CN101935211A - 电介质陶瓷及其制造方法以及层叠陶瓷电容器 - Google Patents
电介质陶瓷及其制造方法以及层叠陶瓷电容器 Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 80
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 9
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical class [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000470 constituent Substances 0.000 claims abstract description 13
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- 238000002441 X-ray diffraction Methods 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- 229910052689 Holmium Inorganic materials 0.000 claims description 6
- 229910052765 Lutetium Inorganic materials 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 6
- 229910052772 Samarium Inorganic materials 0.000 claims description 6
- 229910052771 Terbium Inorganic materials 0.000 claims description 6
- 229910052775 Thulium Inorganic materials 0.000 claims description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
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- 241000278713 Theora Species 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
本发明提供一种即使电介质陶瓷层薄层化也可以得到优良的可靠性的层叠陶瓷电容器。作为构成层叠陶瓷电容器(1)的电介质陶瓷(2)的电介质陶瓷,包含由用通式(Ba1-h-m-xCahSrmRex)k(Ti1-n-yZrnMy)O3表示的各关系的钛酸钡系复合氧化物构成的主成分、作为烧结助剂的副成分,其中,烧结体的结晶粒子的平均粒径为0.6μm以下,所述通式中Re为La等,M为Mg等,且满足0.05≤x≤0.50、0.02≤y≤0.3、0.85≤k≤1.05、0≤h≤0.25、0≤m≤0.5。
Description
技术领域
本发明涉及一种电介质陶瓷及其制造方法及使用该电介质陶瓷而构成的层叠陶瓷电容器,特别是涉及用于提高层叠陶瓷电容器的可靠性的改良。
背景技术
使用层叠陶瓷电容器时的定格电压有多种,特别是关于施加中~高压(数十V~数百V)的层叠陶瓷电容器,对构成电介质陶瓷层的陶瓷材料,要求高的绝缘性(绝缘电阻)及可靠性(高温负荷试验的寿命特性)。
另外,目前,由于对层叠陶瓷电容器的小型化的要求严格,为了确保规定以上的静电容量,即使是为小型,也要求电介质陶瓷层的薄型化。但是,随着电介质陶瓷层的薄型化的推进,电介质陶瓷层的每一层的电场强度更高。因此,对所使用的电介质陶瓷,要求更高的可靠性,特别是在负荷试验中要求更高的寿命特性。
满足这样的要求的电介质陶瓷,例如在国际公开第2004/067473号公报(专利文献1)中已公开。
