CN110828167B - 多层陶瓷电容器 - Google Patents

多层陶瓷电容器 Download PDF

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CN110828167B
CN110828167B CN201811479756.3A CN201811479756A CN110828167B CN 110828167 B CN110828167 B CN 110828167B CN 201811479756 A CN201811479756 A CN 201811479756A CN 110828167 B CN110828167 B CN 110828167B
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dielectric
multilayer ceramic
shell
ceramic capacitor
core
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CN110828167A (zh
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朴今珍
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Samsung Electro Mechanics Co Ltd
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Samsung Electro Mechanics Co Ltd
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Abstract

本发明提供一种多层陶瓷电容器。所述多层陶瓷电容器包括:陶瓷主体,包括介电层和设置为彼此面对的第一内电极和第二内电极,介电层介于所述第一内电极和所述第二内电极之间;以及第一外电极和第二外电极,设置在所述陶瓷主体的外表面上,并分别电连接到所述第一内电极和所述第二内电极,其中,所述介电层包含具有包括核和壳的核‑壳结构的电介质晶粒,并且在所述壳中排列有畴壁。

Description

多层陶瓷电容器
本申请要求于2018年8月9日在韩国知识产权局提交的第10-2018-0092877号韩国专利申请的优先权的权益,所述韩国专利申请的公开内容通过引用被全部包含于此。
技术领域
本公开涉及一种能够提高可靠性的多层陶瓷电容器。
背景技术
通常,诸如电容器、电感器、压电元件、压敏电阻、热敏电阻等的使用陶瓷材料的电子组件包括利用陶瓷材料形成的陶瓷主体、形成在陶瓷主体中的内电极以及安装在陶瓷主体的表面上以连接到内电极的外电极。
近来,随着电子产品的小型化和多功能化,多层陶瓷电容器也已趋于小型化和多功能化。因此,已需要具有小尺寸和高电容的多层陶瓷电容器。
作为同时实现小型化和增大多层陶瓷电容器的电容的方法,存在通过减小介电层和电极层的厚度来增加多层陶瓷电容器中堆叠的介电层和电极层的数量的方法。目前,介电层的厚度约为0.6μm,并且正不断地开发减小介电层的厚度的技术。
此外,为了实现多层陶瓷电容器的电容增大,已需要具有高介电常数的材料。多层陶瓷电容器中使用的典型材料是钛酸钡(BaTiO3),但是由于钛酸钡的固有特性的限制导致难以开发用于增大介电常数的材料。
因此,已进行了对于通过在钛酸钡(BaTiO3)的表面上掺杂添加剂或对钛酸钡(BaTiO3)的表面进行重整来实现高介电常数的技术的研究,但是没有显著的成绩。
同时,已知的是,在实现介电常数的原理中存在90°的畴壁的影响。因此,已经不断进行对用于改善钛酸钡(BaTiO3)的四方性的技术的研究。
由于添加到多层陶瓷电容器的介电材料中以提高多层陶瓷电容器的可靠性并确保多层陶瓷电容器的可烧结性的添加剂,导致电介质具有核-壳结构,但是在壳中不存在畴壁,使得在实现高介电常数方面存在限制。
