CN107793148A - 电介质组合物和层叠电子部件 - Google Patents

电介质组合物和层叠电子部件 Download PDF

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CN107793148A
CN107793148A CN201710756337.9A CN201710756337A CN107793148A CN 107793148 A CN107793148 A CN 107793148A CN 201710756337 A CN201710756337 A CN 201710756337A CN 107793148 A CN107793148 A CN 107793148A
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content
oxide
dielectric composition
dielectric
electronic component
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CN107793148B (zh
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加纳裕士
小田嶋努
百田睦
佐佐木洋
佐藤雅之
高桥俊成
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TDK Corp
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TDK Corp
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Abstract

本发明涉及一种电介质组合物和层叠电子部件。该电介质组合物包含钛酸钡、钇的氧化物和镁的氧化物。在将钇的氧化物的含量以Y2O3换算设定为α摩尔份,将镁的氧化物的含量以MgO换算设定为β摩尔份的情况下,0.70≤α/β≤1.10。

Description

电介质组合物和层叠电子部件
技术区域
本发明涉及一种电介质组合物和层叠电子部件。
背景技术
陶瓷电子部件作为小型、高性能和高可靠性的电子部件而广泛应用,在电气设备和电子设备中使用的数量也在增加。近年来,随着设备的小型化和高性能化,对陶瓷电子部件的进一步小型化、高性能化和高可靠性化的要求日益严格。特别是寻求使高温负荷寿命提高并且相对介电常数也高的电介质组合物和层叠电子部件。
对于这样的要求,在专利文献1中公开了包含电介质层的多层陶瓷片式电容器,其中,所述电介质层含有钛酸钡、Y2O3等。
但是,一直以来难以同时提高高温负荷寿命和相对介电常数,如果要提高相对介电常数,则高温负荷寿命降低,如果要提高高温负荷寿命,则相对介电常数降低。
专利文献1:日本特开2000-315615号公报
发明内容
鉴于上述实际情况,本发明的目的在于提供一种相对介电常数、高温负荷寿命和温度特性良好的电介质组合物和层叠电子部件。
为了达成上述目的,本发明所涉及的电介质组合物为包含钛酸钡、钇的氧化物和镁的氧化物的电介质组合物,
在将钇的氧化物的含量以Y2O3换算设定为α摩尔份,将镁的氧化物的含量以MgO换算设定为β摩尔份的情况下,0.70≤α/β≤1.10。
本发明所涉及的电介质组合物通过将α/β控制在上述的范围内,能够使相对介电常数、高温负荷寿命和温度特性良好。
优选在将所述钛酸钡的含量以BaTiO3换算设定为100摩尔份的情况下,钒的含量以V2O5换算为0.02摩尔份以上。
