CN101786866B - 一种抗还原性铜内电极高频低温烧结陶瓷介质材料 - Google Patents

一种抗还原性铜内电极高频低温烧结陶瓷介质材料 Download PDF

Info

Publication number
CN101786866B
CN101786866B CN2009102141094A CN200910214109A CN101786866B CN 101786866 B CN101786866 B CN 101786866B CN 2009102141094 A CN2009102141094 A CN 2009102141094A CN 200910214109 A CN200910214109 A CN 200910214109A CN 101786866 B CN101786866 B CN 101786866B
Authority
CN
China
Prior art keywords
inner electrode
copper inner
medium material
sintering
property
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2009102141094A
Other languages
English (en)
Other versions
CN101786866A (zh
Inventor
宋蓓蓓
宋永生
莫方策
李娟�
王孝国
郭精华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Fenghua Advanced Tech Holding Co Ltd
Original Assignee
Guangdong Fenghua Advanced Tech Holding Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangdong Fenghua Advanced Tech Holding Co Ltd filed Critical Guangdong Fenghua Advanced Tech Holding Co Ltd
Priority to CN2009102141094A priority Critical patent/CN101786866B/zh
Publication of CN101786866A publication Critical patent/CN101786866A/zh
Priority to PCT/CN2010/079974 priority patent/WO2011076090A1/zh
Priority to US13/377,499 priority patent/US8709962B2/en
Priority to JP2012514341A priority patent/JP5442114B2/ja
Application granted granted Critical
Publication of CN101786866B publication Critical patent/CN101786866B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/20—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in magnesium oxide, e.g. forsterite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62685—Treating the starting powders individually or as mixtures characterised by the order of addition of constituents or additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C04B2235/3203—Lithium oxide or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C04B2235/3267—MnO2
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3436—Alkaline earth metal silicates, e.g. barium silicate
    • C04B2235/3445—Magnesium silicates, e.g. forsterite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/652—Reduction treatment

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Insulating Materials (AREA)
  • Ceramic Capacitors (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Abstract

本发明公开了一种抗还原铜内电极高频低温烧结陶瓷介质材料，可用于铜内电极多层陶瓷电容器制作。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)O3，其中0.8≤x≤0.95，0.05≤y≤0.2，所述的改性添加剂是MnO2、CaO、Li2O、Bi2O3、TiO2中的一种或几种；所述的烧结助熔剂是B2O3、SiO2、ZnO、CuO、K2O、BaO中的一种或几种。上述陶瓷介质材料满足EIA标准COG特性，且材料具备均一、粒度分布均匀、分散性高、成型工艺好的特点，符合环保要求，介电特性优良。

