CN101665354B - 电介质陶瓷及其制造方法、和叠层陶瓷电容器 - Google Patents
电介质陶瓷及其制造方法、和叠层陶瓷电容器 Download PDFInfo
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- CN101665354B CN101665354B CN2009101666644A CN200910166664A CN101665354B CN 101665354 B CN101665354 B CN 101665354B CN 2009101666644 A CN2009101666644 A CN 2009101666644A CN 200910166664 A CN200910166664 A CN 200910166664A CN 101665354 B CN101665354 B CN 101665354B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 130
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 90
- 239000002245 particle Substances 0.000 claims description 41
- 239000000843 powder Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 25
- 239000003990 capacitor Substances 0.000 claims description 21
- 239000004615 ingredient Substances 0.000 claims description 16
- 229910010293 ceramic material Inorganic materials 0.000 claims description 11
- 238000003475 lamination Methods 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052772 Samarium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- 229910002113 barium titanate Inorganic materials 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 description 12
- 239000011575 calcium Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
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- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
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- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052916 barium silicate Inorganic materials 0.000 description 1
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
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Abstract
本发明涉及电介质陶瓷及其制造方法、和叠层陶瓷电容器,其目的是在叠层陶瓷电容器中即便将电介质陶瓷层的厚度变薄为小于1μm,也能够取得良好的寿命特性。作为构成电介质陶瓷层(2)的电介质陶瓷采用了主成分是BaTiO3系,作为副成分包含Li,Li含有量e[摩尔部分]相对于主成分100摩尔部分是0.5≤e≤6.0,关于该电介质陶瓷的颗粒,颗粒径的平均值Rg[μm]是0.06<Rg<0.17,更优选是0.06<Rg<0.14,其标准偏差σg[μm]是σg<0.075。
