KR100276272B1 - A dielectric ceramic composition with low reducibility and a method for manufacturing multi layer ceramic capacitor using it - Google Patents
A dielectric ceramic composition with low reducibility and a method for manufacturing multi layer ceramic capacitor using it Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 7
- 239000000919 ceramic Substances 0.000 title description 8
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 239000011651 chromium Substances 0.000 claims abstract description 13
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 5
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 23
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 13
- 238000010304 firing Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
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- 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
- C04B35/46—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 titanium oxides or titanates
- C04B35/462—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 titanium oxides or titanates based on titanates
- C04B35/465—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 titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—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 titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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- 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
- C04B35/64—Burning or sintering processes
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Abstract
본 발명의 내환원성 유전체 조성물은 티탄산바륨(BaTiO3), 탄산마그네슘(MgCO3), 산화이트륨(Y2O3), 산화크롬(Cr2O3), 산화니오븀(Nb2O5) 및 BaxCa(1-x)SiO3을 포함하고, 그 조성은 a BaTiO3-b MgCO3- c Y2O3- d Cr2O3- e Nb2O5- f BaxCa(1-x)SiO3의 일반식으로 표현할 때 몰비로, a = 100, 0.2≤b≤6.0, 0.05≤c≤1.5, 0.1≤d≤1.5, 0.05≤e≤0.40, 0.2≤f≤3.0으로 이루어지는 것으로서, 이 조성물을 이용하여 적층 세라믹 콘덴서를 제조하는 경우 약 1200~1250℃의 저온에서 소결이 가능하여 유전체층과 Ni내부전극 간의 수축이 감소되어 매우 신뢰성이 있다.The reducing resistant dielectric composition of the present invention is barium titanate (BaTiO 3 ), magnesium carbonate (MgCO 3 ), yttrium oxide (Y 2 O 3 ), chromium oxide (Cr 2 O 3 ), niobium oxide (Nb 2 O 5 ) and Ba x Ca (1-x) SiO 3 , the composition of which is a BaTiO 3 -b MgCO 3 -c Y 2 O 3 -d Cr 2 O 3 -e Nb 2 O 5 -f Ba x Ca (1-x ) Molar ratio expressed by the general formula of SiO 3 , consisting of a = 100, 0.2≤b≤6.0, 0.05≤c≤1.5, 0.1≤d≤1.5, 0.05≤e≤0.40, 0.2≤f≤3.0, and When the multilayer ceramic capacitor is manufactured using the composition, sintering is possible at a low temperature of about 1200 to 1250 ° C., so that shrinkage between the dielectric layer and the Ni internal electrode is reduced, thereby being very reliable.
Description
본 발명은 적층세라믹 콘덴서에 관한 것으로서, 보다 상세하게는 세라믹 유전체 조성물과 이를 이용한 Ni을 내부전극으로 하는 적층 세라믹 콘덴서의 제조방법에 관한 것이다.The present invention relates to a multilayer ceramic capacitor, and more particularly, to a ceramic dielectric composition and a method of manufacturing a multilayer ceramic capacitor using Ni as an internal electrode.
통상 적층 세라믹 콘덴서(multi layer ceramic capacitor)는 유전체, 내부전극 페이스트(paste)와 외부전극 페이스트의 세 가지 재료로 제조된다. 적층 세라믹 콘덴서의 내부전극 재료로서 종래에는 값비싼 Pd 귀금속을 주로 사용하여 왔는데, Pd의 가격 상승에 따른 원가상승을 극복하고 고적층, 고용량품에 대한 수요에 대처하고자 최근에는 상대적으로 가격이 싼 Ni을 내부전극으로 적용하는 추세에 있다.In general, a multilayer ceramic capacitor is made of three materials: a dielectric, an internal electrode paste, and an external electrode paste. Conventionally, expensive Pd noble metals have been mainly used as internal electrode materials for multilayer ceramic capacitors. In order to cope with the cost rise due to the price increase of Pd and to cope with the demand for high lamination and high capacity products, Ni has recently been relatively inexpensive. Is applied to the internal electrode.
