CN104205267B - 层叠陶瓷电容器 - Google Patents
层叠陶瓷电容器 Download PDFInfo
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- CN104205267B CN104205267B CN201280072167.8A CN201280072167A CN104205267B CN 104205267 B CN104205267 B CN 104205267B CN 201280072167 A CN201280072167 A CN 201280072167A CN 104205267 B CN104205267 B CN 104205267B
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- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 229910002785 ReO3 Inorganic materials 0.000 claims abstract description 5
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- YSZJKUDBYALHQE-UHFFFAOYSA-N rhenium trioxide Chemical compound O=[Re](=O)=O YSZJKUDBYALHQE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 18
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 8
- 229910052689 Holmium Inorganic materials 0.000 claims description 8
- 229910052691 Erbium Inorganic materials 0.000 claims description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 abstract description 10
- 239000011777 magnesium Substances 0.000 description 41
- 239000013081 microcrystal Substances 0.000 description 33
- 239000000843 powder Substances 0.000 description 14
- 229910002113 barium titanate Inorganic materials 0.000 description 13
- 239000011572 manganese Substances 0.000 description 12
- 230000008859 change Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 208000000058 Anaplasia Diseases 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910010252 TiO3 Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
在层叠陶瓷电容器中,控制焙烧构成电介质层的电介质颗粒时的颗粒生长以确保晶界,并且将每单位粒径的介电常数设定成较高数值,由此,能够兼顾实现高密度层叠和提高可靠性两者。所述电介质层包含烧结体,上述烧结体中相对于100摩尔的BaTiO3包含a摩尔的ReO3/2、b摩尔的SiO2、c摩尔的MOx、d摩尔的ZrO2、e摩尔的MgO,其中,Re是稀土类元素,M是金属元素且不包括Ba、Ti、Re、Si、Zr、Mg和稀土类元素,x是价数,表示各成分的摩尔数的上述a、b、c、d、e分别满足:0.1≤a≤1.0,0.1≤b≤1.5,0.1≤c≤0.4,0≤d≤1.0,0≤e≤0.03。