发明内容
本公开的一方面可提供一种能够具有提高的可靠性的多层陶瓷电容器。
根据本公开的一方面,一种多层陶瓷电容器可包括:陶瓷主体,包括介电层和设置为彼此面对的第一内电极和第二内电极,介电层介于所述第一内电极和所述第二内电极之间;以及第一外电极和第二外电极,设置在所述陶瓷主体的外表面上,并分别电连接到所述第一内电极和所述第二内电极,其中,所述介电层包含具有包括核和壳的核-壳结构的电介质晶粒,并且在所述壳中排列有畴壁。
附图说明
通过下面结合附图进行的详细描述,本公开的以上和其他方面、特征和优点将被更清楚地理解,在附图中:
图1是示出根据本公开的示例性实施例的多层陶瓷电容器的示意性透视图;
图2是沿着图1的I-I'线截取的截面图;
图3是示出根据现有技术的具有核-壳结构的电介质晶粒的示意图;
图4是根据本公开中的示例性实施例的图2的区域“P”的放大图;
图5是根据本公开中的另一示例性实施例的图2的区域“P”的放大图;
图6是根据本公开中的示例性实施例的透射电子显微镜(TEM)分析照片。
具体实施方式
在下文中,现将参照附图详细地描述本公开的示例性实施例。
图1是示出根据本公开的示例性实施例的多层陶瓷电容器的示意性透视图。
图2是沿着图1的I-I'线截取的截面图。
参照图1和图2,根据本示例性实施例的多层陶瓷电容器100可包括:陶瓷主体110,包括介电层111以及设置为彼此面对的第一内电极121和第二内电极122,介电层111介于第一内电极121和第二内电极122之间;第一外电极131和第二外电极132,设置在陶瓷主体110的外表面上,并分别电连接到第一内电极121和第二内电极122。
在根据本公开中的示例性实施例的多层陶瓷电容器100中,“长度方向”指的是图1的“L”方向,“宽度方向”指的是图1的“W”方向,“厚度方向”指的是图1的“T”方向。这里“厚度方向”指的是堆叠介电层111的方向,即,“堆叠方向”。
陶瓷主体110的形状不被具体地限制,但可以是如示出的长方体形状。
形成在陶瓷主体110中的多个内电极121和122的一端可暴露到陶瓷主体110的一个表面或陶瓷主体110的与该一个表面相对的另一表面。
内电极121和内电极122可具有一对具有不同极性的第一内电极121和第二内电极122。
第一内电极121的一端可暴露到陶瓷主体110的一个表面,第二内电极122的一端可暴露到陶瓷主体110的与该一个表面相对的另一表面。
第一外电极131和第二外电极132可分别形成在陶瓷主体110的一个表面上和陶瓷主体110的与该一个表面相对的另一表面上,并且可分别电连接到第一内电极121和第二内电极122。
第一内电极121和第二内电极122中的每个的材料不被具体地限制,但可以是包含银(Ag)、铅(Pb)、铂(Pt)、镍(Ni)和铜(Cu)中的一种或更多种的导电膏。
第一外电极131和第二外电极132可分别电连接到第一内电极121和第二内电极122,以形成电容,第二外电极132可连接到与第一外电极131连接到的电势不同的电势。
第一外电极131和第二外电极132中的每个中包含的导电材料不被具体地限制,但可以是镍(Ni)、铜(Cu)或它们的合金。
第一外电极131和第二外电极132的厚度可根据目的等而适当地确定,例如,可以为10μm至50μm,但不具体地局限于此。
根据本公开中的示例性实施例,介电层111的原材料不被具体地限制,只要可获得足够的电容即可。例如,介电层111的原材料可以是钛酸钡(BaTiO3)粉末颗粒。
介电层111的材料可根据本公开的目的通过向诸如钛酸钡(BaTiO3)粉末颗粒等的粉末颗粒中添加各种陶瓷添加剂、有机溶剂、塑化剂、粘合剂、分散剂等来制备。
介电层111可呈烧结状态,相邻的介电层可彼此一体化,使得它们之间的边界不容易显而易见。
第一内电极121和第二内电极122可形成在介电层111上,第一内电极121和第二内电极122可通过烧结形成在陶瓷主体110中,介电层111介于第一内电极121和第二内电极122之间。