在上述专利文献1中,公开了一种电介质陶瓷,其包含:用通式(Ba1-h-i-mCahSriGdm)k(Ti1-y-j-nZryHfjMgn)O3表示、且满足0.995≤k≤1.015、0≤h≤0.03、0≤i≤0.03、0.015≤m≤0.035、0≤y<0.05、0≤j<0.05、0≤(y+j)<0.05、及0.015≤n≤0.035各关系的、用Gd置换Ba的一部分且用Mg置换Ti的一部分的钛酸钡系复合氧化物构成的主成分和如下添加成分,即:含有Ma(Ma是Ba、Sr及Ca的至少一种)、Mb(Mb是Mn及Ni的至少一种)及Mc(Mc是Si或Si及Ti双方),其中,Ma相对主成分100mol不足1.5mol(但是不包含0mol。)、Mb相对主成分100mol不足1.0mol(但是不包含0mol)、Mc相对主成分100mol为0.5mol以上且2.0mol以下。
关于上述电介质陶瓷的主成分,由于可以不含有Ca、Sr、Zr及Hf,其特征在于,含有Gd及Mg。如上所述,含有3.5mol%以下的Gd,及含有3.5mol%以下的Mg。
作为稀土类元素的Gd,固溶于以ABO3为代表的钙钛矿(ペロブスカイト)构造的A位置,Mg固溶于B位置,由此,得到高的可靠性。但是,Gd及Mg的置换量均为3.5mol%以下,存在不能得到充分的可靠性这样的问题。
另一方面,在专利文献1中,公开了一种烧结体,其中,关于电介质陶瓷的结晶粒子的粒径优选为2.5μm以下、更优选为1.5μm以下、进一步优选为1μm以下。总之,在专利文献1记载的电介质陶瓷中,由于烧结体的结晶粒子的粒径较大,为0.9μm以上,在推进薄层化时,一个电介质陶瓷层中存在的结晶粒子的数量减少,可靠性容易出现问题。
另外,为了提高可靠性,考虑增加Gd那样的稀土类元素及Mg等元素的置换量的方法,但在该情况下,晶粒直径容易进一步变大。
专利文献1:国际公开第2004/067473号公报
发明内容
因此,本发明的目的在于,提供一种可以解除上述问题的电介质陶瓷及其制造方法。
该发明的目的在于,提供一种使用上述的电介质陶瓷构成的层叠陶瓷电容器。
为了解决上述的技术课题,该发明提供一种电介质陶瓷,其特征在于,包含由用通式(Ba1-h-m-xCahSrmRex)k(Ti1-n-yZrnMy)O3表示的钛酸钡系复合氧化物构成的主成分、和作为烧结助剂的副成分,其中,烧结体的结晶粒子的平均粒径为0.6μm以下,所述通式中Re为La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu以及Y中的至少一种,M为Mg、Ni、Mn、Al、Cr及Zn中的至少一种,且满足0.05≤x≤0.50、0.02≤y≤0.3、0.85≤k≤1.05、0≤h≤0.25、0≤m≤0.50及0≤n≤0.40的各关系的。
需要说明的是,上述的粒径是使用扫描型电子显微镜观察电介质陶瓷的剖面而求得的粒径,平均粒径是例如对30个粒子的粒径进行平均后的粒径。
本发明也涉及制造上述那样的电介质陶瓷的方法。
该发明的电介质陶瓷的制造方法具备:得到如下反应物的第一工序,该反应物由用通式(Ba1-h-m-xCahSrmRex)k(Ti1-n-yZrnMy)O3表示,其中,Re为La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu以及Y中的至少一种,M为Mg、Ni、Mn、Al、Cr及Zn中的至少一种,且满足0.05≤x≤0.50、0.02≤y≤0.3、0.85≤k≤1.05、0≤h≤0.25、0≤m≤0.50及0≤n≤0.40的各关系的钛酸钡系复合氧化物构成;准备作为烧结助剂的副成分的第二工序;在所述第一工序中得到的所述反应物中混合在第二工序中准备的所述副成分的第三工序;以及将在第三工序中得到的混合物进行煅烧的第四工序。
而且,在第一工序中,为了得到所述反应物,实施将包含BaCO3粉末的多个原料粉末进行预烧的工序,并以使预烧后的粉末的X射线衍射解析的BaCO3的(111)衍射峰和BaTiO3的(110)衍射峰的强度比为15/1000以上且200/1000以下的方式残留未反应物,在第三工序中得到的所述混合物包含上述未反应物。
