CN100426427C - 电介质陶瓷组合物、使用该组合物的电容器及其制造方法 - Google Patents

电介质陶瓷组合物、使用该组合物的电容器及其制造方法 Download PDF

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CN100426427C
CN100426427C CNB021526354A CN02152635A CN100426427C CN 100426427 C CN100426427 C CN 100426427C CN B021526354 A CNB021526354 A CN B021526354A CN 02152635 A CN02152635 A CN 02152635A CN 100426427 C CN100426427 C CN 100426427C
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molar part
capacitor
converted
manufacture method
barium titanate
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CN1516208A (zh
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小松和博
长井淳夫
小林惠治
仓光秀纪
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Murata Manufacturing Co Ltd
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Matsushita Electric Industrial Co Ltd
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Abstract

提供一种电介质陶瓷组合物，它包含：作为主要成分的钛酸钡100摩尔份，其中，Ba/Ti之摩尔比为1.001-1.05；并至少包含以下辅助成分：Mg，换算成MgO，为0.5-5.0摩尔份；Dy，换算成Dy2O3，为0.1-3.0摩尔份；Mn，换算成Mn3O4，为0.01-0.4摩尔份；V，换算成V2O5，为0.01-0.26摩尔份；Si，换算成SiO2，为0.3-3.5摩尔份；Al，换算成Al2O3，为0.01-3.0摩尔份。使用本发明的电介质陶瓷组合物，即使用铜等金属形成外部电极，也能得到电介质层不会被还原、具有高绝缘电阻的叠层电容器。

Description

电介质陶瓷组合物、使用该组合物的电容器及其制造方法
技术领域
本发明涉及一种用于具有由镍等贱金属组成的内部电极层的叠层陶瓷电容器的电介质层的电介质陶瓷组合物和使用该组合物的电容器及其制造方法。
背景技术
以往的叠层陶瓷电容器，例如，如日本特许公开公报1 996年第337471号公报所公开的，系将电介质层与镍内部电极层交互叠层，在中性气氛或还原性气氛中焙烧后，用银等形成外部电极。上述电介质层是除了BaTiO3之外，以Dy2O3等稀土类氧化物和CO2O3为主要成分，并含有作为辅助成分的BaO、MnO、MgO、Al2O3和以Li2O-(Si、Ti)-Al2O3为主要成分的氧化物玻璃。
一般地，镍与银不固溶。由此，为确保内部电极与外部电极的电连接，最好使用与银完全固溶的金属(例如，铜等)形成外部电极。但是，要用铜形成外部电极，必须在非氧化环境中形成。具有上述组成的电介质层在形成外部电极时，电介质层的构成成分被还原，导致电介质层的绝缘电阻降低。
一般地，用以钛酸钡为主要成分的电介质陶瓷组合物制造叠层电容时，若Ba/Ti之摩尔比小于1，则在还原气氛中的焙烧工序中和焙烧含于介电质层中的有机粘合剂时等，TiO2容易被还原。被还原的TiO2虽在烧结后的冷却过程中被一定程度的再氧化，但电介质层内部及各结晶粒子的内侧不易再被氧化，仍维持着缺氧的状态。由导致电介质层的绝缘电阻、绝缘破坏强度下降。
