CN1224056C - 介电陶瓷组合物、使用该组合物的多层陶瓷片状电容器及该电容器的制备方法 - Google Patents

介电陶瓷组合物、使用该组合物的多层陶瓷片状电容器及该电容器的制备方法 Download PDF

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CN1224056C
CN1224056C CN02157839.7A CN02157839A CN1224056C CN 1224056 C CN1224056 C CN 1224056C CN 02157839 A CN02157839 A CN 02157839A CN 1224056 C CN1224056 C CN 1224056C
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CN1469397A (zh
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朴海成
许康宪
金佑燮
金俊熙
金钟翰
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Samsung Electro Mechanics Co Ltd
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Abstract

本发明制备了多层陶瓷片状电容器,其满足X5R特性(-55-85℃,ΔC=±15%)要求,并与还原氛烧结条件相适应,从而可使用贱金属如镍和镍合金作为内电极。所述的多层陶瓷片状电容器包含交替层压的介电陶瓷层和内电极层,其中介电陶瓷层中含有BaTiO3和其他成分,且每100摩尔BaTiO3,其他成分的量为MgCO3:0.2-3.0摩尔;选自Y2O3、Ho2O3、Dy2O3和Yb2O3的至少一种:0.05-1.5摩尔;Cr2O3:0.1-1.5摩尔;BaxCa(1-x)SiO3(假设0≤x≤1):0.2-3.0摩尔;和Mn2V2O7:0.01-1.5摩尔。本发明的多层陶瓷片状电容器介电常数高,满足X5R特性,可以在1200-1250℃的低温下烧结。

Description

介电陶瓷组合物、使用该组合物的 多层陶瓷片状电容器及该电容器的制备方法
技术领域
本发明涉及一种不可还原的介电陶瓷组合物,更特别地涉及一种低温烧结时具有高的介电常数,且满足X5R特性(-55-85℃,ΔC=±15%)的不可还原的介电陶瓷组合物,并涉及使用该组合物的多层陶瓷片状电容器及该多层陶瓷片状电容器的制备方法。
背景技术
多层陶瓷片状电容器广泛用作具有小型、大电容量和高可靠性特点的电子元件,在一个电子器件中使用大量的这种电容器。在近来随着器件趋于小型化、高性能,日益需要开发尺寸更小、电容量更大、成本更低和可靠性更高的多层陶瓷片状电容器。多层陶瓷片状电容器一般是通过交替地层叠介电层和内电极层,然后进行烧结制造的。
钯或钯合金一般用作内电极的导体。近来,使用较为便宜的贱金属(base metal)如镍或镍合金作为内电极导体有所增加。贱金属用作内电极导体时,在空气中烧结内电极时它可能被氧化。因此,介电层和内电极层的共烧必须在还原氛中进行。但是,在还原氛中烧结引起介电层还原,使电阻率下降。由此提出了不可还原的介电陶瓷材料。
但是,当施加电场时,使用不可还原的介电陶瓷材料的多层介电陶瓷片状电容器的绝缘电阻(IR)显著劣化。也就是说,它们的问题包括IR的寿命短和可靠性低。当该介电材料受到直流电场作用时,它们产生另外一个问题,即它们的介电常数(εr)随时间下降。如果为了提供尺寸更小、电容量更大的片状电容器而使用更薄的介电陶瓷层,在电容器上施加直流电压会引起介电陶瓷层受到更强的电场,使得介电常数εr随时间的变化更大(即,电容量随时间的变化更大)。也需要电容器的电容量温度特性(TCC)优良。用于特殊目的的电容器需要在恶劣条件下具有稳定的电容量温度特性。电容量温度特性优良的有代表性的温度补偿介电陶瓷材料有(Sr,Ca)(Ti,Zr)O3、Ca(Ti,Zr)O3、Nd2O3-2TiO2和La2O3-2TiO2的组合物。但是,这些材料的介电常数低(一般为100或更低),因此不能用于制备大容量的电容器。
以BaTiO3为主成分,添加有Nb2O5-Co3O4、MgO-Y、稀土元素(Dy、Ho等)、BaTiO3-TiO2等的组合物被公开,其具有高介电常数和固定的电容量温度特性。但是,以BaTiO3为主成分的介电陶瓷组合物在高温下不能满足XR特性(ΔC=±15%),这是因为BaTiO3的居里温度为约130℃。
