CN114956805A - 一种巨介电ccto陶瓷的还原-再氧化制备方法 - Google Patents
一种巨介电ccto陶瓷的还原-再氧化制备方法 Download PDFInfo
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- 238000005245 sintering Methods 0.000 claims abstract description 26
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
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- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 19
- 238000007873 sieving Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
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Abstract
本发明涉及电子陶瓷元器件领域,公开了一种巨介电CCTO陶瓷的还原‑再氧化制备方法,配方中添加少量BN液相烧结助剂以降低烧结温度,同时,配方中可额外添加包含Al、Mg、Ni等元素中的一种或多种元素,以调节介电常数与介电损耗;本发明首先采用惰性气体或惰性气体与氢气的混合气体烧结,同时,结合埋粉或密封烧结,以阻止CCTO陶瓷材料分解并成瓷;然后,结合低温再氧化处理,获得的CCTO陶瓷具备巨介电、低损耗的良好电学性能;本发明所采用的还原‑再氧化法制备工艺,可推进基于CCTO陶瓷材料的多层片式元件采用贱金属Ni/Cu替代贵金属Pd/Ag作为内电极,有利于降低多层片式元件的制作成本,适于大规模生产。
Description
技术领域
本发明涉及电子陶瓷元器件领域,具体涉及一种巨介电CCTO陶瓷的还原-再氧化制备方法。
背景技术
21世纪以来,电子信息产业得到了飞速发展,产品设计日新月异,集成度越来越高,可靠性要求日益严苛。作为电子信息产业基础,集成电路时刻面临着严峻的瞬态过压威胁,导致半导体器件失效或损坏难题。尤其是随着芯片集成度的不断提高,高频、高压浪涌的危害日益显著,浪涌保护设计越来越关键和重要。如今,面临复杂的高频、高压浪涌威胁,简单的集成压敏电阻的电路设计已难以获得可靠的浪涌保护。采用压敏-电容联合应用的保护电路设计,已然成为克服高频、高压浪涌的有效解决方案。
集压敏效应与电容效应于一体的多功能CCTO陶瓷受到了广泛地关注。其介电常数可达104以上,同时,Chung在Nature Materials上提出其压敏系数高达900以上。自1967年被报道以来,研究人员已构筑了系列巨介电、低损耗以及高压敏性能的CCTO陶瓷体系,研制出基于贵金属Ag/Pd内电极的多层片式陶瓷电容器(MLCC)原型器件。贵金属Ag/Pd内电极的应用必然致使生产成本攀升,内电极贱金属化是实现低成本化的关键所在,是多层片式元件发展史上的里程碑式技术突破。
贱金属Ni/Cu内电极必须采用惰性气氛或惰性气体与氢气的混合气氛烧结以避免氧化,然而,惰性气氛或惰性气体与氢气的混合气氛烧结可致使CCTO陶瓷材料出现分解现象,巨介电与压敏性能消失。
发明内容
本发明的目的在于提供一种巨介电CCTO陶瓷的还原-再氧化制备方法,解决以下技术问题:
通过抑制CCTO陶瓷在还原气氛中分解,实现惰性气氛或者惰性气氛与氢气的混合气氛烧结CCTO陶瓷,获得的还原的CCTO陶瓷需经过再氧化处理以进一步降低介电损耗;采用还原-再氧化工艺制备的多层片式CCTO陶瓷可使用贱金属Ni/Cu作为内电极,可降低元件制作成本,适于大规模生产。
本发明的目的可以通过以下技术方案实现:
一种巨介电CCTO陶瓷的还原-再氧化制备方法,包括以下步骤:
S1、将CaCO3、CuO、TiO2以及Bi2O3按化学式Ca1-xBixCu3Ti4-yO12称取,其中0.02≤x≤0.5,0≤y≤0.2,加去离子水进行球磨,
将所得浆料烘干、过筛得到粉体;
S2、将S1中获得的粉体在750℃-950℃下空气气氛进行预烧,根据化学式Ca1- xBixCu3Ti4-yO12+zBN称取BN,其中0≤z≤0.2,再次加去离子水进行球磨,将所得浆料烘干、过筛得到第二粉体;
S3、向S2获得的第二粉体中加入PVA,研磨、过筛并压片成型,获得的生坯在空气气氛中500℃-600℃下进行排胶;
S4、将S3获得的生坯在惰性气体或惰性气体与氢气的混合气体中烧结,烧结温度在900℃-1100℃,获得还原的CCTO陶瓷;
S5、将S4获得的还原的CCTO陶瓷,在氧气或空气气氛中400℃-850℃下进行再氧化处理,获得巨介电CCTO陶瓷。