发明内容
本发明的目的在于提供一种电介质陶瓷组合物、使用该组合物的电容器及其制造方法，所述电介质陶瓷组合物即使在用铜等贱金属形成外部电极的情况下，电介质层也不会被还原、可得到绝缘电阻高的叠层电容器。
本发明的电介质陶瓷组合物的特征在于，包含作为主要成分的钛酸钡100摩尔份，并至少包含以下辅助成分：Mg，换算成MgO，为0.5-5.0摩尔份；Dy，换算成Dy2O3，为0.1-3.0摩尔份；Mn，换算成Mn3O4，为0.01-0.4摩尔份；V，换算成V2O5，为0.01-0.26摩尔份；Si，换算成SiO2，为0.3-3.5摩尔份；Al，换算成Al2O3，为0.01-3.0摩尔份；其中，Ba/Ti之摩尔比为1.001-1.05。
本发明的电介质组合物是在将Ba/Ti之摩尔比设为比1大，为1.001-1.05的同时，通过用5价的V取代一部分4价的Ti而产生的阳离子空孔补偿焙烧时的氧缺陷。结果，可防止TiO2被还原并能防止电介质组合物绝缘电阻的下降。
附图说明
图1是本发明一实施例中的层叠电容器的剖面图。
图中符号：
10    电介质层    11    内部电极层
12    外部电极    13    镍膜
14    钎焊膜
具体实施方式
实施例1
下面，结合图1，对本发明的实施例1进行说明。
首先，准备表1所示钛酸钡，在表1中，符号*表示比较例的组成。
然后，将100摩尔的钛酸钡与0.02摩尔的BaCO3、1.0摩尔的Dy2O3、2.5摩尔的MgO、0.2摩尔的MnO4/3、0.15摩尔V2O5、2.1摩尔的BaO-SiO2-Al2O3系玻璃混合，加入纯水，将氧化锆球作为介质在球磨机中湿式混合17小时，粉碎。然后，将上述组成的混合粉碎物干燥。
然后，将上述混合材料粉碎，放入氧化铝质的坩埚中，在1100℃的温度保持2小时，进行初焙烧。该初焙烧在能使金属碳氧化物分解并使主要成分钛酸钡与辅助成分适度反应的温度下进行。
接着，将上述初焙烧原料在球磨机中湿式粉碎成平均粒径在1.0μm以下，然后干燥，作为电介质材料。
然后，在上述电介质材料中添加作为粘合剂的聚乙烯缩丁醛树脂、作为溶剂的醋酸正丁酯、作为增塑剂的酞酸二丁酯，并与氧化锆球一起在球磨机中混合72小时，制成料浆。
然后，用刮涂法将该料浆制成陶瓷片，使制成的陶瓷片在焙烧后的厚度为14μm。该陶瓷片即后述的电容器电介质层10。
接着，在该陶瓷片表面丝网印刷以镍为主要成分的内部电极糊，干燥，形成内部导极材料层。然后，将形成内部电极材料层的陶瓷片10片层叠，热压合后切割成纵3.3mm、横1.7mm的叠层体。
然后，将上述叠层体放入氧化铝质的烧盆(焙烧容器)中，在镍不会被过度氧化的气氛中烧去有机物。接着，升温，在由氮气、氢气与二氧化碳或水蒸气混合而成的还原性气氛中，在最高温度1220-1340℃保持2小时，进行叠层体的烧结。烧结时的气氛条件是，镍不会被过度氧化且电介质层10能烧结。然后，在降温过程的800-1200℃，在氮气、氢气与二氧化碳或水蒸气构成的还原性气氛中焙烧1小时，将烧结时被还原的电介质层10再氧化。此时，还原性气氛的条件是，镍不会被过度氧化。然后，冷却至室温，制成烧结体。
烧结体的焙烧温度视各电介质材料的组成而异，为可使电介质层10的烧结体密度成为最大的温度。
然后，研磨所得烧结体的表面，涂布以铜为主要成分的外部电极，并使其与露出于端面的内部电极11电连接。接着，在混合了不会使铜氧化的量的氧的混合氮气氛中于850℃焙烧15分钟，形成外部电极12。
然后，在外部电极12表面形成镍膜13、钎焊膜14，完成图1所示叠层电容器。
测定由所得电容器在20℃(室温)、频率1KHz的静电容量算得的介电常数、介电损耗角正切(tanδ)及在-55～+125℃间对于20℃静电容量的变化率。结果示于表2。此外，在室温施加DC电压25V时的绝缘电阻(IR)及为进行加速寿命试验，在125℃连续施加DC200V电压250小时后的绝缘电阻的劣化状况(以IR劣化至1×107Ω以下者为不良进行计算)也一起示表2。