美国专利5,668,694;美国专利5,862,034;日本专利申请公开6-215979号公报;日本专利申请公开2000-311828号公报;和韩国专利申请公开2000-0012080号公报中公开了以BaTiO3为主成分的有代表性的介电陶瓷组合物。
美国专利5,668,694和5,862,034公开了一种多层陶瓷片状电容器,其以BaTiO3为主成分,并含有MgO、Y2O3、BaO、CaO、SiO2、MnO、V2O5和MoO3作为次要成分,各成分存在的量为每100摩尔BaTiO3,MgO:0.1-3摩尔,Y2O3:0-5摩尔,BaO+CaO:2-12摩尔,SiO2:2-12摩尔,MnO:0-0.5摩尔,V2O5:0-0.3摩尔,MoO3:0-0.3摩尔,以及V2O5+MoO3:大于0摩尔。这种电容器满足X7R特性,但其缺点是介电常数低至2600,因此其必须在1300℃的高温下烧结。
日本专利申请公开6-215979号公报公开了一种介电陶瓷组合物,其含有BaTiO3:86.32-97.64摩尔,Y2O3:0.01-10.00摩尔,MgO:0.01-10.00摩尔,V2O5:0.001-0.200摩尔,选自MnO、Cr2O3和Co2O3的至少一种:0.01-1.0摩尔,和BaxCa(1-x)SiO3(假设0≤x≤1):0.5-10摩尔。这种介电组合物的介电常数为2560-3850,满足X7R特性,但其烧结温度高达1300-1380℃。
日本专利申请公开2000-311828号公报公开了一种介电陶瓷组合物,其含有BaTiO3:100摩尔,选自MgO和CaO的至少一种:0.1-3摩尔,MnO:0.05-1.0摩尔,Y2O3:0.1-5摩尔,V2O5:0.1-3摩尔,和BaxCa(1-x)SiO3(假设0≤x≤1):2-12摩尔。这种介电组合物满足X7R特性,但其介电常数小于3000且烧结温度高达1270℃。
韩国专利申请公开2000-0012080号公报公开了一种介电陶瓷组合物,其中每100摩尔主成分BaTiO3,其余成分为Cr2O3:0.1-3摩尔,V2O5:0.01-0.5摩尔,和R1的氧化物(R1:Y、Ho或Dy):0.7-7摩尔,以及MnO:0.5或更少。这种介电组合物的介电常数为1473-3086且满足X8R特性(-55-150C,ΔC=±15%),但需要具有高达1280-1300℃的烧结温度。
这些基于BaTiO3的介电陶瓷组合物满足EIA标准规定的X7R特性(-55-125℃,C=±15%),但介电常数低。特别是当介电常数为3000时,烧结温度太高,例如1300℃或更高。如果烧结温度高达1300℃,则在低于介电陶瓷层的温度下内电极层发生收缩,从而两层界面发生分层。另外,在高的烧结温度下,内电极层间经常发生成块或破损,从而容易发生电容量的下降和内电极层间短路。
发明内容
因此,本发明是针对上述问题进行的,本发明的一个目的是提供一种介电陶瓷组合物,其即使在低烧结温度下也具有高介电常数,满足X5R特性(-55-85℃,C=±15%),可以在还原氛下烧结并显示长寿命的IR。本发明的另一个目的是提供使用该组合物的一种多层陶瓷片状电容器和该多层陶瓷片状电容器的制备方法。
根据本发明的一方面,可以通过提供一种介电陶瓷组合物达到上述目的,该介电陶瓷组合物含有BaTiO3及其他成分,且每100摩尔BaTiO3,其他成分的量为MgCO3:0.2-3.0摩尔;选自Y2O3、Ho2O3、Dy2O3和Yb2O3的至少一种:0.05-1.5摩尔;Cr2O3:0.1-1.5摩尔;BaxCa(1-x)SiO3(假设0≤x≤1):0.2-3.0摩尔;和Mn2V2O7:0.01-1.5摩尔。
根据本发明的另一方面,提供一种多层陶瓷片状电容器,其包括交替层叠的由上述介电陶瓷组合物构成的介电陶瓷层和内电极层。
根据本发明的再一方面,提供一种制备所述的多层陶瓷片状电容器的方法,包括以下步骤:在650-800℃的温度下煅烧MnO和V2O5得到粉末状的Mn2V2O7;混合BaTiO3及其他成分,且每100摩尔BaTiO3,其他成分的量为MgCO3:0.2-3.0摩尔、选自Y2O3、Ho2O3、Dy2O3和Yb2O3的至少一种:0.05-1.5摩尔、Cr2O3:0.1-1.5摩尔、BaxCa(1-x)SiO3(假设0≤x≤1):0.2-3.0摩尔、和Mn2V2O7:0.01-1.5摩尔,得到介电材料;交替层叠介电材料和内电极,得到层叠体;以及烧结层叠体。
附图说明
以下通过结合附图进行的详细说明将更好地理解本发明的上述目的、特征和其它优点,其中:
图1是表示本发明的制备多层陶瓷片状电容器的方法的一个实施方案的框图。
具体实施方式
以下将详细说明本发明。
一般为降低基于BaTiO3的介电陶瓷组合物的烧结温度必须增加BaxCa(1-x)SiO3(以下简称“BCG”)的量。但是,如果BCG的量加大,介电常数降低。
