WO2011076090A1 - 一种与铜内电极匹配的抗还原性高频低温烧结陶瓷介质材料 - Google Patents

一种与铜内电极匹配的抗还原性高频低温烧结陶瓷介质材料 Download PDF

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WO2011076090A1
WO2011076090A1 PCT/CN2010/079974 CN2010079974W WO2011076090A1 WO 2011076090 A1 WO2011076090 A1 WO 2011076090A1 CN 2010079974 W CN2010079974 W CN 2010079974W WO 2011076090 A1 WO2011076090 A1 WO 2011076090A1
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internal electrode
dielectric material
mol
ceramic dielectric
sintering
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PCT/CN2010/079974
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English (en)
French (fr)
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宋蓓蓓
宋永生
莫方策
李娟�
王孝国
郭精华
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广东风华高新科技股份有限公司
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Priority to JP2012514341A priority Critical patent/JP5442114B2/ja
Priority to US13/377,499 priority patent/US8709962B2/en
Publication of WO2011076090A1 publication Critical patent/WO2011076090A1/zh

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Definitions

  • the invention relates to a ceramic dielectric material and a preparation method of the obtained component, in particular to a conformity
  • multi-layer chip ceramic capacitors (hereinafter referred to as MLCC) have basically achieved bismuth metallization, and more than 80% of MLCCs use ruthenium metal internal electrode materials (mainly nickel) instead of palladium silver internal electrode materials, which can effectively reduce about 40 % production cost.
  • ruthenium metal internal electrode materials mainly nickel
  • palladium silver internal electrode materials which can effectively reduce about 40 % production cost.
  • copper electrodes has been put on the road, compared to other base metals, copper not only has a price advantage, but more importantly, in the high frequency field, copper's electrical performance is better.
  • the technical problem to be solved by the present invention is to provide a ceramic dielectric material for the internal electrode capacitor of the anti-reduction copper which meets the requirements of COG ceramic dielectric properties, high material dispersibility, good molding process, and meets RoSH regulations.
  • an anti-reduction copper internal electrode high-frequency low-temperature sintering ceramic dielectric material which is composed of a main crystalline phase, a modifying additive, a sintering flux, and the structural form of the main crystalline phase is Mg. x Ba( 1-x )Zr y Si (1 0 3 , wherein 0.8 ⁇ 0.95, 0.055£y3 ⁇ 4S0.2, the modifying additive is Mn0 2 , CaO, Li 2 0, Bi 2 0 3 , One or more of Ti0 2 ; the sintering flux is one or more of B 2 O 3 , Si0 2 , ZnO, CuO, K 2 0, BaO.
  • the above-mentioned anti-reduction copper internal electrode high-frequency ceramic dielectric material is characterized in that: in terms of mole percent, the main crystalline phase is 80 to 95 mol%, the modifying additive is 1.2 to 10 mol%, and the sintering flux is 2.5 to 18 mol%.
  • the composition of the modified additive in the entire anti-reduction copper internal electrode ceramic high frequency ceramic dielectric material is Mn0 2 0.2 ⁇ 0.5mol%, CaO 0 ⁇ : 1.0 mol%, Li 2 0 1.0 ⁇ 3.0 mol% , Bi 2 0 3 0 to 5.0 mol%, Ti0 2 0 to 1.0 mol%.
  • composition of the sintering flux in the high-frequency low-temperature sintering ceramic dielectric material of the entire anti-reduction copper internal electrode is B 2 0 3 1.0-3.0 mol%, Si0 2 0-6.0 mol%, ZnO 1.5 ⁇ 6.0 mol%, CuO 0 to 1.0 mol%, K 2 0 0 to: 1.0 mol%, BaO 0 to 1.0 mol%.
  • the principal component selects a composite having good high frequency performance.
  • the composite has a low dielectric constant, a low dielectric loss tangent, and a near-linear dielectric-temperature characteristic, which all ensure that the material of the present invention is made of MLCC with excellent electrical properties from the host material.
  • the addition of the modified additive material can keep the dielectric constant of the material at about 10, and adjust the temperature coefficient of the ceramic dielectric material so that the dielectric-temperature characteristics are nearly linear; at the same time, it can suppress the abnormality of the ceramic grains. Growth, uniform grain growth, which plays a good role in improving the compressive strength of the dielectric material, and finally makes the MLCC obtained by the present invention highly reliable.