Description
技术领域
本发明涉及电介质陶瓷及其制造方法和叠层陶瓷电容器,尤其涉及用于实现叠层陶瓷电容器中的电介质陶瓷层的更薄层化的改良。
背景技术
叠层陶瓷电容器具有由叠层的多个电介质陶瓷层和沿着电介质陶瓷层之间的特定界面而形成的多个内部电极来构成的电容器主体。在电容器主体的例如相互对置的各个端面上形成有相互电连接多个内部电极的外部电极。内部电极具有与其中一个外部电极电连接的内部电极和与另一个外部电极电连接的内部电极,与其中一个外部电极电连接的内部电极和与另一个外部电极电连接的内部电极针对叠层方向交互地进行配置。
对于内部电极所包含的导电材料以低成本为目的,通常采用Ni。在制造叠层陶瓷电容器的过程中,为了获得处于烧结状态的电介质陶瓷层,而实施烧成电容器主体的步骤,不过该烧成步骤必需在将内部电极内置于电容器主体的状态下实施。但是,内部电极所包含的Ni为贱金属(base metal),所以在上述烧成步骤中必需应用还元性氛围。
另一方面,作为构成电介质陶瓷层的电介质陶瓷,通常应用可获得高介电常数的BaTiO3系的物质。
在叠层陶瓷电容器中为了增加每一单位体积的静电容量,而进行电介质陶瓷层的薄层化。
为了对电介质陶瓷层进行薄层化,而采用使内部电极薄层化的方法是有效的,不过如果使内部电极变薄,则在还元性氛围下烧成时,容易导致内部电极球状化,结果,内部电极容易断开。为了避免这样的不良情况,有效的方法是通过在更低温中烧成来使电介质陶瓷烧结。为了能够在低温中进行烧结,有效的方法是例如将含有SiO2的烧结催化剂包含在应该烧成的陶瓷材料中,为了实现更有效的低温烧结化,在日本特开2001-89231号公报(专利文献1)中公开了预先包含锂的情况。
即,在专利文献1中公开了具有以下主成分的电介质陶瓷组合物:换算成BaTiO3的89~97摩尔%的钛酸钡、换算成Y2O3的0.1~10摩尔%的氧化钇、换算成MgO的0.1~7摩尔%的氧化镁、换算成V2O5的0.01~0.3摩尔%的氧化钒、换算成MnO的0.5摩尔%以下的氧化锰、以及换算成(Ba·Ca)SiO3的0.5~7摩尔%的硅酸钡·钙,该电介质陶瓷组合物针对上述主成分100摩尔%,将锂化合物换算成Li2O而包含0.01~5.0重量%。
在上述专利文献1所述的电介质陶瓷组合物中,锂起到烧结催化剂的作用,并且有助于电介质陶瓷的介电常数温度特性的提高。
另一方面,随着对叠层陶瓷电容器小型化的要求进一步严格,而希望使电介质陶瓷层的薄层化进展到厚度小于1μm的水平。随着电介质陶瓷层的薄层化,对电介质陶瓷层所施加的电场进一步变大,所以为了满足如上所述的需求,而需要构成电介质陶瓷层的电介质陶瓷有更高的绝缘性以及寿命特性。但是存在如下的问题:当采用具有上述专利文献1所述的组成的电介质陶瓷时,无法获得充分的寿命特性。【专利文献1】日本特开2001-89231号公报
发明内容
因此,本发明的目的是提供可解决上述问题的电介质陶瓷及其制造方法和采用上述电介质陶瓷来构成的叠层陶瓷电容器。
本发明首先涉及的是主成分为BaTiO3系的电介质陶瓷,为了解决上述的技术课题,具有的特征是作为副成分包含Li,Li含有量e[摩尔部分]相对于主成分100摩尔部分是0.5≤e≤6.0,关于该电介质陶瓷的颗粒(grain),颗粒径的平均值Rg[μm]是0.06<Rg<0.17,其标准偏差σg[μm]是σg<0.075。
本发明的电介质陶瓷优选用以下组成式来表示:100(Ba1-xCax)mTiO3+aRO3/2+bMgO+cMO+dSiO2+eLiO1/2(m,a,b,c,d及e表示摩尔比;R包含从La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu以及Y中选出的至少1种;M含有Mn及V的至少一方),且满足以下各条件:0.96≤m≤1.03,0≤x≤0.2,0.2≤a≤5.0,0≤b≤2.0,0.2≤c≤1.0,及0.5≤d≤4.0。
本发明的电介质陶瓷优选满足颗粒径的平均值Rg[μm]是0.06<Rg<0.14、其标准偏差σg[μm]是σg<0.075这样的进一步限定的条件。
