CN1728305A - 叠层陶瓷电容器 - Google Patents

叠层陶瓷电容器 Download PDF

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CN1728305A
CN1728305A CNA2005100888080A CN200510088808A CN1728305A CN 1728305 A CN1728305 A CN 1728305A CN A2005100888080 A CNA2005100888080 A CN A2005100888080A CN 200510088808 A CN200510088808 A CN 200510088808A CN 1728305 A CN1728305 A CN 1728305A
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dielectric layer
layer
capacitor
internal electrode
ceramic capacitor
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岩永大介
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TDK Corp
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Abstract

本发明提供即使是在使介电体层薄型化、实现高容量的情况下,内部电极与介电体层也不容易发生剥离的叠层陶瓷电容器。本发明的电容器(10)(叠层陶瓷电容器)设置有由内部电极(12)(电极)与介电体层(14)所交互叠层的电容器素材(11)、与在其端面设置的外部电极(15)。介电体层(14)包含介电材料的颗粒,且具有在其厚度方向上仅由一个该颗粒所构成的部位。而且,在内部电极(12)与介电体层(14)之间,分散存在有包含选自Si、Li、及B中的至少一种元素的区域(24)。

Description

叠层陶瓷电容器
技术领域
本发明涉及叠层陶瓷电容器。
背景技术
作为叠层陶瓷电容器,一般是具有由陶瓷材料所构成的介电体层与内部电极交互叠层的结构。近年来,作为这样的叠层陶瓷电容器,追求具有小型且静电容量大的特性。为了满足这样的性能,在叠层陶瓷电容器中,在使介电体层薄型化的同时,还增加叠层的数目。
作为这样的叠层陶瓷电容器,介电体层具有作为其构成材料的陶瓷材料仅由一个颗粒组成的结构,即一层一颗粒结构(例如,参考专利文献1)。
专利文献1:专利第3370933号公报。
然而,在叠层陶瓷电容器中使介电体层薄型化的情况下,叠层的数目增加时,介电体层中有易于发生歪斜的倾向。因此,在内部电极与介电体层之间部分地形成孔隙,由此容易引起内部电极与介电体层之间发生剥离(分层)。
发明内容
本发明是鉴于上述问题而提出,其目的在于,提供即使是在实现了介电体层薄型化、高容量的情况下,内部电极与介电体层也不容易发生剥离的叠层陶瓷电容器。
为了达到上述目的,本发明的叠层陶瓷电容器,其特征在于:设置有:一对电极;和配置于一对电极之间、由含有陶瓷材料的介电材料所构成的介电体层,介电体层包含介电材料的颗粒,且具有在其厚度方向上仅由一个该颗粒所构成的部位,在电极与介电体层之间,分散存在有包含选自Si、Li、及B中的至少一种元素的区域。
这样,在本发明的叠层陶瓷电容器中,在内部电极与介电体层之间形成多个包含Si、Li、或B的区域。通过这样的区域而粘结的内部电极及介电体层,与直接将它们粘结的情况相比,能够得到更强固的粘结。其结果是,具有上述结构的叠层陶瓷电容器,尽管具有包含一层一颗粒的薄介电体层,也极难发生内部电极与介电体层的剥离。