陶瓷主体110可包括对形成电容器的电容有贡献的有效部A以及分别形成为有效部A的上表面和下表面上的上边缘部和下边缘部的上覆盖部C和下覆盖部C。
有效部A可通过重复堆叠多个第一内电极121和第二内电极122而形成,在第一内电极121和第二内电极122之间插设有介电层。
上覆盖部C和下覆盖部C可利用与介电层111的材料相同的材料形成,并且除了上覆盖部C和下覆盖部C不包括内电极之外具有与介电层111的构造相同的构造。
也就是说,上覆盖部C和下覆盖部C可包含诸如钛酸钡(BaTiO3)基陶瓷材料的陶瓷材料。
上覆盖部C和下覆盖部C可通过分别在有效部A的上表面上和下表面上在竖直方向上堆叠单个介电层或者两个或更多个介电层而形成,并且可主要用于防止由于化学应力或物理应力导致对第一内电极121和第二内电极122的损坏。
介电层111中的每个的厚度可根据多层陶瓷电容器的电容设计而任意地改变,在本公开中的示例性实施例中,一个介电层111在烧结之后的厚度可以是0.4μm或更小。
另外,第一内电极121和第二内电极122中的每个在烧结之后的厚度可以是0.4μm或更小。
图3是示出根据现有技术的具有核-壳结构的电介质晶粒的示意图。
参照图3,根据现有技术的多层陶瓷电容器的介电层可包含各自具有包括核1a和壳1b的核-壳结构的电介质晶粒1,并且还可包含具有仅包括壳的壳结构的一些电介质晶粒2。
另外,在具有包括核1a和壳1b的核-壳结构的电介质晶粒1中,90°的畴壁可存在于核1a中,但不会存在于壳1b中。
同样地,在根据现有技术的多层陶瓷电容器中,在具有壳结构的电介质晶粒2中不会存在90°的畴壁。
如上所述,在根据现有技术的多层陶瓷电容器中,在壳中不存在畴壁,因此,会在实现高介电常数方面存在限制。
图4是根据本公开中的示例性实施例的图2的区域“P”的放大图。
参照图4,介电层111可包含各自具有包括核11a和壳11b的核-壳结构的电介质晶粒11,畴壁d可排列在壳11b中。
电介质晶粒11可具有以ABO3表示的钙钛矿结构。
这里,A可包括从由钡(Ba)、锶(Sr)、铅(Pb)和钙(Ca)组成的组中选择的一种或更多种,但不限于此。
B不被具体地限制,但可以是可位于钙钛矿结构中的B位点的任何材料,并且可包括例如从由钛(Ti)和锆(Zr)组成的组中选择的一种或更多种。
电介质晶粒可包括基体材料主成分和辅助成分,所述基体材料主成分从由BamTiO3(0.995≤m≤1.010)、(Ba1-xCax)m(Ti1-yZry)O3(0.995≤m≤1.010,0≤x≤0.10,0<y≤0.20)和Bam(Ti1-xZrx)O3(0.995≤m≤1.010且x≤0.10)组成的组中选择的一种或更多种,但不限于此。
根据本公开中的示例性实施例,介电层111可包括可在还原气氛下进行烧结的抗还原介电组合物。将在下文中更详细地描述形成包含电介质晶粒11的介电层111的介电组合物的各个成分。
a)基体材料粉末
介电组合物可包括由BaTiO3表示的基体材料粉末颗粒。
根据本公开中的示例性实施例,基体材料粉末颗粒可由BaTiO3表示,但不限于此。例如,基体材料粉末颗粒可由其中部分地固溶有Ca、Zr等的(Ba1-xCax)(Ti1-yCay)O3、(Ba1- xCax)(Ti1-yZry)O3、Ba(Ti1-yZry)O3等表示。
也就是说,基体材料粉末颗粒可包括从由BaTiO3、(Ba1-xCax)(Ti1-yCay)O3(这里,0≤x≤0.3且0≤y≤0.1)、(Ba1-xCax)(Ti1-yZry)O3(这里,0≤x≤0.3且0≤y≤0.5)和Ba(Ti1- yZry)O3(这里,0<y≤0.5)组成的组中选择的一种或更多种。
基体材料粉末颗粒可具有大于等于40nm且小于等于150nm的平均粒径,但不限于此。
b)第一辅助成分
根据本公开中的示例性实施例,介电组合物可包含包括Mn、V、Cr、Fe、Ni、Co、Cu和Zn中的至少一种的氧化物或碳酸盐作为第一辅助成分。