由表2可知，本发明电容器的初期性能的介电常数达2000以上，且绝缘电阻亦达1×107Ω以上，即使在寿命试验后，也未发现绝缘性劣化。
但是，如试样编号1的比较例所示，若Ba/Ti之摩尔比小于1.001，则不能得到足够的绝缘电阻。这是因为在将叠层体烧结时被再氧化的电介质层10在形成外部电极12时被再度还原的缘故。又如试样编号13的比较例所示，若Ba/Ti之摩尔比超过1.05，则电介质层10不能充分烧结，无法确保绝缘性。
因此，如本实施例那样，若使Ba/Ti为1.001-1.05，则可得到即使在形成外部电极12时，电介质层10也不会被还原，绝缘电阻大，且在寿命试验时绝缘劣化小的叠层电容器。
另外，对使用的钛酸钡的比表面积的影响进行了研究。结果，若比表面积小于2m2/g，则在高温的介电常数的温度变化率变大，而若比表面积超过5m2/g，则存在电介质层10的介电常数变小的倾向。
因此，所用的钛酸钡的比表面积最好为2-5m2/g。
此外，X线衍射角2θ未分成在40-50°的(002)面和(200)面的峰(无裂峰)的钛酸钡，存在高温下的容量温度变大的倾向。
因此，最好使用在40-50°的X线衍射角2θ分成(002)面和(200)面的峰的钛酸钡。
实施例2
首先，如表3组成所示，在100摩尔份钛酸钡中分别加入BaCO3、Dy2O3、MgO2、MnO4/3、V2O5、BaO-SiO2-Al2O3系玻璃并混合，加入纯水，以氧化锆球为介质，在球磨机中湿式混合粉碎17小时，然后干燥，制造混合材料。
这里，使用Ba/Ti摩尔比为1.000、比表面积为3.3m2/g、在40-50°的X线衍射角2θ分成(002)面与(200)面的2个峰的钛酸钡。
然后，测定由所得电容器在20℃(室温)、频率1KHz的静电容量算得的介电常数、介电损耗角正切(tanδ)及在-55～+125℃间对于20℃静电容量的变化率。结果示于表4。此外，在室温施加DC电压25V时的绝缘电阻(IR)及为进行加速寿命试验，在125℃连续施加DC200V电压250小时后的绝缘电阻的劣化状况(以IR劣化至1×107Ω以下者为不良进行计算)也一起示表4。
由表4可知，作为本发明电容器的初期性能，其介电常数达2000以上，绝缘电阻亦达1×107Ω以上，且未发现加速寿命试验后的绝缘性劣化。
在本实施例中，加入MgO不仅可提高电介质层10的烧结性，而且还具有提高绝缘电阻的效果。但由表3及表4可知，若MgO的添加量小于0.5摩尔份，则烧结不充分，而若超过5.0摩尔份，则静电容量的温度变化率变大。因此，将Mg换算成MgO，则相对于100摩尔份的钛酸钡，最好添加0.5-5.0摩尔份的MgO。
此外，加入Dy2O3可防止TiO2被还原，提高绝缘电阻，并具有满足静电容量温度特性、tanδ等电特性的效果。但是，由表及3和表4可知，若Dy2O3的添加量小于0.1摩尔，则在静电容量的温度变化率变大的同时，tanδ也变大。而若Dy2O3的添加量超过3.0摩尔，则介电常数下降至2000以下，变得无法非实用。因此，将Dy换算为Dy2O3，则相对于钛酸钡100摩尔份，最好添加0.1-3.0摩尔份的Dy2O3。此外，使用比表面积为7-15m2/g的Dy2O3，可提高分散性，并使上述效果更加显著。
另外，添加MnO4/3可防止TiO2被还原。此外，即使在中性气氛中或在还原性气氛中大量焙烧叠层体，也能在防止绝缘电阻劣化的同时，抑制静电容量的偏差，并具有得到均质烧结体的效果。但是，若MnO4/3的添加量小于0.01摩尔份，则烧结体被部份地半导体化，绝缘电阻下降，即使在加速寿命试验中，绝缘电阻也大幅度劣化。而若MnO4/3的添加量超过0.4摩尔份，则静电容量的温度变化率、经时变化率也大，且绝缘电阻的劣化亦增多。因此，将Mn换算为MnO4/3，相对于钛酸钡100摩尔份，最好添加0.01-0.4摩尔份的MnO4/3。
