CN1404080A - 温度稳定型的贱金属内电极多层陶瓷电容器介电材料 - Google Patents
温度稳定型的贱金属内电极多层陶瓷电容器介电材料 Download PDFInfo
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- CN1404080A CN1404080A CN02131431A CN02131431A CN1404080A CN 1404080 A CN1404080 A CN 1404080A CN 02131431 A CN02131431 A CN 02131431A CN 02131431 A CN02131431 A CN 02131431A CN 1404080 A CN1404080 A CN 1404080A
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- ceramic capacitor
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- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 20
- 239000003989 dielectric material Substances 0.000 title claims abstract description 14
- 229910052728 basic metal Inorganic materials 0.000 title 1
- 150000003818 basic metals Chemical class 0.000 title 1
- 239000000654 additive Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 11
- 239000000919 ceramic Substances 0.000 claims abstract description 9
- 239000010953 base metal Substances 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004615 ingredient Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 150000003891 oxalate salts Chemical class 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005245 sintering Methods 0.000 abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 abstract 2
- 229910002971 CaTiO3 Inorganic materials 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- -1 SrO2 Chemical compound 0.000 abstract 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 238000009413 insulation Methods 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- MTZOKGSUOABQEO-UHFFFAOYSA-L barium(2+);phthalate Chemical compound [Ba+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O MTZOKGSUOABQEO-UHFFFAOYSA-L 0.000 description 2
- 238000007766 curtain coating Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