本发明还涉及如下的叠层陶瓷电容器,其具有:电容器主体,其由叠层的多个电介质陶瓷层、和沿着上述电介质陶瓷层间的特定界面而形成的多个内部电极构成;以及多个外部电极,其形成在电容器主体外表面上的互不相同的位置处,且与内部电极的特定内部电极电连接。
本发明的叠层陶瓷电容器的特征是位于在内部电极的叠层方向上相邻的内部电极之间的电介质陶瓷层的厚度小于1μm,且电介质陶瓷层由上述本发明所涉及的电介质陶瓷构成。
本发明还涉及电介质陶瓷的制造方法。
本发明的电介质陶瓷的制造方法的特征是具有以下步骤:准备以BaTiO3系为主成分的BaTiO3系陶瓷粉末的步骤;准备包含Li化合物的副成分的步骤;通过在BaTiO3系陶瓷粉末中混合上述副成分来获得陶瓷原料粉末的步骤;通过使陶瓷原料粉末成形来获得陶瓷成形体的步骤;以及通过烧成陶瓷成形体来获得电介质陶瓷的步骤,在上述陶瓷原料粉末中,Li含有量e[摩尔部分]相对于主成分100摩尔部分是0.5≤e≤6.0,在上述BaTiO3系陶瓷粉末中,粒径的平均值Rb[μm]是0.06<Rb<0.17,其标准偏差σb[μm]是σb<0.065。(发明效果)
根据本发明的电介质陶瓷,包含Li作为副成分,并且颗粒径充分小且没有粗大颗粒,所以在为了构成叠层陶瓷电容器的电介质陶瓷层而采用该电介质陶瓷时,即便进行使电介质陶瓷层的厚度小于1μm这样的薄层化,也能够赋予良好的寿命特性。
本发明的电介质陶瓷在用组成式:100(Ba1-xCax)mTiO3+aRO3/2+bMgO+cMO+dSiO2+eLiO1/2来表示、且满足96≤m≤1.03,0≤x≤0.2,0.2≤a≤5.0,0≤b≤2.0,0.2≤c≤1.0以及0.5≤d≤4.0的各个条件时,能够进一步提高寿命特性。
另外,在本发明的电介质陶瓷中,当满足颗粒径的平均值Rg[μm]是0.06<Rg<0.14、其标准偏差σg[μm]是σg<0.075这样的进一步限定的条件时,可进一步提高寿命特性。
根据本发明的电介质陶瓷的制造方法,在粒度分布窄(sharp)的主成分粉末中加入适量的Li可适当抑制烧成所导致的颗粒增长,从而能够获得具有窄的粒度分布的颗粒。其结果是,在为了构成叠层陶瓷电容器的电介质陶瓷层而采用由该制造方法获得的电介质陶瓷时,即便进行使电介质陶瓷层的厚度小于1μm这样的薄层化,也能够赋予良好的寿命特性。附图说明图1是图解地示出本发明一实施方式的叠层陶瓷电容器1的剖视图。符号说明:1叠层陶瓷电容器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
图1是表示应用了本发明的电介质陶瓷的叠层陶瓷电容器1的剖视图。
叠层陶瓷电容器1具有由叠层的多个电介质陶瓷层2和沿着电介质陶瓷层2间的特定界面而形成的多个内部电极3及4构成的电容器主体5。内部电极3及4例如以Ni为主成分。
在电容器主体5的外表面上相互不同的位置处形成第1及第2外部电极6及7。外部电极6及7例如以Cu为主成分。在图1所示的叠层陶瓷电容器1中,第1及第2外部电极6及7形成在电容器主体5的相互对置的各个端面上。内部电极3及4具有与第1外部电极6电连接的多个第1内部电极3和与第2外部电极7电连接的多个第2内部电极4,这些第1及第2内部电极3及4在叠层方向上交互地进行配置。
在这样的叠层陶瓷电容器1中,位于相邻的第1内部电极3和第2内部电极4之间的电介质陶瓷层2的厚度小于1μm。
构成电介质陶瓷层2的电介质陶瓷的主成分是BaTiO3系,作为副成分包含有Li,Li含有量e[摩尔部分]相对于主成分100摩尔部分是0.5≤e≤6.0。另外,关于该电介质陶瓷的颗粒,颗粒径的平均值Rg[μm]是0.06<Rg<0.17,其标准偏差σg[μm]是σg<0.075。
这样,构成电介质陶瓷层2的电介质陶瓷包含有Li并且颗粒径充分小且没有粗大颗粒,所以即便进行使电介质陶瓷层2的厚度小于1μm的薄层化,在叠层陶瓷电容器1中,也能够获得良好的寿命特性。