그러나, 종래의 유전체 조성에 Ni을 내부전극으로 사용하는 경우 산소공공(vacancy) 형성과 함께 발생되는 자유전자에 의해 유전체가 반도체화되어 적층 세라믹 콘덴서에 그대로 적용하기가 곤란하다. 따라서, 내부전극으로 Ni을 사용하려면 유전체의 산화를 방지하기 위해 환원분위기에서 소성해야 하므로 유전체에 내환원 특성을 부여할 필요가 있다. 그리고, 이렇게 내환원성 유전체의 경우 기존의 Pd을 내부전극으로 사용하는 유전체에 비해 내부에 존재하는 산소공공에 의한 신뢰성 저하가 심하다고 알려져 있으므로 이를 해결하기 위해서는 첨가제 조절에 의해 신뢰성 향상을 이루어져야만 한다.However, when Ni is used as an internal electrode in a conventional dielectric composition, the dielectric is semiconductorized by free electrons generated with oxygen vacancies, and thus it is difficult to apply it to a multilayer ceramic capacitor as it is. Therefore, in order to use Ni as the internal electrode, the dielectric material needs to be fired in a reducing atmosphere in order to prevent oxidation of the dielectric. In addition, in the case of the reduction-resistant dielectric, it is known that the degradation of reliability due to the oxygen vacancy present therein is severe compared to the dielectric using the conventional Pd as an internal electrode.
한편, 상기 Ni 내부전극을 사용한 유전체 조성물 가운데 대표적인 예로서, 일본 공개특허 평6-215979에 개시된 바에 의하면, BaTiO3-Y2O3-V2O5계의 내환원성 세라믹 유전체 조성물이 알려져 있다. 구체적으로 상기 조성물은 86.32~97.64mol%의 BaTiO3, 0.01~10.00mol%의 Y2O3, 0.01~10.00mol%의 MgO, 0.001~0.200mol%의 V2O5로 구성되거나 여기에 첨가물로서 0.01~1.0mol%의 MnO, Cr2O3, Co2O3중 적어도 1종 이상 및/또는 0.5~10.0mol%의 (Baα,Ca(1-α))SiO3(0≤α≤1)을 함유한 유전체 조성물로서, EIA(Electric Industry Association) 규격으로 X7R 특성(일본 규격으로는 B 특성)을 만족하는 것이다. 그러나, 상기 일본 공개특허 평6-215979에 개시된 유전체 조성물은 V2O5를 미량으로 첨가하는 경우 유전체의 가속수명을 크게 향상시키지만, 무엇보다도 V2O5가 유독성을 가지고 있어 환경 오염을 유발한다는 단점이 있다.On the other hand, as a representative example of the dielectric composition using the Ni internal electrode, as disclosed in Japanese Patent Laid-Open No. 6-215979, a reduction-resistant ceramic dielectric composition of BaTiO 3 -Y 2 O 3 -V 2 O 5 system is known. Specifically, the composition is composed of 86.32 to 97.64 mol% BaTiO 3 , 0.01 to 10.00 mol% Y 2 O 3 , 0.01 to 10.00 mol% MgO, 0.001 to 0.200 mol% V 2 O 5 , or as an additive thereto. 0.01-1.0 mol% of MnO, Cr 2 O 3 , Co 2 O 3 and at least one and / or 0.5-10.0 mol% of (Ba α , Ca (1-α) ) SiO 3 (0 ≦ α ≦ 1 ), Which satisfies the X7R characteristic (B characteristic in Japanese standard) according to the EIA (Electric Industry Association) standard. However, the dielectric composition disclosed in Japanese Unexamined Patent Publication No. 6-215979 greatly improves the accelerated life of the dielectric when V 2 O 5 is added in a small amount, but above all, V 2 O 5 is toxic and causes environmental pollution. There are disadvantages.
