CN110808163B - 一种晶界层电容器的制备方法 - Google Patents

一种晶界层电容器的制备方法 Download PDF

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CN110808163B
CN110808163B CN201911033493.8A CN201911033493A CN110808163B CN 110808163 B CN110808163 B CN 110808163B CN 201911033493 A CN201911033493 A CN 201911033493A CN 110808163 B CN110808163 B CN 110808163B
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张木森
何创创
杨昌平
庞锦标
肖海波
王学杰
王瑞龙
杨俊�
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Guizhou Zhenhua Electronic Information Industry Technology Research Co ltd
Hubei University
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Abstract

本发明公开了一种晶界层电容器的制备方法，具体步骤为：以SrCO3和TiO2为主料，添加Dy2O3和Ho2O3作为施主掺杂，再加入消泡剂和分散剂，然后球磨，再经流延、干燥、叠片和热压后得到基片生坯；将基片生坯进行排胶处理，排胶后的基片在N2/H2还原气氛中烧结后得到半导化基片；然后将氧化剂均匀涂覆于半导化基片表面，高温保温后，降温，得到绝缘化基片；再利用磁控溅射技术在绝缘化基片正、反面镀上Au电极，然后切片，得到晶界层电容器。本发明通过采用适当的原料、配比以及氧化剂，用二步法制备晶界层电容器，氧化剂和绝缘化物质在晶界层中以纳米晶形式析出，该纳米晶形态对提高电容器的介电性能，特别是绝缘电阻值起到了明显作用。

Description

一种晶界层电容器的制备方法
技术领域
本发明涉及陶瓷电容器及电子信息功能材料领域，更具体的说是涉及一种晶界层电容器的制备方法。
背景技术
单片层电容器由于体积小，介电常数高，温度稳定性好，应用频率宽等优点，在电子对抗、雷达、导航、制导和卫星通讯等领域具有广泛应用。晶界层电容器是单片层电容器中的一种，主体成份一般为BaTiO3和SrTiO3，经过两次烧结制得。SrTiO3由于具有更大绝缘电阻，更高的耐压值以及更好的温度稳定性成为生产晶界层电容器的主要材料，占有市场主要份额。目前市场上单层片式半导体陶瓷材料的生产厂家，国际上主要有DLI、PRESIDIOCOM-PENONT、TECDIA等厂家，国内生产单位主要有广州可纳瑞电子科技有限公司、广州金陶电子有限公司和电子科技大学。对于相同尺寸的STO晶界层电容器，国内产品在电容、损耗、电容温度变化系数和使用频率等诸多性能参数与国际产品相差不大，但绝缘电阻值和耐压值与国外先进产品相差较大，一般为国外产品20％～50％。因此提高国内STO晶界层电容器的绝缘电阻和耐压值，对减小产品与国外同类产品在使用性能上的差异，提高国内产品质量具有重要意义。
STO(SrTiO3)晶界层电容器由表面、STO晶粒和晶界层等部分构成。一般地，为保证电容器具有优良的介电性能和大的绝缘电阻值，金属电极与STO陶瓷表面应接触紧密，以保证两者接触为欧姆接触；STO晶粒应为半导化晶粒，导电性好，电阻值小。STO电容器的介电性能和绝缘电阻等主要取决于晶界层性质，晶界层应尽可能的薄以产生大的电容和介电常数，且电阻应尽可能的大以减小电容器的损耗和增大耐压值。由此可知晶界层的结构和性质决定了STO电容器的性能和使用。
一般地，STO晶界层绝缘电阻值取决于晶界层的电阻，该电阻包含二个方面，一是由晶界层中玻璃化物质产生的欧姆电阻，再就是通过在晶界层掺杂受主离子产生空间电荷区，由空间电荷区产生的势垒电阻。过去，人们利用氧化剂和玻璃化物质在高温条件下通过原子扩散进入STO晶界以增大样品的欧姆电阻和势垒电阻，但由于晶界层中的氧化剂和玻璃化物质处于原子排列无序的非晶状态，晶界层中的空位和缺陷较多，对STO的介电性能，绝缘电阻和损耗等均产生不利影响。