为了进一步提高寿命特性,电介质陶瓷用以下组成式来进行表示:100(Ba1-xCax)mTiO3+aRO3/2+bMgO+cMO+dSiO2+eLiO1/2(m,a,b,c,d及e表示摩尔比;R含有从La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu及Y中选出的至少1种;M含有Mn及V的至少一方),且优选满足以下的各个条件:0.96≤m≤1.03,0≤x≤0.2,0.2≤a≤5.0,0≤b≤2.0,0.2≤c≤1.0,以及0.5≤d≤4.0。
另外,为了进一步提高寿命特性,优选将颗粒径的平均值Rg[μm]进一步限定为0.06<Rg<0.14,将其标准偏差σg[μm]进一步限定为σg<0.075。
在制造叠层陶瓷电容器1的过程中,准备未加工状态的电容器主体5,并对其进行烧成。通过叠层多个陶瓷基片(ceramic green sheet)来获得未加工的电容器主体5,该多个陶瓷基片包含形成了构成内部电极3或4的导电性浆(paste)膜的陶瓷基片。陶瓷基片被烧成时成为电容器主体5所具备的电介质陶瓷层2。
为了制作上述陶瓷基片,首先准备以BaTiO3系为主成分的BaTiO3系陶瓷粉末。该BaTiO3系陶瓷粉末的粒径平均值Rb[μm]是0.06<Rb<0.17,其标准偏差σb[μm]是σb<0.065。
另一方面,准备包含Li化合物的副成分。
并且,在上述BaTiO3系陶瓷粉末中混合上述副成分。由此来获得陶瓷原料粉末。在该陶瓷原料粉末中,Li含有量e[摩尔部分]相对于主成分100摩尔部分是0.5≤e≤6.0。
接着,通过在陶瓷原料粉末中加入粘合剂及有机溶剂后混合来制作陶瓷浆料,通过使该陶瓷浆料成形为片状,可获得陶瓷基片。
如上所述,在用于获得电容器主体5的烧成步骤中,通过在陶瓷基片所包含的粒度分布窄的BaTiO3系陶瓷粉末中加入适量的Li来适当地抑制颗粒增长,从而获得具有窄的粒度分布的颗粒(烧结体的粒子)。因此如前所述,即便进行使电介质陶瓷层2的厚度小于1μm的薄层化,在叠层陶瓷电容器1中也能够取得良好的寿命特性。
另外,适用本发明的叠层陶瓷电容器不仅限于具有如图1所示的构造,例如,可以具有多个内部电极在电容器主体内部中形成串联电容的构造、或者具有如阵列状的叠层陶瓷电容器或低ESL化的叠层陶瓷电容器那样的多端子构造。
以下,对根据本发明来实施的实验例进行说明。
[实验例1]在实验例1中调查了颗粒的粒度分布以及Li添加量给予寿命特性的影响。
(A)电介质原料混合物的制作首先,作为主成分的起始原料,利用BaCO3及TiO2,准备了具有表1所示的平均粒子径(Rb)及标准偏差(σb)的Ba1.007TiO3粉末。平均粒子径(Rb)及标准偏差(σb)通过FE-SEM来进行观察,从300个粒子中对相当于平均圆的直径进行分析并算出平均粒子径(Rb)及标准偏差(σb)。接着,在与副成分混合之前,称量了起始原料的Ba1.007TiO3粉末之后,以水作为介质通过球磨机来进行湿式混合,打破凝聚体。
另一方面,准备Dy2O3、MgCO3、MnCO3、SiO2及Li2CO3的各个粉末作为副成分,将这些与上述Ba1.007TiO3粉末配合,并以水为介质通过球磨机进行混合,以用组成式100Ba1.007TiO3+1.0DyO3/2+0.7MgO+0.3MnO+1.5SiO2+eLiO1/2来表示,且使上述组成式中的系数e成为表1所示的“Li添加量e”。然后,经过蒸发干燥来获得试样1~18各自的电介质原料混合物。另外,关于平均粒子径(Rb)及标准偏差(σb)和Li添加量e,试样1~9与试样10~18是分别相同的,不过在以下进行的叠层陶瓷电容器的制作工序中,陶瓷层的厚度是不同的。
【表1】
试样编号 | 平均粒子径(Rb)(μm) | 标准偏差(σb)(μm) | Li添加量e(摩尔部分) | 陶瓷层厚度(μm) |
1 | 0.1 | 0.04 | 3.5 | 0.9 |
2 | 0.1 | 0.065 | 3.5 | 0.9 |
3 | 0.06 | 0.03 | 3.5 | 0.9 |
4 | 0.17 | 0.04 | 3.5 | 0.9 |
5 | 0.17 | 0.07 | 3.5 | 0.9 |
6 | 0.1 | 0.04 | 0.4 | 0.9 |
7 | 0.1 | 0.04 | 6.2 | 0.9 |