또한, 이 조성물을 이용하여 콘덴서를 제조할 때 소결온도가 1300℃이상으로 높여야 한다는 문제가 있다. 통상 Ni을 내부전극층과 세라믹 유전체층이 교차된 형태의 적층 세라믹 콘덴서를 소성할 때 내부전극층이 세라믹 유전체층보다 저온에서 수축하여 두층간의 벌어짐(delamination)이 발생하기 쉽다. 따라서, 적층 세라믹 콘덴서를 제조하는 경우 소성온도가 높아질수록 전극층의 뭉침 현상이 두드러져 내부전극간 단락(short) 불량의 발생률이 높아지는 단점이 있다.In addition, there is a problem that the sintering temperature should be increased to 1300 ℃ or more when producing a capacitor using this composition. Usually, when firing a multilayer ceramic capacitor in which Ni is intersected with an internal electrode layer and a ceramic dielectric layer, the internal electrode layer shrinks at a lower temperature than the ceramic dielectric layer, and delamination is likely to occur. Therefore, in the case of manufacturing the multilayer ceramic capacitor, as the firing temperature is increased, the aggregation of the electrode layers becomes more prominent, and thus, the incidence rate of short defects between internal electrodes is increased.
본 발명은 상기 종래의 문제점을 해결하기 위하여 제안된 것으로서, 적층 세라믹 콘덴서를 제조할 때 유독성 첨가제를 사용하지 않으면서도 저온 소성이 가능하여 Ni 내부전극층과 유전체간의 수축률의 차이가 감소되고, 이에 따라 높은 신뢰성을 갖는 적층 세라믹 콘덴서 조성물을 제공함에 그 목적이 있다.The present invention has been proposed to solve the above-mentioned problems, and when manufacturing a multilayer ceramic capacitor, low-temperature firing is possible without using toxic additives, so that the difference in shrinkage between the Ni internal electrode layers and the dielectric is reduced. It is an object to provide a multilayer ceramic capacitor composition having reliability.
또한, 본 발명의 다른 목적은 상기한 조성물을 이용하여 종래보다 저온에서 소성을 행하면서도 신뢰성이 우수한 적층 세라믹 콘덴서를 제조하는 새로운 제조방법을 제공함에 있다.In addition, another object of the present invention is to provide a novel manufacturing method for producing a multilayer ceramic capacitor having excellent reliability while firing at a lower temperature than the conventional composition using the above-described composition.
상기 목적 달성을 위한 본 발명은 적층 세라믹 콘덴서에 사용되는 유전체 조성물에 있어서,In the present invention for achieving the above object, in the dielectric composition used in the multilayer ceramic capacitor,
티탄산바륨(BaTiO3), 탄산마그네슘(MgCO3), 산화이트륨(Y2O3), 산화크롬(Cr2O3), 산화니오븀(Nb2O5) 및 BaxCa(1-x)SiO3을 포함하고, 그 조성은 a BaTiO3-b MgCO3- c Y2O3- d Cr2O3- e Nb2O5- f BaxCa(1-x)SiO3의 일반식으로 표현할 때 몰비로, a = 100, 0.2≤b≤6.0, 0.05≤c≤1.5, 0.1≤d≤1.5, 0.05≤e≤0.40, 0.2≤f≤3.0으로 이루어지는 적층 세라믹 콘덴서용 내환원성 유전체 조성물에 관한 것이다.Barium titanate (BaTiO 3 ), magnesium carbonate (MgCO 3 ), yttrium oxide (Y 2 O 3 ), chromium oxide (Cr 2 O 3 ), niobium oxide (Nb 2 O 5 ), and Ba x Ca (1-x) SiO 3 , the composition of which is represented by the general formula of a BaTiO 3 -b MgCO 3 -c Y 2 O 3 -d Cr 2 O 3 -e Nb 2 O 5 -f Ba x Ca (1-x) SiO 3 When molar ratio, a = 100, 0.2≤b≤6.0, 0.05≤c≤1.5, 0.1≤d≤1.5, 0.05≤e≤0.40, 0.2≤f≤3.0. .