因此,在对使用Mn2V2O7作为烧结助剂确保高介电常数的同时完成低温烧结进行研究之后,本发明人发现,如果并用BCG和Mn2V2O7,基于BaTiO3的介电组合物可在低温下烧结。根据本发明,降低BCG量的同时会获得3000或更高的高介电常数。
迄今开发的大多数基于BaTiO3的介电组合物单独使用MnO和V2O5。未得知含有由MnO和V2O5合成的Mn2V2O7的基于BaTiO3的介电陶瓷组合物。含有Mn2V2O7的基于BaTiO3的介电陶瓷组合物可在低温下烧结,但当单独使用MnO和V2O5时,难以期待这种效果。在上述的美国专利5,668,694;美国专利5,862,034;日本专利申请公开6-215979号公报;日本专利申请公开2000-311828号公报和韩国专利申请公开2000-0012080号公报所公开的基于BaTiO3的介电陶瓷组合物的情况下,MnO和V2O5被单独使用,介电组合物在1300℃的高温下烧结。
下述的是本发明的介电陶瓷组合物,考虑到了在基于BaTiO3的介电陶瓷组合物中Mn2V2O7作为烧结助剂的作用及Mn2V2O7与BCG的协同作用。
MgCO3:0.2-3摩尔
MgCO3起提高介电陶瓷组合物的不可还原性的作用。优选限制MgCO3的量是每100摩尔BaTiO3为0.2-3.0摩尔。如果MgCO3的量低于0.2摩尔,介电损耗因数增大,电容量随温度的变化率增大。如果超过3.0摩尔,绝缘电阻寿命缩短,可烧结性下降。
选自Y2O3、Ho2O3、Dy2O3和Yb2O3的至少一种:0.05-1.5摩尔Y2O3、Ho2O3、Dy2O3和Yb2O3有效改善IR和IR寿命及降低电容量随温度的变化率,这是由于它们在Ba2+位置取代了TiO3 2-而引起的。因此,选自Y2O3、Ho2O3、Dy2O3和Yb2O3的至少一种的优选添加量为至少0.05摩尔。如果超过1.5摩尔,可烧结性下降,介电陶瓷组合物转变成半导体。
Cr2O3:0.1-1.5摩尔
Cr2O3有效提高不可还原性。如果Cr2O3的量低于0.1摩尔,介电陶瓷组合物转变成半导体,而如果超过1.5摩尔,IR下降。
BaxCa(1-x)SiO3(假设0≤x≤1):0.2-3.0摩尔
BaxCa(1-x)SiO3以其低熔点及与主成分的良好反应性而用作烧结助剂。如果BCG的量低于0.2摩尔,可烧结性下降,电容量温度特性达不到标准,且IR下降。如果BCG的量超过3.0摩尔,IR寿命缩短,介电常数下降。更优选将BCG的量限制为0.2-1.4摩尔的范围。根据本发明,添加Mn2V2O7有助于减少BCG的量。在BaxCa(1-x)SiO3中,x为0-1,优选0.3-0.6。
Mn2V2O7:0.01-1.5摩尔
Mn2V2O7具有820℃的低熔点,因此用作第二烧结助剂。因此,Mn2V2O7有效提高介电陶瓷组合物的可烧结性。即,Mn2V2O7的存在使介电陶瓷组合物在低温(1200-1250℃)下烧结变为可能。结果,内电极层和介电陶瓷层之间的收缩率的差减小。因此,可以克服高温烧结的缺点例如分层、成块和破损。另外,低温烧结防止过度烧结并减小介电陶瓷层的粒径,从而获得更高的可靠性。添加Mn2V2O7有助于减小BCG的量,从而获得更高的电容量。Mn2V2O7还能够有助于获得在高于居里温度的温度下的稳定的电容量温度特性,并延长IR寿命。Mn2V2O7由于具有熔点低,因此比MnO和V2O5单独存在时具有更均匀的分布。因此,即使少量的Mn2V2O7也赋予上述的优点。即,当MnO和V2O5单独存在时,由于其熔点高,因此它们分别以固相的形式存在。而由于两种成分的合成使介电陶瓷组合物的熔点降低时,低温烧结时它们以液相的形式均匀分布。
如果Mn2V2O7的量低于0.01摩尔,其作为烧结助剂的效力不足,而如果超过1.5摩尔,IR下降,且对电容量温度特性有不利影响。更优选Mn2V2O7的添加量为0.01-1摩尔。
根据本发明,当BaxCa(1-x)SiO3和Mn2V2O7的总量为1-1.6摩尔时,即使在低温下烧结介电陶瓷组合物,介电常数等的特性也很优良。
接下来,将说明本发明的多层陶瓷片状电容器。
本发明的多层陶瓷片状电容器包含交替层叠的由上述的介电陶瓷组合物构成的介电陶瓷层、和内电极层。由于本发明的介电陶瓷组合物是不可还原的,所以可以使用贱金属作为内电极材料。贱金属可是以常用的那些。Ni或Ni合金等的贱金属优选用作内电极材料。
使用本发明的介电陶瓷组合物制备的本发明的多层陶瓷片状电容器具有高的介电常数并满足X5R特性(-55-85℃,ΔC=±15%)。另外,在直流电场中电容量随时间的变化下降,绝缘电阻寿命提高。
接下来,更详细地说明制备本发明的多层陶瓷片状电容器的方法。
多层陶瓷片状电容器可通过常规的印刷或压片法(sheetingmethod)制备。
