CN112592175B - 一种电介质陶瓷、多层陶瓷电容器 - Google Patents
一种电介质陶瓷、多层陶瓷电容器 Download PDFInfo
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Abstract
本发明公开了一种电介质陶瓷、多层陶瓷电容器。本发明的电介质陶瓷中存在含有Al、Mg、Si的二次相粒子，通过使二次相粒子形成长棒状结构，长棒状二次相粒子对介质层和内部电极起到了一定的锚定作用，改善了界面的结合力，从而提高耐热冲击性。并且，本发明通过优化电介质陶瓷的组成，控制了Mg‑Al‑Si二次相粒子的尺寸，从而确保了长棒状二次相粒子既可以提高产品的耐热冲击性能，同时又可避免出现二次相过大导致的寿命恶化问题，从而实现多层陶瓷电容器的介质层的进一步薄层化、多层化，满足小尺寸、大容量的市场需求。
Description
技术领域
本发明涉及一种电介质陶瓷及使用了它的多层陶瓷电容器，特别涉及一种通过材料晶体结构优化而提高陶瓷结构结合力和可靠性的电介质陶瓷，及使用该电介质陶瓷而制造的多层陶瓷电容器。
背景技术
随着电子信息产业的发展，采用陶瓷材料制备的电子元件越来越多，例如电容器、压电装置、变阻器、热敏电阻等。多层陶瓷电容器作为代表性的陶瓷电子元件之一，通常由陶瓷体(由陶瓷材料组成)、内部电极(位于陶瓷体内部，形成多层结构)和外部电极(位于陶瓷体外部，用以连接对应的内部电极)三部分组成，目前陶瓷体所用介电材料以钛酸钡系化合物为主。
随着电子产品的小尺寸多功能化的趋势，电子元件也朝着具有更小尺寸，更好性能的方向发展；相应的，具有大容量且小尺寸的多层陶瓷电容器的需求也日益增长，对此，要求其内部电极和介质层的厚度也随之减薄；因而，对介电陶瓷微观结构及各项性能的要求也愈加苛刻，尤其对于二次相的尺寸、成分、导电性提出了更高的要求，特别是在薄介质层中，二次相的尺寸非常明显的影响到产品的可靠性和耐热冲击性。
为了提高多层陶瓷电容器的可靠性以及耐热冲击性，人们进行了很多研究。CN101628809B公开了一种介电陶瓷，该介电陶瓷以具有钙钛矿(perovskite)型结构的钛酸钡系复合氧化物为主成分，以稀土类元素R，Ni和Ti为主成分的R-Ni-Ti-O系的结晶性复合氧化物作为二次粒子。上述这样的陶瓷即使在高温气氛下，长时间连续外加大的电场，仍具有不会发生异常的高可靠性。然而，该介电陶瓷以ABO3代表的钙钛矿型化合物为主要成分，存在R-Ni-Ti这样的第二相，其抗热震性能较差，在薄膜带，特别是膜带厚度低于1μm的介电陶瓷层中，更容易在热冲击条件下产生裂纹。CN102372484B所公开的电介质陶瓷以ABO代表的钙钛矿型化合物为主要成分，同时含有Al，Mg和Si的结晶性氧化物作为二次相粒子存在，其在不损害介电特性、绝缘性、温度特性、高温负荷特性等性能的同时，具有较好的耐热冲击性，但对于其机理并未解释，且该专利中对于二次相的尺寸没有界定，根据我们的实验结果，当二次相的尺寸达到一定程度，并不能提高产品的耐热冲击性。
发明内容
本发明的目的在于克服现有技术的不足之处而提供一种电介质陶瓷，该电介质陶瓷有利于提高多层陶瓷电容器的可靠性和耐热冲击性。
为实现上述目的，本发明采取的技术方案如下：