在具有上述结构的叠层陶瓷电容器中,优选包含上述元素的区域由内部电极及2个以上的介电体材料的颗粒所包围。在这样的部分上形成上述区域,能够使内部电极与介电体层的粘结性进一步提高。
而且,本发明的另一叠层陶瓷电容器,其特征在于:设置有一对电极;和配置于一对电极之间、由含有陶瓷材料的介电材料所构成的介电体层,介电体层包含上述介电材料的颗粒,且具有在其厚度方向上仅由该一个颗粒所构成的部位,在电极与介电体层之间,分散存在有包含选自Si、Li、及B中的至少一种元素的第一区域,另外,在介电体层内,分散存在有包含选自Si、Li、及B中的至少一种元素的第二区域,进而,第一区域比所述第二区域更多地分散存在。
这样,本发明的叠层陶瓷电容器,不仅是在内部电极与介电体层的边界,而且在介电体层的内层部分也可以具有包含上述的元素的区域。即使是在具有这样结构的叠层陶瓷电容器中,由于在电极与介电体材料的颗粒(介电体层)之间形成上述区域,所以难以发生二者之间的剥离。
这里,上述Si、Li、或B元素,在现有的叠层陶瓷电容器中,是作为烧结助剂而添加于介电体层的元素,具有在电容器制造时降低烧结温度的效果。然而,由于这些烧结助剂与通常构成介电体层的陶瓷材料相比有降低电阻的倾向,所以为了得到实用的烧结温度而多添加烧结助剂时,含有该烧结助剂的低电阻区域会在介电体层中广泛分散,由此有可能会对介电体层的绝缘性造成破坏。
与此相对,在本发明的叠层陶瓷电容器中,含有上述如Si、Li、及B等的氧化物的区域,与介电体层的内层部分相比,更多地形成于与内部电极相邻接的部分。就是说,在介电体层的内层部分成为含有Si、Li、B等的电阻低的区域少的状态。因此,本发明的叠层陶瓷电容器,虽然含有Si、Li、B等的氧化物,但与添加烧结助剂的现有的叠层陶瓷电容器相比,难以发生介电体层的绝缘的破坏。
在具有上述结构的叠层陶瓷电容器中,优选第一区域由内部电极及2个以上的所述颗粒所包围,且第二区域仅由3个以上的上述颗粒所包围。由此,除了进一步提高内部电极与介电体层的粘结性,还能提高介电体层的绝缘性。
在这些叠层陶瓷电容器中,含有Si、Li、及B中至少一种元素的区域优选是主要含有Si的区域。由此,除了进一步提高内部电极与介电体层的粘结性,还能得到良好的绝缘电阻。
进而,优选陶瓷材料是以Ba及Ti为主要成分的复合氧化物。这样,能够得到具有优异静电容量及高绝缘电阻的陶瓷电容器。
发明的效果
根据本发明,形成含有一层一颗粒结构的薄型的介电体层,由此,能够提供即使是在实现高静电容量化的情况下,内部电极与介电体层也难以发生剥离的陶瓷电容器。
附图说明
图1是表示实施方式的叠层陶瓷电容器的结构的模式图。
图2是表示图1所示的叠层陶瓷电容器的内部电极与介电体层的界面附近结构的放大模式图。
图3表示内部电极与介电体层的界面附近结构的透射电镜照片的图。
符号说明:10电容器,11电容器素材,12内部电极,14介电体层,15外部电极,22结晶颗粒,24、25区域,26晶界相。
具体实施方式
下面结合附图详细说明本发明的实施方式。以下对同一要素都赋予同样的符号,其详细说明予以省略。
图1是表示实施方式的叠层陶瓷电容器的结构的模式图。电容器10(叠层陶瓷电容器)设置有由内部电极12与介电体层14交互叠层的长方体形状的电容器素材11,以及在与该电容器素材11对置的端面上分别设置的外部电极15。