Description

一种抗还原性铜内电极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℃)比镍的(1453℃)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-y)O3，其中0.8≤x≤0.95，0.05≤y≤0.2，所述的改性添加剂是MnO2、CaO、Li2O、Bi2O3、TiO2中的一种或几种；所述的烧结助熔剂是B2O3、SiO2、ZnO、CuO、K2O、BaO中的一种或几种。
进一步：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2.5～18mol％。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MnO2 0.2～0.5mol％、CaO 0～1.0mol％、Li2O 1.0～3.0mol％、Bi2O3 0～5.0mol％、TiO2 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B2O3 1.0～3.0mol％、SiO2 0～6.0mol％、ZnO 1.5～6.0mol％、CuO 0～1.0mol％、K2O 0～1.0mol％、BaO 0～1.0mol％。所述的主晶相由Mg(OH)2、SiO2、BaCO3和ZrO2球磨混合均匀后，在1050～1170℃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MgxBa(1-x)ZrySi(1-y)O3，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℃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MgxBa(1-x)ZrySi(1-y)O3体系的非铁电性铜电极介质陶瓷，烧结温度低于1100℃，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℃温度热处理生坯MLCC芯片，以排除有机粘合剂和溶剂，在1000～1100℃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℃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MgxBa(1-x)ZrySi(1-y)O3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步详述，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)O3其中0.8≤x≤0.95，0.05≤y≤0.2，所述的改性添加剂是MnO2、CaO、Li2O、Bi2O3、TiO2中的一种或几种；所述的烧结助熔剂是B2O3、SiO2、ZnO、CuO、K2O、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、0.8mol SiO2、0.2mol BaCO3和0.2molZrO2的混合比例，球磨均匀，在1150℃温度下煅烧该混合物3小时，即得主晶相为Mg0.8Ba0.2Si0.8Zr0.2O3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 G2009102141094D00031
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℃温度热处理生坯MLCC芯片，以排除有机粘合剂和溶剂。在1000～1100℃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℃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℃时，利用HP4278电桥，在1MHz，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℃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
发明材料编号 介电常数   介电损耗DF(×10-4)   温度系数-55~+125℃(ppm/℃) 绝缘电阻(Ω)
  1   10.1   0.9   -10～20   ＞1011
  2   9.8   0.7   5～15   ＞1011
  3   9.5   0.9   13～20   ＞1011
  4   8.9   0.9   -6～17   ＞1011
  5   9.7   1.2   5～13   ＞1011
  6   9.1   1.1   6～9   ＞1011
  7   10.2   0.7   -2～6   ＞1011
  8   11.3   0.9   8～11   ＞1011
  9   10.3   1.5   -5～7   ＞1011
  10   9.8   1.0   -8～2   ＞1011
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 SiO2、0.1mol BaCO3和0.1mol ZrO2的混合比例，球磨均匀，在1150℃温度煅烧该混合物3小时，即得主晶相为Mg0.9Ba0.1Si0.9Zr0.1O3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
Figure G2009102141094D00051
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
发明材料编号 介电常数   介电损耗DF(×10-4) 温度系数-55～+125℃(ppm/℃) 绝缘电阻(Ω)
  11   11.6   1.3   -3～20   ＞1011
  12   11.2   0.8   14～27   ＞1011
  13   10.3   1.5   2～13   ＞1011
  14   9.7   1.0   -8～16   ＞1011
  15   9.3   0.6   10～23   ＞1011
  16   10.6   0.8   4～26   ＞1011
  17   9.2   0.9   -10～22   ＞1011
  18   8.9   1.1   3～17   ＞1011
  19   9.5   0.7   -5～17   ＞1011
  20   10.1   1.0   6～15   ＞1011
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0.95mol Mg(OH)2、0.95mol SiO2、0.05mol BaCO3和0.05molZrO2的混合比例，球磨均匀，在1150℃温度煅烧该混合物3小时，即得主晶相为Mg0.95Ba0.05Si0.95Zr0.05O3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
Figure G2009102141094D00052
Figure G2009102141094D00061
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
发明材料编号 介电常数   介电损耗DF(×10-4) 温度系数-55～+125℃(ppm/℃) 绝缘电阻(Ω)
  21   8.9   0.7   -12～22   ＞1011
  22   9.1   0.8   4～16   ＞1011
  23   9.2   0.6   11～23   ＞1011
  24   9.5   1.0   -8～19   ＞1011
  25   9.7   1.2   10～23   ＞1011
  26   10.0   1.1   5～16   ＞1011
  27   10.4   0.8   -5～20   ＞1011
  28   10.7   1.3   3～19   ＞1011
  29   11.2   1.2   -5～17   ＞1011
  30   11.5   1.0   -6～15   ＞1011

Claims (6)

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MgxBa(1-x)ZrySi(1-y)O3其中0.8≤x≤0.95，0.05≤y≤0.2，所述的改性添加剂是MnO2、CaO、Li2O、Bi2O3、TiO2中的一种或几种；所述的烧结助熔剂是B2O3、SiO2、ZnO、CuO、K2O、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2.5～18mol％。
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(1-x)ZrySi(1-y)O3，其中0.8≤x≤0.95，0.05≤y≤0.2，由Mg(OH)2、BaCO3、ZrO2、SiO2按比例球磨混合均匀后，在1050℃～1170℃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MnO2 0.2～0.5mol％、CaO 0～1.0mol％、Li2O 1.0～3.0mol％、Bi2O3 0～5.0mol％、TiO2 0～1.0mol％。
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B2O3 1.0～3.0mol％、SiO2 0～6.0mol％、ZnO1.5～6.0mol％、CuO 0～1.0mol％、K2O 0～1.0mol％、BaO 0～1.0mol％。
6.根据权利要求1～5中任意一项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在还原气氛下烧结，陶瓷电容器内电极材料使用铜，烧结温度1000℃～1100℃，获得的陶瓷电容器电气性能满足高频COG类陶瓷材料特性。
CN2009102141094A 2009-12-22 2009-12-22 一种抗还原性铜内电极高频低温烧结陶瓷介质材料 Active CN101786866B (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN2009102141094A CN101786866B (zh) 2009-12-22 2009-12-22 一种抗还原性铜内电极高频低温烧结陶瓷介质材料
PCT/CN2010/079974 WO2011076090A1 (zh) 2009-12-22 2010-12-20 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
US13/377,499 US8709962B2 (en) 2009-12-22 2010-12-20 Anti-reductive high-frequency ceramic dielectric material sintered at low temperature and matched with copper internal electrode
JP2012514341A JP5442114B2 (ja) 2009-12-22 2010-12-20 銅内電極と整合する耐還元性高周波低温焼結セラミック媒体材料

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009102141094A CN101786866B (zh) 2009-12-22 2009-12-22 一种抗还原性铜内电极高频低温烧结陶瓷介质材料