首先,在650-800℃的温度下煅烧MnO和V2O5,得到粉末状的Mn2V2O7。煅烧温度的优选范围是650-680℃。如果煅烧温度低于650℃,相合成反应不发生。而如果超过800℃,Mn2V2O7粉末的粒径增大并硬化,从而难以研磨。因此,为有利于研磨,必须在相合成的适当温度下对MnO和V2O5进行热处理。为此,煅烧温度为650-800℃,优选650-680℃。
得到Mn2V2O7粉末后,混合粉末状的原材料得到浆料。即,混合、研磨、脱水并干燥BaTiO3和其他成分,且每100摩尔BaTiO3,其他成分的量为MgCO3:0.2-3.0摩尔;选自Y2O3、Ho2O3、Dy2O3和Yb2O3的至少一种:0.05-1.5摩尔;Cr2O3:0.1-1.5摩尔;BaxCa(1-x)SiO3(假设0≤x≤1):0.2-3.0摩尔;和Mn2V2O7:0.01-1.5摩尔(根据本发明,BCG和Mn2V2O7各自的优选添加量如上所述)。可以在干燥后的粉末中加入粘合剂和有机溶剂,得到浆料。
使用印刷法时,浆料和内电极层形成用糊剂交替地印刷到衬底上,切割成预定的形状并与衬底分离。使用压片法时,由浆料形成生片(green sheet),在各生片上印刷内电极形成用的糊剂,并将印刷后的生片层压。
除去层压体的粘合剂并在还原氛下烧结。此时,在低于1300℃、优选1200-1250℃的低温下进行烧结。本发明的介电陶瓷组合物可以在低温下烧结。因此,即使在1200-1250℃这样的低温下进行烧结时,也可以得到具有高介电常数且满足X5R特性的电容器。
在所得到的烧结体的端面上涂覆内电极形成用的糊剂,并对其进行热处理,得到多层陶瓷片状电容器。外电极没有特别的限制,可以使用Ni、Cu或它们的合金。
以下,将通过非限制性的实施例更详细地说明本发明。
实施例
根据图1的制备方法,制备了多层陶瓷片状电容器。
首先,以1∶1的摩尔比混合起始原材料BaCO3和TiO2,并在900-1200℃下反应,得到BaTiO3。将如此获得的BaTiO3研磨为粒径0.8-1.2μm的BaTiO3粉末。
称量并混合BaTiO3、MgCO3、Y2O3和Cr2O3粉末,及作为烧结助剂的BCG和Mn2V2O7。通过在1000℃或更高温度下将BaCO3、CaCO3和SiO2粉末煅烧2小时,得到BCG。通过在650-680℃的温度下将MnO和V2O5煅烧2小时,得到Mn2V2O7。如此得到的烧结助剂在被研磨至粒径为1.0μm或更小后使用。
将称量的粉末湿式混合、研磨、脱水并干燥。
通过将在有机溶剂中溶解粘合剂制得的有机粘合剂加到干燥的粉末中并混合,得到浆料。对粘合剂没有特别的限制。在本发明的实施例中使用基于聚乙烯基丁基(polyvinylbutyl)的粘合剂。用刮刀法将浆料涂覆在薄膜上形成厚度8μm的介电陶瓷组合物片。
将作为内电极材料的Ni糊剂印刷到所形成的介电陶瓷组合物片上。将15片如此印刷的片层压,将保护性仿制片通过压力贴在所述多层片的顶面和底面上,形成层压体。
根据内电极的型式将层压体切成3.2×1.6mm尺寸后,在200-350℃下10小时或更长时间从切割的层压体上除去粘合剂。除去粘合剂后的层压体在1200-1250℃下烧结2小时,并在700-1000℃下再氧化。
将烧结体进行抛光从而将内电极的末端露出。随后,为得到多层陶瓷片状电容器,在烧结体的端面涂覆由Cu、玻璃粉和载体组成的导电糊剂,干燥并在700-800℃下热处理,形成外电极。最后,通过电镀在外电极形成Sn-Pb在Ni上的涂层。
评价了如上所述制备的样品电容器的电性能,如介电常数(εr)、介电损耗(tanδ)、电阻率(Ω·m)和静电电容量温度特性(TCC(%)),结果如下表2所示。
介电常数(εr)和介电损耗(tanδ)在1KHz、室温(25℃)下测定。电阻率(Ω·m)从IR值获得,IR值在250V下通电流60秒后测得。静电电容量温度特性(TCC(%))作为各温度下的电容量相对于25℃的标准静电电容量的百分比变化来评价,即(TCC(%))=[(CT-C25℃)/C25℃]×100
表1
  样品   BaTiO3   MgCO3   Y2O3   Yb2O3   Ho2O3   Dy2O3   Cr2O3   BCG   Mn2V2O7
  Inv.1   100   1.10   0.50   -   -   -   0.12   1.10   0.084
  Inv.2   100   1.10   0.50   -   -   -   0.12   1.10   0.105
  Comp.1   100   0.10   0.50   -   -   -   0.12   1.10   0.105