또한, 본 발명은 내부전극으로 Ni을 이용한 적층 세라믹 콘덴서의 제조방법에 있어서,In addition, the present invention is a method of manufacturing a multilayer ceramic capacitor using Ni as an internal electrode,
상기한 조성이 되도록 BaTiO3, MgCO3, Y2O3, Cr2O3, Nb2O5분말과 소결조제로서 BaCO3, CaCO3및 SiO2분말을 평량하여 습식혼합하여 건조하는 단계;BaTiO 3 , MgCO 3 , Y 2 O 3 , Cr 2 O 3 , Nb 2 O 5 powder and BaCO 3 , CaCO 3 and SiO 2 powder as a sintering aid so as to have the above composition by wet mixing and drying;
상기 건조된 분말에 바인더와 용매를 첨가하여 슬러리를 제조하는 단계;Preparing a slurry by adding a binder and a solvent to the dried powder;
상기 슬러리를 이용하여 일정 형태의 시트상으로 성형하는 단계;Molding into a sheet having a predetermined shape using the slurry;
성형된 시트 위에 Ni 내부전극을 인쇄하고, 인쇄된 시트를 다수개 적층하여 가압하는 단계;Printing the Ni internal electrodes on the molded sheet, and stacking and pressing a plurality of printed sheets;
상기와 같이 적층된 적층물을 일정 크기로 절단하고, 소부하여 내부의 바인더를 제거하는 단계;Cutting the laminated stack to a predetermined size and baking to remove the binder therein;
탈바인더 처리된 성형체를 1200~1250℃ 온도에서 소결하는 단계; 및Sintering the debindered molded body at a temperature of 1200 to 1250 ° C; And
상기 소결체의 양단에 외부전극을 형성하는 단계; 를 포함하여 구성되는 적층 세라믹 콘덴서의 제조방법에 관한 것이다.Forming external electrodes at both ends of the sintered body; It relates to a method of manufacturing a multilayer ceramic capacitor comprising a.
이하, 본 발명의 조성물을 상세히 설명한다.Hereinafter, the composition of the present invention will be described in detail.
본 발명의 세라믹 유전체 조성물은 티탄산바륨(BaTiO3), 탄산마그네슘(MgCO3), 산화이트륨(Y2O3), 산화크롬(Cr2O3), 산화니오븀(Nb2O5) 및 BaxCa(1-x)SiO3을 포함하여 구성되는 BaTiO3- MgCO3- Y2O3- Cr2O3- Nb2O5- BaxCa(1-x)SiO3유전체 조성물이다.The ceramic dielectric composition of the present invention is barium titanate (BaTiO 3 ), magnesium carbonate (MgCO 3 ), yttrium oxide (Y 2 O 3 ), chromium oxide (Cr 2 O 3 ), niobium oxide (Nb 2 O 5 ) and Ba x Ca (1-x) BaTiO consisting including SiO 3 3 - MgCO 3 - Y 2 O 3 - Cr 2 O 3 - Nb 2 O 5 - Ba x Ca (1-x) SiO 3 is a dielectric composition.
본 발명의 세라믹 유전체 조성물은 a BaTiO3-b MgCO3- c Y2O3- d Cr2O3- e Nb2O5- f BaxCa(1-x)SiO3으로 표시될 때 상기 티탄산바륨은 100몰비를 기준으로 하여 각 성분의 조성은 다음과 같다.The ceramic dielectric composition of the present invention is a titanic acid when expressed as a BaTiO 3 -b MgCO 3 -c Y 2 O 3 -d Cr 2 O 3 -e Nb 2 O 5 -f Ba x Ca (1-x) SiO 3 The composition of each component is as follows based on 100 mol ratio of barium.
먼저, 상기 탄산마그네슘은 유전체의 내환원성을 향상시키는 작용을 하는데,그 조성은 몰비로 0.2≤b≤6.0의 범위를 가짐이 바람직하다. 만일 b가 0.2미만인 경우 손실계수가 상승하고 온도특성이 나빠지며 6.0초과인 경우 가속수명이 저하된다.First, the magnesium carbonate serves to improve the reduction resistance of the dielectric, the composition is preferably in the molar ratio of 0.2≤b≤6.0. If b is less than 0.2, the loss coefficient is increased, the temperature characteristic is deteriorated, and if it is more than 6.0, the acceleration life is reduced.
또한, 상기 산화이트륨은 Ba2+이온자리에 치환되어 수명을 향상시키는 역할을 하는데, 산화이트륨의 경우 몰비로 0.05≤c≤1.5의 범위로 조성됨이 바람직하다. 만일 c가 0.05미만인 경우 가속수명이 저하되고 1.5초과인 경우 반도체화된다.In addition, the yttrium oxide is substituted in the Ba 2+ ion site to improve the life, it is preferable that the yttrium oxide is formed in the range of 0.05≤c≤1.5 in molar ratio. If c is less than 0.05, the accelerated lifetime is reduced, and if it is greater than 1.5, it is semiconductorized.