8 | 0.1 | 0.05 | 0.4 | 0.9 |
9 | 0.17 | 0.075 | 0.4 | 0.9 |
10 | 0.1 | 0.04 | 3.5 | 1.0 |
11 | 0.1 | 0.065 | 3.5 | 1.0 |
12 | 0.06 | 0.03 | 3.5 | 1.0 |
13 | 0.17 | 0.04 | 3.5 | 1.0 |
14 | 0.17 | 0.07 | 3.5 | 1.0 |
15 | 0.1 | 0.04 | 0.4 | 1.0 |
16 | 0.1 | 0.04 | 6.2 | 1.0 |
17 | 0.1 | 0.05 | 0.4 | 1.0 |
18 | 0.17 | 0.075 | 0.4 | 1.0 |
(B)叠层陶瓷电容器的制作在上述电介质原料混合物中加入聚乙烯基丁缩醛系粘合剂及乙醇,并通过球磨机进行湿式混合来获得陶瓷浆料。利用唇状涂布机(lip coater)使该陶瓷浆料成形为片状,由此来获得陶瓷基片。此时如后所述,作为陶瓷基片制作了烧成后厚度为0.9μm和1.0μm这两种厚度的陶瓷基片。
接着,在上述陶瓷基片上丝网印刷(screen printing)以Ni为主成分的导电浆,并形成了用于构成内部电极的导电浆膜。
接着,叠层多张形成有导电浆膜的陶瓷基片,以使导电浆膜的引出侧互不相同,从而获得未加工的电容器主体。然后,将该未加工的电容器主体在N2氛围中加热到300℃的温度,使粘合剂燃烧之后,在由氧分压10-10MPa的H2-N2-H2O气体组成的还元性氛围中以1025℃的温度进行2小时烧成,从而获得烧结的电容器主体。
接着,在上述电容器主体的两端面涂布含有B2O3-Li2O-SiO2-BaO玻璃粉的Cu浆,在N2氛围中以800℃温度进行烧结,形成与内部电极电连接的外部电极,以获得各个试样的叠层陶瓷电容器。
这样获得的叠层陶瓷电容器的外形尺寸为长度2.0mm、宽度1.2mm、厚度1.0mm,介于内部电极之间的电介质陶瓷层的厚度如表2的“陶瓷层厚度”栏所示。另外,有效电介质陶瓷层数为100层,每1层的对置电极面积是1.4mm2。
(C)特性评价及陶瓷微构造观察作为特性评价对介电常数、介电损失(DF)、电容温度特性以及高温负载寿命特性进行了评价。
用于求出介电常数的静电容量及介电损失(DF)是在温度25℃、1kHz以及AC电压0.5Vrms的条件下进行测定的。
电容温度特性是求出了静电容量相对于温度变化的变化率的特性,其采用了以25℃时的静电容量为基准的-55℃~85℃范围内的变化率最大的值。如果-55℃~85℃范围中的变化率是±15%以内,则满足EIA规格的X5R特性。
为了求出高温负载寿命特性,在温度150℃下实施了施加12.5V的直流电压来测定绝缘电阻的经时变化的加速可靠性试验。在该加速可靠性试验中,将绝缘电阻值为105Ω以下的时刻判定为故障,求出到达该故障之前的时间平均值、即平均故障时间。
另外,对陶瓷微构造进行了观察。即,利用FE-SEM来观察作为试样的叠层陶瓷电容器的断裂面,从300个颗粒中,对相当于平均圆的直径进行分析,并算出平均颗粒径Rg及其标准偏差σg。
表2示出以上的特性评价及陶瓷微构造观察的结果。
【表2】
试样编号 | 平均颗粒径(Rg)(μm) | 标准偏差(σg)(μm) | 介电常数 | DF(%) | 温度特性(%) | 平均故障时间(小时) |
1 | 0.1 | 0.04 | 1800 | 1.8 | -8 | 170 |
2 | 0.1 | 0.075 | 1900 | 1.9 | -10 | 50 |
3 | 0.06 | 0.035 | 2300 | 2.2 | -14 | 10 |
4 | 0.17 | 0.045 | 1900 | 2 | -11 | 60 |
5 | 0.17 | 0.08 | 2000 | 2 | -12 | 10 |
6 | 0.1 | 0.045 | 2000 | 2 | -12 | 30 |
7 | 0.1 | 0.05 | 1800 | 1.9 | -11 | 70 |
8 | 0.1 | 0.06 | 2100 | 2.1 | -13 | 20 |
9 | 0.17 | 0.08 | 2400 | 2.3 | -14 | 10 |