该发明还适用于具备:具有沿层叠的多个电介质陶瓷层及电介质陶瓷层间的特定的界面形成的多个内部电极而构成的电容器主体、形成于电容器主体的外表面上的相互不同的位置、且与内部电极的特定部位电连接的多个外部电极的层叠陶瓷电容器。
该发明的层叠陶瓷电容器,其特征在于,电介质陶瓷层由上述的该发明的电介质陶瓷构成。
根据该发明的电介质陶瓷,虽然在主成分组成中含有大量的Re及M,但粒子成长被抑制,结晶粒子的平均粒径减小为0.6μm以下,因此,在层叠陶瓷电容器中,即使电介质陶瓷层的厚度例如不足3μm,也可以得到优良的可靠性、更特定地说,可以得到优良的寿命特性。
即,首先,由于含有大量对提高可靠性有效的Re及M,可以得到优良的可靠性,另外,在对提高可靠性有效的反面来说,即使含有大量具有促进粒子成长的作用的Re及M,由于平均粒径在0.6μm以下时,可抑制粒子成长,因此,从该方面来说,也可以提高可靠性。
根据该发明的电介质陶瓷的制造方法,在用于得到反应物的第一工序的预烧工序中,通过适度残留未反应物,以使预烧后的粉末的X射线衍射解析的BaCO3的(111)衍射峰和BaTiO3的(110)衍射峰的强度比为15/1000以上且200/1000以下,可以抑制粒子成长,由此,可以使作为得到的烧结体的电介质陶瓷的结晶粒子的平均粒径在0.6μm以下。
附图说明
图1是图解表示该发明的电介质陶瓷构成的层叠陶瓷电容器1的剖面图。
符号说明
1 层叠陶瓷电容器
2 电介质陶瓷层
3,4 内部电极
5 电容器主体
6、7 外部电极
具体实施方式
参照图1,首先对应用该发明的电介质陶瓷的层叠陶瓷电容器1进行说明。
层叠陶瓷电容器1具备:具有层叠的多个电介质陶瓷层2和沿电介质陶瓷层2之间的特定界面形成的多个内部电极3及4而构成的电容器主体5。内部电极3及4例如以Ni作为主要成分。
在电容器主体5的外表面上的相互不同的位置形成第一及第二外部电极6及7。外部电极6及7例如以Ag或Cu作为主要成分。在图1所示的层叠陶瓷电容器1中,第一及第二的外部电极6及7形成于电容器主体5的相互对向的各端面上。内部电极3及4具有与第一外部电极6电连接的多个第一内部电极3、和与第二外部电极7电连接的多个第二内部电极4,这些第一及第二内部电极3及4在层叠方向上交替配置。
另外,层叠陶瓷电容器1可以是具备两个外部电极6及7的二端子型电容器,也可以是具备多个外部电极的多端子型电容器。
电介质陶瓷层2由成为该发明的特征的如下所述的电介质陶瓷构成。
即,一种由电介质陶瓷构成电介质陶瓷层2,该电介质陶瓷包括由用通式:(Ba1-h-m-xCahSrmRex)k(Ti1-n-yZrnMy)O3表示的钛酸钡系复合氧化物构成的主成分、和作为烧结助剂的副成分,其中,烧结体的结晶粒子的平均粒径为0.6μm以下,所述通式中Re为La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu以及Y中的至少一种,M为Mg、Ni、Mn、Al、Cr及Zn中的至少一种,且满足0.05≤x≤0.50、0.02≤y≤0.3、0.85≤k≤1.05、0≤h≤0.25、0≤m≤0.50及0≤n≤0.40的各关系。
根据如上所述的电介质陶瓷,在主成分组成中,虽然含有大量的Re及M,但由于粒子成长被抑制,结晶粒子的平均粒径也较小,为0.6μm以下,因此,即使电介质陶瓷层2的厚度例如变薄为不足3μm,也可以得到优良的可靠性,更特定地说,可得到优良的寿命特性。
接着,对图1所示的层叠陶瓷电容器1的制造方法进行说明,同时,对该发明的电介质陶瓷的制造方法的最佳实施方式进行说明。
首先,准备构成电介质陶瓷层2的电介质陶瓷的原料粉末。该原料粉末优选如下进行制作。
首先,实施得到反应物的第一工序,该反应物由用通式:(Ba1-h-m-xCahSrmRex)k(Ti1-n-yZrnMy)O3表示的钛酸钡系复合氧化物构成,其中,Re为La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu以及Y中的至少一种,M为Mg、Ni、Mn、Al、Cr及Zn中的至少一种,且满足0.05≤x≤0.50、0.02≤y≤0.3、0.85≤k≤1.05、0≤h≤0.25、0≤m≤0.50及0≤n≤0.40的各关系。