  Comp.2   100   4.00   0.50   -   -   -   0.12   1.10   0.105
  Inv.3   100   1.10   0.50   -   -   -   0.12   1.40   0.084
  Inv.4   100   1.10   0.50   -   -   -   0.12   1.40   0.105
  Comp.3   100   1.80   0.01   -   -   -   0.12   1.40   0.084
  Comp.4   100   1.80   3.00   -   -   -   0.12   1.40   0.084
  Inv.5   100   2.10   0.50   -   -   -   0.12   1.10   0.084
  Inv.6   100   2.10   0.50   -   -   -   0.12   1.10   0.105
  Comp.5   100   1.80   0.50   -   -   -   0.01   1.10   0.105
  Comp.6   100   1.80   0.50   -   -   -   2.00   1.10   0.105
  Inv.7   100   2.10   0.50   -   -   -   0.12   1.40   0.084
  Inv.8   100   2.10   0.50   -   -   -   0.12   1.40   0.105
  Comp.7   100   1.80   0.50   -   -   -   0.12   0.10   0.105
  Comp.8   100   1.80   0.50   -   -   -   0.12   4.00   0.105
  Inv.9   100   1.80   0.30   -   -   -   0.12   1.10   0.084
  Inv.10   100   1.80   0.30   -   -   -   0.12   1.10   0.105
  Comp.9   100   1.80   0.50   -   -   -   0.12   1.10     0.005
  Comp.10   100   1.80   0.50   -   -   -   0.12   1.10     3.00
  Inv.11   100   1.80   0.30   -   -   -   0.12   1.10     0.126
  Inv.12   100   1.80   0.30   -   -   -   0.12   1.10     0.150
  Inv.13   100   1.10   0.40   0.30   -   -   0.12   1.10     0.105
  Inv.14   100   1.10   0.40   0.20   -   -   0.12   1.10     0.105
  Inv.15   100   1.80   0.30   0.40   -   -   0.12   1.10     0.105
  Inv.16   100   1.10   0.40   -   0.20   -   0.12   1.10     0.105
  Inv.17   100   1.80   0.30   -   0.30   -   0.12   1.10     0.105
  Inv.18   100   1.10   0.40   -   -   0.20   0.12   1.10     0.105
  Inv.19   100   1.80   0.30   -   -   0.30   0.12   1.10     0.105
  Inv.20   100   1.80   0.50   -   -   -   0.12   0.80     0.400
  Inv.21   100   1.80   0.50   -   -   -   0.12   0.70     0.500
Inv.:本发明例;Comp.:比较例
表2
  样品     介电常数(εr)   介电损耗(tanδ)   电阻率(Ω·m)               TCC(%)     烧结密度(g/cm3)     评价
  -55℃   85℃   125℃
  Inv.1     4085     3.25   2.13E+09   -5.20   -13.78   -22.50     5.92     好