优选在将所述钛酸钡的含量以BaTiO3换算设定为100摩尔份的情况下,钇的含量以Y2O3换算为0.78~2.03摩尔份。
优选在将所述钛酸钡的含量以BaTiO3换算设定为100摩尔份的情况下,镁的含量以MgO换算为1.12~1.85摩尔份。
优选在将所述钛酸钡的含量以BaTiO3换算设定为100摩尔份的情况下,硅的含量以SiO2换算为1.39~2.80摩尔份。
另外,本发明所涉及的层叠电子部件为具备电介质层、内部电极层和外部电极的层叠电子部件,
所述电介质层由上述的电介质组合物构成。
优选层叠电子部件的截面中,Y偏析的区域所占的面积比例为2.0%以下。
优选层叠电子部件的截面中,Mg偏析的区域所占的面积比例为2.0%以下。
附图说明
图1为本发明的一个实施方式所涉及的层叠陶瓷电容器的截面图。
图2为纵轴表示高温负荷寿命,横轴表示α/β的图表。
图3为纵轴表示Y的偏析区域所占的面积比例,横轴表示α/β的图表。
图4为纵轴表示Si的偏析区域所占的面积比例,横轴表示α/β的图表。
图5为纵轴表示Mg的偏析区域所占的面积比例,横轴表示α/β的图表。
图6为纵轴表示高温负荷寿命,横轴表示Y的偏析区域所占的面积比例的图表。
图7为将图6的一部分放大的图表。
符号的说明:
1…层叠陶瓷电容器
2…电介质层
3…内部电极层
4…外部电极
10…电容器元件主体
具体实施方式
以下,基于附图所示的实施方式来说明本发明。
层叠陶瓷电容器1
如图1所示,本发明的一个实施方式所涉及的层叠陶瓷电容器1具有电介质层2与内部电极层3交替层叠而构成的电容器元件主体10。内部电极层3以各端面交替地露出于电容器元件主体10的相对的2个端部的表面的方式进行层叠。一对外部电极4形成于电容器元件主体10的两端部,与交替配置的内部电极层3的露出端面连接,构成电容电路。
电容器元件主体10的形状没有特别限制,但是如图1所示,通常为长方体状。另外,其尺寸也没有特别限制,只要根据用途制成适当尺寸即可。
电介质层2
电介质层2由电介质组合物构成,所述电介质组合物至少含有钛酸钡、钇的氧化物和镁的氧化物。
在本实施方式中,作为钛酸钡,优选以组成式BamTiO2+m表示,可以优选使用m为0.995≤m≤1.002,Ba和Ti的比为0.995≤Ba/Ti≤1.002的钛酸钡。以下,将钛酸钡的组成式记为BaTiO3
另外,在本实施方式中,也可以在钛酸钡中混合钛酸钙和/或钛酸锶来使用。钛酸钙和/或钛酸锶的含量没有特别限制,可以以不损害所获得的电介质组合物的特性的程度含有钛酸钙和/或钛酸锶。例如,相对于100摩尔份的钛酸钡,可以含有合计0.1摩尔份以下的钛酸钙和/或钛酸锶。
本实施方式所涉及的电介质组合物,在将钇的氧化物的含量以Y2O3换算设定为α摩尔份,将镁的氧化物的含量以MgO换算设定为β摩尔份的情况下,0.70≤α/β≤1.10。
本实施方式所涉及的电介质组合物通过0.70≤α/β≤1.10,从而成为相对介电常数、高温负荷寿命和温度特性全部优异的电介质组合物。特别是成为兼顾了高的相对介电常数高和优异的高温负荷寿命的电介质组合物。如果α/β在上述范围外,则高温负荷寿命降低。
进一步,本实施方式所涉及的电介质组合物由于成为即使不使用涂层材料,相对介电常数、高温负荷寿命和温度特性也全部优异的电介质组合物,因此,能够降低成本。
另外,在想要获得高温负荷寿命特别优异的电介质组合物的情况下,优选0.81≤α/β≤1.04。在想要获得相对介电常数特别优异的电介质组合物的情况下,优选0.70≤α/β≤0.81。
钇的氧化物的含量没有特别限制,优选相对于100摩尔份的BaTiO3,以Y2O3换算含有0.78~2.03摩尔份。通过将钇的氧化物的含量设定在上述的范围内,从而倾向于高温负荷寿命变得良好。