本发明公开了属于电容器材料制备技术范围的一种温度稳定型(X7R型)贱金属内电极多层陶瓷电容器材料。它是价格低廉的金属,比如金属Ni、Cu及其合金等作为多层电容器内电极,与主要成份为BaTiO3,添加剂包括CaO、CaTiO3、BaO、SiO2、SrO、MnO2、MgO、Co2O3、Co3O4、Fe2O3、Y2O3以及一种或一种以上的稀土氧化物以及盐类按比例配合而成的陶瓷材料,在以氮气和氢气混合的加湿气体控制的还原气氛中,在1200℃到1350℃的温度范围内进行烧结。获得性能优良的X7R型MLCC材料,材料的室温介电常数可以控制在2000和3500之间,容温变化率≤±15%,室温介电损耗≤2%,陶瓷的晶粒大小可以控制在1000nm范围内,介电损耗小,材料均匀性好,适用于生产大容量、超薄介电层(介电层厚度小于10μm)的多层陶瓷电容器。并且具有高绝缘电阻率,性能稳定。
Description
技术领域
本发明属于电容器材料技术领域,特别涉及一种温度稳定型贱金属内电极多层陶瓷电容器介电材料。
背景技术
随着多种类型的电子设备诸如数码相机、移动电话、笔记本电脑、掌上电脑等移动电子设备的高速发展,小型化和轻型化是必然的趋势,构成这些电子设备的元器件也必须减小体积和重量,以适应电子元件的安装技术转变为表面贴装技术(SMD)的需要,表面贴装技术要求的元器件为片式元器件。多层陶瓷电容器是片式元件中应用最广泛的一类。多层陶瓷电容器(Multilayer CeramicCapacitors)简称MLCC。它是将电极材料与陶瓷坯体以多层交替并联叠合起来,并同时烧成一个整体。根据国际电子工业协会EIA(Electronic IndustriesAssociation)标准,温度稳定(X7R)型MLCC是指以25℃的电容值为基准,在温度从-55到+125℃的范围之内,容温变化率<±15%,介电损耗(DF)≤2.5%。X7R型MLCC按组成分两大类:一类由含铅的铁电体组成,另一类以BaTiO3基非铅系的铁电体组成。而后者由于对环境无污染,并且机械强度及可靠性优于前者,因此非铅系BaTiO3基X7R型MLCC具有广阔的应用前景。
当以钛酸钡为基的多层陶瓷电容器在空气中烧结时,需要使用贵金属(Pt、Au、Pd金属及其合金等)作为内电极。贵金属内电极的成本为多层陶瓷电容器生产成本的30%~70%。因此使用贵金属作为内电极成为降低MLCC成本的障碍。基于降低成本的考虑,使用诸如Ni、Fe、Co等贱金属作为MLCC的内电极,但是当这些贱金属内电极在介电陶瓷材料的常规空气中烧结条件下会发生氧化,因此失去作为内电极的作用。为了防止贱金属内电极在烧结过程中的氧化,必须使用中性或者还原性气氛。同时要保证钛酸钡基介电陶瓷在中性或还原气氛下烧结后不成为半导体,而且有足够的绝缘电阻和优良的介电性能。一般将介电层与内电极相互叠加形成生坯,接着在由N2、H2和水蒸气产生的还原气氛下,在1200℃~1400℃的温度范围内进行烧结,然后在1000℃~1100℃的温度下,在具有10-6atm以上氧分压的气氛中进行退火,以提高陶瓷的抗击穿能力,之后加上端电极。目前,在日本专利JP-A-63-103861,陶瓷材料的基本组成为BaTiO3-MnO-MgO-稀土氧化物。这个组成的绝缘电阻和介电温度系数受钛酸钡主料的晶粒大小影响,因此很难通过控制材料组成来获得温度稳定的介电性能。在美国专利US-005403797A,陶瓷材料的基本组成是BaTiO3-Y2O3-MgO-V2O5。该组成基本满足X7R性能要求,室温介电常数为2500以上,但是烧结温度过高,大于1350℃;介电温度系数较大,在-55℃接近-15%;损耗较大,基本都高于2.0%。因此不适合用于大规模生产。
发明内容
本发明的目的是提供一种制备工艺简便,配方简单可调,烧结工艺易控,具有较高介电常数的温度稳定型贱金属内电极多层陶瓷电容器介电材料,主要由钛酸钡主料和二次添加剂组成,其特征在于:所述主料BaTiO3在配方中所占的摩尔数为94~99%;所述二次添加物的用量占材料总量的1~6mol%。
所述主料钛酸钡的粒度要求在小于1000nm之间。
所述的二次添加剂包括CaTiO3、CaO、BaO、SiO2、SrO、MnO2、MgO、Co2O3、Co3O4、Fe2O3、Y2O3以及一种或一种以上的稀土氧化物Re2O3以及这些氧化物的前驱体;所述的各材料配比为(以摩尔计):CaTiO3:0~1mol%;CaO:0~3mol%;BaO:0.01~2mol%;SiO2:0.1~5mol%;SrO:0~2mol%;MnO2:0.01~3mol%;MgO:0~2mol%;Co2O3:0~2mol%;Co3O4:0~1mol%;Fe2O3:0~1mol%;Y2O3:0~4mol%;Re2O3:0~4mol%。
稀土氧化物Re2O3的前驱体包括碳酸盐、氢氧化物、草酸盐、醋酸盐、硝酸盐。
所述稀土氧化物Re2O3中Re代表:镧系元素镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)。
