一项所述的电介质陶瓷构成。
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| CN103515092A (zh) * | 2012-06-27 | 2014-01-15 | 太阳诱电株式会社 | 层叠陶瓷电容器及其制造方法 |
| CN105669192A (zh) * | 2014-12-08 | 2016-06-15 | 三星电机株式会社 | 陶瓷介电组合物以及包含其的多层陶瓷电容器 |
| CN111362694A (zh) * | 2014-12-08 | 2020-07-03 | 三星电机株式会社 | 陶瓷介电组合物以及包含其的多层陶瓷电容器 |
| CN110382441A (zh) * | 2017-03-02 | 2019-10-25 | Tdk株式会社 | 电介质组合物和电子器件 |
| CN110382441B (zh) * | 2017-03-02 | 2022-10-04 | Tdk株式会社 | 电介质组合物和电子器件 |
| CN109545552A (zh) * | 2017-09-22 | 2019-03-29 | 太阳诱电株式会社 | 层叠陶瓷电容器 |
| CN109545552B (zh) * | 2017-09-22 | 2021-11-23 | 太阳诱电株式会社 | 层叠陶瓷电容器 |
| CN110357618A (zh) * | 2019-06-20 | 2019-10-22 | 安徽理工大学 | 低温烧结温度稳定型锆酸盐微波介质陶瓷材料及其制备方法 |
| CN110357618B (zh) * | 2019-06-20 | 2021-08-24 | 安徽理工大学 | 低温烧结温度稳定型锆酸盐微波介质陶瓷材料及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101333108B (zh) | 2011-09-28 |
| JP4786604B2 (ja) | 2011-10-05 |
| US20090046410A1 (en) | 2009-02-19 |
| US7830645B2 (en) | 2010-11-09 |
| JP2009007209A (ja) | 2009-01-15 |
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