作为本发明进一步的方案,所述S1中还加入包含Al、Ni、Mg元素中任意一种元素组成的化合物,加入总量不超过混合物的40mol%。
作为本发明进一步的方案,所述S4中需要结合埋粉或密封烧结以形成富铜气氛。
一种巨介电CCTO陶瓷,由上述方法制备,所述巨介电CCTO陶瓷的组成为:
Ca1-xBixCu3Ti4-yO12+zBN
其中,0.02≤x≤0.5,0≤y≤0.2,0≤z≤0.2。
本发明的有益效果:
(1)通过抑制CCTO在低氧分压烧结条件下分解现象,实现烧结气氛从传统空气气氛转变为惰性气氛或者惰性气氛与氢气的混合气氛;采用还原-再氧化工艺制备的多层片式CCTO陶瓷可采用贱金属Ni/Cu内电极替换贵金属Ag/Pd内电极,有效地降低元件制备成本;
(2)在惰性气氛或者惰性气氛与氢气的混合气氛中完成烧结,同时向CCTO粉体中加入BN,能有效促进CCTO在低温烧结过程中成瓷;
(3)首先在惰性气氛或者惰性气氛与氢气的混合气氛中完成烧结,然后在空气气氛中在较低温度下进行热处理,降低巨介电CCTO陶瓷介电损耗;CCTO陶瓷的介电常数可达104以上,介电损耗可低至0.1。
附图说明
图1是本发明的实例1-9样品在高纯N2气氛中1050℃烧结后的XRD图;
图2是本发明的实例1-9样品在100Hz-1MHz条件下,介电常数与介电损耗;
图3是本发明的实例10-13样品在100Hz-1MHz条件下,介电常数与介电损耗;
图4是本发明的实例14-17样品在100Hz-1MHz条件下,介电常数与介电损耗;
图5是本发明的实例18-21样品在100Hz-1MHz条件下,介电常数与介电损耗。
具体实施方式
下面将结合说明书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作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
本发明涉及的CCTO陶瓷材料的主要组成为:Ca1-xBixCu3Ti4-yO12+zBN,其中,0.02≤x≤0.5,0≤y≤0.2,0≤z≤0.2。
通过固相法合成CCTO陶瓷粉体,经压片成型、排胶。将CCTO生坯置于惰性气氛或惰性气氛与氢气的混合气氛中烧结,烧结过程要结合埋粉或密封烧结,获得的还原的CCTO陶瓷须在空气中再氧化处理,依次包括下述步骤:
S1、将CaCO3、CuO、TiO2以及Bi2O3按化学式Ca1-xBixCu3Ti4-yO12称取(0.02≤x≤0.5,0≤y≤0.2),加去离子水进行球磨,将所得浆料烘干、过筛得到粉体。
S2、将S1获得的粉体在750℃-950℃下空气气氛进行预烧,按化学式Ca1- xBixCu3Ti4-yO12+zBN称取适量的BN(0≤z≤0.2),加入预烧后的CCTO粉体,再次加去离子水进行球磨,将所得的浆料烘干、过筛得到粉体。
S3、向步骤S2获得的粉体中加入PVA,研磨、过筛并压片成型,获得的生坯在空气气氛中500℃-600℃下进行排胶。
S4、将步骤S3获得的生坯在惰性气体或惰性气体与氢气的混合气体中烧结,同时,需要结合埋粉或密封烧结以形成富铜气氛,烧结温度在900℃-1100℃。
S5、将步骤S4获得的还原的CCTO陶瓷,在氧气或空气气氛中400℃-850℃下进行再氧化处理,获得巨介电CCTO陶瓷。
在本发明的另一个实施例中,还额外向步骤S1所述混合物中加入包含Al、Ni、Mg等元素中任意一种元素组成的化合物,加入总量不超过所述混合的40mol%。
实施例1-9
实施例1-9中,CCTO陶瓷材料的主要组成为:Ca1-xBixCu3Ti4-yO12+zBN,其中,x=0、0.02、0.04、0.06、0.08、0.10、0.12、0.14、0.16,y=x/4,z=0.03。初始原材料选自CaCO3、CuO、TiO2、Bi2O3。
材料制备按以下实验的工艺步骤进行:
S1、按上述化学式称取CaCO3、CuO、TiO2以及Bi2O3,加去离子水球磨2小时,将所得浆料烘干、过筛得到粉体。
S2、将步骤S1获得的粉体在850℃空气气氛中预烧4小时,称3mol%的BN,加入预烧后的CCTO粉体,再次加去离子水球磨2小时,将所得的浆料烘干、过筛得到粉体。
S3、向步骤S2获得的粉体中加入5wt%的PVA粘合剂,研磨、过筛并压片成型,获得的生坯在空气气氛中550℃下排胶4小时。
S4、将步骤S3获得的生坯掩埋于相同组份的CCTO粉体中,在高纯N2气氛中烧结,烧结温度为1150℃,烧结时间为2小时。还原的样品XRD分析如图1所示。
S5、将步骤S4获得的CCTO陶瓷,置于空气气氛中800℃下再氧化2小时。
在获得的CCTO陶瓷上下两面涂铟镓合金电极,测试介电常数与介电损耗。
表1实施例1-9材料在1kHz条件下性能指标。
表1