10 | 0.1 | 0.045 | 1800 | 1.8 | -8 | 200 |
11 | 0.1 | 0.075 | 1900 | 1.9 | -10 | 160 |
12 | 0.06 | 0.04 | 2300 | 2.2 | -14 | 50 |
13 | 0.17 | 0.05 | 1900 | 2 | -11 | 160 |
14 | 0.17 | 0.075 | 2000 | 2 | -12 | 150 |
15 | 0.1 | 0.04 | 2000 | 2 | -12 | 160 |
16 | 0.1 | 0.05 | 1800 | 1.9 | -11 | 160 |
17 | 0.1 | 0.06 | 2100 | 2.1 | -13 | 70 |
18 | 0.17 | 0.08 | 2400 | 2.3 | -14 | 70 |
首先,针对表2所示的全部试样,介电常数是1500以上,DF小于5%,温度特性满足X5R特性。
在陶瓷层厚度是0.9μm的试样1~9中全部满足Li添加量e[摩尔部分]是0.5≤e≤6.0、平均颗粒径Rg[μm]是0.06<Rg<0.17和其标准偏差σg[μm]是σg<0.075这三个条件的试样1中,能够获得良好的寿命特性。由此可知,通过上述Rg、σg及e这3个要素的相乘效果,即使在陶瓷层的厚度小于1μm的薄层品中也能够获得良好的寿命特性。
这可以进行以下推测。在副成分中Li在0.5≤e≤6.0范围内存在,由此Li作为抑制剂抑制颗粒增长,从而作用成使颗粒径分布窄。通过使颗粒径分布变窄,来改善可靠性。此外,在副成分中Li存在于0.5≤e≤6.0的范围内时,当采用平均粒子径Rb[μm]是0.06<Rb<0.17、标准偏差σb[μm]是σb<0.065的包含钛酸钡系陶瓷粉末作为主成分的陶瓷原料粉末时,烧结后的电介质陶瓷中的颗粒的粒度分布显著变窄,由此即使是陶瓷层的厚度小于1.0μm的薄层,也能够使加速可靠性试验中的平均故障时间为100小时以上从而提高了可靠性。
另外,在陶瓷层的厚度是1.0μm的试样10~18中也如试样1那样,如果全部满足Li添加量e[摩尔部分]是0.5≤e≤6.0、平均颗粒径Rg[μm]是0.06<Rg<0.17、其标准偏差σg[μm]是σg<0.075这3个条件,则如试样10那样可获得良好的寿命特性。但是,关于寿命特性,在陶瓷层厚度小于1.0μm的试样之间进行比较的情况与在陶瓷层厚度为1μm以上的试样之间进行比较的情况相比,满足上述3个条件的试样和除此以外的试样之间的差别非常显著。
[实验例2]实验例2是对于提高寿命特性,为了规定更好的组成范围而实施的。
(A)电介质原料混合物的制作首先,作为主成分的起始原料,准备BaCO3、CaCO3及TiO2的各个粉末,称量这些粉末,使其成为分别具有表3所示的m及x的(Ba1-xCax)mTiO3的组成,然后进行热处理,以获得具有表3所示的平均粒子径(Rb)及标准偏差(σb)的(Ba1-xCax)mTiO3粉末。接着,在与副成分混合之前,称量了起始原料的(Ba1-xCax)mTiO3粉末之后,以水为介质通过球磨机进行湿式混合,打破凝聚体。
另一方面,准备了R(R是从La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu及Y中选出的1种)、Mg、M(M是Mn及V的至少一方)、Si及Li的各个氧化物或碳酸盐的各粉末来作为副成分,将这些与上述(Ba1-xCax)mTiO3粉末相配合,并以水为介质通过球磨机来进行混合,以用组成式100(Ba1-xCax)mTiO3+aRO3/2+bMgO+cMO+dSiO2+eLiO1/2来表示,且分别采用在表3中一一示出的M成分及R成分,并成为具有系数a、b、c、d及e的组成。之后,经过蒸发干燥来获得试样101~128各自的电介质原料混合物。
(B)叠层陶瓷电容器的制作经过与实验例1同样的操作来获得各试样的叠层陶瓷电容器。电介质陶瓷层的厚度为0.8μm。
(C)特性评价及陶瓷微构造观察对与实验例1同样的特性评价及陶瓷微构造进行了观察。结果在表4中示出。
【表4】