Description
技术领域
本发明涉及通过电介质层的高密度层叠来实现小型大容量化的层叠陶瓷电容器(MLCC)。
背景技术
随着移动电话等数字电子仪器的小型化和薄型化,在安装于电子电路基板的层叠陶瓷电容器(MLCC:Multi-Layer ceramic capacitor)中,对所要求的芯片尺寸的小型化和大容量化的需求逐年增大。一般来讲,存在如果缩小电容器的尺寸,则与电介质层相对的内部电极的面积必然会变小,由此静电电容减少的关系。因此,为了实现芯片尺寸的小型化并确保电容器的容量,必然需要将内部电极间的电介质层做薄,且多层地层叠电介质层的高密度层叠化技术。
在层叠陶瓷电容器中,为了将内部的电介质层做薄实现高密度化,认为要尽量使作为电介质的主要成分的例如BaTiO3(钛酸钡)的粒径减小。但是,如果在电介质层薄层化的同时减小电介质的粒径,则根据其尺寸效果,介电常数就会下降,作为电容器整体无法获得足够的容量。因此,在陶瓷电容器的高密度层叠中采用以下这种技术:通过焙烧电介质的微粉末使粒径生长,防止介电常数下降以确保容量。
例如,根据专利文献1,在将电介质层形成为1μm左右的薄层时,作为原料粉末,将用Ca置换BaTiO3的一部分得到的Ba1-XCaXTiO3(也称作“BCT”)调制成0.1~0.2μm的粒径,使其颗粒生长直至电介质颗粒的直径(晶粒粒径)变成0.35~0.65μm,由此得到6000以上的介电常数。一般情况下,为了抑制因焙烧所引起的电介质的还原,添加Mg作为受主元素。在专利文献1中,包含在电介质中的MgO的量相对于100摩尔的Ba1-XCaXTiO3为0.05~3.0摩尔。
现有技术文献
专利文献
专利文献1:日本特开2010-180124号公报
发明内容
发明所要解决的课题
为了实现层叠陶瓷电容器的更加小型化以及大容量化,在将电介质的层厚设定在1μm以下的情况下,该电介质层厚与颗粒的粒径大体相等,变成接近所谓的一层一颗粒的构造。越是一层一颗粒的构造,颗粒间的晶界就越少,因此,容易导致电气绝缘性的恶化和寿命劣化。其原因在于,与电介质颗粒相比,晶界的绝缘性更高,另外,发挥晶界阻止静电场中产生的氧缺陷的移动(电场迁移)的作用。另一方面,如果为了确保晶界,抑制焙烧时的电介质的颗粒生长以保持小的粒径,则根据上述的尺寸效果,就会产生介电常数下降这样相反的问题。
本发明就是为了解决这种问题,其目的在于,提供一种层叠陶瓷电容器,抑制焙烧构成电介质层的电介质颗粒时的颗粒生长以确保晶界,并且将每单位粒径的介电常数设定成高数值,由此,能够兼顾实现高密度层叠以及提高可靠性。
用于解决课题的方法
本发明是一种层叠陶瓷电容器,该层叠陶瓷电容器包括:电介质层与内部电极层交替层叠而成的层叠体;和作为上述层叠体的层叠方向上下的最外层形成的覆盖层,上述电介质层包含烧结体,上述烧结体中相对于100摩尔的BaTiO3包含a摩尔的ReO3/2、b摩尔的SiO2、c摩尔的MOx、d摩尔的ZrO2、e摩尔的MgO,其中,Re是稀土类元素,M是金属元素且不包括Ba、Ti、Re、Si、Zr、Mg和稀土类元素,x是价数,表示相对于100摩尔的BaTiO3的各成分的摩尔数的上述a、b、c、d、e分别满足:0.1≤a≤1.0,0.1≤b≤1.5,0.1≤c≤0.4,0≤d≤1.0,0≤e≤0.03。
另外,在层叠陶瓷电容器中,上述覆盖层中,相对于100摩尔的BaTiO3包含2.0摩尔以下的Mg。
另外,上述Re是选自Y、Eu、Gd、Dy、Ho、Er和Yb中的至少一种稀土类元素,优选上述Re是选自Y、Ho和Gd中的至少一种稀土类元素。