因此，如何提供一种绝缘电阻大、耐压值高的晶界层电容器，成为本领域技术人员亟需解决的技术问题。
发明内容
有鉴于此，本发明提供了一种晶界层电容器的制备方法，通过采用适当的原料、配比以及氧化剂，用二步法制备晶界层电容器，氧化剂和绝缘化物质在晶界层中以纳米晶形式析出，该纳米晶形态对提高电容器的介电性能，特别是绝缘电阻值起到了明显作用，从通常处理的1.7GΩ提升到11.5GΩ，提高近600％。
为了实现上述目的，本发明采用如下技术方案：
一种晶界层电容器的制备方法，包括以下步骤：
1)用流延法制备基片生坯：以SrCO3和TiO2为主料，添加Dy2O3和Ho2O3作为施主掺杂，再加入消泡剂和分散剂，然后球磨14-18h后得到流延浆料，再经流延、干燥、叠片和热压(流延厚60um,叠4层，压强100MP)后得到长、宽45mmx45mm，厚0.25mm的基片生坯；
2)基片生坯半导化：将所述步骤1)制备的基片生坯在空气中500-700℃下进行0.5-1.0h的排胶处理，排胶后的基片在N2/H2还原气氛中，温度为1200-1500℃进行1-3h烧结后得到半导化基片；
3)半导化基片绝缘化：将氧化剂均匀涂覆于步骤2)制备的半导化基片表面，再将涂好氧化剂的基片在950-1150℃，保温1.5-3.5h后，以0.1-0.3℃/min降温，经3-7h降至700-1000℃，再通过自然降温从700-1000℃降至室温，得绝缘化基片；
4)晶界层电容器的制备：利用磁控溅射技术在步骤3)制备的绝缘化基片正、反面镀上Au电极，然后切片，得晶界层电容器。
优选的，所述步骤3)中氧化剂组分包括：Pb3O4、Bi2O3、CuO、B2O3和Al2O3，分别按重量比15-25：30-40：20-30：8-12：8-12进行混合得到氧化剂浆料。
优选的，所述步骤1)中Dy2O3和Ho2O3添加量分别为主料重量的0.4-0.6％。
优选的，所述步骤1)中的消泡剂为正丁醇；分散剂为三油酸甘油酯。
优选的，所述步骤1中添加的消泡剂和分散剂各占主料重量的0.5-1.5％。
优选的，所述步骤2)中N2与H2的比例为11–15):0.5-1.5。
本发明技术原理为：本发明所采两步法制得晶界层电容器，所谓二步法就是基片半导化和绝缘化分开进行。第一步称为半导化，即基片在还原性气氛中和较高烧结温度完成。第二步称为绝缘化，即在半导化基片上涂敷包含受主离子和玻璃化物质的氧化剂，在空气中和较低温度保温以完成氧化剂扩散至晶界，以纳米晶形式析出，该纳米晶形态对提高电容器的介电性能，特别是绝缘电阻值起到了明显作用，同时也增大了耐压值。
经由上述的技术方案可知，与现有技术相比，本发明有有益效果如下：
1、与现有技术相比，在第一步烧结制备半导化基片中，本发明除选用SrCO3和TiO2作为主料外，还适当添加了少量三价重稀土氧化物Dy2O3与Ho2O3作为施主掺杂以促进SrTiO3半导化。
2、本发明在第二步绝缘化中，采用Bi2O3、CuO、B2O3、PbO和Al2O3作为氧化剂在950-1150℃保温2～3小时，待氧化剂完成扩散反应后，以极缓慢速度从950-1150℃降至700-1000℃，然后再经自然降温从900℃降至室温得到绝缘化基片。之后利用磁控溅射技术将绝缘化瓷片镀上Au电极。其主要优点在于选用三价重稀土氧化物Dy2O3与Ho2O3作为施主掺杂制备半导化基片。在第二步绝缘化中，选用Al2O3作为氧化剂的有效组成部分，以极缓慢速度从950-1150℃绝缘化温度降至一中间温度(700-1000℃)。在此过程中，氧化剂以纳米晶形式在晶界处析出，该结晶形态对提高晶界层电容器介电性能，特别是绝缘电阻起到了明显作用。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。
图1为实施例1制备的晶界层电容器的晶界处在不同放大倍数下的TEM图。
图2为实施例1制备的晶界层电容器晶界处EDS能谱。
图3为实施例1制备的晶界层电容器晶界处Sr、Ti、O、Bi、Pb、Cu、Al的含量(根据图2能谱数据中计算得出)，B由于原子序数较小，未能被所用设备探测到。
图4为实施例1制备的晶界层电容器室温介电常数测试结果。