镁的氧化物的含量没有特别限制,优选相对于100摩尔份的BaTiO3,以MgO换算含有1.12~1.85摩尔份。通过将镁的氧化物的含量设定在上述的范围内,从而倾向于电阻率变得良好。
另外,本实施方式所涉及的电介质组合物也可以进一步含有硅的氧化物。硅的氧化物的含量没有特别限制,优选相对于100摩尔份的BaTiO3,以SiO2换算含有1.39~2.80摩尔份。通过将硅的氧化物的含量设定在上述的范围内,从而倾向于相对介电常数变得良好。
通过将α/β控制在规定的范围内而能够获得相对介电常数、高温负荷寿命和温度特性全部优异的电介质组合物的理由不明确,但本发明者们认为如下。
一直以来,使用了钛酸钡的电介质组合物由于钛酸钡是铁电体,因此,相对介电常数高,另一方面,稳定性低,高温负荷寿命不足。
钇等稀土元素(顺电体)在电介质组合物的制造过程中,与钛酸钡发生反应并固溶,由此使电介质组合物的稳定性提高,有助于改善电介质组合物的高温负荷寿命。
另一方面,含有钇等稀土元素、镁和硅的电介质组合物在制造过程中,形成稀土元素、镁和硅的偏析。
偏析后的稀土元素没有固溶于钛酸钡,因此,对改善高温负荷寿命没有贡献。即,如果稀土元素过量偏析,则有难以得到高温负荷寿命的改善效果的倾向。进一步,稀土元素和钛容易同时偏析,稀土元素和钛同时偏析的部分会成为电阻劣化的起点。因此,如果稀土元素和钛同时偏析的部分过量存在,则有使高温负荷寿命恶化的倾向。
另外,在镁的偏析过度地发生时,倾向于相对介电常数降低,除此以外,倾向于后述的内部电极层和外部电极的接触性劣化、电容降低。在硅的偏析过度地发生时,倾向于相对介电常数降低,除此以外,倾向于后述的内部电极层和外部电极的接触性劣化、电容降低。倾向于接触性劣化是由于镁的偏析和硅的偏析同时、且容易在电极周围(特别是电极端部周围)发生,发生的偏析倾向于阻碍内部电极层与外部电极的接触。
在此,本发明者们发现,通过作为稀土元素使用钇,并且将α/β控制在0.70以上且1.10以下,从而能够抑制钇的偏析、镁的偏析和硅的偏析的发生。并且,发现能够使相对介电常数和温度特性保持良好,并且显著地提高高温负荷寿命。
钇、镁和硅的偏析量的评价方法没有特别限制。例如,可以通过STEM(扫描透射电子显微镜)或者EPMA(电子束显微分析仪)观察截面,制成元素分布图像,对元素分布图像进行图像处理,特定偏析区域,根据偏析区域的面积的大小来评价偏析量。
作为一个例子,对利用EPMA的偏析量的评价方法进行详细说明。
首先,切断层叠陶瓷电容器1。此时,与层叠方向垂直地切断。
接着,利用EPMA对切断的截面进行观察。倍率或视野的大小没有特别地限制,例如,以倍率1000~5000倍对视野20~115μm×15~86μm的视场,进行Mg元素、Si元素和Y元素的元素测绘,获得Mg元素的元素分布图像、Si元素的元素分布图像和Y元素的元素分布图像。
接着,算出各元素的元素分布图像中的各元素的平均强度。接下来,以抽出成为各元素的平均强度的2倍以上强度的区域的方式进行图像处理。将成为各元素的平均强度的2倍以上强度的区域设定为各元素偏析的区域。此外,本实施方式中,也可以在元素分布图像的视野内包含内部电极层3,也包括作为内部电极层3的部分在内来计算各元素的平均强度。此外,元素分布图像整体的视野中作为内部电极层3的部分所占的面积比例没有特别限制,但优选为30%以下。
计算各元素偏析的区域的面积比,根据各元素的面积比评价偏析量。此外,计算各元素偏析的区域的面积比时的总量中,也包含作为内部电极层3的部分所占的面积。