试样编号 | 平均颗粒径(Rg)[μm] | 标准偏差(σg)[μm] | 介电常数 | DF[%] | 温度特性[%] | 平均故障时间[小时] |
101 | 0.11 | 0.04 | 2200 | 2.3 | -9 | 160 |
102 | 0.11 | 0.04 | 1700 | 1.8 | -8 | 190 |
103 | 0.11 | 0.04 | 1900 | 2.0 | -9 | 180 |
104 | 0.10 | 0.04 | 2000 | 2.3 | -9 | 170 |
105 | 0.10 | 0.04 | 1900 | 2.1 | -10 | 180 |
106 | 0.11 | 0.04 | 1900 | 1.8 | -13 | 160 |
107 | 0.11 | 0.04 | 2000 | 1.8 | -9 | 160 |
108 | 0.11 | 0.04 | 1800 | 1.7 | -10 | 180 |
109 | 0.11 | 0.04 | 2100 | 2.1 | -10 | 160 |
110 | 0.11 | 0.04 | 1800 | 1.8 | -8 | 180 |
111 | 0.11 | 0.04 | 1900 | 2.0 | -8 | 190 |
112 | 0.11 | 0.04 | 1900 | 2.0 | -9 | 180 |
113 | 0.11 | 0.04 | 2000 | 2.2 | -11 | 160 |
114 | 0.11 | 0.04 | 2200 | 2.3 | -13 | 160 |
115 | 0.11 | 0.04 | 2100 | 2.1 | -11 | 160 |
116 | 0.11 | 0.04 | 1800 | 1.9 | -12 | 190 |
117 | 0.11 | 0.04 | 1700 | 1.9 | -13 | 180 |
118 | 0.11 | 0.04 | 1800 | 1.9 | -12 | 180 |
119 | 0.10 | 0.04 | 1900 | 2.0 | -14 | 130 |
120 | 0.10 | 0.04 | 1400 | 1.5 | -10 | 120 |
121 | 0.10 | 0.04 | 1600 | 1.7 | -14 | 130 |
122 | 0.11 | 0.04 | 1900 | 1.9 | -12 | 110 |
123 | 0.11 | 0.04 | 1700 | 1.8 | -17 | 140 |
124 | 0.11 | 0.04 | 1600 | 1.7 | -14 | 120 |
125 | 0.11 | 0.04 | 1800 | 1.8 | -13 | 110 |
126 | 0.11 | 0.04 | 1900 | 1.9 | -13 | 120 |
127 | 0.11 | 0.04 | 1700 | 1.8 | -14 | 110 |
128 | 0.11 | 0.04 | 2000 | 2.0 | -16 | 110 |
首先,表4所示的试样的全部都处于本发明的范围内,DF小于5%,并示出110小时以上的平均故障时间。
但是,在表4示出的试样中尤其是试样101~118在组成式:100(Ba1-xCax)mTiO3+aRO3/2+bMgO+cMO+dSiO2+eLiO1/2中,满足0.96≤m≤1.03,0≤x≤0.2,0.2≤a≤5.0,0≤b≤2.0,0.2≤c≤1.0,以及0.5≤d≤4.0的各个条件,结果,介电常数为1500以上,温度特性满足X5R特性,平均故障时间是150小时以上,寿命特性进一步提高。
针对这些,关于m在作为m<0.960的试样119中,平均故障时间小于150小时,另一方面,在作为m>1.030的试样120中,介电常数低于1500,平均故障时间小于150小时。
另外,关于x在作为x>0.20的试样121中,平均故障时间小于150小时。
另外,关于a在作为a<0.2的试样122中,平均故障时间小于150小时,另一方面,在作为a>5.0的试样123中,介电常数的温度变化率的绝对值在15%以上,平均故障时间小于150小时。