  • One of the main functions of the sintering flux is to reduce the sintering temperature of the ceramic material of the present invention, so that the material can be densely sintered at a temperature of less than 1100 ° C, and the sintered ceramic body has uniform grain growth and high density, which further ensures The finished MLCC has high reliability.
  • the invention adopts a reducing atmosphere for sintering
  • the non-ferroelectric copper electrode dielectric ceramic of the system has a sintering temperature lower than 1100 ° C.
  • the porcelain material can be matched with the copper (Cu) internal electrode paste, and the porcelain material has superior performance.
  • MLCC ceramic material is prepared according to a conventional porcelain production process, including porcelain slurry preparation, production of a dielectric film, alternating overprinting of internal electrodes and dielectric layers, and drying of the compact. , lamination, cutting, debinding, sintering, chamfering, capping, burning end process. That is, a solvent such as an organic binder and ethanol is added in the production process of a sheet type MLCC to form a slurry, and the slurry is cast into a film sheet, and a copper Cu inner electrode is printed on the film, and the required number of layers are alternately laminated.
  • a solvent such as an organic binder and ethanol
  • the sintering temperature of the product is low, the requirements on the process equipment are simple, the particle size distribution of the ceramic dielectric material is uniform, the grain growth of the ceramic body in the sintering is uniform and compact, and the electrical performance of the MLCC product is excellent.
  • the gist of the present invention is to use MgxBad ⁇ ZrySi ⁇ yPs system as the main crystal phase of the material, adding a modifying additive to adjust the performance, and adding a sintering flux to help reduce the sintering temperature, and adopting a conventional process to prepare a desired powder, and obtaining a conformity COG porcelain dielectric properties, high material dispersibility, low-temperature sintering ceramic dielectric materials with good molding process, and low temperature, uniform grain growth and compactness in the production of MLCC products, no defects or small defects.
  • the content of the present invention will be further described in detail below with reference to the embodiments. The contents mentioned in the examples are not intended to limit the invention, and the material formulation selection can be adapted to the local conditions without substantial influence on the results.
  • an anti-reduction copper high-frequency low-temperature sintering ceramic dielectric material consisting of a main crystalline phase, a modifying additive, and a sintering flux
  • the structural formula of the main crystalline phase is M gx Ba (1 -x) Zr y Si (1-y) 0 3 , wherein 0.8 x 0.95, 0.05 ⁇ y ⁇ 0.2
  • the modifying additive is Mn0 2 , CaO, Li 2 0, Bi 2 0 3 , Ti0 2
  • the sintering aid is one or more of 3 ⁇ 40 3 , SiO 2 , ZnO, CuO, K 2 0, BaO.
  • a high-frequency low-temperature sintering ceramic dielectric material for anti-reduction copper internal electrodes using a raw material with a purity of 99.5% or more, and a mixing ratio of 0.8 mol Mg(OH) 2 , 0.8 mol Si0 2 , 0.2 mol BaC0 3 and B 0.2 mol Zr0 2
  • the ball was evenly milled, and the mixture was calcined at a temperature of 115 CTC for 3 hours to obtain a main crystal phase of Mgo. 8 Bao. 2 Sio. 8 Zro. 20 3 material.
  • the modifying additive and the sintering aid as shown in Table 1 were added in a predetermined ratio.
  • Table 1 Main crystal phase, modified additive, sintering flux formulation
  • the ceramic medium porcelain material is prepared according to the ceramic material production process commonly used by those skilled in the art, and then the organic binder and the solvent such as ethanol are added according to the common MLCC production process to form a slurry, and the slurry is formed.
  • the material is cast into a film sheet, and a copper Cu inner electrode is printed on the film, and the required number of layers are alternately laminated to form a green MLCC chip, and then the green MLCC chip is heat-treated at a temperature of 200 to 300 ° C to exclude organic bonding. Agents and solvents.
  • the outer electrode is heat treated within the range.
  • the MLCC product can be obtained by a process such as electroplating.
  • the MLCC product has the characteristics of stable capacity and good performance. Test the insulation capacity of the MLCC product at ⁇ , 1.0V (AC) at room temperature 25 °C using HP4278 bridge. Apply insulation voltage of 100V DC for 10 seconds using SF2512 fast insulation machine. Low temperature box, between -55 ⁇ +125°C, test dielectric constant-temperature coefficient; use HP4991A to test the frequency characteristics of this MLCC product; product performance test parameters such as MLCC test corresponding to material formula 1 ⁇ 10 of Table 2 parameter.