所述二次添加剂中SiO2、BaO、CaO、和CaTiO3的一部分是以玻璃态的形式作为添加剂的,(BaACa(1-A)O)x·(SiBTi(1-B)O2)(0≤A,B≤1,0.9≤x≤1.1),占陶瓷重量的0~3wt%。
所述玻璃料(BaACa(1-A)O)x·(SiBTi(1-B)O2(0≤A,B≤1,0.9≤x≤1.1)是将SiO2、BaO、CaO、和CaTiO3或相应的前驱体,按照A、B、x的配比进行混合,然后在1000~1200℃下煅烧得到的。
制造MLCC的具体工艺步骤如下:
①将主料钛酸钡与添加剂进行混合,以水为介质,球磨24小时;
②烘干:在70~120℃温度下烘10小时;
③流延成介电层:介电层厚度为10μm或10μm以下;
④与贱金属内电极层相互叠加,制造出生坯;
⑤排胶:在300℃,空气中,保温20个小时;若高于300℃排胶温度的话,可以使用氮气保护;
⑥在还原气氛下烧结:烧结过程中通入N2/H2,同时加湿,将氧分压控制在10-8~10-12atm的范围内;例如:以200℃/小时的速度升温到1250℃,保温时间为2小时;
⑦在弱氧化条件下退火:炉温在800℃~1100℃,保温4小时,氧分压控制在10-5~10-4atm的范围内;
⑧冷却至室温;
⑨端电极工艺:端电极为Cu或Ag,炉温在600℃~800℃,保温1小时,氮气保护,自然冷却后,即得到X7R型内电极为贱金属的多层陶瓷电容介电材料。
本发明的有益效果为按本发明的材料配方,可以在1200℃~1350℃的温度下烧结出性能优异的X7R型MLCC材料。其室温介电常数可以控制在2000~3500之间,满足X7R性能要求,容温在-55℃~+125℃范围内的变化率<±15%,变化率小,介电损耗小,材料均匀性好。适用于生产大容量、超薄介电层(介电层厚度小于10μm)的多层陶瓷电容器。并且具有高绝缘电阻率,性能稳定。
附图说明
图1为实施例1样品的介电常数随温度变化的特性曲线;
图2为实施例1样品的电容变化率随温度变化的曲线;
图3为实施例2样品的介电常数随温度变化的特性曲线;
图4为实施例2样品的电容变化率随温度变化的曲线。
图5为实施例3样品的介电常数随温度变化的特性曲线;
图6为实施例3样品的电容变化率随温度变化的曲线。
具体实施方式
本发明是一种制备工艺简便,配方简单可调,烧结工艺易控,具有较高介电常数的温度温度型贱金属内电极多层陶瓷电容器介电材料,它由粒度小于1000nm的钛酸钡BaTiO3主料所占的摩尔数为94~99%,和二次添加物的用量占材料总量的1~6mol%。其二次添加剂包括CaTiO3、CaO、BaO、SiO2、SrO、MnO2、MgO、Co2O3、Co3O4、Fe2O3、Y2O3以及一种或一种以上的稀土氧化物Re2O3以及这些氧化物的前驱体(包括碳酸盐、氢氧化物、草酸盐、醋酸盐、硝酸盐)。所述的各材料配比为(以摩尔计):CaTiO3:0~1mol%;CaO:0~3mol%;BaO:0.01~2mol%;SiO2:0.1~5mol%;SrO:0~2mol%;MnO2:0.01~3mol%;MgO:0~2mol%;Co2O3:0~2mol%;Co3O4:0~1mol%;Fe2O3:0~1mol%;Y2O3:0~4mol%;Re2O3:0~4mol%。
上述稀土氧化物Re2O3中Re代表:镧系元素镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)。
上述二次添加剂中SiO2、BaO、CaO、和CaTiO3的一部分是以玻璃态的形式作为添加剂的,(BaACa(1-A)O)x·(SiBTi(1-B)O2)(0≤A,B≤1,0.9≤x≤1.1),占陶瓷重量的0~3wt%。该玻璃料是将SiO2、BaO、CaO、和CaTiO3或相应的前驱体(包括碳酸盐、氢氧化物、草酸盐、醋酸盐、硝酸盐)按照A、B、x的配比进行混合,然后在1000~1200℃下煅烧得到的。制造MLCC的具体工艺步骤如下:
①将主料钛酸钡与添加剂进行混合,以水为介质,然后球磨24小时;
②在70~120℃下,烘10小时;
③在流延机上流延成介电层厚度为10μm或10μm以下;
④与贱金属内电极层相互叠加,制造出生坯;
⑤排胶(300℃,空气中,保温20个小时;更高排胶温度的话,可以使用氮气保护);
⑥在还原气氛下烧结(烧结过程中通入N2/H2,同时加湿,将氧分压控制在10-8~10-12atm的范围内)例如:以200℃/小时的速度升温到1250℃;保温时间为2小时;
⑦在弱氧化条件下退火(炉温在800℃~1100℃,保温4小时,氧分压控制在10-5~10-4atm的范围内);