  Inv.2     3947     4.02   2.61E+09   -0.21   -12.45   -27.11     5.91     好
  Comp.1     4085     8.75   2.13E+09   -5.20   -19.78   -32.12     5.89     A
  Comp.2     3247     5.02   2.61E+08   -0.21   -13.45   -22.11     5.74     B
  Inv.3     4157     3.74   9.75E+08   0.72   -13.69   -27.20     5.92     好
  Inv.4     4359     4.15   2.54E+09   -2.46   -12.52   -29.85     5.90     好
  Comp.3     4322     4.74   9.75E+07   0.72   -14.69   -27.20     5.91     C
  Comp.4                                         转变成半导体
  Inv.5     4022     3.27   4.05E+08   -0.99   -11.96   -29.25     5.93     好
  Inv.6     3957     3.77   3.96E+08   -3.21   -12.19   -23.11     5.91     好
  Comp.5                                         转变成半导体
  Comp.6     3557     3.77   8.96E+07   -3.21   -13.19   -23.11     5.90     C
  Inv.7     4129     2.93   1.29E+09   -2.28   -13.42   -23.20     5.91     好
  Inv.8     3807     2.87   3.02E+08   -5.46   -13.63   -25.85     5.90     好
  Comp.7     4129     5.93   1.29E+08   -6.28   -18.42   -29.20     5.75     B
  Comp.8     2607     2.87   3.02E+08   -5.46   -14.63   -25.85     5.91     D
  Inv.9     4374     2.02   7.18E+08   -2.25   -14.90   -24.71     5.92     好
  Inv.10     4323     2.93   6.84E+08   -1.88   -15.02   -25.20     5.92     好
  Comp.9     4074     8.02   5.38E+08   -3.99   -17.50   -25.41     5.89     A
  Comp.10     3823     3.93   1.94E+07   -2.28   -17.40   -25.50     5.92     C
  Inv.11     4316     3.88   1.04E+09   -5.46   -15.10   -28.15     5.90     好
  Inv.12     4311     2.83   2.16E+09   -3.99   -14.20   -28.35     5.91     好
  Inv.13     4112     3.82   1.16E+09   -1.39   -11.99   -25.35     5.92     好
  Inv.14     4103     3.91   1.96E+09   -1.79   -12.20   -26.13     5.91     好
  Inv.15     4209     3.98   1.33E+09   -2.99   -13.63   -26.26     5.91     好
  Inv.16     4121     3.85   1.03E+09   -1.97   -12.79   -27.56     5.90     好
  Inv.17     4089     3.77   1.54E+09   -1.86   -13.56   -26.97     5.90     好
  Inv.18     4133     4.05   1.05E+09   -2.09   -11.63   -24.34     5.91     好