另外,上述M可以是选自Mn和/或V中的金属元素。
另外,构成上述电介质层的电介质颗粒的每平均粒径(相对于平均粒径)的介电常数的值是15nm-1以上。
另外,构成上述电介质层的电介质颗粒的平均粒径可以是500nm以下。
发明效果
根据本发明,抑制焙烧电介质层时的颗粒生长以确保晶界,并且能够将每单位粒径的介电常数设定成较高数值。由此,能够兼顾实现层叠陶瓷电容器中的高密度层叠和提高可靠性两者。
附图说明
图1是本发明的实施方式的层叠陶瓷电容器的概略纵截面图。
图2是为了说明“晶粒粒径”所表示的电介质层的截面图。
图3是表示Mg量与介电常数(相对介电常数)的关系的图。
图4是将图3的纵坐标换算成相对于晶粒粒径的介电常数而表示Mg量与介电常数的关系的图。
图5是为了比较表示将Mg量扩大的范围中,Mg与相对晶粒粒径的介电常数的关系的图。
图6是详细表示与图5的虚线所示的范围中的Mg与相对于晶粒粒径的介电常数的关系的图。
图7是关于本实施例(Mg的摩尔数e为0≤e≤0.03)与比较例(Mg的摩尔数e为0.05≤e≤3.00)表示晶粒粒径与介电常数的关系的图。
具体实施方式
下面,说明本发明的一个实施方式的层叠陶瓷电容器。图1是层叠陶瓷电容器1的概略纵截面图。层叠陶瓷电容器1大体由:具有按照规格确定的芯片尺寸以及形状(例如1.0×0.5×0.5mm的长方体)的陶瓷烧结体10;和形成于陶瓷烧结体10两侧的一对外部电极20构成。陶瓷烧结体10包括:例如以BaTiO3(钛酸钡)为主成分,在内部交替层叠电介质层12与内部电极13而成的层叠体11;和作为层叠方向上下的最外层形成的覆盖层15。
层叠体11根据静电容量和所要求的耐压等的规格,具有被两个内部电极层13夹着的电介质层12的一层厚度为1μm以下(例如300nm左右),且整体的层叠数为数百层的高密度多层构造。形成于层叠体11的最外层部分的覆盖层15保护电介质层12和内部电极层13不受来自外部的湿气和污染物等的污染,防止它们的经时劣化。
层叠陶瓷电容器1例如按照以下的方式制造。首先,将以BaTiO3为主成分的微颗粒的原料粉末与添加化合物一起进行湿式混合,然后进行干燥、粉碎,调制电介质原料粉末。利用聚乙烯醇缩醛树脂和有机溶剂对所调制的电介质原料粉末进行湿式混合,例如采用刀刮法涂敷1μm以下的带状电介质生片并将其干燥。接着,在电介质生片的表面丝网印刷包含有机粘合剂的导电膏,从而配置内部电极层13的图案。此外,导电膏中作为金属粉末例如优选使用Ni。另外,作为共材(共用材料),也可以均匀地分散粒径为50nm以下的BaTiO3。
然后,例如将冲裁为15cm×15cm大小并且一致的电介质生片按照内部电极层13互相错开的方式层叠规定层数。在所层叠的电介质生片的上下压接作为覆盖层15的覆盖片,切割成规定芯片尺寸(例如1.0×0.5mm),然后,将作为外部电极20的导电膏涂敷在层叠体的两侧并使其干燥。由此,得到层叠陶瓷电容器1的成型体。
在大约350℃的N2气体气氛中对由此获得的成型体进行脱粘合剂,然后,在N2、H2、H2O的混合气体(氧分压约为1.0×10-11MPa)中、在1220~1280℃下焙烧10分钟~2小时。焙烧后,在大约1000℃的N2气体气氛中进行大约1小时的电介质的氧化处理,从而得到使构成电介质层的电介质颗粒生长为所希望的晶粒粒径(在本说明书中如后所述,是指焙烧后的电介质颗粒的平均粒径)的层叠陶瓷电容器1。
在层叠陶瓷电容器1中,电介质层12包括相对于100摩尔的BaTiO3含有a摩尔的ReO3/2、b摩尔的SiO2、c摩尔的MOx、d摩尔的ZrO2、e摩尔的MgO(此处,Re是稀土类元素,M是金属元素(但是,Ba、Ti、Re、Si、Zr、Mg以及稀土类元素除外),x是价数)的烧结体。组成式中的系数a、b、c、d及e表示相对于100摩尔的BaTiO3的摩尔数,分别满足0.1≤a≤1.0,0.1≤b≤1.5,0.1≤c≤0.4,0≤d≤1.0和0≤e≤0.03的关系。MgO的摩尔数优选0.01≤e≤0.03。