在该第一工序中,为了得到上述反应物,实施将包含BaCO3的粉末的多个原料粉末进行预烧的工序。更具体来说,是在上述BaCO3粉末的基础上,将分别包含上述的通式中所含的元素的化合物的粉末,按照赋予规定的组成比的方式进行混合,并在大气中进行预烧,接着进行粉碎。
而且,在第一工序中,按照残留规定量的未反应物的方式控制预烧温度等预烧条件,以使预烧后的粉末的X射线衍射解析的BaCO3的(111)衍射峰和BaTiO3的(110)衍射峰的强度比为15/1000以上且200/1000以下。另外,除预烧条件之外,也要充分考虑起始原料的比表面积及粉碎条件等对未反应物的残留量的影响。这样的未反应物具有有利于抑制后述的煅烧工序中的粒子成长的作用。
另一方面,实施准备MnO及SiO2等作为烧结助剂的副成分的第二工序。
接着,实施在上述的第一工序得到的反应物中混合第二工序中准备的副成分的第三工序。在该第三工序中得到的混合物成为电介质陶瓷的原料粉末,其也含有上述的未反应物。
接着,对在第三工序中得到的混合物,即电介质陶瓷的原料粉末中添加有机粘合剂及溶剂并进行混合,由此制成浆料,使用该浆料成形成为电介质陶瓷层2的陶瓷生片。
接着,在特定的陶瓷生片上印刷例如以Ni为导电成分的导电性浆料,形成应成为内部电极3或4的导电性浆料膜。
接着,如上所述,层叠形成有导电性浆料膜的多个陶瓷生片,同时,按照夹持这些陶瓷生片的方式,层叠没有形成导电性浆料膜的陶瓷生片,进行压接后,根据需要进行切割,由此得到应成为电容器主体5的坯料层叠体。在该坯料层叠体中,使导电性浆料膜的端缘在任一端面露出。
接着,实施对上述的第三工序中得到的混合物进行煅烧的第四工序。更具体来说,实施将上述的坯料层叠体在还原性环境中进行煅烧的工序。由此,得到如图1所示的烧结后的电容器主体5,在电容器主体5中,上述陶瓷生片构成由电介质陶瓷构成的电介质陶瓷层2,导电性浆料膜构成内部电极3或4。
作为构成上述电介质陶瓷层2的烧结体的电介质陶瓷,其平均晶粒直径为0.6μm以下。
接着,按照分别与内部电极3及4的露出的各端缘电连接的方式,在电容器主体5的各端面上,分别通过例如含有Ag的导电性浆料的烧制形成外部电极6及7。
其后,根据需要,在外部电极6及7上形成镍、铜等的镀膜及在其上形成焊剂、锡等的镀膜。
如上操作,完成层叠陶瓷电容器1。
接着,基于实施例对该发明更具体地进行说明。
[实施例1]
作为应成为电介质陶瓷的主成分的起始原料,准备BaCO3、CaCO3、SrCO3、TiO2、ZrO2、Gd2O3及MgO的各粉末。另外,作为BaCO3粉末,选择比表面积11m2/g的材料,作为TiO2粉末,选择比表面积13m2/g的材料。
接着,称量上述起始原料,以得到(Ba0.89Ca0.01Sr0.01Gd0.10)(Ti0.93Zr0.01Mg0.06)O3的组成比。
接着,对于表1所示的试料1~4,将上述称量好的原料粉末100g和水130g一同在直径0.8mm的PSZ玉石的球磨机中进行50小时湿式混合,粉碎后进行干燥,在空气中以表1的“预烧温度”栏所示的950~1150℃的范围的各温度预烧2小时,得到钛酸钡系原料粉末。
表1所示的试料5~8是比较例。
在试料5中,如表1的“预烧温度”栏所示,除在预烧时适用1150℃的温度以外,进行与上述试料1~4同样的处理。
在试料6中,如表1的“预烧温度”的栏所示,除在预烧时适用400℃的温度以外,进行与上述试料1~4同样的处理。
在试料7中,相对BaTiO3粉末100摩尔份分别添加CaCO3粉末1摩尔份、SrCO3粉末1摩尔份、ZrO2粉末1摩尔份、Gd2O3粉末10摩尔份、及MgO粉末6摩尔份,将得到的混合物不经预烧而制成原料粉末。
试料8是在最初的混合及预烧时不添加,其后添加MgO粉末的试料。即,对于(Ba0.89Ca0.01Sr0.01Gd0.10)(Ti0.99Zr0.01)O3的组成,如表1的“预烧温度”栏所示,适用110℃的预烧温度实施预烧,其后,添加MgO粉末使其含量达到6摩尔份。
接着,对于上述预烧后的粉末,对X射线衍射解析(XRD)的BaCO3的(111)衍射峰和BaTiO3的(110)衍射峰的强度比进行评价。其结果示于表1的“峰值比”栏中。