添加V2O3可抑制TiO2被还原，且具有提高绝缘电阻和防止绝缘电阻劣化的效果。但是，若V2O5的添加量超过0.26摩尔份，则在静电容量的温度变化率增大的同时，绝缘电阻劣化。而若V2O3的添加量小于0.01摩尔份，则绝缘电阻较小，并且会在加速试验中劣化。因此，相对于钛酸钡100摩尔份，V的添加量最好为0.01-0.26摩尔份。
此外，添加BaO-SiO2-Al2O3系玻璃可在较低温度焙烧时促进电介质层10的烧结，并具有减小静电容量、绝缘电阻的偏差的效果。但若添加量于0.6摩尔份，则电介质层10烧结不充分。而若超过5.0摩尔份，则虽然电介质层10的烧结性会提高，但介电常数下降，静电容量的温度变化率变大而失去实用性。因此，相对于钛酸钡100摩尔份，BaO-SiO2-Al2O3系玻璃的添加量最好为0.6-5.0摩尔份。
在本实施例中虽然使用的是Ba/Ti摩尔比为1.000、比表面积为3.3m2/g、在40-50°的X线衍射角2θ分成为(002)面与(200)面的2个峰的钛酸钡，但使用比表面积为2-5m2/g、在40-50°的X线衍射角2θ分成为(002)面与(200)面的2个峰的钛酸钡，使电介质材料中的Ba/Ti摩尔比为1.001-1.05，也可得到同样的效果。
实施例3
首先，相对于钛酸钡100摩尔份，添加0.02摩尔份的BaCO3、2.5摩尔份的MgO、0.2摩尔份的MnO4/3、2.1摩尔份的BaO-SiO2-Al2O3系玻璃。另外，添加表5所示量的Dy2O3和Ho2O3。使用按与实施例2相同的方法进行过调整的钛酸钡。
然后，除将电介质层1的厚度改为3μm之外，按与实施例1相同的方法制作叠层电容器。
然后，按与实施例1同样的方法对所得叠层电容器进行评价。但加速寿命试验中的施加电压为64V。结果示于表6。
如表6所示，加入合计0.1-3.0摩尔份的Dy2O3和Ho2O3，并使Dy/(Dy+Ho)之摩尔比为0.3-0.9，这样，即使将电介质层10的厚度薄层化至5μm以下，也可得到绝缘电阻高、即使在加速寿命试验中绝缘电阻也不会劣化、静电容量的温度变化率小的叠层电容器。
对其原因进行说明。Dy虽具有防止绝缘电阻劣化的效果，但将电介质层10薄层化，会有静电容量的温度特性恶化的倾向。此外，在本发明的电介质陶瓷组合物中加入Ho，可提高温度特性。因此，以合适的组成加入Dy和Ho两者，则即使将电介质层10薄层化，也可得到容量温度特性及绝缘电阻高的叠层电容器。
此时，若Dy/(Dy+Ho)摩尔比小于0.1，则会加速绝缘电阻的劣化，而若超过0.9，则静电容量的温度变化率会变大。
此外，若Dy2O3与Ho2O3的合计添加量小于0.1摩尔份，则静电容量的温度变化率会增大，同时，tanδ亦会变大。而若合计添加量超过3.0摩尔份，则介电常数会下降至2000以下，失去实用性。因此，相对于钛酸钡100摩尔份，Dy2O3和Ho2O3的合计添加量最好为0.1-3.0摩尔份。若使用的Dy2O3和Ho2O3的表面积均为7-15m2/g、球状形状且二次凝集粒子较少，则可提高分散性，使本发明的效果更加显著。
实施例4
首先，相对于钛酸钡100摩尔份，加入0.02摩尔份的BaCO3、0.2摩尔份的MnO4/3、2.1摩尔份的BaO-SiO2-Al2O3系玻璃，并加入合计1摩尔份的Dy2O3和Ho2O3，且使Dy/(Dy+Ho)之摩尔比为0.75，再加入表7所示量的用气相法合成的Mg(OH)2。所用的钛酸钡与实施例2中的相同。。
然后，除使电介质层10的厚度为3μm以外，按与实施例1相同的方法制作叠层电容器。
接着，按与实施例1相同的方法对所得叠层电容器进行评价。但是，加速寿命试验中的施加电压为64V。结果示于表8。
如表8所示，与使用MgO相比，使用Mg(OH)2作为Mg化合物，可进一步提高静电容量的温度特性，并具有防止绝缘电阻劣化防止的效果。
这是因为用气相法合成的Mg(OH)2，其粒子形状为球状且不易形成二次凝集体，由此，在电介质材料中的分散性得以提高。