覆盖层15中的Mg的含量与包含在该覆盖层15中的100摩尔的BaTiO3相比,可以是2.0摩尔以下。
包含在电介质层12中的Re(稀土类元素)可以选自Y(钇)、Eu(铕)、Gd(钆)、Dy(镝)、Ho(钬)、Er(铒)以及Yb(镱)中的至少一种,优选选自Y、Ho、Gd中的至少一种。
包含在电介质层12中的M(金属元素)可以选自Mn(锰)和/或者V(钒)。
根据按照以上条件所制作的本实施方式的层叠陶瓷电容器1,能够得到构成电介质层12的电介质颗粒的每平均粒径(晶粒粒径)的介电常数值为15nm-1以上。另外,此时的平均粒径可以是500nm以下。
实施例
下面,说明本发明的层叠陶瓷电容器(以下称作“MLCC”)的实施例。
<MLCC的制作>
(1)电介质原料粉末的调制
首先,作为电介质的原料粉末,将平均粒径为110nm的高纯度BaTiO3粉末、表1~7所示的ReO3/2、SiO2、MOX(准备用作MnCO3;通过焙烧CO2分离变成MnO)、ZrO2、MgO的各化合物准备用作电介质的原料粉末。原料粉末的平均粒径是通过用SEM观察钛酸钡的粉末样品,样品数为500,取其中值粒径而求出的。接着,称量并混合各个化合物使得MLCC的电介质层、即变成烧结体时的组成比变成表1~7所示的组成比。用水湿式混合按照上述方式混合的各试样的原料粉末,进行干燥、干式粉碎,调制电介质原料粉末。覆盖层用的电介质原料粉末也按照同样的组成化合物进行准备。
(2)MLCC成型体的制作
利用聚乙烯醇缩醛类树脂以及有机溶剂将所调制的电介质原料粉末进行湿式混合,采用刀刮法涂敷1.0μm厚的陶瓷生片并将其干燥。对于覆盖层用的陶瓷覆盖片,厚度采用10μm。在作为电介质层的生片上按照规定的图案丝网印刷Ni导电膏,由此来配置内部电极。层叠101个配置有电极图案的生片,在电介质层的层叠数n达到100后,在该层叠体的上下,在单侧各压接20个10μm厚的覆盖片,然后,将其切割成1.0×0.5mm。然后,将作为外部电极的Ni导电膏涂敷在层叠体的两侧并使其干燥,从而得到MLCC成型体的试样。
(3)MLCC成型体的焙烧
在N2气体气氛中在350℃下对MLCC成型体的试样进行脱粘合剂。然后,在N2、H2、H2O的混合气体(氧分压约为1.0×10-11MPa)中、在1220~1280℃下焙烧10分钟~2小时。适当调整焙烧的温度以及时间以得到目标晶粒粒径(300nm)。焙烧后,在N2气体气氛中在1000℃下进行1小时的电介质的氧化处理。
对于由此得到的MLCC,按照后述的方式进行各种评价。此外,从所得到的MLCC剥离覆盖层,粉碎剥离了覆盖层后的MLCC,利用ICP分析(Inductively Coupled Plasma:感应耦合等离子体分析)进行分析,检测出关于构成电介质层的各个成分的定量数据,将相对BaTiO3的定量数据的各个成分的定量数据换算成摩尔数,计算出组成比,确认变成表1~7所示的组成比。另外,对于包含在覆盖层中的Mg,用ICP分析进行对所剥离的覆盖层的分析,将所得到的相对BaTiO3的定量数据的MgO的定量数据换算成摩尔数而计算出,由此确认变成表1~表7所示的组成比。
<MLCC的评价方法>
(1)晶粒粒径的评价方法
通过研磨MLCC的一部分截面进行抽取,根据用扫描式电子显微镜(SEM)拍摄电介质层的截面的图片,测定电介质颗粒的晶粒粒径。图2是示意地表示电介质层的截面的图。在本说明书中将“晶粒粒径”定义为:与内部电极层平行的方向(即,与电场方向正交的方向)上的焙烧后的电介质颗粒(晶粒)的最大长度的平均值。即,参照图2,晶粒粒径Dg是通过用取样的电介质颗粒的最大长度Dgs的总和除以其取样个数而求得的。此外,对于测定晶粒粒径的电介质颗粒的取样,取样数为500个以上,在一处的观察部位(例如一张通过SEM放大2000倍时的图片)有500个以上的情况下,对其中的所有电介质颗粒取样,在小于500个的情况下,在多处进行观察(拍摄),使取样数成为500个以上。此外,为了清晰地拍摄SEM图片中的粒界的边界线,预先在与焙烧工艺相同的气体气氛(N2、H2、H2O的混合气体)中,在1180℃下进行5分钟的热处理,实施颗粒界面的热蚀刻。