또한, 상기 산화크롬은 내환원성을 강화시키는 역할을 하는데, 그 함량은 몰비로 0.1≤d≤1.5의 범위로 조성됨이 바람직하다. 만일 d가 0.1미만인 경우 반도체화되고 1.5 초과이면 절연저항이 저하된다.In addition, the chromium oxide serves to strengthen the reduction resistance, the content is preferably in the range of 0.1≤d≤1.5 in molar ratio. If d is less than 0.1, it is semiconductorized and if it is more than 1.5, the insulation resistance is lowered.
또한, 상기 산화니오븀은 신뢰성을 향상시키는 역할을 하는데, 그 함량은 몰비로 0.05≤e≤0.40의 범위로 조성됨이 바람직하다. 만일 e가 0.05미만이면 가속수명이 저하되고 0.40초과면 유전율과 절연저항이 감소된다.In addition, the niobium oxide serves to improve the reliability, the content is preferably in the range of 0.05≤e≤0.40 in molar ratio. If e is less than 0.05, the acceleration lifetime is lowered, and if it exceeds 0.40, the dielectric constant and insulation resistance are reduced.
또한, 상기 BaxCa(1-x)SiO3은 소결조제로서 몰비로, 0.2≤f≤3.0의 범위를 가짐이 바람직하다. 만일 f가 0.2미만이면 소결성이 나빠지고 온도특성이 규격에서 벗어나며 3.0초과면 유전율이 저하된다. 바람직하게는 상기 BaxCa(1-x)SiO3은 0.2≤x≤0.7로 구성된 것을 사용하는 것이다.The Ba x Ca (1-x) SiO 3 is preferably in a molar ratio as a sintering aid and has a range of 0.2 ≦ f ≦ 3.0. If f is less than 0.2, the sinterability deteriorates, the temperature characteristic is out of specification, and if it exceeds 3.0, the dielectric constant decreases. Preferably, Ba x Ca (1-x) SiO 3 is used that consists of 0.2≤x≤0.7.
이상과 같이 구성된 본 발명의 세라믹 유전체 조성물은 내환원성 조성이므로 Ni을 내부전극으로 하는 X7R규격(B특성)의 적층세라믹콘덴서의 유전체로 제조할 수 있다.Since the ceramic dielectric composition of the present invention configured as described above is a reducing-resistant composition, it can be made of a dielectric of a multilayer ceramic capacitor of X7R standard (B characteristic) using Ni as an internal electrode.
이하, 본 발명의 유전체 조성물을 이용하여 적층 세라믹 콘덴서를 제조하는 방법에 대하여 상세히 설명한다.Hereinafter, a method of manufacturing a multilayer ceramic capacitor using the dielectric composition of the present invention will be described in detail.
본 발명은 내부전극으로 Ni을 이용한 적층 세라믹 콘덴서의 제조에 매우 유용하다. 먼저, 상기한 조성이 되도록 BaTiO3, MgCO3, Y2O3, Cr2O3, Nb2O5분말과 소결조제로서 BaCO3, CaCO3및 SiO2분말을 평량하여 습식혼합하여 건조한다. 본 발명에서는 상기 Ba-Ca-Si-O는 소결조제로서 BaCO3, CaCO3및 SiO2분말을 미리 하소(calcination)하여 분쇄한 것을 사용하므로써, 하소전 pressing 처리작업을 없앨 수 있어 제조공정을 보다 단순화하는 잇점이 있다. 상기 소결조제 분말의 하소는 적어도 1000℃이상에서 2시간이상 행함이 바람직하다. 이렇게 하소된 소결조제는 그 입경이 약 0.85㎛이하가 되도록 planetary mill 등을 사용하여 분쇄한 다음, 건조함이 바람직하다.The present invention is very useful for the production of multilayer ceramic capacitors using Ni as the internal electrode. First, BaTiO 3 , MgCO 3 , Y 2 O 3 , Cr 2 O 3 , Nb 2 O 5 powder and BaCO 3 , CaCO 3 and SiO 2 powder as a sintering aid so as to have the composition described above are wet mixed and dried. In the present invention, the Ba-Ca-Si-O is calcined by calcination of BaCO 3 , CaCO 3 and SiO 2 powder in advance as a sintering aid, it is possible to eliminate the pressing treatment before calcination, the production process more There is an advantage to simplify. It is preferable that calcination of the said sintering aid powder is performed at least 1000 degreeC or more for 2 hours. The calcined sintering aid is preferably pulverized using a planetary mill or the like so that the particle size thereof is about 0.85 μm or less, and then dried.