本实施方式中,在Mg偏析的区域的面积比为2.0%以下的情况下,Mg的偏析量少比较好。更优选为0.01~2.0%,进一步优选为0.1~1.8%。
在Si偏析的区域的面积比为4.0%以下的情况下,Si的偏析量少比较好。另外,Si偏析的区域的面积比进一步优选为2.0%以下。
在Y偏析的区域的面积比为2.0%以下的情况下,Y的偏析量少比较好。更优选为0.01~2.0%,进一步优选为0.1~1.8%。
本实施方式所涉及的电介质组合物也可以进一步根据所希望的特性含有其它成分。其它成分的例子如下所示。
本实施方式所涉及的电介质组合物也可以含有钛酸钡以外的钡的氧化物。钡的氧化物的含量没有特别限制,但优选相对于100摩尔份的BaTiO3,以BaO换算为0.57~1.33摩尔份。通过将钡的氧化物的含量设定在上述的范围内,从而倾向于抑制由使烧成温度变化而产生的相对介电常数的变动。
本实施方式所涉及的电介质组合物也可以包含钙的氧化物。钙的氧化物的含量没有特别限制,但优选相对于100摩尔份的BaTiO3,以CaO换算为0.41~1.30摩尔份。通过将钙的氧化物的含量设定在上述的范围内,从而倾向于高温负荷寿命和电阻率变得良好。另外,上述的硅的氧化物、钡的氧化物和钙的氧化物可以分别添加,也可以以(Ba,Ca)SiO3的形式一起添加。
本实施方式所涉及的电介质组合物也可以包含铬的氧化物。铬的氧化物的含量没有特别限制,但优选相对于100摩尔份的BaTiO3,以Cr2O3换算为0.14~0.20摩尔份。通过将铬的氧化物的含量设定在上述的范围内,从而有耐还原性提高、电阻率变得良好的倾向。另外,可以代替铬的氧化物而包含锰的氧化物。锰的氧化物的含量没有特别限制,但优选相对于100摩尔份的BaTiO3,以MnO换算为0.14~0.20摩尔份。当然,也可以包含铬的氧化物和锰的氧化物两者。
本实施方式所涉及的电介质组合物也可以包含钒的氧化物。钒的氧化物的含量没有特别限制,相对于100摩尔份的BaTiO3,优选以V2O5换算为0.02摩尔份以上,进一步优选以V2O5换算为0.02~0.10摩尔份。钒的氧化物的含量越多,则越倾向于高温负荷寿命和温度特性提高。另外,钒的氧化物的含量越少,则越倾向于相对介电常数和电阻率提高。
另外,本实施方式所涉及的电介质组合物,除了上述氧化物以外,可以进一步包含本技术领域中使用的其它氧化物。其它氧化物的种类和含量没有特别限制,可以以不损害所获得的电介质组合物的特性的程度含有其它氧化物。
内部电极层3
内部电极层3所含的导电材料没有特别限制,由于电介质层2的构成材料具有耐还原性,因此,可以使用比较廉价的贱金属。作为导电材料使用的贱金属,优选为Ni或者Ni合金。作为Ni合金,优选为从Mn、Cr、Co和Al中选择的一种以上的元素与Ni的合金,合金中的Ni的含量优选为95重量%以上。此外,在Ni或者Ni合金中,也可以包含0.1重量%左右以下的P等各种微量成分。内部电极层3的厚度只要根据用途等适当确定即可,通常优选为1.0~1.5μm,特别优选为1.0~1.2μm左右。
外部电极4
外部电极4所含的导电材料没有特别限制,本发明中可以使用廉价的Ni、Cu或者这些的合金。外部电极4的厚度只要根据用途等适当确定即可,通常优选为10~50μm左右。
层叠陶瓷电容器1的制造方法
本实施方式的层叠陶瓷电容器1可以与现有的层叠陶瓷电容器同样地通过使用了膏体的通常的印刷法或片材法制作生坯芯片,将其烧成之后,将外部电极印刷或转印并烧成来制造。以下,对制造方法进行具体地说明。
首先,准备电介质层用膏体所含的电介质原料(混合原料粉末),将其涂料化,调制电介质层用膏体。
电介质层用膏体可以为将电介质原料和有机载体混炼而成的有机系的涂料,也可以为水系的涂料。