在100Hz-1MHz条件下,实施例1-9材料的性能如图2所示。
实施例1-9说明了Bi掺杂的CCTO陶瓷在经过还原气氛烧结并进行再氧化处理之后,仍然具有巨介电性能;适量的Bi掺杂可有效的降低CCTO陶瓷的介电损耗。
实施例10-13
实施例10-13中,CCTO陶瓷材料的主要组成为:Ca1-xBixCu3Ti4-yO12+zBN,其中,x=0.06,y=0.015,z=0.03,同时,还额外向上述混合物中添加0.05mol、0.10mol、0.2mol、0.3mol的含镍元素的氧化物,初始原材料选自CaCO3、CuO、TiO2、Bi2O3以及NiO。
材料制备的实验工艺步骤与实施例1-9中的步骤S1-S5相同。
在获得的CCTO陶瓷上下两面涂铟镓合金电极,测试介电常数与介电损耗。
表2实施例10-13材料在1kHz条件下的性能指标。
表2
在100Hz-1MHz条件下,实施例10-13材料的性能如图3所示。
实施例10-13结果表明0.05mol与0.1mol的Ni掺杂可进一步降低所获得的CCTO陶瓷的介电损耗。
实施例14-17
实施例14-17中,CCTO陶瓷材料的主要组成为:Ca1-xBixCu3Ti4-yO12+zBN,其中,x=0.06,y=0.015,z=0.03,同时,还额外向上述混合物中添加0.1mol、0.2mol、0.3mol、0.4mol的镁氧化物,初始原材料选自CaCO3、CuO、TiO2、Bi2O3以及MgO。
材料制备的实验工艺步骤与实施例1-9中的步骤(1)-(5)相同。
在获得的CCTO陶瓷上下两面涂铟镓合金电极,测试介电常数与介电损耗。
表3实施例14-17材料在1kHz条件下的性能指标。
表3
在100Hz-1MHz条件下,实施例14-17材料的性能如图4所示。
实施例14-17结果表明掺杂Mg元素可显著提高还原-再氧化工艺制备的CCTO陶瓷的介电常数。
实施例18-21
实施例18-21中,CCTO陶瓷材料的主要组成为:Ca1-xBixCu3Ti4-yO12+zBN,其中,x=0.1,y=0.025,z=0.03,同时,还额外向上述混合物中添加0.010mol、0.2mol、0.3mol、0.4mol的铝氧化物,初始原材料选自CaCO3、CuO、TiO2、Bi2O3以及Al2O3。
材料制备的实验工艺步骤与实施例1-9中的步骤(1)-(5)相同。
在获得的CCTO陶瓷上下两面涂铟镓合金电极,测试介电常数与介电损耗。
表4实施例18-21材料在1kHz条件下的性能指标。
表4
在100Hz-1MHz条件下,实施例18-21材料的性能如图5所示。
实施例18-21结果表明Al掺杂可有效降低还原-再氧化工艺制备的CCTO陶瓷的介电损耗,1kHz条件下,介电损耗可低至0.105。
以上对本发明的一个实施例进行了详细说明,但所述内容仅为本发明的较佳实施例,不能被认为用于限定本发明的实施范围。凡依本发明申请范围所作的均等变化与改进等,均应仍归属于本发明的专利涵盖范围之内。
Claims (4)
1.一种巨介电CCTO陶瓷的还原-再氧化制备方法,其特征在于,包括以下步骤:
S1、将CaCO3、CuO、TiO2以及Bi2O3按化学式Ca1-xBixCu3Ti4-yO12称取,其中0.02≤x≤0.5,0≤y≤0.2,加去离子水进行球磨,将所得浆料烘干、过筛得到粉体;
S2、将S1中获得的粉体在750℃-950℃下空气气氛进行预烧,根据化学式Ca1- xBixCu3Ti4-yO12+zBN称取BN,其中0≤z≤0.2,再次加去离子水进行球磨,将所得浆料烘干、过筛得到第二粉体;
S3、向S2获得的第二粉体中加入PVA,研磨、过筛并压片成型,获得的生坯在空气气氛中500℃-600℃下进行排胶;
S4、将S3获得的生坯在惰性气体或惰性气体与氢气的混合气体中烧结,烧结温度在900℃-1100℃,获得还原的CCTO陶瓷;
S5、将S4获得的还原的CCTO陶瓷,在氧气或空气气氛中400℃-850℃下进行再氧化处理,获得巨介电CCTO陶瓷。
2.根据权利要求1所述的一种巨介电CCTO陶瓷的还原-再氧化制备方法,其特征在于,所述S1中还包含Al、Ni、Mg元素中任意一种元素组成的化合物,加入总量不超过混合物的40mol%。
3.根据权利要求1所述的一种巨介电CCTO陶瓷的还原-再氧化制备方法,其特征在于,所述S4中需要结合埋粉或密封烧结以形成富铜气氛。
4.一种巨介电CCTO陶瓷,由权利要求1-3任一所述的巨介电CCTO陶瓷的还原-再氧化制备方法制备,其特征在于,所述巨介电CCTO陶瓷的组成为:
Ca1-xBixCu3Ti4-yO12+zBN
其中,0.02≤x≤0.5,0≤y≤0.2,0≤z≤0.2。
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