在电容器10中,内部电极12的一侧的端部从电容器素材11的端面露出而形成,而且,各内部电极12的该端部在电容器素材11对置的端面上交互露出而叠层。作为这些内部电极12的构成材料,只要是作为叠层型电子元件的内部电极而通常使用的导电材料,可以没有特别限制地使用。作为这样的导电材料,例如可以列举出Ni或Ni合金等。作为Ni合金,优选含有95质量%以上的Ni、与Mn、Cr、Co、Al等中的至少一种元素。
外部电极15分别设置于电容器素材11中内部电极12的端部露出的端面上。由此,内部电极12与外部电极15相连接,实现二者的导通。作为外部电极15,可以列举出Cu或Cu合金、Ni或Ni合金、Ag或Ag合金(例如Ag-Pd合金)、Sn或Sn合金等。还有,从降低电容器10的制造成本的观点出发,优选使用比较廉价的Cu、Ni或它们的合金。
介电体层14由包含陶瓷材料的介电体材料所构成。作为介电体材料中所包含的陶瓷材料,通常可以使用可适用于陶瓷电容器的公知的高介电常数陶瓷材料。例如可以列举钛酸钡(BaTiO3)类的材料、铅复合钙钛矿化合物类材料、钛酸锶(SrTiO3)类的材料等。
其中,作为陶瓷材料,由于以Ba和Ti为主要成分的复合氧化物BaTiO3类的材料具有优异的介电常数,能够达到高静电容量,所以是所优选的。根据这样的BaTiO3类的材料,存在能够由高电阻层24得到非常好的提高绝缘性的效果。
作为BaTiO3类的材料,优选是其基本成分为BaTiO3、该组成中的Ba和Ti被其它的金属元素所适当置换的材料。例如可以列举出Ba的一部分被Ca或Sr所置换的材料、Ti的一部分被Zr所置换的材料等。具体地,作为BaTiO3类的材料,优选是[(Ba1-x-yCaxSry)O]m(Ti1-xZrx)O2。这里,分别优选x为0~0.25,更优选为0.05~0.10,y为0~0.05,更优选为0~0.01,z为0.1~0.3,更优选为0.15~0.20,m为1.000~1.020,更优选为1.002~1.015。
介电材料除了上述陶瓷材料,也可含有使介电体层14的稳定性及绝缘性提高的成分。作为这样的成分,例如可以列举出Sr、Y、Gd、Tb、Dy、V、Mo、Zn、Cd、Ti、Ca、Sn、W、Mn、Si、P等单质或氧化物。
这里,参照图2对内部电极12与介电体层14的界面附近的结构加以说明。图2是表示图1所示的叠层陶瓷电容器的内部电极12与介电体层14的界面附近结构的放大模式图。
如图所示,介电体层14具有多个结晶颗粒22(颗粒)配置排列的结构。在该结晶颗粒22的周围,形成由包含与构成该颗粒22的介电材料同样元素的陶瓷材料构成的晶界相26。而且,内部电极12与介电体层14之间,分散存在有包含选自Si、Li、及B中至少一种元素的区域24(第一区域)。进而,在介电体层14的内层部分,分散存在有包含这些元素的区域25(第二区域)。
结晶颗粒22是由上述介电材料所构成。在实施方式的电容器10中,介电体层14在其厚度方向具有仅由一个结晶颗粒22所构成的部位(一层一颗粒结构)。该一层一颗粒结构优选在介电体层14的宽度方向上对于其全长形成10~80%程度,更优选形成40%程度。还有,该一层一颗粒结构的比例,可以有以下所示的方法计算出。即,首先,在相对内部电极12垂直的方向上切断电容器10。接着,观察该切断面,测定在该面上露出的各结晶颗粒22的粒径之后,计算出它们的平均粒径。接着,在该切断面上以上述平均粒径的间隔划出与内部电极12垂直的直线,对其中涉及一层一颗粒结构的直线的数目进行计数。这样,计算出对于全部直线数目的涉及一层一颗粒结构的直线的比例,将该比例作为介电体层14中一层一颗粒结构的比例。
晶界相26是含有与介电材料同样元素的相。但是,该晶界相26的组成没有必要是与介电材料相同。还有,晶界相26还可以在不改变介电体层14的特性的范围内含有介电材料以外的杂质。