그 다음, 건조된 분말에 바인더와 용매를 첨가하여 슬러리를 제조한다. 바인더로는 통상적인 바인더라면 어느 것이나 가능한데, 예를들면 폴리비닐부틸계 또는 아크릴계를 들 수 있다.Next, a binder and a solvent are added to the dried powder to prepare a slurry. As a binder, any conventional binder can be used, for example, polyvinyl butyl-type or acryl-type.
그 다음, 이 슬러리를 이용하여 통상의 방법과 마찬가지로 일정 형태의 시트상으로 성형하고, 성형된 시트 위에 Ni 내부전극을 인쇄한다. 그리고, 인쇄된 시트를 다수개 적층하여 가압하여 가압된 성형체를 일정 크기로 절단하고, 소부(baking out)하여 내부의 바인더를 제거한다.Then, this slurry is used to form a sheet into a certain form in the same manner as in the usual method, and Ni internal electrodes are printed on the formed sheet. Then, a plurality of printed sheets are laminated and pressed to cut the press-formed body into a predetermined size, and baking out to remove the binder therein.
이렇게 탈바인더 처리된 성형체는 1200~1250℃ 온도에서 소결한다. 본 발명의 유전체 조성물은 1200~1250℃의 온도에서 소결이 가능하므로 원가를 절감하며 유전체 결정립(grain) 크기의 저하로 높은 신뢰성을 얻을 수 있다.The binder removed in this way is sintered at a temperature of 1200 to 1250 ° C. Since the dielectric composition of the present invention can be sintered at a temperature of 1200 to 1250 ° C., cost can be reduced and high reliability can be obtained by decreasing the dielectric grain size.
이후, 상기 소결체의 양단에 외부전극을 형성하면 Ni을 내부전극으로 한 적층 세라믹 콘덴서가 얻어진다. 이와같이, 본 발명에 의해 제조된 콘덴서는 유독성 물질을 사용하지 않고도 저온소성이 가능하고 그 유전율이 2200이상인 X7R 특성을 보인다.Subsequently, when external electrodes are formed at both ends of the sintered body, a multilayer ceramic capacitor having Ni as an internal electrode is obtained. As described above, the capacitor manufactured by the present invention is capable of low temperature firing without using a toxic substance and exhibits X7R characteristics with a dielectric constant of 2200 or more.
이하, 본 발명을 다음의 실시예에서 구체적으로 설명하지만, 본 발명의 조성과 제조조건은 다음의 실시예로 한정되는 것이 아님은 물론이다.Hereinafter, the present invention will be described in detail in the following examples, but the composition and manufacturing conditions of the present invention are not limited to the following examples.
[실시예]EXAMPLE
출발원료로 99.5%이상의 순도를 갖는 BaTiO3, Y2O3, Cr2O3, Nb2O5, BaxCa(1-x)SiO3분말을 하기 표1의 각 조성이 되도록 평량하였다. 이때, 상기 BaxCa(1-x)SiO3분말은 BaCO3, CaCO3및 SiO2분말을 미리 하소하여 분쇄한 후 적용하였다.BaTiO 3 , Y 2 O 3 , Cr 2 O 3 , Nb 2 O 5 , Ba x Ca (1-x) SiO 3 powder having a purity of 99.5% or more as a starting material were weighed to have each composition of Table 1 below. At this time, the Ba x Ca (1-x) SiO 3 powder was applied after calcining and grinding BaCO 3 , CaCO 3 and SiO 2 powder in advance.