作为电介质原料,首先,准备钛酸钡的原料和Y、Mg等各元素的氧化物的原料。作为这些的原料,可以使用上述成分的氧化物或其混合物、复合氧化物,此外,也可以从通过烧成而成为上述氧化物或复合氧化物的各种化合物,例如碳酸盐、草酸盐、硝酸盐、氢氧化物、有机金属化合物等中适当选择、混合并使用。另外,α/β的调整方法没有特别限制,例如,通过调整Y的氧化物的原料与Mg的氧化物的原料的含量比来进行。
钛酸钡的原料可以使用通过所谓的固相法、除此以外的各种液相法(例如,草酸盐法、水热合成法、醇盐法、溶胶-凝胶法等)制造的材料等通过各种方法制造的材料,也可以使用市售的钛酸钡。
另外,钛酸钡的原料的BET比表面积值优选为1.7~2.5m2/g。使用具有这样的BET比表面积值的钛酸钡的原料,由此有高温负荷寿命变得良好且相对介电常数变高的倾向。
本实施方式所涉及的电介质组合物中,即使作为钛酸钡原料采用比现有的更廉价的钛酸钡原料,具体而言为平均粒径大的钛酸钡原料,也能够得到高温负荷寿命等优异的电介质组合物。
另外,在钛酸钡的原料粉末的表面可以包覆Y、Mg等各元素的氧化物的原料粉末。包覆的方法没有特别限制,可以采用公知的方法。另外,本实施方式所涉及的电介质组合物,即使对于原料粉末不使用涂层材料也能够得到优异的特性,并且能够降低成本。但是,也可以使涂层材料包覆钛酸钡等的原料粉末的表面。
电介质原料中的各化合物的含量只要以烧成后成为上述的电介质组合物的组成的方式确定即可。通常在烧成前后电介质组合物的组成实质上没有变化。在进行涂料化之前的状态下,电介质原料的粒径通常平均粒径为0.70~0.90μm左右。
有机载体是将粘合剂溶解于有机溶剂中而成的。有机载体中使用的粘合剂没有特别限制,可以从乙基纤维素、聚乙烯醇缩丁醛等通常的各种粘合剂中适当选择。使用的有机溶剂也没有特别限制,可以根据印刷法或者片材法等采用的方法从萜品醇、丁基卡必醇、丙酮、甲苯等各种有机溶剂中适当选择。
另外,在将电介质层用膏体制成水系的涂料时,只要混炼将水溶性的粘合剂或分散剂等溶解于水中而得到的水系载体和电介质原料即可。水系载体中使用的水溶性粘合剂没有特别限制,例如,可以使用聚乙烯醇、纤维素、水溶性丙烯酸树脂等。
内部电极层用膏体通过将由上述的各种导电性金属或合金构成的导电材料、或者烧结后成为上述导电材料的各种氧化物、有机金属化合物、树脂盐酸等、与上述的有机载体进行混炼来制备。另外,也可以在内部电极层用膏体中含有常见材料(common material)。作为常见材料,没有特别限制,但优选具有与主成分相同的组成。
外部电极用膏体只要与上述的内部电极层用膏体同样地制备即可。
上述的各膏体中的有机载体的含量没有特别限制,通常的含量,例如粘合剂只要设定为2~6重量%左右、溶剂只要设定为15~55重量%左右即可。另外,各膏体中也可以根据需要含有从各种分散剂、增塑剂、电介质、绝缘体等中选择的添加物。它们的总含量优选设定为10重量%以下。
在使用印刷法的情况下,将电介质层用膏体及内部电极层用膏体在PET等基板上印刷、层叠,切断成规定形状之后,从基板剥离,制成生坯芯片。
另外,在使用片材法的情况下,使用电介质层用膏体形成生坯片材,在生坯片材上印刷内部电极层用膏体形成内部电极图案之后,将它们层叠,制成生坯芯片。
在烧成前,对生坯芯片实施脱粘合剂处理。作为脱粘合剂条件,优选将升温速度设为20~300℃/小时,优选将保持温度设为180~400℃,优选将温度保持时间设为0.5~20小时。另外,脱粘合剂气氛设为空气或还原性气氛。
生坯芯片的烧成中,优选将升温速度设为200~2000℃/小时。