作为第一辅助成分包含的包括Mn、V、Cr、Fe、Ni、Co、Cu和Zn中的至少一种的氧化物或碳酸盐的含量基于100mol%的基体材料粉末颗粒可以是0.05mol%至2.0mol%。
第一辅助成分可用于降低使用介电组合物的多层陶瓷电容器的烧结温度并改善多层陶瓷电容器的高温耐受电压特性。
第一辅助成分的含量和下面将描述的第二辅助成分至第六辅助成分的含量可以是基于100mol%的基体材料粉末颗粒的含量,并且可具体的限定为相应辅助成分中包括的金属离子的mol%。
当第一辅助成分的含量小于0.05mol%时,烧结温度会提高,且高温耐受电压特性会劣化到一定程度。
当第一辅助成分的含量大于2.0mol%时,高温耐受电压特性和室温电阻率会劣化。
具体地,根据本公开中的示例性实施例的介电组合物基于100mol%的基体材料粉末颗粒可包括具有0.05mol%至2.0mol%的含量的第一辅助成分。因此,介电组合物可在低温下进行烧结,并且可获得高温耐受电压特性。
c)第二辅助成分
根据本公开中的示例性实施例,介电组合物可包括第二辅助成分,第二辅助成分为包含固定价受体元素Mg的氧化物或碳酸盐。
介电组合物可包括作为包含固定价受体元素Mg的氧化物或碳酸盐并基于100mol%的基体材料粉末颗粒具有0.0mol%至2.0mol%的含量的第二辅助成分。
作为固定价受体元素或包括固定价受体元素的化合物的第二辅助成分可在介电组合物中调节微观结构(抑制异常晶粒生长)并赋予抗还原性。
当第二辅助成分的含量基于100mol%的基体材料粉末颗粒超过2.0mol%时,介电常数会降低,这不是优选的。
d)第三辅助成分
根据本公开中的示例性实施例,介电组合物可包括第三辅助成分,第三辅助成分为包含Y、Dy、Ho、Er、Gd、Ce、Nd、Pm、Eu、Tb、Tm、Yb、Lu和Sm中的至少一种的氧化物或碳酸盐。
介电组合物可包括作为包含Y、Dy、Ho、Er、Gd、Ce、Nd、Pm、Eu、Tb、Tm、Yb、Lu和Sm中的至少一种的氧化物或碳酸盐并且基于100mol%的基体材料粉末颗粒具有0.0mol%至4.0mol%的含量的第三辅助成分。
第三辅助成分可用于防止本公开中的示例性实施例中的使用介电组合物的多层陶瓷电容器的可靠性降低。
当第三辅助成分的含量超过4.0mol%时,多层陶瓷电容器的可靠性会降低,介电组合物的介电常数会降低,且高温耐受电压特性会劣化。
e)第四辅助成分
根据本公开中的示例性实施例,介电组合物可包括第四辅助成分,第四辅助成分为包含Ba的氧化物或碳酸盐。
介电组合物可包括作为包含Ba的氧化物或碳酸盐并且基于100mol%的基体材料粉末颗粒具有0.0mol%至4.15mol%的含量的第四辅助成分。
第四辅助成分的含量可以基于第四辅助成分中包括的Ba的含量,而不区分诸如氧化物或碳酸盐的添加形式。
第四辅助成分可用于促进烧结并调节介电组合物中的介电常数,当第四辅助成分的含量基于100mol%的基体材料粉末颗粒超过4.15mol%时,会出现诸如介电常数降低或烧结温度升高的问题。
f)第五辅助成分
根据本公开中的示例性实施例,介电组合物可包括包含从由Ca和Zr中的一种或更多种的氧化物或碳酸盐组成的组中选择的一种或更多种的第五辅助成分。
介电组合物可包括作为包含Ca和Zr中的至少一种的氧化物或碳酸盐并且基于100mol%的基体材料粉末颗粒具有0.0mol%至20.0mol%的含量的第五辅助成分。
第五辅助成分的含量可以基于第五辅助成分中包括的Ca和Zr中的至少一种的含量,而不区分诸如氧化物或碳酸盐的添加形式。
第五辅助成分可用于在介电组合物中形成核-壳结构,以提高介电常数和可靠性,当第五辅助成分的含量基于100mol%的基体材料粉末颗粒为20.0mol%或更小时,可提供实现高介电常数并且高温耐受电压特性良好的介电组合物。
当第五辅助成分的含量基于100mol%的基体材料粉末颗粒超过20.0mol%时,室温介电常数会降低,且高温耐受电压特性会劣化。
g)第六辅助成分