(2)介电常数的评价方法
将焙烧后进行了氧化处理的MLCC在150℃的恒温槽内静置1小时,然后在室温25℃下静置24小时,在条件齐备后,使用阻抗分析仪测定静电容量Cm。用于测定的电压施加条件为1kHz、1.0Vrms。根据所测定的静电容量Cm,使用下述式(1)求出介电常数(相对介电常数)ε。
Cm=ε×ε0×n×S/t…式(1)
此处,ε0是真空的介电常数,n、S、t分别是电介质层的层叠数、内部电极层的面积、电介质层的一层的厚度。
另外,在本实施例中,如下面的表1~7所示,采用每单位晶粒粒径的介电常数(ε/Dg)作为电容器的容量特性的评价值。
<MLCC的评价结果>
参照表1~7说明对于根据以上的条件所制作的MLCC的电介质层的评价结果。
(1)试样No.1~12
[表1]
试样No.1~12是相对于100摩尔的BaTiO3,使所添加的Mg(镁)元素的摩尔(mol)数e在0~0.04之间变化,包含在其他的添加物中的Re(稀土类,具体而言是Ho(钬))元素的摩尔数a固定为0.50,Si(硅)元素的摩尔数b固定为0.50,M(金属,具体而言是Mn(锰)与V(钒))元素的摩尔数c固定为0.20(等比),Zr(锆)元素的摩尔数d固定为0.10时的样品例子。
在试样No.1~9中,Mg的摩尔数e在0≤e≤0.03的范围,实现了介电常数(相对介电常数)ε>5000。同时,得到ε/Dg(介电常数与晶粒粒径之比)>15(nm-1)。在Mg的摩尔数e为0.04≤e的试样No.10~12中,介电常数ε小于5000。
(2)试样No.13~16
[表2]
试样No.13~16是相对于100摩尔(mol)的BaTiO3,使Re(Ho)元素的摩尔数a在0~1.50之间变化,Si元素的摩尔数b固定为0.50,M(Mn与V)元素的摩尔数c固定为0.20(等比),Zr元素的摩尔数d固定为0.10,Mg元素的摩尔数e固定为0.01时的例子。
在试样No.14和15中,Re的摩尔数a在0.10≤a≤1.00的范围,实现了介电常数ε>5000,且得到ε/Dg>15(nm-1)。
在Re的摩尔数a为0的试样No.13中,因还原推进半导体化,丧失电容特性。在Re的摩尔数a为1.50的试样No.16中,介电常数ε小于5000。
(3)试样No.17~23
[表3]
试样No.17~23是相对于100摩尔的BaTiO3,使Si元素的摩尔数b在0~2.00之间变化,Re(Ho)元素的摩尔数a固定为0.50,M(Mn与V)元素的摩尔数c固定为0.20(等比),Zr元素的摩尔数d固定为0.10,Mg元素的摩尔数固定e为0.01时的例子。
在试样No.18~22中,Si的摩尔数b在0.10≤b≤1.50的范围,实现了介电常数ε>5000,且得到ε/Dg>15(nm-1)。在Si的摩尔数b为0的试样No.17中,评价为烧结体的致密化不足。在Si的摩尔数b为2.00的试样No.23中,介电常数ε小于5000。
(4)试样No.24~33
[表4]
试样No.24~33是相对于100摩尔的BaTiO3,使M(Mn以及/或者V)元素的摩尔数c在0~0.50之间变化,Re(Ho)元素的摩尔数a固定为0.50,Si元素的摩尔数b固定为0.50,Zr元素的摩尔数d固定为0.10,Mg元素的摩尔数e固定为0.01时的例子。
M(Mn以及/或者V)的摩尔数c在0.10≤c≤0.40的范围的试样No.27、28、30、32中,实现了介电常数ε>5000,且得到ε/Dg>15(nm-1)。在M的摩尔数c为0~0.05的试样No.24~26中,通过还原丧失了电容特性。在M的摩尔数c为0.50~0.60的试样No.29、31、33中,介电常数ε小于5000。