Publications (2)

Publication Number Publication Date
CN101786866A CN101786866A (zh) 2010-07-28
CN101786866B true CN101786866B (zh) 2012-12-05

Family

ID=42530266

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009102141094A Active CN101786866B (zh) 2009-12-22 2009-12-22 一种抗还原性铜内电极高频低温烧结陶瓷介质材料

Country Status (4)

Country Link
US (1) US8709962B2 (zh)
JP (1) JP5442114B2 (zh)
CN (1) CN101786866B (zh)
WO (1) WO2011076090A1 (zh)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2933611B1 (fr) 2008-07-10 2012-12-14 Oreal Procede de maquillage et dispositif pour la mise en oeuvre d'un tel procede.
FR2933582B1 (fr) * 2008-07-10 2011-10-07 Oreal Dispositif de traitement des matieres keratiniques humaines
FR2933583B1 (fr) * 2008-07-10 2011-10-07 Oreal Dispositif pour appliquer une composition sur les matieres keratiniques humaines
CN101786866B (zh) * 2009-12-22 2012-12-05 广东风华高新科技股份有限公司 一种抗还原性铜内电极高频低温烧结陶瓷介质材料
CN102956355B (zh) * 2012-10-26 2015-07-29 广东风华高新科技股份有限公司 多层陶瓷电容器的制造方法及烧结铜端电极的设备
CN104341144B (zh) * 2013-08-01 2016-04-27 北京元六鸿远电子技术有限公司 低温烧结c0g特性微波介质材料及其制备方法
CN105347801B (zh) * 2015-11-20 2019-02-22 中国计量科学研究院 一种纳米陶瓷材料组合物和标准电容器及其制备方法
CN111933451A (zh) * 2020-07-08 2020-11-13 四川华瓷科技有限公司 一种射频片式多层陶瓷电容器的制备方法
CN112759378B (zh) * 2021-02-01 2022-09-02 郴州功田电子陶瓷技术有限公司 低温共烧微波介质陶瓷材料及其制备方法、电子元器件
CN114262219B (zh) * 2021-12-31 2022-09-06 北京元六鸿远电子科技股份有限公司 一种具备超高温度稳定性的微波介质陶瓷材料及其制备方法和应用
CN115947598B (zh) * 2022-10-21 2024-03-22 西安交通大学 一种可与贱金属内电极共烧的反铁电材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6301092B1 (en) * 1999-06-17 2001-10-09 Murata Manufacturing Co., Ltd. Ceramic capacitor and method for making the same
CN1317459A (zh) * 2000-04-07 2001-10-17 株式会社村田制作所 非还原性介电陶瓷和使用该陶瓷的单块陶瓷电容器
CN1801417A (zh) * 2005-12-13 2006-07-12 清华大学 细晶贱金属内电极多层陶瓷片式电容器介质材料

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01141838A (ja) * 1987-11-26 1989-06-02 Shoei Kagaku Kogyo Kk 回路基板用誘電体材料
JP3030558B2 (ja) * 1987-11-28 2000-04-10 ティーディーケイ株式会社 誘電体磁器材料
EP0838446B1 (en) * 1996-10-25 2007-08-15 Ngk Spark Plug Co., Ltd A dielectric material, a method for producing the same and a dielectric resonator device comprising same
JP2000276947A (ja) * 1999-01-19 2000-10-06 Taiyo Yuden Co Ltd 電子部品用セラミックス組成物、電子部品用セラミックス焼結体及び電子部品
JP2001313470A (ja) * 1999-10-27 2001-11-09 Ngk Spark Plug Co Ltd コンデンサ内蔵配線基板
US6602623B1 (en) * 1999-10-27 2003-08-05 Ngk Spark Plug Co., Ltd. Low-temperature firing ceramic composition, process for producing same and wiring substrate prepared by using same
JP2002173367A (ja) * 1999-10-27 2002-06-21 Ngk Spark Plug Co Ltd 低温焼成磁器組成物及びその製造方法並びにそれを用いた配線基板
US6514895B1 (en) * 2000-06-15 2003-02-04 Paratek Microwave, Inc. Electronically tunable ceramic materials including tunable dielectric and metal silicate phases
JP4110978B2 (ja) * 2003-01-24 2008-07-02 株式会社村田製作所 誘電体セラミックおよびその製造方法ならびに積層セラミックコンデンサ
JP4403705B2 (ja) * 2003-02-17 2010-01-27 Ｔｄｋ株式会社 誘電体磁器組成物および電子部品
CN100464382C (zh) 2003-12-31 2009-02-25 广东风华高新科技股份有限公司 钛酸锌镁系陶瓷介质材料及所得的陶瓷电容器
CN1273408C (zh) 2004-03-23 2006-09-06 浙江大学 低温烧结(Ca,Mg)SiO3系微波介质陶瓷及制备工艺
JP2005281010A (ja) 2004-03-26 2005-10-13 Sanyo Electric Co Ltd 誘電体セラミック材料及び積層セラミック基板
JP4736342B2 (ja) * 2004-04-09 2011-07-27 株式会社村田製作所 ガラスセラミック原料組成物、ガラスセラミック焼結体およびガラスセラミック多層基板
JP4185056B2 (ja) * 2005-01-26 2008-11-19 株式会社東芝 絶縁膜、および半導体装置
CN101323521A (zh) 2008-07-16 2008-12-17 上海大学 微波介质陶瓷材料
JP5582406B2 (ja) * 2008-11-25 2014-09-03 宇部興産株式会社 高周波用誘電体磁器組成物及びその製造方法、高周波用誘電体磁器並びにその製造方法およびそれを用いた高周波回路素子
CN101786866B (zh) * 2009-12-22 2012-12-05 广东风华高新科技股份有限公司 一种抗还原性铜内电极高频低温烧结陶瓷介质材料