烧成时的保持温度优选为1230~1310℃,其保持时间优选为0.2~4小时,更优选为2~3小时。如果保持温度和/或保持时间小于上述范围,则烧结会变得不充分,钇、镁和/或硅的偏析量容易变得过量。如果保持温度和/或保持时间超过上述范围,则容易产生由于内部电极层的异常烧结而导致的电极间断,或者由于内部电极层构成材料的扩散造成的容量温度特性的劣化、电介质组合物的还原。
烧成气氛优选设为还原性气氛,作为气氛气体,例如可以将N2和H2的混合气体加湿使用。
另外,烧成时的氧分压只要根据内部电极层用膏体中的导电材料的种类适当确定即可,在采用Ni或Ni合金等贱金属作为导电材料时,烧成气氛中的氧分压优选为10-14~10-10MPa。如果氧分压小于上述范围,则内部电极层的导电材料有时会发生异常烧结而间断。另外,如果氧分压超过上述范围,则有内部电极层发生氧化的倾向。降温速度优选为50~500℃/小时。
在还原性气氛中烧成之后,优选对电容器元件主体实施退火。退火是用于将电介质层再氧化的处理,由此能够延长高温加速寿命。
退火气氛中的氧分压优选为10-9~10-5MPa。如果氧分压小于上述范围,则电介质层难以再氧化;如果氧分压超过上述范围,则有内部电极层进行氧化的倾向。
退火时的保持温度优选为950~1150℃。如果保持温度小于上述范围,则电介质层的氧化变得不充分,因此,高温加速寿命容易降低。另一方面,如果保持温度超过上述范围,则不仅内部电极层氧化容量会降低,而且内部电极层会与电介质基底反应,容易发生温度特性的劣化和高温加速寿命的降低。此外,退火可以仅由升温过程和降温过程构成。即,也可以将温度保持时间设为零。在该情况下,保持温度与最高温度相同含义。
作为除此以外的退火条件,优选将温度保持时间设为0~20小时,优选将降温速度设为50~500℃/小时。另外,作为退火的气氛气体,例如,优选使用加湿后的N2气体等。
上述的脱粘合剂处理、烧成和退火中,为了将N2气体或者混合气体等加湿,例如可以使用湿润剂等。该情况下,水温优选为5~75℃左右。
脱粘合剂处理、烧成和退火可以连续进行,也可以独立地进行。
对于由此得到的电容器元件主体,通过例如滚筒研磨或喷砂等实施端面研磨,涂布外部电极用膏体进行烧成,形成外部电极4。然后,根据需要,在外部电极4表面通过镀敷等形成包覆层。
这样制造的本实施方式的层叠陶瓷电容器1通过焊接等安装于印刷基板上等,并用于各种电子设备等。
以上,对本发明的实施方式进行了说明,但本发明不被上述的实施方式作任何限定,可以在不脱离本发明的要点的范围内进行各种改变。
另外,在上述的实施方式中,作为本发明所涉及的层叠电子部件例示了层叠陶瓷电容器,但作为本发明所涉及的层叠电子部件,不限定于层叠陶瓷电容器,只要是具有上述结构的层叠电子部件即可。
实施例
以下,基于更详细的实施例来说明本发明,但本发明不限定于这些实施例。
首先,作为原料粉末,分别准备BaTiO3粉末、Y2O3粉末、MgCO3粉末、BaO粉末、CaO粉末、SiO2粉末、Cr2O3粉末和V2O5粉末。另外,以最终得到的电容器样品的电介质层的组成成为表1所示的组成的方式称量各原料粉末。此外,BaTiO3粉末的BET比表面积值为2.2m2/g。
接着,将上述准备的各原料粉末在球磨机中湿法混合、粉碎10小时,进行干燥,得到混合原料粉末。此外,MgCO3在烧成后,以MgO包含在电介质组合物中。
接着,将得到的混合原料粉末:100重量份、聚乙烯醇缩丁醛树脂:10重量份、作为增塑剂的邻苯二甲酸二辛酯(DOP):5重量份、和作为溶剂的乙醇:100重量份在球磨机中混合并膏体化,得到电介质层用膏体。
另外,与上述分开,将Ni颗粒:44.6重量份、萜品醇:52重量份、乙基纤维素:3重量份和苯并三唑:0.4重量份利用三辊进行混炼,进行膏体化,制作内部电极层用膏体。