(5)试样No.34~39
[表5]
试样No.34~39是相对于100摩尔的BaTiO3,使Zr元素的摩尔数d在0~1.25之间变化,Re(Ho)元素的摩尔数a固定为0.50,Si元素的摩尔数b固定为0.50,M(Mn与V)元素的摩尔数c固定为0.20(等比),Mg元素的摩尔数e固定为0.01时的例子。
在试样No.34~38中,Zr元素的摩尔数d在0≤d≤1.00的范围,实现了介电常数ε>5000,且得到ε/Dg>15(nm-1)。在Zr元素的摩尔数d为1.25的试样No.39中,介电常数ε小于5000。
(6)试样No.40~47
[表6]
试样No.40~45是相对于100摩尔的BaTiO3,Re(稀土类)元素的摩尔数a为0.50,Si元素的摩尔数b为0.50,M(Mn与V)元素的摩尔数c为0.20(等比),Zr元素的摩尔数d为0.10,Mg元素的摩尔数e为0.01,将Re的种类分别改变成Y(钇)、Eu(铕)、Gd(钆)、Dy(镝)、Er(铒)以及Yb(镱)时的例子。试样No.46是试样No.40~45的各个成分的组成比量的条件相同,但是作为Re(稀土类)等比混合(各自摩尔数为0.25)Ho与Dy两种元素时的例子。试样No.47为作为Re(稀土类)等比混合(各自摩尔数为0.25)Ho、Gd、Er、Yb的各个元素,关于其他成分的组成比量与试样No.40~45相同条件时的例子。
在试样No.40~45中的任一情况下,也实现了介电常数ε>5000,且能够得到ε/Dg>15(nm-1)。特别是通过适当选择Ho(试样No.34~38)、Y(试样No.40)、Eu(试样No.41)、Gd(试样No.42)等稀土类元素,能够实现较高的介电常数。
(7)试样No.48~52
[表7]
试样No.48~52是相对于100摩尔的BaTiO3,使Re(Ho)元素的摩尔数a固定为0.50,Si元素的摩尔数b固定为0.50,M(Mn与V)元素的摩尔数c固定为0.20(等比),Zr元素的摩尔数d固定为0.1,Mg元素的摩尔数e固定为0.01,仅使覆盖层的Mg元素的摩尔数在0.5~2.50之间增量变化。
在试样No.48~51中,在覆盖层的Mg元素的摩尔数为2.00以下的范围,实现了介电常数ε>5000,且得到ε/Dg>15(nm-1)。在覆盖层的Mg元素的摩尔数为2.50的试样No.52中,介电常数ε小于5000。
(8)其他晶粒粒径中的例子
对于将目标晶粒粒径设定在200nm和500nm并使晶粒生长的试样,也调查Mg添加量与介电常数(相对介电常数)的关系。图3是将晶粒粒径(200nm、300nm、500nm)作为参数,按照Mg量与介电常数的关系画出各个实测值的图表。另外,图4是关于图3,将其纵坐标换算成介电常数与晶粒粒径之比(ε/Dg)并进行评价的图。在图3及图4中,记号“◆”表示晶粒粒径为200nm时的测定值,记号“□”表示晶粒粒径为300nm时的测定值,记号“▲”表示晶粒粒径为500nm时的测定值。
如图3和图4所示,Mg组成摩尔数e在0≤e≤0.03的范围,晶粒粒径为200nm、300nm、500nm中的任一个的情况下,也实现了介电常数ε>5000,且确认了介电常数与粒径之比ε/Dg>15(nm-1)。
(9)与基于其他组成比条件的参考例的比较
图5是关于图4在将Mg组成量扩大至0~3.00摩尔的范围中,介电常数与晶粒粒径之比(ε/Dg)的关系的曲线图。另外,图6是在图5的虚线所示的范围中详细表示特性倾向的图。在图5和图6中,记号“●”表示比较例(Mg量为0.05mol≤Mg≤3.00mol,粒径为350~600nm)的测定值,记号“◆”表示晶粒粒径为200nm时的测定值,记号“□”表示晶粒粒径为300nm时的测定值,记号“▲”表示晶粒粒径为500nm时的测定值。