一种电介质陶瓷，包含以(Ba1-x-yCaxSry)m(Ti1-p-qZrpHfq)O3作为主成分的主相粒子，以及含有元素Mg、Al和Si的二次相粒子，二次相粒子的形状包括长棒状，且1/10＜长棒状二次相粒子的有效长度/多层陶瓷电容器的介质层的厚度＜1/3；所述电介质陶瓷的组成以100(Ba1-x-yCaxSry)m(Ti1-p-qZrpHfq)O3+a MgO+b Al2O3+c SiO2+d M1+e M2表示的情况下，M1为La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y中至少一种，M2为Mn、V、Cr、Fe、W、Mo、Fe、Ni、Zn中至少一种；0≤x≤0.2，0≤y≤0.02，0≤p≤0.02，0≤q≤0.02，0.995≤m≤1.03，a-e表示摩尔数，0＜a≤3，0＜b≤2，0＜c≤7，0＜d≤5，0＜e≤2，1.1≤(b+c)/a≤3。
二次相粒子的形状多为长棒状、椭圆状，然而，发明人试验发现，二次相粒子的形状、尺寸与多层陶瓷电容器产品的可靠性和耐热冲击性密切相关。对于长棒状二次相粒子而言，当长棒状二次相粒子的有效长度大于多层陶瓷电容器的介质层的厚度的2/3时，会加速多层陶瓷电容器的寿命恶化；当长棒状二次相粒子的有效长度大于多层陶瓷电容器的介质层的厚度的1/3且小于多层陶瓷电容器的介质层的厚度的2/3时，对于产品层间结合力没有改善效果；当长棒状二次相粒子的有效长度小于多层陶瓷电容器的介质层的厚度的1/10时，对于产品层间结合力没有改善效果；当长棒状二次相粒子的有效长度大于多层陶瓷电容器的介质层的厚度的1/10，且小于多层陶瓷电容器的介质层的厚度的1/3时，加速寿命特性和层间结合力均有明显改善。
对于椭圆状二次相粒子而言，椭圆状二次相粒子对于产品的耐热冲击性没有明显改善作用。
本发明的电介质陶瓷中存在含有Al、Mg、Si的二次相粒子，通过调控二次相粒子形成长棒状结构，当该电介质陶瓷应用于多层陶瓷电容器时，长棒状二次相粒子对介质层和内部电极起到了一定的锚定作用，改善了界面的结合力，从而提高耐热冲击性。
电介质陶瓷的组成是影响二次相的形成、分布及尺寸大小的主要因素，本发明电介质陶瓷中ABO3钛酸钡系化合物为主成分，且A位元素至少含有Ba，B位元素至少含有Ti；
所述电介质陶瓷的组成以100(Ba1-x-yCaxSry)m(Ti1-p-qZrpHfq)O3+a MgO+b Al2O3+cSiO2+d M1+e M2表示的情况下，
M1元素，作为掺杂元素改善产品容量温度特性(TCC)，提高产品的可靠性；M1优选为La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y中至少一种；
M2元素，提高介质陶瓷粉体在还原性气氛中的可烧结性，增强上述主成分ABO3钛酸钡系化合物的抗还原性；M2优选为Mn、V、Cr、Fe、W、Mo、Fe、Ni、Zn中至少一种；
0≤x≤0.2，0≤y≤0.02；
0≤p≤0.02，0≤q≤0.02；
当MgO添加量过多时，烧成温度上升，烧结性恶化，从而抑制物质移动，导致加速寿命恶化；添加量过少时，抑制晶粒成长的效果低下，电阻率变低，同时晶粒长大，TCC恶化，产品耐热冲击性下降，因此，本发明优选0<a≤3，更优选0.2≤a≤2；
Al2O3添加量过多时，晶粒容易长大，TCC恶化；添加量过少时，烧成温度上升，烧结性恶化，加速寿命恶化，产品耐热冲击性下降，因此，本发明优选0＜b≤2，更优选0＜b≤1；
SiO2添加量过多时，晶粒容易长大，TCC特性恶化；添加量过少时，烧成温度上升，烧结性恶化，加速寿命恶化，产品耐热冲击性下降，因此，本发明优选0＜c≤7，更优选0.5≤c≤5；
M1元素添加量过多时，静电容量温度系数稳定化，电容率低，烧结性低下，绝缘电阻劣化；当添加量过少时，高温绝缘电阻低，高温寿命时间缩短，可靠性降低，因此，本发明优选0＜d≤5，更优选0.3≤d≤3；
M2元素添加量过少时，耐还原性低下，绝缘电阻减小；添加量过多时，容易发生半导化，老化率及DC-bias特性低下，可靠性降低，因此，本发明优选0＜e≤2，更优选0＜e≤1；