接着,相对各试料的钛酸钡系原料粉末100摩尔份,进一步添加1摩尔份Ba/Ti比补正用的BaCO3,同时,分别添加作为烧结助剂的副成分原料的MnO粉末1摩尔份、及SO2粉末2摩尔份,用球磨机进行湿式混合、粉碎后,进行干燥。
接着,将干燥后的上述混合粉末与聚乙烯醇缩丁醛系粘合剂等混合,通过球磨机进行湿式混合,调制浆料。将该浆料通过刮刀法成形为片,得到矩形的陶瓷生片。另外,在此,对从陶瓷生片得到的烧结后的电介质陶瓷层,如表1所示,调整成形的陶瓷生片的厚度,以得到1.5μm、3μm及4.5μm各厚度。
接着,在上述陶瓷生片上印刷以Ni为主体的导电性浆料,形成应成为内部电极的导电性浆料膜。
接着,按照引出导电性浆料膜的一侧相互不同的方式,层叠102枚形成有导电性浆料膜的陶瓷生片,得到应成为电容器主体的生的层叠体。
接着,在N2环境中将生的层叠体加热到350℃的温度,使粘合剂燃烧后,在氧分压为1-910-12MPa的、由H2-N2-H2O气体构成的还原性环境中,在1000~1200℃的范围内的温度下进行煅烧,得到烧结而成的电容器主体。
接着,在烧结后的电容器主体的两端面,涂布含有B2O3-Li2O-SiO2-BaO系玻璃料的Ag浆料,并在N2环境中,在600℃的温度下进行烧制,形成与内部电极电连接的外部电极,得到作为试料的层叠陶瓷电容器。
这样,得到的层叠陶瓷电容器的外形尺寸为长度3.2mm及宽度1.6mm。
接着,如表1所示,对各试料的层叠陶瓷电容器的“粒径”及“故障率”进行评价。
表1所示的“粒径”是使用扫描型电子显微镜对各试料的电容器主体的层叠方向的剖面进行观察,选择30个以上的结晶粒子,并对各个粒径进行测定,并将这些粒径进行平均后的数据。
表1所示的“故障率”表示可靠性的优劣,所以,通过对各试料的层叠陶瓷电容器实施高温负荷试验,进行绝缘劣化寿命的评价,表示在100个试验中,经过50小时后产生故障的试料数量。在高温负荷试验中,按照在温度190℃下,电场强度为30kA/mm的方式,对各试料的层叠陶瓷电容器施加电压,试验后的绝缘电阻比试验前的绝缘电阻低3位以上的情况判定为故障。
表1
从表1可知,如试料1~4,如果峰值比为15/1000以上且200/1000以下,则可以得到满足平均粒径为0.6μm以下这一条件的电介质陶瓷。
另外,根据满足上述条件的试料1~4,即使电介质陶瓷层的厚度变薄为1.5μm的情况下,故障率也在10%以内,也可以得到优良的可靠性。可以说,越变为薄层,该可靠性提高的效果越显著。这是因为,与作为比较例的例5中,电介质陶瓷层的厚度为3μm及4.5μm的各试料相比,在厚度为1.5μm的试料中,故障率急速上升。
在作为比较例的试料6中,在预烧工序,由于没有合成BaTiO3,不能进行峰值比判定。另外,烧结体的粒径变大,故障率变高。
另外,在试料7中,由于在粒子内不存在充分的作为Re元素的Gd及作为M元素的Mg,粒径变小,但故障率变得非常高。
在试料8中,由于在粒子内不存在充分的作为M元素的Mg,虽然粒径变小,但故障率全部为100/100。
[实施例2]
作为应成为电介质陶瓷的主成分的起始原料,准备BaCO3、CaCO3、SrCO3、TiO2及ZrO2各粉末,作为Re的氧化物的La2O3、CeO2、Pr6O11、Nd2O3、Sm2O3、Eu2O3、Gd2O3、Tb4O7、Dy2O3、Ho2O3、Er2O3、Tm2O3、Yb2O3、Lu2O3及Y2O3各粉末,以及作为M的氧化物的MgO、NiO、MnO、Al2O3、Cr2O3、以及ZnO各粉末。另外,关于BaCO3粉末及TiO2粉末,选择与在实施例1中选择的材料相同的比表面积的材料。
接着,将上述起始原料按照在(Ba1-h-m-xCahSrmRex)k(Ti1-n-yZrnMy)O3中,得到如表2所示的组成比的方式进行称量。
接着,与实施例1的情况相同,将上述称量好的原料粉末在进行湿式混合、粉碎后,进行干燥,在空气中,在表2的“预烧温度”栏所示的950~1150℃的范围的各温度下进行2小时预烧,得到钛酸钡系原料粉末。