图5为实施例1制备的晶界层电容器室温介电损耗测试结果。
图6为实施例1和实施例2(对比例)制备的晶界层电容器室温绝缘电阻值。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
晶界层电容器的制备方法具体如下：
(1)用流延法制备生坯：以SrCO3和TiO2为主料，添加少量三价重稀土离子氧化物Dy2O3和Ho2O3作为施主掺杂，添加量分别为主料重量的0.5％。加入消泡剂(正丁醇)和分散剂三油酸甘油酯)各取主料重量的1％，经行星式球磨机球磨16h后得到流延浆料。再经流延、干燥、叠片和热压(流延厚60um,叠4层，压强100MP)后得到长、宽45mmx45mm，厚0.25mm的正方形基片生坯。
(2)基片半导化：将步骤(1)制备的基片生坯在空气中600℃下进行0.5h的排胶处理，排胶后的基片在N2/H2还原气氛中，温度为1300℃进行2h烧结后得到半导化基片。
(3)基片绝缘化：采用本发明制备的氧化剂涂覆浆料，氧化剂成分为Pb3O4、Bi2O3、CuO、B2O3和Al2O3，分别按重量比20：35：25：10：10进行混合得到氧化剂浆料，使用匀胶机将氧化剂均匀涂满基片表面，再将涂好氧化剂的基片在1050℃，保温2.5h后，以极缓慢速度0.2℃/min，经5.0h降至900℃，再通过自然降温从900℃降至室温。
(4)利用磁控溅射技术在绝缘化基片正、反面镀上Au电极，得到可测试介电性能的样品；
(5)切片：将镀好Au电极，长、宽分别为45x45cm的大瓷片切成1×1mm样品，最后得到晶界层电容器。
参见图1，不同放大倍数下STO晶界层电容器的晶界处TEM图，从图中可以看出晶界宽约50nm，氧化剂和绝缘化物质在晶界处以纳米晶结构存在。
实施例2
进一步地，设置对比例，作为实施例1的对比，其它步骤均相同，仅是步骤(3)的降温步骤不同，具体方法为：以相同氧化剂和相同扩散条件保温后(1050℃，2.5h)，对比例样品以通常速度2.0℃/min，经0.5h降至900℃，再通过自然降温从900℃降至室温。
实施例3
电容器绝缘电阻及介电参数测量
1、绝缘电阻测量
用同惠TH2681型绝缘电阻测试仪进行测试。测量电压为50V，电压加载60s后读取电阻值。
参见图6，测试实施例1以及实施例2制备的样品个数约200个，测试电压为50V。从图6可以看出，实施例1中氧化剂在1050℃退火2.5小时，经0.5时降温至900℃时，样品平均电阻为11.5GΩ。但实施例2经长时间冷却(5.0小时)至900℃时，样品平均电阻大幅提高至1.7GΩ。
2、电容及损耗测量
用安捷伦(AgilentTechnologies)4284A型LCR测试仪测量电容器的电容及损耗，测量电压为1V，测量频率为1MHz。
参见图4，测试电压为1.0V，频率为1MHz，在不同区域选择实施1制备的27个样品进行测量。可以看出介电常数分布均匀，基本稳定在30000左右。样品采用Dy2O3与Ho2O3施主掺杂，选用Bi2O3、CuO、B2O3、PbO和Al2O3作为氧化剂，从绝缘化保温温度1050℃，经极缓慢降温至900℃制得。
参见图5，测试电压1.0V，频率1MHz，在不同区域选择实施1制备的27个样品进行测量，可见样品介电损耗较小，大多数在0.4％以下。样品采用Dy2O3与Ho2O3施主掺杂，选用Bi2O3、CuO、B2O3、PbO和Al2O3作为氧化剂，从绝缘化保温温度1050℃，经极缓慢降温至900℃制得。
实施例4
晶界层电容器的制备方法具体如下：
(1)用流延法制备生坯：以SrCO3和TiO2为主料，添加少量三价重稀土离子氧化物Dy2O3和Ho2O3作为施主掺杂，添加量分别为主料重量的0.4％。加入消泡剂(正丁醇)和分散剂三油酸甘油酯)各取主料重量的1.5％，经行星式球磨机球磨18h后得到流延浆料。再经流延、干燥、叠片和热压(流延厚60um,叠4层，压强100MP)后得到长、宽45mmx45mm，厚0.25mm的正方形基片生坯。
(2)基片半导化：将步骤(1)制备的基片生坯在空气中700℃下进行1h的排胶处理，排胶后的基片在N2/H2还原气氛中，温度为1500℃进行3h烧结后得到半导化基片。