0.995≤m≤1.03，当m值小于0.995时，容易导致晶粒异常长大，绝缘电阻减小；当m值大于1.03时，烧结性下降；
当(b+c)/a比例过大时，二次相粒子尺寸明显增大，其有效长度接近整层介质层，使得介质层的有效厚度降低，甚至二次相粒子贯穿整个介质层，从而导致产品加速寿命特性恶化，耐热冲击性下降；当(b+c)/a比例过小时，可烧结性恶化，加速寿命恶化，耐热冲击性下降，因此，本发明优选1.1≤(b+c)/a≤3，更优选1.5≤(b+c)/a≤2.5。
本发明通过优化电介质陶瓷的组成，控制了Mg-Al-Si二次相粒子的尺寸，从而确保了长棒状二次相粒子既可以提高产品的耐热冲击性能，同时又可避免出现二次相过大导致的寿命恶化问题，从而实现多层陶瓷电容器的介质层的进一步薄层化、多层化，满足小尺寸、大容量的市场需求。
本发明的电介质陶瓷在制备过程中，元素Al、Mg、Si、M1、M2可以采用氧化物、包含含有该种元素的碳酸盐、草酸盐、硝酸盐等形式添加。
本发明还提供了一种多层陶瓷电容器，该多层陶瓷电容器包括陶瓷烧结体和多个外部电极，所述陶瓷烧结体具有被层叠的多个介质层、以及沿着所述介质层间的界面形成的多个内部电极，所述外部电极形成于所述陶瓷烧结体的外表面、并与所述内部电极电连接，所述介质层由上述的电介质陶瓷形成。
在多层陶瓷电容器产品中，由于润湿性的问题，金属内部电极和介质层之间的结合力较差，在还原性气氛中烧结时，其界面形成过渡层的可能性较小，因此金属内部电极和介质层的结合力较差；本发明通过在金属内部电极和介质层之间形成Mg-Al-Si二次相，并通过控制二次相粒子的尺寸，对介质层和内部电极起到了一定的锚定作用，改善了内部电极与介质层之间界面的结合力，从而提高耐热冲击性。
与现有技术相比，本发明的有益效果为：
本发明的电介质陶瓷中存在含有Al、Mg、Si的二次相粒子，通过调控二次相粒子形成长棒状结构，当该电介质陶瓷应用于多层陶瓷电容器时，长棒状二次相粒子对介质层和内部电极起到了一定的锚定作用，改善了界面的结合力，从而提高耐热冲击性。
本发明通过对电介质陶瓷组成进行调控，控制了Mg-Al-Si二次相粒子的尺寸，从而确保了长棒状二次相粒子既可以提高产品的耐热冲击性能，同时又可避免出现二次相过大导致的寿命恶化问题，从而实现多层陶瓷电容器的介质层的进一步薄层化、多层化，满足小尺寸、大容量的市场需求。
具体实施方式
为更好地说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明进一步说明。本领域技术人员应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
实施例中，所使用的实验方法如无特殊说明，均为常规方法，所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1-9和对比例1-8的多层陶瓷电容器包括陶瓷烧结体和多个外部电极，所述陶瓷烧结体具有被层叠的多个介质层、以及沿着所述介质层间的界面形成的多个内部电极，所述外部电极形成于所述陶瓷烧结体的外表面、并与所述内部电极电连接，所述介质层由电介质陶瓷形成，其中实施例1-9和对比例1-8的电介质陶瓷的组成如表1所示。
实施例1-9和对比例1-8的多层陶瓷电容器的制备方法，包括以下步骤：
(1)准备Ba化合物、Ti化合物，根据实际需要准备Ca化合物、Sr化合物、Zr化合物和Hf化合物，制备平均粒径为0.1-0.3μm的钛酸钡系化合物粉体作为主成分，钛酸钡系化合物粉体可通过固相法、共沉淀法、水热法、草酸盐法等方法制备得到；