根据本公开中的示例性实施例,介电组合物可包括包含Si和Al中的至少一种的氧化物或者包含Si的玻璃化合物作为第六辅助成分。
介电组合物可包括作为包含Si和Al中的至少一种的氧化物或者包含Si的玻璃化合物并且基于100mol%的基体材料粉末颗粒具有0.0mol%至4.0mol%的含量的第六辅助成分。
第六辅助成分的含量可以基于第六辅助成分中包括的Si和Al中的至少一种的含量,而不区分诸如玻璃、氧化物的添加形式。
第六辅助成分可用于降低使用介电组合物的多层陶瓷电容器的烧结温度并改善多层陶瓷电容器的高温耐受电压特性。
当第六辅助成分的含量基于100mol%的基体材料粉末颗粒超过4.0mol%时,可能存在诸如可烧结性劣化和密度劣化、形成第二相等问题,这不是优选的。
近来,随着电子产品的小型化和多功能化,多层陶瓷电容器也趋于小型化和多功能化。因此,已需要具有小尺寸和大容量的多层陶瓷电容器。
作为同时实现小型化和增大多层陶瓷电容器的电容的方法,存在通过减小介电层和电极层的厚度来增加多层陶瓷电容器中堆叠的介电层和电极层的数量的方法。目前,介电层的厚度约为0.6μm,并且正不断地开发减小介电层的厚度的技术。
同时,为了实现多层陶瓷电容器的电容增大,已需要具有高介电常数的材料。多层陶瓷电容器中使用的典型材料是钛酸钡(BaTiO3),但是由于钛酸钡的固有特性的限制导致难以开发增大介电常数的材料。
此外,由于添加到多层陶瓷电容器的介电材料中以提高多层陶瓷电容器的可靠性并确保多层陶瓷电容器的可烧结性的添加剂导致,电介质具有核-壳结构,但是在壳中不存在畴壁,使得在实现高介电常数方面存在限制。
通常,具有核-壳结构的电介质晶粒中的核中包含的钛酸钡(BaTiO3)是具有高四方性(tetragonality)的材料,由于在核中的钛酸钡(BaTiO3)上少量掺杂辅助成分添加剂,因此,由于钛酸钡(BaTiO3)的固有高四方性而在核中存在90°的畴壁。
另一方面,在壳区域中的钛酸钡(BaTiO3)上掺杂大量辅助成分添加剂,使得钛酸钡(BaTiO3)不具有四方结构,而是呈伪立方状态。因此,畴壁不存在于壳区域中。
其结果是,壳区域的介电常数变得比核的介电常数小,使得难以确保多层陶瓷电容器的高电容。
返回图4,根据本公开中的示例性实施例,介电层111可包含各自具有包括核11a和壳11b的核-壳结构的电介质晶粒11,畴壁d可排列在壳11b中,使得可实现具有高电容的多层陶瓷电容器100。
也就是说,与根据现有技术的多层陶瓷电容器不同,在根据本公开中的示例性实施例的多层陶瓷电容器100中,在设置在介电层111中并具有核-壳结构的电介质晶粒11中,畴壁d可排列在壳11b中。
在使畴壁d排列在壳11b中的方法中,可能重要的是使核11a和壳11b的晶格结构均匀。
为此,当在烧结期间在钛酸钡(BaTiO3)上掺杂作为辅助成分的添加剂的同时形成壳时,可以赋予高热能以使晶格稳定地形成,或者可以预先在钛酸钡(BaTiO3)上掺杂一些辅助成分添加剂以使晶格形成在稳定的位置处,从而使晶格均匀。
对此,在下面将描述更详细的内容。
根据本公开中的示例性实施例,在核11a中包括的基于基体材料主成分的含量的辅助成分的含量和在壳11b中包括的基于基体材料主成分的含量的辅助成分的含量可彼此不同。
也就是说,在核11a中测量的辅助成分添加剂的含量和在壳11b中测量的辅助成分添加剂的含量可彼此不同。
详细地,在壳11b中,基于100mol基体材料主成分,辅助成分的含量可以是0.5mol至30mol。
如上所述,在电介质晶粒11中,测量的辅助成分的含量基于100mol的基体材料主成分在0.5mol至30mol的范围内的区域可被定义为壳区域。
根据本公开中的示例性实施例,测量的辅助成分的含量基于100mol的基体材料主成分在0.5mol至30mol的范围内的区域可以是壳11b,畴壁d可形成在壳11b中。
接着,在核11a中,基于100mol的基体材料主成分,辅助成分的含量可以是0.1mol或更少。