如图5所示,如果增加Mg的添加量使其组成摩尔量e变成e>0.03,则可知介电常数与晶粒粒径之比ε/Dg在15(nm-1)附近几乎不会变化。即,如果Mg的摩尔数e>0.03,则对电介质的介电常数的影响小到可以忽略的程度。
另一方面,如图6所示可知,在Mg的摩尔数e≤0.03的范围,Mg的量越少,每单位粒径的介电常数明显提高。即,通过尽量减少Mg的添加量,有利于确保介电常数。
图7是对于Mg的摩尔数e为0≤e≤0.03的本实施例、与Mg的摩尔数e为0.05≤e≤3.00的比较例,表示晶粒粒径与介电常数的关系的图。在图7中,记号“●”表示比较例(Mg量为0.05mol≤Mg≤3.00mol,晶粒粒径为350~600nm)的测定值,记号“◆”表示晶粒粒径为200nm时的测定值,记号“□”表示晶粒粒径为300nm时的测定值,记号“▲”表示晶粒粒径为500nm时的测定值。如图7所示可知,如果是相同晶粒粒径的电介质,则本实施例能够确保更高的介电常数。此外,为了通过确保晶界以进一步提高可靠性,优选0.01≤e≤0.03。
符号说明
1 层叠陶瓷电容器
10 陶瓷烧结体
11 层叠体
12 电介质层
13 内部电极层
15 覆盖层
20 外部电极
Claims (9)
1.一种层叠陶瓷电容器,其包括:电介质层与内部电极层交替层叠而成的层叠体;和作为所述层叠体的层叠方向上下的最外层形成的覆盖层,该层叠陶瓷电容器的特征在于:
所述电介质层包含烧结体,所述烧结体中相对于100摩尔的BaTiO3包含a摩尔的ReO3/2、b摩尔的SiO2、c摩尔的MOx、d摩尔的ZrO2、e摩尔的MgO,其中,Re是稀土类元素,M是金属元素且不包括Ba、Ti、Re、Si、Zr、Mg和稀土类元素,x是价数,
表示相对于100摩尔的BaTiO3的各成分的摩尔数的所述a、b、c、d、e分别满足:
0.1≤a≤1.0,
0.1≤b≤1.5,
0.1≤c≤0.4,
0≤d≤1.0,
0≤e≤0.03,
构成所述电介质层的电介质颗粒的每平均粒径的介电常数的值是15nm-1以上。
2.如权利要求1所述的层叠陶瓷电容器,其特征在于:
所述覆盖层中,相对于100摩尔的BaTiO3包含2.0摩尔以下的Mg。
3.如权利要求1所述的层叠陶瓷电容器,其特征在于:
所述Re是选自Y、Eu、Gd、Dy、Ho、Er和Yb中的至少一种稀土类元素。
4.如权利要求2所述的层叠陶瓷电容器,其特征在于:
所述Re是选自Y、Eu、Gd、Dy、Ho、Er和Yb中的至少一种稀土类元素。
5.如权利要求3所述的层叠陶瓷电容器,其特征在于:
所述Re是选自Y、Ho和Gd中的至少一种稀土类元素。
6.如权利要求4所述的层叠陶瓷电容器,其特征在于:
所述Re是选自Y、Ho和Gd中的至少一种稀土类元素。
7.如权利要求1~6中任一项所述的层叠陶瓷电容器,其特征在于:
所述M是选自Mn和/或V中的金属元素。
8.如权利要求1~6中任一项所述的层叠陶瓷电容器,其特征在于:
构成所述电介质层的电介质颗粒的平均粒径是500nm以下。
9.如权利要求1~6中任一项所述的层叠陶瓷电容器,其特征在于:
所述电介质层中的MgO的所述摩尔数e为0.01≤e≤0.03。
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JP2013229551A (ja) | 2013-11-07 |
JP5205544B1 (ja) | 2013-06-05 |
CN104205267A (zh) | 2014-12-10 |
WO2013145421A1 (ja) | 2013-10-03 |
KR20140129088A (ko) | 2014-11-06 |
KR101646913B1 (ko) | 2016-08-09 |
US9287046B2 (en) | 2016-03-15 |
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