(2)根据表1组成，准备稀土类化合物、过渡金属化合物、以及Si化合物等副成分，并按预定的比例称重；然后将这些称量物与BaTiO3粉体、粉碎介质以及纯水一同投入到球磨机，以湿式方式充分进行混合粉碎，并进行混合，实施干燥处理，得到陶瓷原料粉末；
(3)将上述陶瓷原料粉末与有机粘合剂、有机溶剂、粉碎介质一同投入到球磨机并进行湿式混合，制作陶瓷浆料，并通过唇式涂布法(lip method)、刮刀法等对陶瓷浆料实施成型加工，制作陶瓷生片，使其烧成后的厚度为2μm左右或2μm以下；
(4)准备以Ni等贱金属材料为主成分的内部电极用导电膏，然后，使用该内部电极用导电膏在陶瓷生片上实施丝网印刷，在上述陶瓷生片的表面形成给定图案的导电膜；
(5)将形成了导电膜的陶瓷生片在给定方向上层叠多片，将未形成导电膜的陶瓷片配置在最上层，并进行压合，切断为给定尺寸而制作陶瓷层叠体；
(6)将陶瓷层叠体在大气气氛下以250～350℃的温度进行热处理，使粘合剂燃烧而除去，然后，在由H2-N2-H2O气体构成的强还原性气氛下(例如，氧分压为10-11～10-13Pa)以1100～1300℃的烧成温度进行大约2小时的烧成处理；在陶瓷烧结体的两端面涂敷外部电极用导电膏，以600～900℃的温度进行烘烤处理，形成外部电极。另外，关于在外部电极用导电膏中含有的导电性材料，虽然也没有特别限定，但是从低成本化的观点出发，优选使用Ag、Cu或者以它们的合金为主成分的材料。
在其它实施方式中，作为外部电极的形成方法，也可以在陶瓷层叠体的两端面涂敷了外部电极用导电膏之后，与陶瓷层叠体同时实施烧成处理。
(7)实施电解镀覆而在外部电极的表面形成由Ni、Cu、Ni-Cu合金等构成的第一镀覆膜，进而在该第一镀覆膜的表面形成由焊料、锡等构成的第二镀覆膜，从而得到所述多层陶瓷电容器。
对上述实施例和对比例制备得到的多层陶瓷电容器进行性能测试，具体测试方法如下：
(1)介电常数(K值)：使用自动桥接式测定器，在频率1kHz、实效电压0.5Vrms、温度25℃的条件下测定静电电容C，再结合样品尺寸，计算出该样的介电常数。
(2)介电损耗：使用自动桥接式测定器，在频率1kHz、实效电压0.5Vrms、温度25℃的条件下测定样品介电损耗。
(3)静电容量的温度特性：利用高低温快速循环箱，在25℃、125℃测试产品的静电电容，计算125℃温度下容值与室温(+25℃)容值的温度变化率△C+125/C25，进行评价，静电电容的温度变化率在±15％以内，即可满足EIA规格的X7R特性。
(4)耐热冲击性：每组样品取40只，在温度设定为250℃和350℃的焊料槽中分别进行3分钟浸渍，再从焊料槽中取出，用树脂固定后，进行研磨，再进行SAT扫描，确认是否存在裂缝，只要存在裂缝，该样即判定为NG品，NG只数越少耐热冲击性越好，热冲击不良比例＝100％*NG品个数/40。
(5)加速寿命试验：每个试样取样40只，利用高加速寿命试验箱，在150℃下，按10V/μm加压测试，记录发生失效的时间，时间越长，相对样品寿命越好。
(6)介质层厚度的测试方法：首先使样品立起而垂直，使用树脂将各试样的周围固定。此时，各试样的LT侧面露出，使用研磨机，研磨LT侧对面，层叠体的W方向的1/2深度处结束研磨，露出LT截面，对该面进行离子研磨，去除因为研磨而产生的垂挂；在LT界面的L方向1/2处引出与内部电极正交的垂线，接着，将试样的层叠有内部电极的区域在T方向进行3等分，分为上侧部，中间部，和下侧部。然后从各区域各自的高度方向中央部选择20层介质层厚度进行测量，取平均值；