이렇게 평량된 조성분말에 폴리비닐부틸(PVB)계 바인더와 용매를 첨가하여 슬러리를 제조한 후 20㎛두께의 테입으로 성형하였다. 이 성형체에 Ni 내부전극을 인쇄한 후 상기 테입 성형체를 5층 적층하고, 절단하여 규격 3216 크기의 적층 콘덴서를 제조하였다.A polyvinyl butyl (PVB) -based binder and a solvent were added to the composition powder thus weighted to prepare a slurry, and then molded into a tape having a thickness of 20 μm. After the Ni internal electrode was printed on the molded body, five layers of the tape molded body were laminated and cut to prepare a multilayer capacitor having a standard size of 3216.
그 다음, 탈바인더 처리 후 표2와 같은 적정온도에서 2시간 소결하였다. 그리고, 소결된 칩의 양단에 In-Ga 전극처리를 하여 정전용량 및 유전손실을 -55∼125℃의 온도에서 LCR meter로 측정하였고, 유전율은 환산하여 표2에 기재하였다.Then, the binder was sintered at an appropriate temperature as shown in Table 2 for 2 hours. In-Ga electrode treatment was performed on both ends of the sintered chip to measure capacitance and dielectric loss with an LCR meter at a temperature of −55 to 125 ° C., and the dielectric constants thereof were shown in Table 2 below.
표2에 나타난 바와 같이, 산화니오븀이 적게 함유된 유전체 조성물을 사용한 비교재1의 경우 온도변화에 따른 용량변화가 심하고, 많이 첨가된 비교재2의 경우 유전체의 특성을 잃어 버렸다.As shown in Table 2, in Comparative Material 1 using a dielectric composition containing less niobium oxide, the capacity change was severe according to the temperature change, and in the case of Comparative Material 2 which was added a lot, the characteristics of the dielectric material were lost.
또한, Ba-Ca-Si-O계 소결조제가 적은 비교재3의 경우 저온 소성이 불가능하였으며, 보다 많이 첨가된 비교재4의 경우에는 유전율이 크게 떨어져 바람직하지 않음을 알 수 있다.In addition, low-temperature firing was not possible in the case of the comparative material 3 containing less Ba-Ca-Si-O-based sintering aid, and in the case of the comparative material 4 added more, the dielectric constant was greatly decreased, which is not preferable.
그리고, 주 첨가제인 MgCO3, Y2O3또는 Cr2O3가 조건범위를 만족하지 않는 비교재(5-9)의 경우에는 온도에 따른 용량이 떨어지거나 반도체화되어 버림을 알 수 있다.In the case of the comparative material (5-9) in which the main additive MgCO 3 , Y 2 O 3, or Cr 2 O 3 does not satisfy the condition range, it can be seen that the capacity according to temperature falls or becomes semiconductor.
반면, 본 발명의 유전체 조성물을 사용한 발명재(1-10)의 경우에는 유전율이 2200이상을 상회하는 X7R 특성을 갖으면서도 저온소성에 의해 유전층과 Ni내부전극간의 수축률이 감소되어 신뢰성이 큰 내환원성 적층 세라믹 콘덴서가 얻어짐을 알 수 있다.On the other hand, in the case of the inventive material (1-10) using the dielectric composition of the present invention, the shrinkage between the dielectric layer and the Ni internal electrode is reduced by low temperature sintering, but the X7R characteristic has a dielectric constant of more than 2200 or more, thereby reducing the reliability. It can be seen that a multilayer ceramic capacitor is obtained.
상술한 바와 같이, 본 발명의 유전체 조성물은 일단 유독성 첨가제가 함유되지 않으며, 이러한 유전체 조성물을 이용하여 적층 세라믹 콘덴서를 제조할 경우 저온 소성이 가능하여 Ni 내부전극층과 유전체간의 수축률의 차이가 감소되고, 이에 따라 높은 신뢰성을 보여 X7R 특성에 매우 적합한 적층 세라믹 콘덴서에 유용한 효과가 있다.As described above, the dielectric composition of the present invention does not contain toxic additives once, and when the multilayer ceramic capacitor is manufactured using the dielectric composition, low-temperature firing is possible, thereby reducing the difference in shrinkage between the Ni internal electrode layers and the dielectric, As a result, it has a high reliability and is useful for multilayer ceramic capacitors which are very suitable for X7R characteristics.
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