另外,关于b在作为b>2.0的试样124中,平均故障时间小于150小时。
另外,关于c在作为c<0.2的试样125中,平均故障时间小于150小时,另一方面,即使作为c>1.0的试样126,平均故障时间也小于150小时。
另外,关于d在作为d<0.5的试样127中,平均故障时间小于150小时,另一方面,在作为d>4.0的试样128中,介电常数的温度变化率的绝对值在15%以上,平均故障时间小于150小时。
[实验例3]实验例3是要针对平均颗粒径来求出更好的范围的实施例。
(A)电介质原料混合物的制作除了采用具有表5所示的平均粒子径(Rb)及标准偏差(σb)的BaTiO3系粉末的情况之外,与实验例1中的试样1的电介质原料混合物的情况相同,从而获得了试样201及202各自的电介质原料混合物。
【表5】
试样编号 | 平均粒子径(Rb)(μm) | 标准偏差(σb)(μm) |
201 | 0.07 | 0.03 |
202 | 0.15 | 0.06 |
(B)叠层陶瓷电容器的制作经过与实验例1同样的操作来获得各试样的叠层陶瓷电容器。电介质陶瓷层的厚度为0.9μm。
(C)特性评价及陶瓷微构造观察对与实验例1的情况同样的特性评价及陶瓷微构造进行了观察。特性评价的结果在表6中示出。
【表6】
试样编号 | 平均颗粒径(Rg) | 标准偏差(σg)(μm) | 介电常数 | DF(%) | 温度特性(%) | 平均故障时间(小时) |
201 | 0.07 | 0.03 | 1700 | 1.8 | -7 | 170 |
202 | 0.15 | 0.06 | 2200 | 2.3 | -11 | 120 |
如表6所示,平均颗粒径Rg[μm]处于0.06<Rg<0.14范围内的试样201与该范围以外的试样202相比,寿命特性更加良好。
Claims (5)
1.一种电介质陶瓷,其主成分是BaTiO3系,其特征在于,
作为副成分包含Li,Li含有量e摩尔部分相对于主成分100摩尔部分是0.5≤e≤6.0,
关于该电介质陶瓷的颗粒,颗粒径的平均值Rg微米是0.06<Rg<0.17,其标准偏差σg微米是σg<0.075。
2.根据权利要求1所述的电介质陶瓷,其特征在于,
该电介质陶瓷用以下组成式来表示:100(Ba1-xCax)mTiO3+aRO3/2+bMgO+cMO+dSiO2+eLiO1/2,
其中m、a、b、c、d及e表示摩尔比,R含有从La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu以及Y中选出的至少1种,M含有Mn及V的至少一方,
且满足以下各条件:
0.96≤m≤1.03,
0≤x≤0.2,
0.2≤a≤5.0,
0≤b≤2.0,
0.2≤c≤1.0,及
0.5≤d≤4.0。
3.根据权利要求1或2所述的电介质陶瓷,其特征在于,
颗粒径的平均值Rg微米是0.06<Rg<0.14,其标准偏差σg微米是σg<0.075。
4.一种叠层陶瓷电容器,其具有:
电容器主体,其由叠层的多个电介质陶瓷层、和沿着上述电介质陶瓷层间的特定界面而形成的多个内部电极构成;以及
多个外部电极,其形成在上述电容器主体外表面上的互不相同的位置处,且与上述内部电极的特定内部电极电连接,
位于在上述内部电极的叠层方向上相邻的内部电极之间的上述电介质陶瓷层的厚度小于1微米,且上述电介质陶瓷层由权利要求1至3中任一项所述的电介质陶瓷构成。
5.一种电介质陶瓷的制造方法,其具有以下步骤:
准备以BaTiO3系为主成分的BaTiO3系陶瓷粉末的步骤;
准备包含Li化合物的副成分的步骤;
通过在上述BaTiO3系陶瓷粉末中混合上述副成分来获得陶瓷原料粉末的步骤;
通过使上述陶瓷原料粉末成形来获得陶瓷成形体的步骤;以及
通过烧成上述陶瓷成形体来获得电介质陶瓷的步骤,
在上述陶瓷原料粉末中,Li含有量e摩尔部分相对于主成分100摩尔部分是0.5≤e≤6.0,
在上述BaTiO3系陶瓷粉末中,粒径的平均值Rb微米是0.06<Rb<0.17,其标准偏差σb微米是σb<0.065。
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