因此，即使将电介质层10的厚度薄层化至5μm以下，也可得到绝缘电阻高且没有绝缘电阻劣化、静电容量的温度变化率小的叠层电容器。
但是，与MgO同样，相对于钛酸钡100摩尔份，若Mg(OH)2的添加量小于0.5摩尔份，则电介质层10不会烧结，而若Mg(OH)2的添加量超过5.0摩尔份，则静电容量的温度变化率就变大。因此，Mg(OH)2的添加量最好为0.5-5.0摩尔份。
实施例5
首先，相对于实施例2中使用的钛酸钡100摩尔份，加入0.02摩尔份的BaCO3、2.5摩尔份的MgO、1.0摩尔份的Dy2O3、0.2摩尔份的MnO4/3、2.1摩尔份的BaO-SiO2-Al2O3系玻璃，在初焙烧后的粉碎时，再加入表9所示量的Al2O3。
然后，按与实施例1同样的方法制作叠层容器。
接着，按与实施例1同样的方法对所得叠层电容器进行评价。结果示于表10。
本发明的电介质陶瓷组合物容易形成二次相。若形成二次相，则有叠层电容器的机械性强度劣化之虞。
但是，如表10所示，再添加Al2O3，则能抑制二次相的生成，不会使特性恶化，且能提高机械性强度。
若Al2O3的添加量超过3.0摩尔份，则静电容量的温度变化率与介质损耗增大，而若Al2O3的添加量小于0.1摩尔份，则添加效果不显著。
因此，为不使特性恶化和提高机械性强度，相对于钛酸钡100摩尔份，Al2O3的添加量最好为0.1-3.0摩尔份。
该Al2O3是在将其他出发原料初焙烧之后添加。与其他出发原料同样，也可在最初添加，但在初焙烧后添加更能提高温度特性，因此，较为适宜。
以下就本发明的要点进行说明。
(1).在上述实施例中，将电介质陶瓷组合物基本成分中的Si与Al作为BaO-SiO2-Al2O3系玻璃添加。添加该玻璃时，将Si、Al换算为SiO2、Al2O3，则相对于钛酸钡100摩尔份，分别添加0.3-3.5摩尔份和0.01-3.0摩尔份。
此外，同时添加的BaO的量为钛酸钡和/或碳酸钡，电介质材料中的Ba/Ti摩尔比为1.001-1.05。
(2).玻璃的形式添加Si和Al，但也可分别添加Si化合物和Al化合物。
(3).用MnO4/3作为Mn化合物。与MnO等相比，MnO4/3的分散性优异，与MnO同量添加时，添加效果显著。
(4).在上述实施例中，所用的钛酸钡的Ba/Ti为1.000，但合成钛酸钡时以调整至1.001-1.006者作为出发原料，则可得到具有更均一的烧结粒径的烧结体。通过该组成，可提高防止在寿命试验中绝缘电阻劣化的效果。
(5).在上述实施例中，电介质层的再氧化在叠层体烧结后的降温过程中进行，但也可将烧结后的叠层体先予冷却，然后再通过热处理进行再氧化。
本发明的电介质陶瓷组合物具有非常优异的耐还原性。若在贱金属形成内部电极和外部电极的叠层电容器上使用本发明的电介质陶瓷组合物，则可得到绝缘电阻高、其劣化亦非常小、且具有优异的长期可靠性的叠层电容器。此外，本发明的电介质陶瓷组合物的介电常数高、静电容量的偏差、温度变化率及经时变化率小。
此外，铜等贱金属自不待言，即使用银等贵金属形成叠层电容器，也同样可得到电气特性优良的叠层电容器。
表1
  試料No.   Ba/Ti摩尔比   比表面積(m<sup>2</sup>/g)   (200)面和(002)面的裂峰
  *   1   0.999   2.5   有
  2   1.002   1.5   有
  3   1.002   2.4   有
  4   1.002   3.0   有
  5   1.002   3.0   无
  6   1.002   4.3   有
  7   1.002   4.3   无
  8   1.002   5.3   有
  9   1.006   3.2   有
  10   1.007   2.8   有
  11   1.020   2.8   有
  12   1.040   2.8   有
  *   13   1.050   2.8   有
*表示比较例