如上所述,在电介质晶粒11中,测量的辅助成分的含量基于100mol的基体材料主成分在0.1mol或更少的范围内的区域可被定义为核区域。
根据本公开中的示例性实施例,测量的辅助成分的含量基于100mol的基体材料主成分在0.1mol或更少的范围内的区域可以是核11a,在核11a中,掺杂的辅助成分的量可以非常少,使得由于钛酸钡的固有高四方性而使畴壁d可排列在核11a中。
如上所述,根据本公开中的示例性实施例,与根据现有技术的畴壁不存在于壳中的结构不同,畴壁d可排列在测量的辅助成分的含量基于100mol的基体材料主成分在0.5mol至30mol的范围内的壳11b中,使得可实现具有高电容的多层陶瓷电容器100。
辅助成分可以是如上所述添加到介电组合物的第一辅助成分至第六辅助成分,辅助成分的具体示例可包含诸如镝(Dy)、钬(Ho)或钇(Y)的稀土元素、镁(Mg)、锰(Mn)、铝(Al)等。
壳11b可具有相当于电介质晶粒11的直径的0.1%至45%的厚度,厚度的具体绝对数值可以是大于等于1nm且小于等于100nm。然而,壳11b的厚度不必然限于此。
也就是说,测量的辅助成分的含量基于100mol的基体材料主成分在0.5mol至30mol的范围内的壳区域可具有相当于电介质晶粒11的直径的0.1%至45%的厚度。
根据本公开中的示例性实施例,在壳11b中排列的畴壁d的数量可以是三个或更多个。
由于在壳11b中排列的畴壁d的数量为三个或更多个,因此畴壁d之间的距离可减小,使得可在具有相同尺寸的电介质晶粒11中实现高介电常数。
也就是说,为了在具有相同尺寸的电介质晶粒11中实现高介电常数,在壳11b中排列的畴壁d的数量需要为三个或更多个,由于畴壁d的数量增大,因此,畴壁d之间的距离可减小,使得可确保高介电常数,但是电介质晶粒11的尺寸被限制,使得畴壁d的数量不得不被限制于预定数量。
同时,参照图4,除了具有包括核和壳的核-壳结构的电介质晶粒11之外,还可存在具有仅包括壳的壳结构的一些电介质晶粒21。
具有壳结构的电介质晶粒21可具有不存在核的结构,由于在具有壳结构的电介质晶粒21中的整个区域中,测量的辅助成分的含量基于100mol的基体材料主成分在0.5mol至30mol的范围内,因此,具有壳结构的电介质晶粒21可被确定为具有不存在核的结构。
根据本公开中的示例性实施例,畴壁d还可排列在具有壳结构的电介质晶粒21中。
根据现有技术的多层陶瓷电容器的介电层中也可存在具有壳结构的电介质晶粒。然而,即使在这种情况下,具有壳结构的电介质晶粒中不存在畴壁。
然而,在根据本公开中的示例性实施例中,畴壁d还可排列在具有壳结构的电介质晶粒21中,因而可由于高介电常数而确保高电容。
图5是根据本公开中的另一示例性实施例的图2的区域“P”的放大图。
根据本公开中的另一示例性实施例,介电层111还可包含具有仅包括壳的壳结构的电介质晶粒21,畴壁d可排列在具有壳结构的电介质晶粒21中。
在具有壳结构的电介质晶粒21中排列的畴壁d的数量可以是三个或更多个。
图5中示出的本公开中的示例性实施例与在以上描述并在图4中示出的本公开中的示例性实施例的不同之处可在于,介电层111中的具有壳结构的电介质晶粒21的分数比在以上描述并在图4中示出的本公开中的示例性实施例中的具有壳结构的电介质晶粒的分数大。
也就是说,根据本公开中的另一示例性实施例,在介电层111中具有壳结构的电介质晶粒21的分数可比本公开中的示例性实施例中的具有壳结构的电介质晶粒的分数大,并且可比具有核-壳结构的电介质晶粒11的分数大。
当在制造介电组合物的过程中基体材料主成分(即,钛酸钡粉末颗粒)预先掺杂辅助成分添加剂的比例高时,介电层111中的电介质晶粒21的分数可增大。
除了以上描述的差异之外的特征可与根据本公开中的示例性实施例的特征相同。
在下文中,将通过发明示例和对比示例更详细地描述本公开。然而,它们的目的在于帮助详细理解本公开,并且本公开的范围不受发明示例的限制。
(发明示例1)