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6301092B1 (en) * 1999-06-17 2001-10-09 Murata Manufacturing Co., Ltd. Ceramic capacitor and method for making the same
CN1317459A (zh) * 2000-04-07 2001-10-17 株式会社村田制作所 非还原性介电陶瓷和使用该陶瓷的单块陶瓷电容器
CN1801417A (zh) * 2005-12-13 2006-07-12 清华大学 细晶贱金属内电极多层陶瓷片式电容器介质材料

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
N.Nanakorn et al..Dielectric and ferroelectric properties of Ba(ZrxTi1-x)O3 ceramics.《Ceramics International》.2007,第34卷779－782. *
朱文奕等.镍内电极多层陶瓷电容器介质材料的研究.《功能材料》.2000,第31卷(第3期),292-293、295. *

Also Published As

Publication number Publication date
US20120250222A1 (en) 2012-10-04
US8709962B2 (en) 2014-04-29
WO2011076090A1 (zh) 2011-06-30
CN101786866A (zh) 2010-07-28
JP5442114B2 (ja) 2014-03-12
JP2012529412A (ja) 2012-11-22

Similar Documents

Publication Publication Date Title
CN101786866B (zh) 一种抗还原性铜内电极高频低温烧结陶瓷介质材料
CN101786864B (zh) 一种与镍内电极匹配的陶瓷介质材料及所得电容器的制备方法
JP5332807B2 (ja) 誘電体磁器組成物
KR100983046B1 (ko) 소결조제용 붕규산염계 유리 조성물, 유전체 조성물 및 이를 이용한 적층 세라믹 커패시터
CN101367651B (zh) 一种高频低温烧结陶瓷介质材料及所得电容器的制备方法
JP5077362B2 (ja) 誘電体セラミック及び積層セラミックコンデンサ
KR101730184B1 (ko) 도전성 페이스트 조성물 및 이를 이용한 적층 세라믹 콘덴서의 제조방법
TWI803471B (zh) 介電體磁器組成物及陶瓷電子零件
KR101994745B1 (ko) 저온 소성 유전체 조성물 및 적층 세라믹 커패시터
CN101386534A (zh) 一种高性能中低温烧结高压陶瓷电容器介质
CN102101774B (zh) 一种抗还原镍电极陶瓷介质材料
CN102964122A (zh) 介电陶瓷组合物及其电子元器件制作方法
CN103408301A (zh) 一种超高压陶瓷电容器介质及其制备方法
CN103351161B (zh) 一种低温烧结高压陶瓷电容器介质
CN1327462C (zh) 可低温烧结的电介质陶瓷组合物及使用它的多层陶瓷片状电容器
CN101913863B (zh) 一种与镍内电极匹配的陶瓷介质材料
KR100790682B1 (ko) 저온 소결용 유리 조성물과 이를 이용한 유리 프릿, 유전체조성물, 적층 세라믹 커패시터
CN101333105B (zh) 薄介质x7r mlcc介质瓷料
JP5151039B2 (ja) 誘電体セラミックおよびその製造方法ならびに積層セラミックコンデンサ
CN102627456B (zh) 一种低损耗高压陶瓷电容器介质
TWI412504B (zh) A dielectric ceramic composition, a method for preparing a dielectric ceramic composition, and an electronic component
CN100372802C (zh) 高频热稳定的钛钡钕系陶瓷介质材料及多层片式陶瓷电容器
TWI393693B (zh) 低溫共燒介電組合物
CN114436647A (zh) 低温共烧钛酸铋钠基介质陶瓷的制备方法
TWI443079B (zh) Dielectric ceramic compositions and electronic components

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant