CN105693236B - 低温烧结介电组合物以及由其形成的多层陶瓷电容器 - Google Patents

低温烧结介电组合物以及由其形成的多层陶瓷电容器 Download PDF

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CN105693236B
CN105693236B CN201510941384.1A CN201510941384A CN105693236B CN 105693236 B CN105693236 B CN 105693236B CN 201510941384 A CN201510941384 A CN 201510941384A CN 105693236 B CN105693236 B CN 105693236B
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mol
dielectric
dielectric composition
borosilicate
low temperature
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CN105693236A (zh
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洪旻熙
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Samsung Electro Mechanics Co Ltd
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Abstract

提供一种低温烧结介电组合物以及由其形成的多层陶瓷电容器，所述低温烧结介电组合物包括作为主要成分的钛酸钡(BaTiO3)和辅助成分，所述辅助成分基于100mol％的主要成分包括1.0mol％至2.0mol％的碳酸钡(BaCO3)、0.5mol％至1.0mol％的从由Y2O3、Ho2O3、Dy2O3和Yb2O3组成的组中选择至少一种的稀土氧化物、0.1mol％至1.0mol％的氧化锰(MnO)和1.0mol％至2.0mol％的硼硅酸盐基玻璃。

Description

低温烧结介电组合物以及由其形成的多层陶瓷电容器
本申请要求于2014年12月16日在韩国知识产权局提交的第10-2014-0181526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包含于此。
技术领域
本公开涉及一种低温烧结介电组合物以及由其形成的多层陶瓷电容器。更具体地，本公开涉及一种能够实现X7R温度特性的低温烧结介电组合物以及由其形成的多层陶瓷电容器。
背景技术
能够确保稳定的电气性能和器件稳定操作的可靠性的X5R或X7R型多层陶瓷电容器的发展已经变成电子器件市场的一种必然，纤薄和高电压容量已经同时被看作是发展对应多层陶瓷电容器的重要因素。
纤薄和高电压容量增加了施加到介电主体的电场的强度，这使DC偏置特性和耐压特性劣化，且精细结构中的缺陷在诸如击穿电压(BDV)和高温特性(高温绝缘电阻(IR))的耐压特性上有明显更大的影响。为了解决上述问题，必须要雾化(atomize)基底材料。然而，在雾化基底材料的情况下，由于可能难以实现产品的电容特性和温度特性，因此会难以开发介电组合物。
为了解决该问题，当开发产品时，对介电基底材料粉末与添加成分的开发、设置、内电极以及热处理的整个过程进行全面地改善和开发十分重要。在上述中，开发在多层陶瓷电容器的特性中起关键作用的添加剂尤其重要。
作为多层陶瓷电容器的介电材料，已经主要使用钛酸钡(BaTiO3)，且为了改善介电特性和可靠性，各种添加粉末可混合或添加到该基底材料粉末。
根据相关技术，作为主要成分的包含{Ba1-xCaxO}mTiO3的介电组合物已经在JP2000-058378中公开。根据相关技术，公开的介电组合物是在主要成分中应当使用钙(Ca)的介电组合物。然而，在使用对应的介电添加成分的情况下，可确保介电特性和可靠性，但是应当在1200℃或更高的高温下执行热处理。
发明内容
本公开的一方面可提供一种在主要成分中不包含Ca的情况下能够实现X7R温度特性的低温烧结介电组合物以及由其形成的多层陶瓷电容器。
根据本公开的一方面，低温烧结介电组合物可包含：作为主要成分的钛酸钡(BaTiO3)和辅助成分，所述辅助成分基于100mol％的主要成分包括1.0mol％至2.0mol％的碳酸钡(BaCO3)、0.5mol％至1.0mol％的从由Y2O3、Ho2O3、Dy2O3和Yb2O3组成的组中选择的至少一种的稀土氧化物、0.1mol％至1.0mol％的氧化锰(MnO)和1.0mol％至2.0mol％的硼硅酸盐基玻璃。
作为示例，硼硅酸盐基玻璃的量是碳酸钡(BaCO3)的量的一半至两倍那么多。
钛酸钡(BaTiO3)的平均粒径可以是100nm至200nm。
硼硅酸盐基玻璃可包含作为基本成分的氧化硼(B2O3)和氧化硅(SiO2)，并且还包含碱性硼硅酸盐基玻璃，所述碱性硼硅酸盐基玻璃包含碱性氧化物以及碱土金属氧化物和碱土金属氟化物中的至少一种。
可在1000℃至1100℃的低温下烧结介电组合物。
根据本公开的另一方面，多层陶瓷电容器可包括：介电主体，包括覆盖部和多个有源层；多个内电极，形成在介电主体中以使每个有源层被插入在相邻的内电极之间；外电极，电连接到多个内电极。所述介电主体可由上述的低温烧结介电组合物形成。
形成有源层的介电组合物的平均粒径可以是150nm至300nm，形成覆盖部的介电组合物的平均粒径可比形成有源层的介电组合物的平均粒径大。形成覆盖部的介电组合物的平均粒径可以是300nm至400nm。
内电极可由镍(Ni)材料形成。
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、特征和优点将会被更清楚地理解，在附图中：
图1是示意性示出根据本公开的示例性实施例的多层陶瓷电容器的截面图；
图2A和图2B是示出与根据本公开的示例性实施例的低温烧结介电组合物相比的对比示例的照片；
图3A和图3B是示出根据本公开的示例性实施例的低温烧结介电组合物的照片；
图4A和图4B是示出根据本公开的另一示例性实施例的低温烧结介电组合物的照片。
具体实施方式
在下文中，将参照附图详细描述本公开的实施例。
然而，本公开可按照多种不同的形式实施，并不应该被解释为局限于在此阐述的实施例。确切地说，提供这些实施例以使本公开将是彻底的和完整的，并且将把本公开的范围充分地传达给本领域技术人员。
在附图中，为了清晰起见，可夸大元件的形状和尺寸，并且相同的标号将始终用于表示相同或相似的元件。
将详细描述根据示例性实施例的低温烧结介电组合物。
根据示例性实施例的低温烧结介电组合物可包含作为主要成分的钛酸钡(BaTiO3)。由于钛酸钡(BaTiO3)具有高介电常数，因此钛酸钡可用作需要超高介电常数的多层陶瓷电容器的介电材料。根据示例性实施例，钛酸钡(BaTiO3)可具有100nm至200nm的平均粒径。例如，烧结之前的钛酸钡(BaTiO3)的平均粒径是100nm至200nm的低温烧结介电组合物可在如图1中所示的多层陶瓷电容器的介电主体10中形成有源层11。有源层11可被限定为插在内电极之间的介电层。相反，如图1所示，覆盖最外面的内电极的外部的介电层可被称为覆盖部13。例如，在低温烧结介电组合物形成了多层陶瓷电容器的介电主体10的覆盖部13的情况下，烧结前的钛酸钡(BaTiO3)的平均粒径可超出100nm至200nm的范围。
在介电颗粒的平均粒径过小(<100nm)的情况下，会难以实现电容量，在介电颗粒的平均粒径过大(>200nm)的情况下，可容易实现电容量，但会增加烧结温度，且高温绝缘电阻会劣化。此外，在平均粒径大于200nm的范围，由于颗粒的平均比表面积增大，因此不能呈现出本公开中建议的辅助成分含量范围的效果。因此，例如，在使用低温烧结组合物形成多层陶瓷电容器的有源层11的情况下，烧结前的钛酸钡(BaTiO3)的平均粒径可以是100nm至200nm。例如，当钛酸钡(BaTiO3，主要成分)与辅助成分彼此混合并烧结的情况下，与烧结前的介电组合物的平均粒径相比，烧结后的介电组合物的平均粒径会增大。
除了主要成分之外的辅助成分可包括碳酸钡(BaCO3)、稀土氧化物、氧化锰(MnO)和硼硅酸盐基玻璃。
在这种情况下，基于100mol％的主要成分，碳酸钡(BaCO3)的含量可以是1.0mol％至2.0mol％，稀土氧化物的含量可以是0.5mol％至1.0mol％，氧化锰(MnO)的含量可以是0.1mol％至1.0mol％，硼硅酸盐基玻璃的含量可以是1.0mol％至2.0mol％。在下文中，应注意的是，除非在此另外限定，否则将基于100mol％的主要成分说明辅助成分的含量。
稀土氧化物可以是从由Y2O3、Ho2O3、Dy2O3和Yb2O3组成的组中选择的至少一种。这里，稀土氧化物可以是有助于形成钛酸钡(BaTiO3，主要成分)的核壳结构并改善多层陶瓷电容器的高温绝缘电阻和平均寿命的成分。基于100mol％的主要成分，稀土氧化物的含量可以是0.5mol％至1.0mol％。在稀土氧化物的含量小于0.5mol％的情况下，高温绝缘电阻会减小，或者高温(100℃至150℃)下的多层陶瓷电容器的平均寿命会减小。相反，在添加的稀土氧化物的含量大于1.0mol％的情况下，钛酸钡(BaTiO3)颗粒的壳厚度可增大，因此，可使电容温度系数(TCC)进一步稳定，但是，烧结材料的介电常数会减小，且烧结性会劣化。因此，在这种情况下，介电组合物会不适于诸如在1100℃或以下烧结的低温烧结。
可包含1.0mol％至2.0mol％的含量的碳酸钡(BaCO3，辅助成分)，碳酸钡(BaCO3)用于抑制由于晶粒的反应导致的晶粒生长。在碳酸钡(BaCO3)的含量小于1.0mol％的情况下，碳酸钡(BaCO3)可能无法恰当地用于抑制晶粒生长，从而导致不规则晶粒生长。相反，在碳酸钡(BaCO3)的含量大于2.0mol％的情况下，介电材料的可靠性会劣化，且壳部分会增大，从而使介电常数劣化。
可包含0.1mol％至1.0mol％含量的氧化锰(MnO，辅助成分)，氧化锰(MnO)除了当在还原气氛下进行烧结时有助于改善介电材料的还原阻力之外，还用于增大介电材料的室温和高温绝缘电阻。在氧化锰(MnO)的添加量小于0.1mol％的情况下，还原阻力会劣化，绝缘电阻会减小，在其添加量大于1.0mol％的情况下，老化速率还会增大并且电容量也会根据施加的直流电压而降低。
此外，可包含1.0mol％至2.0mol％含量的硼硅酸盐基玻璃(辅助成分)。硼硅酸盐基玻璃(烧结助剂)可用于降低钛酸钡(BaTiO3)的烧结温度并改善烧结性。在使用硼硅酸盐基玻璃作为烧结助剂的情况下，可降低进行低温烧结时的钛酸钡(BaTiO3)的下限温度，但是，也会使进行烧结之后的介电材料的高温绝缘电阻特性劣化。因此，通过在1.0mol％至2.0mol％的范围内调节作为烧结助剂的硼硅酸盐基玻璃的含量可获得能够在低温烧结并改善高温绝缘电阻特性的介电组合物。在硼硅酸盐基玻璃的含量小于1.0mol％的情况下，烧结温度会增大，在硼硅酸盐基玻璃的含量大于2.0mol％的情况下，烧结性会劣化，且介电材料的高温绝缘电阻会迅速降低。参照下面的[表2]，可领会的是，当硼硅酸盐基玻璃的含量为2.5mol％或3.0mol％时，高温绝缘电阻故障频繁出现。例如，参照下面的[表2]，在烧结温度是1100℃或更小且高温绝缘电阻被评价为“好”或“一般”的介电组合物中，硼硅酸盐基玻璃的含量是1.0mol％至2.0mol％。
根据示例性实施例，硼硅酸盐基玻璃可包含作为基本成分的氧化硼(B2O3)和氧化硅(SiO2)，还可包含碱性硼硅酸盐基玻璃，所述碱性硼硅酸盐基玻璃包含碱性氧化物以及碱土金属氧化物和碱土金属氟化物中的至少一种。在这种情况下，当硼硅酸盐基玻璃的各个成分的摩尔数之和为100时，氧化硼(B2O3)的含量可以是10至30，氧化硅(SiO2)的含量可以是50至80，碱性氧化物的含量可以是2至10，碱土金属氧化物的含量可以是0至30，碱土金属氟化物的含量可以是1至5。
例如，包含在硼硅酸盐基玻璃中的碱性氧化物可以是从氧化锂(Li2O)和氧化钾(K2O)中选择的至少一种。碱土金属氟化物可以是从氟化钙(CaF2)和氟化钡(BaF2)中选择的至少一种。碱土金属氧化物可以是从氧化钙(CaO)和氧化钡(BaO)中选择的至少一种。在这种情况下，由于当钙(Ca)化物或氧化物构成玻璃时被选择性地添加为硼硅酸盐基玻璃的成分的钙(Ca)化物或氧化物处于反应终止状态，因此，根据本公开的介电组合物与包含钙(Ca)作为主要成分的相关现有技术中公开的介电组合物不同。
可在1200℃或更低的温度下烧结介电组合物。例如，根据示例性实施例，可在1000℃至1100℃的低温下烧结介电组合物。例如，参照下面的[表2]，可在1050℃至1100℃的低温下烧结介电组合物。
下面的[表1]示出了根据示例性实施例的低温烧结介电组合物的成分比，下面的[表2]示出了在示例和对比示例中通过评价使用低温烧结介电组合物制造的多层陶瓷电容器样品的电特性和可靠性而获得的结果。这里，如下所述来制造多层陶瓷电容器样品。在[表2]中，相对于具有[表1]示出的成分比的介电组合物，硼硅酸盐基玻璃基于主要成分的含量在1.0mol％至2.0mol％的范围的情况与示例相对应，相对于具有[表1]示出的相同成分比的介电组合物，硼硅酸盐基玻璃基于主要成分的含量在2.5mol％至3.0mol％的范围内的情况与对比示例相对应。
首先，在低温烧结介电组合物被混合并分散到有机溶剂然后与有机粘合剂混合来制备浆料之后，通过将浆料涂敷在大约2μm厚的膜上来分别制造用于有源层的介电片和用于覆盖部13的片。在用于有源层的介电片上印刷镍(Ni)内电极并使其上印刷了内电极的100个介电片堆叠之后，在堆叠的介电片的上端和下端另外地堆叠用于覆盖部的介电片。然后，对多层主体进行冷等静压制，然后切割，从而制造样品。通过在300℃热处理4小时或更长来去除有机粘合剂、分散剂等，然后使用可控制温度和气氛的烧结炉在1050℃至1150℃烧结这些样品。在这种情况下，烧结气氛中的氧分压被控制在10-9-10-13标准大气压。将铜(Cu)外电极涂敷在完成烧结的样品上。并在700℃至900℃进一步烧结。在完成电极的烧结之后，在其上执行镀覆，从而制造样品。
为了检测在下面的[表2]中示出的特性，使用电容计(安捷伦科技(AgilentTechnologies)，4278A)在1KHz和1V下测量基于0.01V至10V的AC电压变化每个样品的电容变化与介电损耗。其中，测量了介电层的每单位厚度施加的电压是1V/μm时的电容量和介电损耗，在下面的表达式中替换电容量、烧结样品的介电层的平均厚度、堆叠的介电层的数量和电极面积等，从而获得基于每个烧结温度的介电材料的介电常数。
表达式：C＝εr·ε0·N·S/td
这里，C是电容量，εr是介电材料的介电常数，ε0是真空介电常数，N是堆叠的介电层的数量，S是内电极的面积，td是介电层的厚度。
通过[表2]中的高温绝缘电阻和防潮绝缘电阻的测量结果来评价多层陶瓷电容器的可靠性。当测量高温绝缘电阻时，在150℃恒温状态下1Vr的额定电压被设置为当介电层的每单位厚度施加的电压是6.3V时的电压(6.3V/μm)，并测量绝缘电阻。在这种情况下，随着每30分钟升高施加电压(增大DC电压)，样品的绝缘击穿临界电压被设置为样本的绝缘电阻减小到105Ω或更小时的电压。
[表1]
Figure GDA0002603324640000071
表1是示出主要成分和辅助成分的含量情况的表。
[表2]
Figure GDA0002603324640000072
Figure GDA0002603324640000081
在[表2]中，玻璃的添加量被限定为基于100mol％的主要成分的a mol％的玻璃，在高温绝缘电阻评价中，“○”被限定为指临界绝缘电阻被评定为“好”(大于7Vr)，“Δ”被限定为指临界绝缘电阻被评定为“一般”(3至7Vr)，“X”被限定为指临界绝缘电阻被评定为“差”(小于3Vr)。
如[表2]中所示，在根据本公开的示例的样品中，高温绝缘电阻被评定为“好”或“一般”并且烧结温度或TCC也被评定为“好”。然而，在对比样品的情况中，包括了发生高温绝缘电阻故障的情况，烧结温度高，并且TCC中的差异也尤其高。根据本公开的示例中的样品在可靠性方面是优异的。具体地，在示例2、6至9和19的样品中，烧结温度减小，可靠性和TCC特性显著改善。
作为示例，硼硅酸盐基玻璃的量是碳酸钡(BaCO3)的量的一半至两倍那么多。例如，参照[表2]，在烧结温度是1100℃或更小且高温绝缘电阻被评定为“好”或“一般”的介电组合物中，硼硅酸盐基玻璃的量是1.0mol％至2.0mol％。在与其对应的示例1至19的介电组合物中，125℃下的TCC在-15％以内的介电组合物是示例2至14、18和19中的介电组合物。在这种情况下，125℃下的TCC在-15％以内的介电组合物中，硼硅酸盐基玻璃的量和碳酸钡(BaCO3)的量之间的比在0.5至2.0的范围内。
在这种情况下，作为另一示例，基于100mol％的钛酸钡(BaTiO3)，硼硅酸盐基玻璃的量可以是1.0mol％至2.0mol％。例如，参照[表2]，在烧结温度是1100℃或更小且高温绝缘电阻被评定为“好”或“一般”的介电组合物中，硼硅酸盐基玻璃的含量是1.0mol％至2.0mol％。
作为另一示例，碳酸钡(BaCO3)的量是硼硅酸盐基玻璃的量的一半至1.5倍那么多。例如，参照[表2]，在硼硅酸盐基玻璃的含量是1.0mol％至2.0mol％的介电组合物中，高温绝缘电阻被评定为“好”且125℃下的TCC在-15％以内的介电组合物是示例2、7、8、9、11、12和19中的介电组合物，碳酸钡(BaCO3)和硼硅酸盐基玻璃之间的比可在0.5至1.5的范围内。
接着，将参照图2A至图4B描述根据本公开示例性实施例的低温烧结介电组合物。在图2A至图4B中，标号11指有源层，标号13指覆盖部，标号30指内电极。
图2A和图2B是示出与根据示例性实施例的低温烧结介电组合物相比的对比示例的介电组合物的图。图2A(示出在1055℃低温烧结的现有X7R型多层陶瓷电容器的有源层的图)示出了对比示例中的介电组合物。图2B(示出在1055℃低温烧结的现有X7R型多层陶瓷电容器的覆盖部的图)示出了对比示例中的介电组合物。图2A和图2B中的对比示例的介电组合物包含作为主要成分的100mol％的钛酸钡(BaTiO3)以及作为辅助成分的1.0mol％的稀土氧化物、1.5mol％的碳酸钡(BaCO3)和1.0mol％的氧化硅(SiO2)。
图3A和图3B是示出根据示例性实施例的低温烧结介电组合物的图。图3A是示出在1055℃低温烧结的根据示例性实施例的多层陶瓷电容器的有源层的图，图3B是示出在1055℃低温烧结的覆盖部的图。根据示例性实施例，图3A和图3B的介电组合物可包含作为主要成分的100mol％的钛酸钡(BaTiO3)以及作为辅助成分的0.5mol％的稀土氧化物、0.1mol％的氧化锰(MnO)、1.0mol％的碳酸钡(BaCO3)和1.0mol％的硼硅酸盐基玻璃。
图4A和图4B是示出根据另一示例性实施例的低温烧结介电组合物的图。图4A是示出在1055℃低温烧结的根据本公开另一示例性实施例的多层陶瓷电容器的有源层的图，图4B是示出在1055℃低温烧结的覆盖部的图。根据本公开另一示例性实施例，图4A和图4B的介电组合物可包含作为主要成分的100mol％的钛酸钡(BaTiO3)以及作为辅助成分的0.7mol％的稀土氧化物、0.1mol％的氧化锰(MnO)、1.0mol％的碳酸钡(BaCO3)和1.5mol％的硼硅酸盐基玻璃。
将示例2A和2B(对比示例)与图3A和图3B以及图4A和图4B进行比较，在图2A和图2B的对比示例中，在1055℃的低温烧结时，有源层和覆盖部不具有致密结构，但在图3A和图3B以及图4A和图4B的示例中，在1055℃的低温烧结时，与图2A和图2B的对比示例相比，有源层和覆盖部具有明显更致密的结构。由于在图3A和图3B以及图4A和图4B中示出的致密结构，使得多层陶瓷电容器可具有良好的防潮性和高温绝缘电阻。
接着将参照附图详细描述根据另一示例性实施例的多层陶瓷电容器。这里，将参照上述根据示例性实施例的低温烧结介电组合物，因此将省略重复的描述。
图1是示意性示出根据示例性实施例的多层陶瓷电容器的截面图。
参照图1，根据示例性实施例的多层陶瓷电容器可包括介电主体10、内电极30和外电极50。将详细描述每个结构。
介电主体10可由覆盖部13和有源层11形成。覆盖部13可形成多层主体的上外边缘和下外边缘。多个有源层11可形成在覆盖部13之间。这里，介电主体可由根据上述示例性实施例的低温烧结介电组合物形成。
介电组合物可包含作为主要成分的钛酸钡(BaTiO3)和辅助成分。例如，根据示例性实施例，钛酸钡(BaTiO3，主要成分)可具有100nm至200nm的平均粒径。除了主要成分之外的辅助成分可包括碳酸钡(BaCO3)、稀土氧化物、氧化锰(MnO)和硼硅酸盐基玻璃。在这种情况下，基于100mol％的主要成分，碳酸钡(BaCO3)的含量可以是1.0mol％至2.0mol％，稀土氧化物的含量可以是0.5mol％至1.0mol％，氧化锰(MnO)的含量可以是0.1mol％至1.0mol％，硼硅酸盐基玻璃的含量可以是1.0mol％至2.0mol％。此外，稀土氧化物可以是从由Y2O3、Ho2O3、Dy2O3和Yb2O3组成的组中选择的至少一种。
例如，根据示例性实施例，介电组合物的硼硅酸盐基玻璃可包含作为基本成分的氧化硼(B2O3)和氧化硅(SiO2)，并且还可包含碱性硼硅酸盐基玻璃，所述碱性硼硅酸盐基玻璃包含碱性氧化物以及碱土金属氧化物和碱土金属氟化物中的至少一种。在这种情况下，当硼硅酸盐基玻璃的各个成分的摩尔数之和为100时，氧化硼(B2O3)的含量可以是10至30，氧化硅(SiO2)的含量可以是50至80，碱性氧化物的含量可以是2至10，碱土金属氧化物的含量可以是0至30，碱土金属氟化物的含量可以是1至5。
可在1200℃或更低的低温下烧结介电主体。例如，根据示例性实施例，可在1000℃至1100℃低温烧结介电主体。例如，参照[表2]，可在1050℃至1100℃的低温下烧结介电组合物。
此外，有源层11的厚度不受具体限定。然而，根据示例性实施例，为了实现具有超减小厚度的高电容量电容器，单个有源层的厚度可是1.5μm或更小，更优选0.5μm至1.5μm。
此外，根据示例性实施例，形成有源层11的介电组合物的平均粒径可在150nm至300nm的范围内。由于主要成分和辅助成分被混合在一起并被烧结，因此形成有源层11的介电组合物在烧结之后的粒径会变得比主要成分的粒径大。在这种情况下，形成覆盖部13的介电组合物的平均粒径可比形成有源层11的介电组合物的粒径大。例如，根据另一示例性实施例，形成覆盖部13的介电组合物的平均粒径可在300nm至400nm的范围内。
由于上述根据示例性实施例的低温烧结介电组合物被应用于形成介电主体的介电组合物，因此，可参照上述根据示例性实施例的低温烧结介电组合物的描述，以理解未详细描述的内容。
参照图1，内电极30可由形成在介电主体中的多个电极层组成。形成在介电主体中的多个电极层可形成为使得每个有源层11可插入在每个电极层之间。在这种情况下，多个电极层可沿与在厚度方向的上下表面平行的方向交替地暴露到介电主体10的背对的端部，并电连接到外电极50。
例如，根据示例性实施例，内电极30可由材料镍(Ni)形成。
接着，将描述外电极50。外电极50可沿与内电极30垂直的方向形成在介电主体的背对的端部上，并电连接到内电极30。
根据本示例性实施例的制造多层陶瓷电容器的方法不受具体地限制。例如，可使用本领域使用的一般方法。例如，可使用包含陶瓷介电材料的浆料形成生片，可将内电极印刷在生片上，然后烧结，从而制造多层陶瓷电容器。
将描述制造多层陶瓷电容器的方法的示例。首先，在将低温烧结介电组合物混合并分散在有机溶剂中然后与有机粘合剂混合来制备浆料之后，通过将浆料涂敷在大约2μm厚的膜上来分别制造用于有源层11的介电片和用于覆盖部13的介电片。接着，在将镍(Ni)内电极印刷在用于有源层的介电片上之后，堆叠100个印刷了内电极的介电片，再将用于覆盖部的介电片另外地堆叠在堆叠的介电片的上端和下端上。然后，切割多层主体，通过使切割后的多层主体在300℃下热处理4小时或更长来去除有机粘合剂和分散剂等，然后，使用可控制温度和气氛的烧结炉在300℃至1150℃下烧结这些主体。在这种情况下，烧结气氛中的氧分压被控制在10-9-10-13标准大气压。将铜(Cu)外电极涂敷在完成烧结的样品上，并在700℃至900℃下进行烧结。在完成电极的烧结之后，在其上执行镀覆，从而制造多层陶瓷电容器。
如上所述，可制造根据示例性实施例的满足X7R温度特性的低温烧结介电组合物以及使用低温烧结介电组合物作为介电材料的多层陶瓷电容器。具体地，根据示例性实施例，可不使用钙(Ca)的氧化物而确保高介电常数和高温可靠性。此外，根据示例性实施例，可使用镍(Ni)内电极。此外，可获得能够在还原气氛下在1200℃或更低(例如1100℃或更低)的温度下烧结并具体地具有2000或以上的介电常数的介电组合物。
如上阐述，根据示例性实施例，可制造在主要成分中不包含钙(Ca)的满足X7R温度特性的低温烧结介电组合物以及使用低温烧结介电组合物作为介电材料的多层陶瓷电容器。
此外，可提供能够在还原气氛下在1200℃或更低(例如，1100℃或更低)的温度烧结的介电组合物，因此，可实现高介电常数，并且可通过利用低温烧结控制晶粒生长改善高温特性。
此外，可获得能够在还原气氛下在1200℃或更低(例如，1100℃或更低)的温度烧结并具有2000或更高的介电常数的介电组合物。
虽然已经示出并描述了示例性实施例，本领域的技术人员将清楚的是，在不脱离权利要求所限定的本发明范围的情况下，能做出修改和变型。

Claims (11)

1.一种低温烧结介电组合物，包括：
作为主要成分的钛酸钡和辅助成分，
其中，所述辅助成分基于100mol％的主要成分包括1.0mol％至2.0mol％的碳酸钡、0.5mol％至1.0mol％的稀土氧化物、0.1mol％至1.0mol％的氧化锰和1.0mol％至2.0mol％的硼硅酸盐基玻璃，
所述稀土氧化物是从由Y2O3、Ho2O3、Dy2O3和Yb2O3组成的组中选择的至少一种，
所述硼硅酸盐基玻璃包含作为基本成分的氧化硼和氧化硅，并且还包含碱金属氧化物和碱土金属氟化物，
当硼硅酸盐基玻璃的各个成分的摩尔数之和是100时，氧化硼的含量是10至30，氧化硅的含量是50至80，碱金属氧化物的含量是2至10，碱土金属氟化物的含量是1至5。
2.根据权利要求1所述的低温烧结介电组合物，其中，所述碳酸钡与硼硅酸盐基玻璃之间的比在0.5至2.0的范围内。
3.根据权利要求2所述的低温烧结介电组合物，其中，所述碳酸钡与硼硅酸盐基玻璃之间的比在0.5至1.5的范围内。
4.根据权利要求1所述的低温烧结介电组合物，其中，钛酸钡的平均粒径是100nm至200nm。
5.根据权利要求1所述的低温烧结介电组合物，其中，所述硼硅酸盐基玻璃还包含碱土金属氧化物，当硼硅酸盐基玻璃的各个成分的摩尔数之和是100时，碱土金属氧化物的含量是为大于0且小于等于30。
6.根据权利要求1所述的低温烧结介电组合物，其中，在1000℃至1100℃的低温下烧结所述介电组合物。
7.一种多层陶瓷电容器，包括：
介电主体，包括形成上外边缘和下外边缘的覆盖部以及形成在覆盖部之间的多个有源层；
多个内电极，形成在介电主体中以使每个有源层被插入在相邻的内电极之间，并沿与厚度方向上的上下表面平行的方向暴露到介电主体的背对的端部；
外电极，设置在介电主体的背对的端部并电连接到多个内电极，
其中，所述介电主体通过如权利要求1至5中任一项所述的低温烧结介电组合物形成。
8.根据权利要求7所述的多层陶瓷电容器，其中，形成有源层的介电组合物的平均粒径是150nm至300nm，
形成覆盖部的介电组合物的平均粒径比形成有源层的介电组合物的平均粒径大。
9.根据权利要求8所述的多层陶瓷电容器，其中，形成覆盖部的介电组合物的平均粒径是300nm至400nm。
10.根据权利要求7所述的多层陶瓷电容器，其中，所述内电极通过镍材料形成。
11.根据权利要求7所述的多层陶瓷电容器，其中，在1000℃至1100℃的低温下烧结所述介电主体。
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