(3)基片绝缘化：采用本发明制备的氧化剂涂覆浆料，氧化剂成分为Pb3O4、Bi2O3、CuO、B2O3和Al2O3，分别按重量比25：40：30：12：12进行混合得到氧化剂浆料，使用匀胶机将氧化剂均匀涂满基片表面，再将涂好氧化剂的基片在1150℃，保温3.5h后，以极缓慢速度0.3℃/min，经7h降至1000℃，再通过自然降温从1000℃降至室温。
(4)利用磁控溅射技术在绝缘化基片正、反面镀上Au电极，得到可测试介电性能的样品；
(5)切片：将镀好Au电极，长、宽分别为45x45cm的大瓷片切成1×1mm样品，最后得到晶界层电容器。
实施例5
晶界层电容器的制备方法具体如下：
(1)用流延法制备生坯：以SrCO3和TiO2为主料，添加少量三价重稀土离子氧化物Dy2O3和Ho2O3作为施主掺杂，添加量分别为主料重量的0.4％。加入消泡剂(正丁醇)和分散剂三油酸甘油酯)各取主料重量的0.5％，经行星式球磨机球磨14h后得到流延浆料。再经流延、干燥、叠片和热压(流延厚60um,叠4层，压强100MP)后得到长、宽45mmx45mm，厚0.25mm的正方形基片生坯。
(2)基片半导化：将步骤(1)制备的基片生坯在空气中500℃下进行0.5h的排胶处理，排胶后的基片在N2/H2还原气氛中，温度为1200℃进行1h烧结后得到半导化基片。
(3)基片绝缘化：采用本发明制备的氧化剂涂覆浆料，氧化剂成分为Pb3O4、Bi2O3、CuO、B2O3和Al2O3，分别按重量比15：30：20：8：8进行混合得到氧化剂浆料，使用匀胶机将氧化剂均匀涂满基片表面，再将涂好氧化剂的基片在950℃，保温1.5h后，以极缓慢速度0.1℃/min，经3h降至700℃，再通过自然降温从700℃降至室温。
(4)利用磁控溅射技术在绝缘化基片正、反面镀上Au电极，得到可测试介电性能的样品；
(5)切片：将镀好Au电极，长、宽分别为45x45cm的大瓷片切成1×1mm样品，最后得到晶界层电容器。
本说明书中各个实施例采用递进的方式描述，每个实施例重点说明的都是与其他实施例的不同之处，各个实施例之间相同相似部分互相参见即可。对于实施例公开的装置而言，由于其与实施例公开的方法相对应，所以描述的比较简单，相关之处参见方法部分说明即可。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (5)

1.一种晶界层电容器的制备方法，其特征在于，包括以下步骤：
1)用流延法制备基片生坯：以SrCO3和TiO2为主料，添加Dy2O3和Ho2O3作为施主掺杂，再加入消泡剂和分散剂，然后球磨14-18h后得到流延浆料，再经流延、干燥、叠片和热压后得到基片生坯；其中，所述Dy2O3和Ho2O3添加量分别为主料重量的0.4-0.6％；
2)基片生坯半导化：将所述步骤1)制备的基片生坯在空气中500-700℃下进行0.5-1.0h的排胶处理，排胶后的基片在N2/H2还原气氛中，温度为1200-1500℃进行1-3h烧结后得到半导化基片；
3)半导化基片绝缘化：将氧化剂均匀涂覆于步骤2)制备的半导化基片表面，再将涂好氧化剂的基片在950-1150℃，保温1.5-3.5h后，以0.1-0.3℃/min降温，经3-7h降至700-1000℃，再通过自然降温从700-1000℃降至室温，得绝缘化基片；其中，所述氧化剂组分包括：Pb3O4、Bi2O3、CuO、B2O3和Al2O3，分别按重量比15-25：30-40：20-30：8-12：8-12进行混合得到氧化剂浆料；
4)晶界层电容器的制备：利用磁控溅射技术在步骤3)制备的绝缘化基片正、反面镀上Au电极，然后切片，得晶界层电容器。
2.根据权利要求1所述的一种晶界层电容器的制备方法，其特征在于，所述步骤1)中的消泡剂为正丁醇；分散剂为三油酸甘油酯。
3.根据权利要求2所述的一种晶界层电容器的制备方法，其特征在于，所述步骤1中添加的消泡剂和分散剂各占主料重量的0.5-1.5％。
4.根据权利要求2所述的一种晶界层电容器的制备方法，其特征在于，所述步骤2)中N2与H2的比例为11–15:0.5-1.5。
5.根据权利要求1所述的一种晶界层电容器的制备方法，其特征在于，所述步骤1)中流延厚度为60um，叠片层数为4层，热压的压强为100MPa ；基片生坯的规格为长、宽45mmx45mm，厚0.25mm。
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