然后,使用上述中制作的电介质层用膏体,在PET膜上以干燥后的厚度成为2μm的方式形成生坯片材。接着,在生坯片材上使用内部电极层用膏体,以规定图案印刷电极层后,从PET膜上剥离片材,制作具有电极层的生坯片材。接着,将具有电极层的生坯片材层叠多片,并进行加压粘接,由此,制成生坯层叠体,通过将该生坯层叠体切断成规定尺寸,得到生坯芯片。
接着,对于得到的生坯芯片,在下述条件下进行脱粘合剂处理、烧成及退火,得到层叠陶瓷烧成体。
脱粘合剂处理条件设为,升温速度:25℃/小时、保持温度:260℃、温度保持时间:8小时、气氛:空气中。
烧成条件设为,升温速度:2000℃/小时、保持温度:1200℃,将保持时间设为2小时。降温速度设为2000℃/小时。此外,气氛气体设为加湿后的N2+H2混合气体,使氧分压成为10-12MPa。
退火条件设为,升温速度:200℃/小时、保持温度:1000℃、温度保持时间:2小时、降温速度:200℃/小时、气氛气体:加湿后的N2气(氧分压:10-7MPa)。
此外,在烧成及退火时的气氛气体的加湿中使用了湿润剂。
接着,通过喷砂对得到的层叠陶瓷烧成体的端面进行研磨之后,作为外部电极,涂布Cu,得到图1所示的层叠陶瓷电容器的样品。得到的电容器样品的尺寸为3.2mm×1.6mm×0.6mm,电介质层的厚度设为1.5μm,内部电极层的厚度设为1.0μm,被夹持于内部电极层的电介质层的数量设为200。
对于得到的电容器样品,确认电介质层的组成为表1的组成。进一步,分别通过下述所示的方法进行相对介电常数εs的测定、高温负荷寿命η(hr)的测定、125℃下的静电容量变化率TC(%)的测定、电阻率ρ(Ω·m)的测定以及Mg、Y的偏析区域所占的面积比例的测定。结果如表1所示。
相对介电常数εs的测定
对于得到的电容器样品,在基准温度25℃下,利用数字LCR测试仪,以频率1kHz、输入信号电平(测定电压)1Vrms的条件下进行测定,根据测得的静电容量算出(没有单位)。将相对介电常数εs为2400以上设定为良好,将2600以上设定为更良好。
高温负荷寿命η的测定
对于得到的电容器样品,以200℃在25V/μm的电场下保持直流电压的施加状态,测定寿命时间。在本实施例中,将从直流电压施加开始到绝缘电阻下降1位数的时间作为该电容器样品的寿命时间。对20个电容器样品实施上述的评价,将寿命时间的平均值作为高温负荷寿命η。将高温负荷寿命η为15小时以上设定为良好,将30小时以上设定为更良好。
静电容量变化率TC的测定
对于得到的电容器样品,在基准温度25℃和测定温度125℃下,使用数字LCR测试仪,以频率1kHz、输入信号电平(测定电压)1Vrms的条件测定静电容量,计算出测定温度125℃下的静电容量相对于基准温度25℃下的静电容量的变化率。在本实施例中,将TC在±10%以内的情况设定为良好。
电阻率ρ的测定
对于得到的电容器样品,在基准温度25℃下,以10V施加电压30秒,然后,使用绝缘电阻计测定绝缘电阻IR。然后,基于电介质层的厚度、有效电极面积和测定的结果所得到的绝缘电阻IR,算出电阻率ρ。将电阻率ρ为1.5E+10Ω·m以上的情况设定为良好。此外,1.5E+10是指1.5×1010。但是,即使电阻率ρ不良好,也能够达成本申请发明的目的。
Mg、Si、Y的偏析区域所占的面积比例的观察
对于得到的电容器样品,与层叠方向垂直地切断。然后,用EPMA(电子束显微分析仪)对得到的截面进行观察。以倍率3000倍对视野为38.4μm×28.8μm的范围,进行Mg元素、Si元素和Y元素的元素测绘,得到Mg元素的元素分布图像、Si元素的元素分布图像和Y元素的元素分布图像。