在发明示例中,诸如Si、Mg、Mn和Dy的添加剂、粘合剂和诸如乙醇的有机溶剂被添加到包括钛酸钡(BaTiO3)粉末颗粒的介电原材料粉末颗粒并与包括钛酸钡(BaTiO3)粉末颗粒的介电原材料粉末颗粒湿混合,以制备电介质浆体。然后,将电介质浆体涂敷到载体膜上并使其干燥,以形成陶瓷生片,得到介电层。
在这种情况下,所有元素的添加剂都是单分散的,并以钛酸钡粉末颗粒的尺寸的40%或更小的尺寸添加。
陶瓷生片可通过下述方法制造:通过将陶瓷粉末颗粒、粘合剂和溶剂彼此混合制备浆体,通过刮刀法将浆体制造为具有几μm的厚度的片状。
接着,可制备用于内电极的导电膏,用于内电极的导电膏包含40至50重量份的平均粒径为0.1μm至0.2μm的镍粉末颗粒。
通过丝网印刷法将用于内电极的导电膏涂敷到陶瓷生片,以形成内电极,堆叠其上设置有内电极图案的陶瓷生片以形成层叠体,然后对层叠体进行压制和切割。
然后,对切割的层叠体进行加热,以去除粘合剂,并在高温还原气氛下进行烧结,以形成陶瓷主体。
在烧结工艺中,在还原气氛(0.1%H2/99.9%N2和H2O/H2/N2的气氛)下执行烧结,在预定区域执行快速升温。在1284℃的烧结温度执行烧结两小时,在氮气(N2)气氛下在1000℃执行再氧化三小时,以执行热处理。
然后,可使用铜(Cu)膏在烧结的陶瓷主体上执行封端工艺(terminationprocess)和电极烧结工艺,以完成外电极。
此外,在烧结之后,陶瓷主体110中的介电层111以及第一内电极121和第二内电极122被制造为具有0.4μm或更小的厚度。
(发明示例2)
通过水热合成法(hydrothermal synthesis)在1200℃对掺杂有Dy和Mg的钛酸钡(BaTiO3)粉末颗粒进行热处理。
将热处理之后形成的钛酸钡(BaTiO3)湿磨并干燥,将诸如Si和Mn的添加剂、粘合剂和诸如乙醇的有机溶剂添加到包含钛酸钡(BaTiO3)和预先制造的预先掺杂有添加剂的粉末颗粒的电介质原材料粉末颗粒并与其进行湿混,以制备电介质浆体。然后,将电介质浆体涂敷到载体膜上并使其干燥,以形成陶瓷生片。
接着,可制备用于内电极的导电膏,用于内电极的导电膏包含40至50重量份的平均粒径为0.1μm至0.2μm的镍粉末颗粒。
通过丝网印刷法将用于内电极的导电膏涂敷到陶瓷生片,以形成内电极,并堆叠其上设置有内电极图案的陶瓷生片,以形成层叠体,然后对层叠体进行压制和切割。
然后,对切割的层叠体进行加热,以去除粘合剂,并在高温还原气氛下进行烧结,以形成陶瓷主体。
在烧结工艺中,在还原气氛(0.1%H2/99.9%N2和H2O/H2/N2的气氛)下执行烧结,在预定区域执行快速升温。在1192℃的烧结温度执行烧结两小时,在氮气(N2)气氛下在1000℃执行再氧化三小时,以执行热处理。
(发明示例3)
通过与发明示例2的方法相同的方法制造多层陶瓷电容器,仅采用预先掺杂有添加剂的钛酸钡,但不执行快速升温。
(比较示例)
通过与发明示例1的方法相同的方法制造多层陶瓷电容器,但不执行快速升温,并且在1192℃的温度执行烧结。
对于发明示例1至3和比较示例(如上所述完成的原型多层陶瓷电容器(MLCC)样本),评价标称介电常数、介电常数、击穿电压(BDV)、绝缘电阻(IR)缺陷率、防潮负荷缺陷率等。
使用LCR测量仪在1kHz和AC 3.0V/μm的条件下测量MLCC的介电常数。
在对每个样本取10个样品施加DC 10V/μm的状态下,经过60秒后测量绝缘电阻IR。
使用Keithely测量仪测量BDV,并且测量在自0V以1.00000V的增量以扫描方式施加电压的同时电流值变为10mA的瞬间的电压值作为BDV值。
下面的表1示出了根据实验示例(发明示例和对比示例)的原型多层陶瓷电容器(MLCC)的电特性。
[表1]
Figure BDA0001893079420000131
发明示例1至发明示例3可以是在烧结期间当在钛酸钡(BaTiO3)上掺杂添加剂(辅助成分)的同时形成壳时,利用通过赋予高热能使晶格稳定形成或者通过在钛酸钡(BaTiO3)上预先掺杂一些辅助成分添加剂使晶格设置在稳定位置的方法,通过使晶格结构均匀在壳11b中排列畴壁d的情况,对比示例(通过根据现有技术的方法制造多层陶瓷电容器的情况)可以是在壳中没有排列畴壁d的情况。