接着,与实施例的情况相同,对上述预烧粉末评价X射线衍射解析的BaCO3的(111)衍射峰和BaTiO3的(110)衍射峰的强度比。其结果,示于表2的“峰值比”栏。
接着,相对各试料的钛酸钡系原料粉末100摩尔份,进一步添加表2的“后添加”栏所示的摩尔份的、作为烧结助剂的副成分原料的MnO粉末及SiO2粉末,与实施例1的情况相同,得到各试料的层叠陶瓷电容器。另外,在实施例2中,对全部的试料,将烧结后的电介质陶瓷层的厚度都设定为1.5μm。
接着,对各试料的层叠陶瓷电容器,按照与实施例1的情况相同的要领,如表2所示,对“粒径”及“故障率”进行评价。
表2
从表2可知,可以得到满足如下条件的电介质陶瓷,只要构成(Ba1-h-m-xCahSrmRex)k(Ti1-n-yZrnMy)O3的各元素的含量满足0.05≤x≤0.50、0.02≤y≤0.3、0.85≤k≤1.05、0≤h≤0.25、0≤m≤0.50及0≤n≤0.40的各关系,无论Re元素及M元素的种类及组合,只要峰值比为15/1000以上200/1000以下,则平均粒径为0.6μm以下。而且,只要平均粒径为0.6μm以下,即使电介质陶瓷层的厚度变薄为1.5μm,故障率也极低,可以得到优良的绝缘劣化寿命特性。
与此相对,对于Re量x及M量y中的任一个超出0.05≤x≤0.50及0.02≤y≤0.3的范围的试料20及21,都难以将粒径抑制在0.6μm以下,因此,表现为100/110的故障率,绝缘劣化寿命也变差。
另外,可以确认,在为上述的试料20及21那样的组成的情况下,假设预烧温度下降,在进行本煅烧时,未反应物也会扩散固溶而不能抑制粒子成长。
在以上的实施例中,Re元素如上述通式所示,以向钛酸钡的A位置固溶为前提进行称量,在实际合成的粉末中,即使Re向B位置固溶,对于本发明的效果也不会产生任何问题。
Claims (3)
1.一种电介质陶瓷,其特征在于,
包含由用通式:(Ba1-h-m-xCahSrmRex)k(Ti1-n-yZrnMy)O3表示的钛酸钡系复合氧化物构成的主成分和作为烧结助剂的副成分,其中,烧结体的结晶粒子的平均粒径为0.6μm以下,所述通式中Re为La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu及Y中的至少一种,M为Mg、Ni、Mn、Al、Cr及Zn中的至少一种,且满足0.05≤x≤0.50、0.02≤y≤0.3、0.85≤k≤1.05、0≤h≤0.25、0≤m≤0.50及0≤n≤0.40的各关系。
2.一种电介质陶瓷的制造方法,其特征在于,具备:
得到如下反应物的第一工序,该反应物由用通式(Ba1-h-m-xCahSrmRex)k(Ti1-n-yZrnMy)O3表示,其中,Re为La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu以及Y中至少一种,M为Mg、Ni、Mn、Al、Cr及Zn中至少一种,且满足0.05≤x≤0.50、0.02≤y≤0.3、0.85≤k≤1.05、0≤h≤0.25、0≤m≤0.50及0≤n≤0.40的各种关系的钛酸钡系复合氧化物构成,
准备作为烧结助剂的副成分的第二工序,
在所述第一工序中得到的所述反应物中混合在所述第二工序中准备的所述副成分的第三工序,和
将在所述第三工序中得到的混合物进行煅烧的第四工序;
在所述第一工序中,为了得到所述反应物,实施将包含BaCO3粉末的多个原料粉末进行预烧的工序,并以使预烧后的粉末的X射线衍射解析的BaCO3的(111)衍射峰和BaTiO3的(110)衍射峰的强度比为15/1000以上且200/1000以下的方式,残留未反应物,
在所述第三工序中得到的所述混合物也包含所述未反应物。
3.一种层叠陶瓷电容器,具备:具有层叠的多个电介质陶瓷层及沿所述电介质陶瓷层间的特定的界面形成的多个内部电极而构成的电容器主体以及形成于所述电容器主体的外表面上的相互不同的位置且与所述内部电极的特定部位电连接的多个外部电极,
所述电介质陶瓷层由权利要求1所述的电介质陶瓷构成。
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