表2
Figure C0215263500121
*表示比较例
表3
  試料No.   BaCO<sub>3</sub>   MgO   Dy<sub>2</sub>O<sub>3</sub>   MnO<sub>4/3</sub>   BaO·SiO<sub>2</sub>·Al<sub>2</sub>O<sub>3</sub>   V<sub>2</sub>O<sub>5</sub>
  *   14   0.02   0.4   1.5   0.2   2.1   0.15
  *   15   0.02   6   0.5   0.2   2.1   0.15
  16   0.001   0.5   1.5   0.2   2.1   0.15
  17   0.001   5   1.5   0.2   2.1   0.15
  18   0.04   0.5   1.5   0.2   2.1   0.15
  19   0.04   5   1.5   0.2   2.1   0.15
  *   20   0.02   2.5   0.05   0.2   2.1   0.15
  *   21   0.02   2.5   3.5   0.2   2.1   0.15
  22   0.001   2.5   0.1   0.2   2.1   0.15
  23   0.001   2.5   3   0.2   2.1   0.15
  24   0.04   2.5   0.1   0.2   2.1   0.15
  25   0.04   2.5   3   0.2   2.1   0.15
  *   26   0.02   2.5   1.5   0   2.1   0.15
  *   27   0.02   2.5   1.5   0.5   2.1   0.15
  28   0.001   2.5   1.5   0.01   2.1   0.15
  29   0.001   2.5   1.5   0.4   2.1   0.15
  30   0.04   2.5   1.5   0.01   2.1   0.15
  31   0.04   2.5   1.5   0.4   2.1   0.15
  *   32   0.02   2.5   1.5   0.2   0.5   0.15
  *   33   0.02   2.5   1.5   0.2   5.5   0.15
  34   0.001   2.5   1.5   0.2   0.6   0.15
  35   0.04   2.5   1.5   0.2   0.6   0.15
  36   0.001   2.5   1.5   0.2   5   0.15
  37   0.04   2.5   1.5   0.2   5   0.15
  *   38   0.02   2.5   1.5   0.2   2.1   0
  *   39   0.02   2.5   1.5   0.2   2.1   0.3
  40   0.02   2.5   1.5   0.2   2.1   0.15
  41   0.02   2.5   1.5   0.2   2.1   0.01
  42   0.02   2.5   1.5   0.2   2.1   0.26
*表示比较例
表4
Figure C0215263500141
*表示比较例
表5
  試料No.   Dy/(Dy+Ho)   (Dy+Ho)添加量(mol)
  *   43   0.25   1.5
  44   0.3   1.5
  45   0.45   1.5
  46   0.9   1.5
  *   47   0.95   1.5
  *   48   0.45   0.05
  *   49   0.45   3