区域24及区域25是具有与结晶颗粒22及晶界相26不同组成或晶体结构的区域。这些区域24、25可以是包含Si、Li、及B中至少一种元素的颗粒,而且,在晶界相26中,可以是由该相26中所包含的这些元素的析出而形成的析出相。在该区域24、25中,Si、Li、及B以单质或氧化物的形式存在,作为后者即氧化物的优选的形式,分别可以列举出SiO2、LiO、B2O3等。
作为区域24、25中所包含的元素,即使在Si、Li、及B中,优选是Si,更优选是Si的氧化物(例如SiO2)。具有包含Si或Si的氧化物的区域24的电容器10,能够使内部电极12与介电体层14的粘结性特别优异。而且,具有包含Si或Si的氧化物的区域24、25的电容器10,具有制造时能够采用低温烧结的优点。还有,区域24、25,除了上述元素的单质或氧化物之外,还可以包含与构成结晶颗粒22及晶界相26的材料同样的元素。
在电容器10中,区域24形成于2以上的结晶颗粒22及内部电极12所包围的部分,区域25形成于在仅由3以上的结晶颗粒22所包围的部分。这里,由于介电体层14具有上述一层一颗粒的结构,所以在该层14中,成为与前者的部分相比后者的部分的数目大幅度减少的状态。因此,在电容器10中,区域25的数目比区域24的少。
这样,在电容器10中,区域24比区域25更多地分散存在,在介电体层14的内层部分区域25减少。由于这些区域24、25中所包含的Si、Li、B等元素,如上所述是低电阻的材料,所以在以往作为烧结助剂而被添加的情况下,会在介电体层中均匀分散,使绝缘性能下降。与此相对,在电容器10,由于在介电体层14的内层部分中区域25非常少,所以能够抑制由Si、Li、B等元素的添加而引起的绝缘性的下降。
还有,在介电体层14中,Si、Li、B等元素除了在区域24、25之外,还可以包含在例如晶界相26中。这在通过如上所述的析出而形成区域24、25的情况下能够产生。
虽然结晶颗粒22也可以同样地含有Si、Li、B等元素,但从充分维持介电体层14的绝缘性的观点来看,优选实质上不含有这些元素。在结晶颗粒22含有上述元素的情况下,优选其含有量不足5质量%。
结晶颗粒22、区域24、25或晶界相26中Si、Li、B等元素的含有比例,例如可以作为对于这些规定体积的全部质量的、该体积中所含有的上述元素的质量的比例(质量%)来表示。这样的金属元素的含有比例,例如可以使用公知的组成分析来计算。作为组成分析法,例如有能量分散型X线分光法(EDS)。
优选实施方式的电容器10具有长度1.5~1.7mm×宽度0.7~0.9mm左右的尺寸。在这样尺寸的电容器10中,优选内部电极12的厚度为1~5μm,更优选为1~3μm左右,优选外部电极12的厚度为10~50μm左右。而且,优选介电体层14的厚度为1~6μm,更优选为1~4μm。
具有上述结构的电容器10例如可以由以下所示的公知的叠层陶瓷电容器的制造方法所制造。就是说,首先准备并称量构成介电材料的陶瓷材料,接着对该原材料添加上述Si、Li、或B等原料化合物及其它成分,由球磨等方式进行湿式混合,对该化合物干燥后,在800~1300℃进行预烧结。
其后,由射流粉碎或球磨粉碎将所得到的预烧结物粉碎为所希望的粒径。在该粉碎物中混合粘结剂、可塑剂等,调制成介电体膏。同时,将内部电极12用的导电材料与含有粘结剂及溶剂的有机载体混合,调制内部电极膏。
通过将该介电体膏与内部电极膏进行交互涂敷并叠层,得到介电体膏层与内部电极膏层交互叠层的叠层体。其后,将该叠层体切断为所希望的尺寸,得到烧前芯片(green chip)之后,通过对该烧前芯片加热而进行脱粘接。接着在N2及H2等不活泼性气体环境下进行1200~1400℃的烧结,得到电容器元件11。而且,在所得到的电容器元件11的两端烧上外部电极15用的膏,得到电容器10。