⑧冷却至室温;
⑨端电极工艺(端电极为Cu或Ag,炉温在600℃~800℃,保温1小时,氮气保护)。下面再举实施例进一步说明如下:
实施例1,先按照BaTiO3:96mol%;(晶粒大小为400nm)CaTiO3 0.5mol%;CaO:0.3mol%;SiO2 0.8mol%;SrO:0.3mol%;MnO2:0.2mol%;MgO:0.2mol%;Co2O3:0.2mol%;Y2O3:0.5mol%;Sm2O3:1.0mol%配比称量。然后再加入玻璃料(BaACa(1-A)O)x·(SiBTi(1-B)O2)(A=0.4,B=0.9,x=1.1),占上述混料的2wt%。将上述材料进行混合,球磨,然后干燥。该瓷料流延成膜片,与Ni电极叠加,制成MLCC生坯,排胶后,在还原气氛下烧结(烧结过程中通入N2/H2,同时加湿,将氧分压控制在10-10atm,以200℃/小时的速度升温到1250℃,保温时间为2小时),然后在弱氧化条件下退火(炉温在1100℃,保温4小时,氧分压控制为10-5atm)。之后加上Cu端电极(炉温在700℃,保温1小时,氮气保护)。对多层陶瓷电容其进行性能测试,介电性能参数见表一。图1的曲线给出的是本实施例样品的介电常数随温度变化的特性曲线,图2给出样品的电容变化率随温度变化的曲线。
表1
样品 | 烧结条件 | 介点常数 | TCC(%) | 介点常数(25℃) | 介点常数 | TCC(%) | TGδ(25℃)(%) |
-55℃ | 125℃ | ||||||
1 | 1250℃ | 2509 | -11.9 | 2850 | 3100 | 8.7 | 0.89 |
实施例2,先按照BaTiO3:95.2mol%;(晶粒大小为200nm)CaTiO3:0.7mol%;CaO:0.4mol%;SiO2:0.8mol%;SrO:0.3mol%;MnO2:0.3mol%;MgO:0.3mol%;Co2O3:0.2mol%;Y2O3:0.8mol%;Lu2O3:1.0mol%配比称量。然后再加入玻璃料(BaACa(1-A)O)x·(SiBTi(1-B)O2)(A=0.5,B=0.8,x=1),占上述混料的1.5wt%。将上述材料进行混合,球磨,然后干燥。该瓷料流延成膜片,与Ni电极叠加,制成MLCC生坯,排胶后,在还原气氛下烧结(烧结过程中通入N2/H2,同时加湿,将氧分压控制在10-9atm,以200℃/小时的速度升温到1200℃,保温时间为2小时),然后在弱氧化条件下退火(炉温在1100℃,保温4小时,氧分压控制为10-5atm)。之后加上Cu端电极(炉温在700℃,保温1小时,氮气保护)。对多层陶瓷电容其进行性能测试,介电性能参数见表二。图3的曲线给出的是本实施例样品的介电常数随温度变化的特性曲线,图4给出样品的电容变化率随温度变化的曲线。
表2
样品 | 烧结条件 | 介点常数 | TCC(%) | 介点常数(25℃) | 介点常数 | TCC(%) | TGδ(25℃)(%) |
-55℃ | 125℃ | ||||||
2 | 1200℃ | 1895 | -9.6 | 2097 | 2088 | -0.4 | 0.92 |
实施例3,先按照BaTiO3:95mol%;(晶粒大小为500nm)CaTiO3:0.7mol%;CaO:0.4mol%;SiO2:0.7mol%;SrO:0.3mol%;MnO2:0.5mol%;MgO:0.4mol%;Co2O3:0.2mol%;Y2O3:0.7mol%;Gd2O3:1.1mol%配比称量。然后再加入玻璃料(BaACa(1-A)O)x·(SiBTi(1-B)O2)(A=0.5,B=0.9,x=1.1),占上述混料的2.5wt%。将上述材料进行混合,球磨,然后干燥。该瓷料流延成膜片,与Ni电极叠加,制成MLCC生坯,排胶后,在还原气氛下烧结(烧结过程中通入N2/H2,同时加湿,将氧分压控制在10-9atm,以200℃/小时的速度升温到1280℃,保温时间为2小时),然后在弱氧化条件下退火(炉温在1100℃,保温4小时,氧分压控制为10-5atm)。之后加上Cu端电极(炉温在700℃,保温1小时,氮气保护)。对多层陶瓷电容其进行性能测试,介电性能参数见表三。图5的曲线给出的是本实施例样品的介电常数随温度变化的特性曲线,图6给出样品的电容变化率随温度变化的曲线。
表3
样品 | 烧结条件 | 介点常数 | TCC(%) | 介点常数(25℃) | 介点常数 | TCC(%) | TGδ(25℃)(%) |
-55℃ | 125℃ | ||||||
3 | 1280℃ | 2771 | -10.6 | 3100 | 3503 | 13 | 0.71 |
另外,陶瓷材料的绝缘电阻和击穿电压测试结果见表4。
表4
样品编号 | 烧结条件 | 绝缘电阻率(1012×Ω·cm) | 击穿场强(KV/mm) |
1 | 1250℃-2h | 10.0 | 6.13 |
2 | 1200℃-2h | 15.5 | 8.21 |
3 | 1280℃-2h | 14.9 | 7.78 |
在1200~1350℃的温度范围内,制备了满足X7R性能指标要求的钛酸钡基贱金属内电极MLCC瓷料。MLCC的室温介电常数可以控制在2000到3500之间,容温变化率小于±15%,介电损耗小于2.5%。绝缘电阻率约为1013Ω·cm,击穿电压大于5KV/mm。利用本发明的配方和工艺,可获得烧结温度低,性能可调,烧结温度范围宽,稳定性和再现性良好的钛酸钡基X7R型MLCC材料。而且材料的晶粒均匀,晶粒大小可以控制在100nm~1000nm的范围内。可以应用于大容量,超薄层(介电层厚度小于10μm)多层陶瓷电容器,是一种具有广泛应用前景的MLCC材料。
上述图1~图6为对应于实施例1~3的各样品介电常数的温度特性曲线和电容随温度变化率的温度曲线。测试温度为-60℃~130℃。
表1~表3中各参数代表的意义如下:TCC(-55℃):-55℃时容温变化率;TCC(125℃):125℃时容温变化率;tgδ(25℃):室温时介电损耗;TCC(T)%=100×(ε(T)-ε(25℃))/ε(25℃):容温变化率。
Claims (7)
1.一种温度稳定型贱金属内电极多层陶瓷电容器介电材料,主要由钛酸钡主料和二次添加剂组成,其特征在于:所述主料BaTiO3在配方中所占的摩尔数为94~99%;所述二次添加物的用量占材料总量的1~6mol%。
2.根据权利要求1所述温度稳定型贱金属内电极多层陶瓷电容器介电材料,其特征在于:所述主料钛酸钡的粒度要求小于1000nm。
3.根据权利要求1所述温度稳定型贱金属内电极多层陶瓷电容器介电材料,其特征在于:所述的二次添加剂包括CaTiO3、CaO、BaO、SiO2、SrO、MnO2、MgO、Co2O3、Co3O4、Fe2O3、Y2O3以及一种或一种以上的稀土氧化物Re2O3以及这些氧化物的前驱体;所述的各材料配比为(以摩尔计):CaTiO3:0~1mol%;CaO:0~3mol%;BaO:0.01~2mol%;SiO2:0.1~5mol%;SrO:0~2mol%;MnO2:0.01~3mol%;MgO:0~2mol%;Co2O3:0~2mol%;Co3O4:0~1mol%;Fe2O3:0~1mol%;Y2O3:0~4mol%;Re2O3:0~4mol%。
4.根据权利要求3所述温度稳定型贱金属内电极多层陶瓷电容器介电材料,其特征在于:稀土氧化物Re2O3的前驱体包括碳酸盐、氢氧化物、草酸盐、醋酸盐、硝酸盐。
5.根据权利要求3所述温度稳定型贱金属内电极多层陶瓷电容器介电材料,其特征在于:所述稀土氧化物Re2O3中Re代表:镧系元素镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)。
6.根据权利要求3所述温度稳定型贱金属内电极多层陶瓷电容器介电材料,其特征在于:所述二次添加剂中SiO2、BaO、CaO、和CaTiO3的一部分是以玻璃态的形式作为添加剂的,玻璃料:(BaACa(1-A)O)x·(SiBTi(1-B)O2)(O≤A,B≤1,0.9≤x≤1.1),占陶瓷重量的0~3wt%。
7.根据权利要求6所述温度稳定型贱金属内电极多层陶瓷电容器介电材料,其特征在于:所述玻璃料(BaACa(1-A)O)x·(SiBTi(1-B)O2)(0≤A,B≤1,0.9≤x≤1.1)是将SiO2、BaO、CaO、和CaTiO3或相应的前驱体,按照A、B、x的配比进行混合,然后在1000~1200℃下煅烧得到的。
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CN114014649B (zh) * | 2021-12-13 | 2023-07-25 | 深圳先进电子材料国际创新研究院 | 共掺杂钛酸钡陶瓷介电材料、制备方法及其应用 |
CN115504781A (zh) * | 2022-08-24 | 2022-12-23 | 深圳先进电子材料国际创新研究院 | 一种宽温稳定型陶瓷介电材料及其制备方法和应用 |
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