接着,计算出各元素的元素分布图像中的各元素的平均强度。接着,以抽出成为各元素的平均强度的2倍以上强度的区域的方式进行图像处理。将成为各元素的平均强度的2倍以上强度的区域设定为各元素偏析的区域。
然后,通过图像分析计算出各元素偏析的区域的面积,计算出各元素的偏析面积比。
[表1]
*为比较例
根据表1,Y2O3/MgO的组合比(=α/β)在0.70~1.10的范围内的实施例(样品编号4~11)与α/β在0.70~1.10的范围外的比较例(样品编号1~3、12~14)相比较,高温负荷寿命η更优异。进一步,样本编号4~11的其它特性也良好。
在此,以高温负荷寿命η为纵轴,α/β为横轴,将表1的样品编号1~14制图,制成图2。进一步,分别做出以Y的偏析区域所占的面积比例为纵轴的图3、以Si的偏析区域所占的面积比例为纵轴的图4、和以Mg的偏析区域所占的面积比例为纵轴的图5。进一步,图6为以高温负荷寿命为纵轴并且以Y的偏析区域所占的面积比例为横轴的半对数图表,图7为将图6的一部分放大的图表。
根据图2可知,在α/β在0.70~1.10的范围内的情况下,与在范围外的情况相比较,高温负荷寿命η更优异。进一步,根据图3~图5,在α/β在0.70~1.10的范围内的情况下,与在范围外的情况相比较,Y、Mg和Si的偏析区域所占的面积比例有缩小的倾向。
进一步,根据图6和图7可知,Y的偏析区域所占的面积比例越小,则高温负荷寿命越趋于良好,在4%左右高温负荷寿命显著地变化。另外,Y的偏析区域超过4%的情况大多是本来发生烧结不足的情况,在发生烧结不足的情况下,倾向于高温负荷寿命显著降低。
实施例2
对于实施例1的样品编号7,改变钒的含量,制作样品编号16、17,以与实施例1同样的方式评价特性。另外,对于实施例1的样品编号4,改变钒的含量,制作样品编号18、19,以与实施例1同样的方式评价特性。结果如表2所示。
[表2]
根据表2可知,钒的含量越多,则高温负荷寿命越趋于提高,另一方面,电阻率ρ越趋于降低。

Claims (8)

1.一种电介质组合物,其特征在于:
包含钛酸钡、钇的氧化物和镁的氧化物,
在将钇的氧化物的含量以Y2O3换算设定为α摩尔份,将镁的氧化物的含量以MgO换算设定为β摩尔份的情况下,0.70≤α/β≤1.10。
2.如权利要求1所述的电介质组合物,其特征在于:
在将所述钛酸钡的含量以BaTiO3换算设定为100摩尔份的情况下,钒的含量以V2O5换算为0.02摩尔份以上。
3.如权利要求1或2所述的电介质组合物,其特征在于:
在将所述钛酸钡的含量以BaTiO3换算设定为100摩尔份的情况下,钇的含量以Y2O3换算为0.78~2.03摩尔份。
4.如权利要求1~3中任一项所述的电介质组合物,其特征在于:
在将所述钛酸钡的含量以BaTiO3换算设定为100摩尔份的情况下,镁的含量以MgO换算为1.12~1.85摩尔份。
5.如权利要求1~4中任一项所述的电介质组合物,其特征在于:
在将所述钛酸钡的含量以BaTiO3换算设定为100摩尔份的情况下,硅的含量以SiO2换算为1.39~2.80摩尔份。
6.一种层叠电子部件,其特征在于:
所述层叠电子部件具备电介质层、内部电极层和外部电极,
所述电介质层由权利要求1~5中任一项所述的电介质组合物构成。
7.如权利要求6所述的层叠电子部件,其特征在于:
层叠电子部件的截面中,Y偏析的区域所占的面积比例为2.0%以下。
8.如权利要求6或7所述的层叠电子部件,其特征在于:
层叠电子部件的截面中,Mg偏析的区域所占的面积比例为2.0%以下。
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