在这样的制造方法中,作为形成区域24、25的方法,例如,如上所述,可以列举出在晶界相26上析出该相26所包含Si、Li、B等元素的方法。该析出可以通过改变Si、Li、B等原料化合物的添加量而调制,由此能够对电容器10中区域24、25的形成进行所希望的控制。
这里,参照图3对实施方式的电容器中内部电极与介电体层的界面附近的结构进行具体的说明。图3表示内部电极与介电体层的界面附近结构的透射电镜照片的图。在图3中,12是内部电极,14是结晶颗粒(介电体层),24是含有Si、Li、及B中至少一种的区域(第一区域)。这样,区域24形成于2个结晶颗粒14与内部电极12所包围的区域。由使用EDS对电容器10的区域24进行元素分析的结果可知,该区域24包含38.7质量%的BaO,4.7质量%的TiO2,1.9质量%的ZrO2,0.8质量%的Y2O3,0.4质量%的MnO,0.8质量%的V2O5,49.4质量%的SiO2,3.3质量%的NiO。还有,这些是将各元素换算为氧化物得到的值。这样,在实施方式的电容器10中,可以确认在内部电极12与介电体层14之间形成了含Si的区域24。
由以上的说明,实施方式的电容器10由于具有包含一层一颗粒结构的薄的介电体层14,所以成为具有极大的静电容量。而且,该电容器10是在内部电极12与介电体层14之间分散存在有包含选自Si、Li、及B中的元素的区域24的状态。因此,内部电极12与介电体层14与直接将它们粘结的情况相比,能够得到更强固的粘结。其结果是,电容器10尽管具有包含一层一颗粒结构的薄的介电体层14,但是却难以发生内部电极12与介电体层14之间发生剥离(分层)。
而且,Si、Li、B等元素,以往是作为烧结助剂而被分散于介电体层,具有使电容器的绝缘电阻下降的作用。与此相对,在电容器10中,尽管形成了包含这些元素的区域24、25,但介电体层内的区域25极少。因此,电容器10与现有的叠层陶瓷电容器相比,由因包含Si、Li、B等元素而引起的绝缘电阻的下降变得极少。

Claims (7)

1.一种叠层陶瓷电容器,其特征在于:设置有
一对电极;和
配置于所述一对电极之间、由含有陶瓷材料的介电材料所构成的介电体层,
所述介电体层包含所述介电材料的颗粒,且具有在其厚度方向上仅由一个该颗粒所构成的部位,
在所述电极与所述介电体层之间,分散存在有包含选自Si、Li、及B中的至少一种元素的区域。
2.根据权利要求1所述的叠层陶瓷电容器,其特征在于:
所述区域由所述内部电极及2个以上的所述颗粒所包围。
3.根据权利要求1或2所述的叠层陶瓷电容器,其特征在于:
所述区域主要包含Si。
4.一种叠层陶瓷电容器,其特征在于:设置有
一对电极;和
配置于所述一对电极之间、由含有陶瓷材料的介电材料所构成的介电体层,
所述介电体层包含所述介电材料的颗粒,且具有在其厚度方向上仅由该一个颗粒所构成的部位,
在所述电极与所述介电体层之间,分散存在有包含选自Si、Li、及B中的至少一种元素的第一区域,
在所述介电体层内,分散存在有包含选自Si、Li、及B中的至少一种元素的第二区域,
所述第一区域比所述第二区域多地分散存在。
5.根据权利要求4所述的叠层陶瓷电容器,其特征在于:
所述第一区域由所述内部电极及2个以上的所述颗粒所包围,且所述第二区域仅由3个以上的所述颗粒所包围。
6.根据权利要求4或5所述的叠层陶瓷电容器,其特征在于:
所述第一区域及第二区域主要含有Si。
7.根据权利要求1~6中任一项所述的叠层陶瓷电容器,其特征在于:
所述陶瓷材料是以Ba及Ti为主要成分的复合氧化物。
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