  • An anti-reduction copper internal electrode high-frequency low-temperature sintering ceramic dielectric material adopting a raw material with a purity of 99.5% or more, and 0.9 mol of Mg(OH) 2 , 0.9 mol of Si0 2 , O.lmol of BaC 3 3 and 0.1 mol of Zr0 2
  • the mixing ratio, ball milling was uniform, and the mixture was calcined at a temperature of 1150 ° C for 3 hours to obtain a main crystal phase of Mgo.gBao.iSio.gZrdOs material.
  • the modifying additive and the sintering aid as shown in Table 3 were added in a predetermined ratio.
  • Table 3 Composition of main crystalline phase, modified additive, and sintering flux formulation
  • a high-frequency low-temperature sintering ceramic dielectric material for anti-reduction copper internal electrodes using a raw material with a purity of 99.5% or more, with a mixture of 0.95 mol Mg(OH) 2 , 0.95 mol Si0 2 , 0.05 mol BaC0 3 and 0.05 mol Zr0 2 The ratio was uniform, and the mixture was calcined at a temperature of 1150 ° C for 3 hours to obtain a main crystal phase of Mgo.95Bao.05Sio.95Zro.05O3. Then, the modifying additive and the sintering aid as shown in Table 5 were added in a predetermined ratio.
  • Table 5 Composition of main crystalline phase, modified additive, sintering flux formulation

Description

一种与铜内电极匹配的抗还原性高频低温烧结
陶瓷介质材料
技术领域
本发明涉及陶瓷介质材料及所得元器件的制备方法， 尤其涉及一种符合
COG特性， 且能与铜内电极匹配的高频低温烧结的陶瓷介质材料。 背景技术
随着产品高性能、 低成本的市场需求， 迫使陶瓷电容器制造商不断寻找既 能降低生产成本又能满足更高性能要求的替代材料， 是制造商们面临的重大挑 战之一。 目前的多层片式陶瓷电容器 （以下简称 MLCC) 已基本实现用贱金属 化， 80%以上的 MLCC使用贱金属内电极材料 （以镍为主） 取代钯银内电极材 料， 可有效降低约 40%的生产成本。 更进一步的研究， 铜电极的使用被提上日 程， 相对于其他贱金属而言， 铜不仅具有价格上的优势， 同时更重要的是在高 频领域，铜的电气性能更为优秀。不过铜比镍更容易氧化，且铜的熔点（1083 Ό ) 比镍的 （1453°C ) 低， 而目前通用瓷料的烧结温度很高， 与铜电极难以匹配， 从而影响 MLCC的电性能。 若要使用铜作为内电极材料， 首先必然要获得满足 要求的陶瓷介质材料。 发明内容
本发明需解决的技术问题是提供一种符合 COG瓷介特性、 材料分散性高、 成型工艺好、 满足 RoSH条例要求、 抗还原铜内电极电容器用陶瓷介质材料。
为解决上述技术问题， 本发明提供的技术方案是： 一种抗还原铜内电极高 频低温烧结陶瓷介质材料,由主晶相、 改性添加剂、 烧结助熔剂组成， 主晶相的 结构式是 MgxBa(1-x)ZrySi(1 03， 其中 0.8ί≤χί≤0.95， 0.055£y¾S0.2， 所述的改性 添加剂是 Mn02、 CaO、 Li20、 Bi203、 Ti02中的一种或几种； 所述的烧结助熔剂 是 B203、 Si02、 ZnO、 CuO、 K20、 BaO中的一种或几种。
进一歩： 上述抗还原铜内电极高频陶瓷介质材料， 其特征在于： 按摩尔百 分比计， 主晶相 80〜95mol%、 改性添加剂 1.2〜10mol %、 烧结助熔剂 2.5〜18 mol%。 按摩尔百分比计， 改性添加剂在整个抗还原铜内电极陶高频陶瓷介质材 料中的组成是 Mn02 0.2〜0.5mol%、 CaO 0〜： l .0mol%、 Li20 1.0〜3.0mol%、 Bi203 0〜5.0mol%、 Ti02 0〜1.0mol%。按摩尔百分比计， 所述的烧结助熔剂在整个抗 还原铜内电极高频低温烧结陶瓷介质材料中的组成是 B203 1.0〜3.0mol%、 Si02 0〜6.0mol%、 ZnO 1.5〜6.0mol%、 CuO 0〜1.0mol%、 K20 0〜： l .0mol%、 BaO 0〜1.0mol%。所述的主晶相由 Mg(OH)2、 Si02、 BaC03和 Zr02球磨混合均勾后， 在 1050〜1170°C温度预煅烧制得。
上述组成中， 主成分选择具有良好高频性能的复合物
Figure imgf000003_0001
该复合物介电常数较低， 较低的介质损耗角正切值， 和近乎线性的介电-温度特 性， 这些都能从主材料上保证了本发明材料制作成 MLCC具有优良的电性能。 改性添加剂材料的加入， 能够使材料的介电常数保持在 10左右， 并且很好的调 节陶瓷介质材料的温度系数， 使介电-温度特性近乎线性； 同时还能抑制瓷体晶 粒的异常生长， 使晶粒生长均匀， 这对提高介质材料的耐压强度起到很好的作 用， 并最终使本发明获得的 MLCC具有高可靠性。 烧结助熔剂的一个主要作用 是降低本发明陶瓷材料的烧结温度， 使材料能在小于 1100°C的温度下进行致密 烧结， 烧结后的陶瓷体晶粒生长均匀， 具有高致密度， 进一步保证了制成的 MLCC具有高可靠性。本发明采用了还原气氛烧结的
Figure imgf000003_0002
体系 的非铁电性铜电极介质陶瓷， 烧结温度低于 1100°C， 瓷料可与铜 （Cu) 内电极 浆料匹配， 瓷料性能优越。
在用上述高频低温烧结陶瓷介质材料制备 MLCC产品的方法中， 按常规瓷 料生产工艺流程制作 MLCC瓷料， 包括瓷浆制备、 制作介质膜片、 交替叠印内 电极和介质层、 坯块干燥、 层压、 切割、 排胶、 烧结、 倒角、 封端、 烧端工艺。 即按片式 MLCC的制作流程加入有机粘合剂和乙醇等溶剂， 从而形成浆料， 把 浆料流延制作成薄膜片， 在膜片上印刷铜 Cu内电极， 交替层叠所需层数， 形成 生坯 MLCC芯片， 然后在 200〜300°C温度热处理生坯 MLCC芯片， 以排除有 机粘合剂和溶剂， 在 1000〜1100°C温度烧结 2.5〜5小时 MLCC芯片， 然后,经 表面处理,再在芯片的两端封上一对外部铜 Cu电极,使外部电极与内部电极连接, 在 830〜900°C温度范围内热处理外电极,再经电镀处理等工艺，即可得到 MLCC 产品。 该制备方法中， 产品烧结温度低， 对工艺设备的要求简单， 陶瓷介质材 料粒度分布均匀， 烧结中瓷体晶粒生长均匀、 致密， MLCC产品电气性能优良。 具体实施方式 本发明的主旨是采用 MgxBad^ZrySi^yPs体系为材料主晶相， 加入改性添加 剂调节性能， 并加入烧结助熔剂帮助降低烧结温度， 采用常规的工艺制成所需粉 体， 得到一种符合 COG瓷介特性、 材料分散性高、 成型工艺好的低温烧结陶瓷 介质材料， 且在制作 MLCC产品时， 烧结温度低、 晶粒生长均匀、 致密， 产品无 缺陷或缺陷小。 下面结合实施例对本发明的内容作进一歩详述， 实施例中所提 及的内容并非对本发明的限定， 材料配方选择可因地制宜而对结果无实质性的 影响。
首先， 简述本发明材料配方的基本方案： 一种抗还原铜高频低温烧结陶瓷 介质材料， 由主晶相、 改性添加剂、 烧结助熔剂组成， 主晶相的结构式是 MgxBa(1-x)ZrySi(1-y)03 , 其中 0.8 x 0.95， 0.05^y^0.2 , 所述的改性添加剂是 Mn02、 CaO、 Li20、 Bi203、 Ti02中的一种或几种； 所述的烧结助瑢剂是 ¾03、 Si02、 ZnO、 CuO、 K20、 BaO中的一种或几种。 实施例 1
一种抗还原铜内电极高频低温烧结陶瓷介质材料，采用纯度为 99.5%以上的 原材料， 以 0.8mol Mg(OH)2、 0.8 mol Si02、 0.2 mol BaC03禾 B 0.2 molZr02的混 合比例， 球磨均匀， 在 115CTC温度下煅烧该混合物 3 小时， 即得主晶相为 Mgo.8Bao.2Sio.8Zro.203材料。然后按预定比例添加如表 1所示的改性添加剂和烧结 助剂。
表 1: 主晶相、 改性添加剂、 烧结助熔剂配方组成
Figure imgf000004_0001
按本领域技术人员常用的瓷料生产工艺流程制作陶瓷介质瓷料， 然后按照 常用的 MLCC的制作流程加入有机粘合剂和乙醇等溶剂， 从而形成浆料， 把浆 料流延制作成薄膜片， 在膜片上印刷铜 Cu内电极， 交替层叠所需层数， 形成生 坯 MLCC芯片， 然后在 200〜300°C温度热处理生坯 MLCC芯片， 以排除有机 粘合剂和溶剂。在 1000〜1100°C温度烧结 2.5〜5小时 MLCC芯片， 经表面抛光 处理， 再在芯片的两端封上一对外部铜 Cu电极， 使外部电极与内部电极连接， 在 830〜900°C温度范围内热处理外电极。再经电镀处理等工艺，即可得到 MLCC 产品。该 MLCC产品具有容量稳定、性能好的特点。在室温 25°C时，利用 HP4278 电桥， 在 ΙΜΗζ, 1.0V (AC)下测试本 MLCC产品容量、 损耗； 利用 SF2512快 速绝缘机， 施加 100V的 DC额定电压 10秒， 测试绝缘电阻； 利用高低温箱， 在 -55〜+125°C之间， 测试介电常数 -温度系数； 利用 HP4991A测试本 MLCC产 品频率特性等； 产品性能测试参数如表 2的 1〜10号材料配方对应的 MLCC测 试参数。
表 2: 根据上述陶瓷介质材料制得的 MLCC产品性能参数
Figure imgf000005_0001
实施例 2
一种抗还原铜内电极高频低温烧结陶瓷介质材料，采用纯度为 99.5%以上的 原材料， 以 0.9mol Mg(OH)2、 0.9mol Si02、 O.lmol BaC03和 O.lmol Zr02的混合 比例， 球磨均匀， 在 1150°C温度煅烧该混合物 3 小时， 即得主晶相为 Mgo.gBao.iSio.gZrdOs材料。然后按预定比例添加如表 3所示的改性添加剂和烧结 助剂。
表 3: 主晶相、 改性添加剂、 烧结助熔剂配方组成
主晶相
发明
Mgo.9Ba0.iSio 改性添加剂 （mol %) 烧结助熔剂 （mol%) 材料
Zral03
编号 (mol%) Li20 Ti02 MnO CaO Bi203 B203 ZnO Si02 CuO K20 BaO 11 80 3.0 0 0.5 0 5.0 2.0 6.0 1.0 1.0 0.5 1.0
12 81 2.5 1.0 0.4 0+5 4.0 3.0 60 1.8 0 0 0.0
13 83 2.2 0.8 0.4 1 +0 3.0 2.1 4.5 1.6 0.4 1.0 0
14 86 2.0 0.6 0.3 0+7 2.0 2.2 4.2 2.0 0 0 0
15 88 2.0 0.4 0.3 0+4 1.0 1.8 3.5 2.3 0 0 0.3
16 90 2.0 0.2 0.2 0.2 0 1.6 3.3 2.5 0 0 0
17 90 2.0 0 0.2 0 0.5 2.0 3.0 1.0 0.8 0 0.5
18 91 1.8 0 0.2 0 0 2.0 3.8 0 1.0 0 0.2
19 93 1.5 0 0.2 0 0 1.5 2.5 0.7 0 0.6 0
20 95 1.0 0 0.2 0.3 0 1.0 2.0 0 0.2 0.3 按实施例 1的方法制造和测试 MLCC的电性能， 测试结果如表 4所示:
表 4: 根据上述陶瓷介质材料制得的 MLCC产品性能参数
Figure imgf000006_0001
实施例 3
一种抗还原铜内电极高频低温烧结陶瓷介质材料，采用纯度为 99.5%以上的 原材料,以 0.95 mol Mg(OH)2、 0.95 mol Si02、 0.05 mol BaC03禾口 0.05 mol Zr02 的混合比例， 球磨均匀， 在 1150°C温度煅烧该混合物 3 小时， 即得主晶相为 Mgo.95Bao.05Sio.95Zro.05O3材料。 然后按预定比例添加如表 5所示的改性添加剂和 烧结助剂。
表 5: 主晶相、 改性添加剂、 烧结助熔剂配方组成
发明 主晶相
改性添加剂 （mol %) 烧结助熔剂 （mol %) 材料
编号 Li20 Ti02 MnO CaO Bi203 B2O3 ZnO Si02 CuO K20 BaO
21 80 3.0 1.0 0.5 0 5.0 2.0 6.0 1.0 0 0.5 1.0
22 82 2.5 0.8 0.4 1.0 4.0 3.0 5.0 1.3 0 0 0.0
23 84 2.2 0.6 0.4 0.8 2.0 2.1 4.5 2.4 0 1.0 0
24 86 2.0 0. 4 0.3 0.6 1.0 2.2 4.5 0 1.0 1.0 1.0
25 88 2.0 0.2 0.3 0.4 0 1.8 4.0 2.5 0 0 0.8
26 90 2.0 0 0.2 0.2 0 1.6 3.3 2.5 0 0 0.4
27 92 2.0 0 0.2 0 0 2.0 3.0 0 0.8 0 0
28 92 2.0 0 0.2 0 0 2.0 3.8 0 1.0 0 0 94 1.5 0 0.2 0 0 1.5 2.5 0.3 0 0 0
95 1.0 0 0.2 0 0 1.0 1.5 0 0 0 1.3 按实施例 1的方法制造和测试 MLCC的电性能， 测试结果如表 6所示:
表 6: 根据上述陶瓷介质材料制得的 MLCC产品性能参数
介电损耗 温度系数
发明材料编号 介电常数 绝缘电阻 （Ω)
DF (χΐθ"4) -55〜+125°C (ppm/°C)
21 8.9 0.7 一 12〜22 >10π
22 9.1 0.8 4〜16 >10π
23 9.2 0.6 11〜23 >10π
24 9.5 1.0 -8〜19 >10π
25 9.7 1.2 10〜23 >10π
26 10.0 1.1 5〜16 >10π
27 10.4 0.8 -5〜20 >10π
28 10.7 1.3 3〜19 >10π
29 11.2 1.2 -5〜17 >10π
30 11.5 1.0 -6〜15 >10π

Claims

权 利 要 求 书
1、 一种抗还原铜内电极高频低温烧结陶瓷介质材料， 由主晶相、 改性添加 剂、 烧结助熔剂组成， 其特征在于： 主晶相的结构式是
Figure imgf000008_0001
, 其 中 0.8 x 0.95， 0.05^y^0.2,所述的改性添加剂是 Mn02、 CaO、 Li20、 Bi203、 Ti02中的一种或几种； 所述的烧结助熔剂是 B203、 Si02、 ZnO、 CuO、 K20、 BaO 中的一种或几种。
2、 根据权利要求 1所述的抗还原铜内电极高频低温烧结陶瓷介质材料， 其 特征在于： 按摩尔百分比计， 主晶相 80〜95mol%、 改性添加剂 1.2〜10mol%、 烧结助熔剂 2.5〜18 mol%。
3、 根据权利要求 2所述的抗还原铜内电极高频低温烧结陶瓷介质材料， 其 特征在于：所述的主晶相 MgxBa( )ZrySi(h O3，其中 0.8 x 0.95， 0.05 y 0.2， 由 Mg(OH)2、 BaC03、 Zr02、 Si02按比例球磨混合均匀后， 在 1050°C〜1170°C 温度预煅烧制得。
4、 根据权利要求 2所述的抗还原铜内电极陶高频低温烧结陶瓷介质材料， 其特征在于： 按摩尔百分比计， 改性添加剂在整个抗还原铜内电极陶高频陶瓷 介质材料中的组成是 Mn02 0.2〜0.5mol%、 CaO 0〜1.0mol%、 Li20 1.0〜 3.0mol%、 Bi203 0〜5.0mol%、 TiO20〜1.0mol%。
5、 根据权利要求 2所述的抗还原铜内电极高频低温烧结陶瓷介质材料， 其 特征在于： 按摩尔百分比计， 所述的烧结助熔剂在整个抗还原铜内电极高频低 温烧结陶瓷介质材料中的组成是 B203 1.0〜3.0mol%、 Si02 0〜6.0mol%、 ZnO 1.5〜6.0mol%、 CuO 0〜1.0mol%、 K20 0〜1.0mol%、 BaO 0〜1.0mol%。
6、 根据权利要求 1至 5的其中之一所述的抗还原铜内电极高频低温烧结陶 瓷介质材料， 其特征在于： 用该陶瓷介质材料制作的陶瓷电容器可在还原气氛 下烧结， 陶瓷电容器内电极材料可使用铜， 烧结温度 1000°C〜1100°C， 获得的陶 瓷电容器电气性能满足高频 COG类陶瓷材料特性。
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