(7)二次相粒子的有效长度测试方法：首先使样品立起而垂直，使用树脂将各试样的周围固定。此时，各试样的LT侧面露出，使用研磨机，研磨LT侧对面，层叠体的W方向的1/2深度处结束研磨，露出LT截面，对该面进行离子研磨，去除因为研磨而产生的垂挂；整个研磨面取中间部以及四个电极边缘处，共计五个位置处，20μm/20μm的视野范围内进行SEM观察；视野范围内采用EDX测试，Al、Mg、Si三种元素同时存在，且其长径比大于1，被确定为有效的长棒状二次相粒子；首先测量其实际长度L，再界定该二次相和电极层方向的夹角为α，则其有效长度为L*tan(90-α)(角度制)，测量数量为10个；
上述多层陶瓷电容器的性能测试结果如表2所示。
表1
表2
对比例2-4结果可知，当Mg，Al，Si三种元素有任一元素为零时，其二次相的长度会比较短，但由于其在界面的锚定作用减弱，从而使得其在350℃条件下热冲击不良比例明显上升；
对比例6-8结果可知，当Mg，Al，Si三种元素含量较高时，其更容易形成长棒状的二次相，并且二次相的长度也较大，甚至贯穿了整个电极层，从而使得其在250℃条件下热冲击不良比例大幅度增加，在350℃条件下，几乎全部热冲击开裂；
对比例5结果可知，在M1和M2添加量过少，甚至为零时，其可靠性有明显的恶化；在烧结过程中，M1和Mg元素进行协同作用，形成core-shell结构，但由于M1元素的缺失，使得其core-shell结构shell层较薄，甚至为零，在施加电压过程中，其对载流子的阻碍作用减弱，从而使得其可靠性降低；
实施例4具有比较适中的(b+c)/a值，m值，其二次相长度也符合1/10＜长棒状二次相粒子的有效长度/多层陶瓷电容器的介质层的厚度＜1/3的要求，在保证了产品寿命特性的同时，提高了产品的耐热冲击性。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。
Claims (4)
1.一种电介质陶瓷，其特征在于，包含以（Ba1-x-yCaxSry）m（Ti1-p-qZrpHfq）O3作为主成分的主相粒子，以及含有元素Mg、Al和Si的二次相粒子，二次相粒子的形状包括长棒状，且1/10＜长棒状二次相粒子的有效长度/多层陶瓷电容器的介质层的厚度＜1/3；所述电介质陶瓷的组成以100（Ba1-x-yCaxSry）m（Ti1-p-qZrpHfq）O3+ a MgO +b Al2O3 +c SiO2+ d M1 + e M2表示的情况下，M1为La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y中至少一种， M2为Mn、V、Cr、Fe、W、Mo、Ni、Zn中至少一种；0≤x≤0.2，0≤y≤0.02，0≤p≤0.02，0≤q≤0.02，0.995≤m≤1.03，a-e 表示摩尔数，0.2＜a≤2，0＜b≤1，0.5＜c≤5，0.3＜d≤3，0.1＜e≤2 ，1.1≤（b+c）/a≤3；
所述二次相粒子的有效长度测试方法为：采用EDX测试， Al、Mg、Si三种元素同时存在，且其长径比大于1，确定为有效的长棒状二次相粒子；所述长棒状二次相粒子的有效长度为L*tan（90-α），其中L为长棒状二次相粒子的实际长度，所述α为该长棒状二次相粒子与电极层方向的夹角。
2.根据权利要求1所述的电介质陶瓷，其特征在于，0.1＜e≤1。
3.根据权利要求1所述的电介质陶瓷，其特征在于，1.5≤（b+c）/a≤2.5。
4.一种多层陶瓷电容器，其特征在于，包括陶瓷烧结体和多个外部电极，所述陶瓷烧结体具有被层叠的多个介质层、以及沿着所述介质层间的界面形成的多个内部电极，所述外部电极形成于所述陶瓷烧结体的外表面、并与所述内部电极电连接，所述介质层由权利要求1-3任一项所述的电介质陶瓷形成。
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