  Inv.19     4194     4.11   1.17E+09   -2.43   -12.21   -25.26     5.92     好
  Inv.20     4291     4.12   1.76E+09   -2.69   -14.45   -27.34     5.92     好
  Inv.21     4302     4.06   1.82E+09   -3.66   -14.87   -28.96     5.91     好
A:tanδ增大;B:没有烧结;C:IR降低;D:介电常数下降;E:高温下的电容量温度特性超出标准范围
如表1和表2所示,BCG的量小但加入Mn2V2O7作为第二烧结助剂时,本发明的介电陶瓷组合物在低温下烧结时具有优良的可烧结性。
本发明的介电陶瓷组合物具有约4000的介电常数,满足X5R特性,并可在低温下烧结。因此,内电极层和介电陶瓷层之间不会发生分层,内电极层之间的成块和破损减少。另外,避免了过度烧结且介电层的晶体粒径减小,从而提高了可靠性。
从上面的描述明显可以看出,本发明提供的介电陶瓷组合物具有高介电常数,且满足EIA标准规定的X5R特性(-55-85℃,C=±15%)。另外,该组合物可在还原氛下低温烧结,并具有长绝缘电阻寿命。使用本发明的介电陶瓷组合物提供的多层陶瓷片状电容器可靠性高,且满足X5R特性。对于该多层陶瓷片状电容器,直流电场下电容量随时间的变化小,绝缘电阻的寿命长。
尽管出于说明的目的揭示了本发明的优选实施方式,但本领域的技术人员应理解在不偏离附带的权利要求书所揭示的本发明的范围和思想的情况下,可以进行多种变更、添加和替换。

Claims (13)

1.一种不可还原的可低温烧结的介电陶瓷组合物,其包含:
BaTiO3和其它成分,且每100摩尔BaTiO3,其它成分的量为
MgCO3:0.2-3.0摩尔;
选自Y2O3、Ho2O3、Dy2O3和Yb2O3的至少一种:0.05-1.5摩尔;Cr2O3:0.1-1.5摩尔;
BaxCa(1-x)SiO3:0.2-3.0摩尔,其中0≤x≤1;
Mn2V2O7:0.01-1.5摩尔。
2.如权利要求1所述的组合物,其中BaxCa(1-x)SiO3的添加量为0.2-1.4摩尔。
3.如权利要求1所述的组合物,其中在BaxCa(1-x)SiO3中,x为0.3-0.6。
4.如权利要求1所述的组合物,其中Mn2V2O7的添加量为0.01-1.0摩尔。
5.如权利要求1所述的组合物,其中BaxCa(1-x)SiO3和Mn2V2O7的总量为1-1.6摩尔。
6.一种多层陶瓷片状电容器,包含交替层压的介电陶瓷层和内电极层,其中介电陶瓷层包含:
BaTiO3和其它成分,且每100摩尔BaTiO3,其它成分的量为
MgCO3:0.2-3.0摩尔;
选自Y2O3、Ho2O3、Dy2O3和Yb2O3的至少一种:0.05-1.5摩尔;Cr2O3:0.1-1.5摩尔;
BaxCa(1-x)SiO3:0.2-3.0摩尔,其中0≤x≤1;
Mn2V2O7:0.01-1.5摩尔。
7.如权利要求6所述的电容器,其中内电极层包含选自Ni和Ni合金的导体。
8.一种制备多层陶瓷片状电容器的方法,包括以下步骤:
在650-800℃的温度下煅烧MnO和V2O5,得到粉末状的Mn2V2O7
混合BaTiO3和其它成分,得到介电材料,其中每100摩尔BaTiO3,其它成分的量为
MgCO3:0.2-3.0摩尔;
选自Y2O3、Ho2O3、Dy2O3和Yb2O3的至少一种:0.05-1.5摩尔;Cr2O3:0.1-1.5摩尔;
BaxCa(1-x)SiO3:0.2-3.0摩尔,其中0≤x≤1;
Mn2V2O7:0.01-1.5摩尔;
交替层压介电材料和内电极,得到层压体;和
烧结层压体。
9.如权利要求8所述的方法,其中BaxCa(1-x)SiO3的添加量为0.2-1.4摩尔。
10.如权利要求8所述的方法,其中Mn2V2O7的添加量为0.01-1.0摩尔。
11.如权利要求8所述的方法,其中BaxCa(1-x)SiO3和Mn2V2O7的总量为1-1.6摩尔。
12.如权利要求8所述的方法,其中煅烧过程在650-680℃下进行。
13.如权利要求8所述的方法,其中烧结过程在1200-1250℃下进行。
CN02157839.7A 2002-07-05 2002-12-20 介电陶瓷组合物、使用该组合物的多层陶瓷片状电容器及该电容器的制备方法 Expired - Fee Related CN1224056C (zh)

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