从上面表1可以领会的是,与对比示例中相比,在发明示例1至发明示例3中,介电常数和BDV高,IR缺陷率和防潮负荷缺陷率低。
图6是根据本公开中的示例性实施例的透射电子显微镜(TEM)分析照片。
在图6中,示出了发明示例2的电介质微观结构。按照通过TEM拍摄的图像观察电介质微观结构。
参照图6,可以领会的是,在根据本公开中的示例性实施例的电介质晶粒中,畴壁排列在壳中以及核中。
在执行TEM分析时,根据分析角度,可能不会观察到实际存在的畴壁。在使电介质晶粒以几个角度倾斜的同时执行分析时,可观察到畴壁。
根据本公开中的示例性实施例,由于畴壁还排列在壳中,因此,可提高介电常数,使得可实现具有高电容的多层陶瓷电容器。
如以上阐述,根据本公开中的示例性实施例,陶瓷主体中的电介质晶粒可包含具有核-壳结构的电介质晶粒,并且畴壁可排列在壳中,使得可实现具有高电容的多层陶瓷电容器。
虽然以上已示出并描述了示例性实施例,但对本领域的技术人员将显而易见的是,在不脱离由所附的权利要求限定的本发明的范围的情况下,可做出修改和变型。

Claims (13)

1.一种多层陶瓷电容器,包括:
陶瓷主体,包括介电层和设置为彼此面对的第一内电极和第二内电极,介电层介于所述第一内电极和所述第二内电极之间;以及
第一外电极和第二外电极,设置在所述陶瓷主体的外表面上,并分别电连接到所述第一内电极和所述第二内电极,
其中,所述介电层包含具有包括核和壳的核-壳结构的电介质晶粒,并且
在所述壳和所述核中均排列有畴壁。
2.根据权利要求1所述的多层陶瓷电容器,其中,所述电介质晶粒中的每个包括基体材料主成分和辅助成分,所述基体材料主成分为从由BamTiO3、(Ba1-xCax)m(Ti1-yZry)O3和Bam(Ti1-xZrx)O3组成的组中选择的一种或更多种,在BamTiO3中,0.995≤m≤1.010,在(Ba1- xCax)m(Ti1-yZry)O3中,0.995≤m≤1.010,0≤x≤0.10且0<y≤0.20,在Bam(Ti1-xZrx)O3中,0.995≤m≤1.010且x≤0.10。
3.根据权利要求2所述的多层陶瓷电容器,其中,所述核中包括的基于基体材料主成分的含量的辅助成分的含量和所述壳中包括的基于基体材料主成分的含量的辅助成分的含量彼此不同。
4.根据权利要求2所述的多层陶瓷电容器,其中,所述壳是基于100mol的基体材料主成分的辅助成分的含量为0.5mol至30mol的区域。
5.根据权利要求2所述的多层陶瓷电容器,其中,所述核是基于100mol的基体材料主成分的辅助成分的含量为0.1mol或更少的区域。
6.根据权利要求2所述的多层陶瓷电容器,其中,所述基体材料主成分具有大于等于40nm且小于等于150nm的平均粒径。
7.根据权利要求1所述的多层陶瓷电容器,其中,所述介电层的厚度为0.4μm或更小,所述第一内电极和所述第二内电极中的每个的厚度为0.4μm或更小。
8.根据权利要求1所述的多层陶瓷电容器,其中,所述壳具有对应于所述电介质晶粒的直径的0.1%至45%的厚度。
9.根据权利要求1所述的多层陶瓷电容器,其中,所述壳具有大于等于1nm且小于等于100nm的厚度。
10.根据权利要求1所述的多层陶瓷电容器,其中,在所述壳中排列的畴壁的数量为三个或更多个。
11.根据权利要求1所述的多层陶瓷电容器,其中,所述介电层还包含具有仅包括壳的壳结构的电介质晶粒,并且
在具有所述壳结构的所述电介质晶粒中排列有畴壁。
12.根据权利要求11所述的多层陶瓷电容器,其中,在具有所述壳结构的所述电介质晶粒中排列的畴壁的数量为三个或更多个。
13.根据权利要求1所述的多层陶瓷电容器,其中,所述核中的畴壁的方向与所述壳中的畴壁的方向基本平行。
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