*表示比较例
表6
Figure C0215263500151
表7
  試料No.   Mg化合物   添加量(mol)
  50   MgO   2.5
  51   Mg(OH)<sub>2</sub>   2.5
  *   52   Mg(OH)<sub>2</sub>   0.4
  *   53   Mg(OH)<sub>2</sub>   6
*表示比较例
表8
Figure C0215263500161
*表示比较例
表9
  試料No.   Al<sub>2</sub>O<sub>3</sub>添加量(mol)
  *   54   0
  *   55   3.5
  56   0.1
  57   3
*表示比较例
表10
Figure C0215263500162
*表示比较例

Claims (12)

1.电容器，它具有：
将电介质层与用贱金属制成的内部电极层交互叠层而成的叠层体和设在叠层体内部电极层露出端面的外部电极，
所述电介质层包含：
作为主要成分的钛酸钡100摩尔份，其中，Ba/Ti之摩尔比为1.001-1.05；
并至少包含以下辅助成分：
Mg，换算成MgO，为0.5-5.0摩尔份、
Dy，换算成Dy2O3，为0.1-3.0摩尔份、
Mn，换算成Mn3O4，为0.01-0.4摩尔份、
V，换算成V2O5，为0.01-0.26摩尔份、
Si，换算成SiO2，为0.3-3.5摩尔份、
Al，换算成Al2O3，为0.01-3.0摩尔份。
2.如权利要求1所述的电容器，其特征在于，它再含有换算成Al2O3，为0.1-3.0摩尔份的Al。
3.如权利要求1所述的电容器，其特征在于，以Dy+Ho替代Dy，而Dy/(Dy+Ho)的摩尔比为0.3-0.9，将Dy和Ho分别换算为Dy2O3和Ho2O3时，其合计量为0.1-3.0摩尔份。
4.电容器的制造方法，它包含以下步骤：
用电介质材料制作陶瓷片的步骤，所述电介质材料包含：
作为主要成分的钛酸钡100摩尔份，其中，Ba/Ti之摩尔比为1.001-1.05；
并至少包含以下辅助成分：
Mg，换算成MgO，为0.5-5.0摩尔份、
Dy，换算成Dy2O3，为0.1-3.0摩尔份、
Mn，换算成Mn3O4，为0.01-0.4摩尔份、
V，换算成V2O5，为0.01-0.26摩尔份、
Si，换算成SiO2，为0.3-3.5摩尔份、
Al，换算成Al2O3，为0.01-3.0摩尔份；
将上述陶瓷片与以贱金属为主要成分的内部电极层交互叠层、制作叠层体的步骤；
将上述层叠体焙烧的步骤；
在上述叠层体内部电极层露出端面形成外部电极的步骤。
5.如权利要求4所述的电容器的制造方法，其特征在于，用以铜为主要成分的金属形成外部电极。
6.如权利要求4所述的电容器的制造方法，其特征在于，所述钛酸钡的比表面积为2-5m2/g。
7.如权利要求4所述的电容器的制造方法，其特征在于，所述钛酸钡在40-50°的X线衍射角2θ具有来自(200)面与(002)面的2个衍射峰。
8.如权利要求4所述的电容器的制造方法，其特征在于，所述Mg来自Mg(OH)2。
9.如权利要求4所述的电容器的制造方法，其特征在于，在所述陶瓷片的制作步骤中，再添加换算为Al2O3，为0.1-3.0摩尔份的Al化合物。
10.如权利要求9所述的电容器的制造方法，其特征在于，所述Al化合物在其他的电介质材料的初焙烧后添加。
11.如权利要求4所述的电容器的制造方法，其特征在于，在所述电介质材料中，以Dy+Ho替代Dy，而Dy/(Dy+Ho)的摩尔比为0.3-0.9，将Dy和Ho分别换算为Dy2O3和Ho2O3时，其合计量为0.1-3.0摩尔份。
12.如权利要求4所述的电容器的制造方法，其特征在于，在所述焙烧步骤的降温过程或焙烧步骤与形成外部电极的步骤之间设置将叠层体中的电介质层再氧化的步骤。
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