KR100206388B1 - Dielectric composition of non-reductive property - Google Patents
Dielectric composition of non-reductive property Download PDFInfo
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- KR100206388B1 KR100206388B1 KR1019970022936A KR19970022936A KR100206388B1 KR 100206388 B1 KR100206388 B1 KR 100206388B1 KR 1019970022936 A KR1019970022936 A KR 1019970022936A KR 19970022936 A KR19970022936 A KR 19970022936A KR 100206388 B1 KR100206388 B1 KR 100206388B1
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Abstract
본 발명은 [(Ba, Ca, Sr)O]m[(Ti, Zr)O2]를 기본조성으로 하되, Ni 전극의 산화를 억제하는 첨가제를 첨가하므로서, 강한 환원성 분위기에서 소결후에도 절연저항의 열화가 거의 없는 내환원성 유전체 조성물을 제공하고자 하는데, 그 목적이 있다.The present invention is based on [(Ba, Ca, Sr) O] m [(Ti, Zr) O 2 ], but by adding an additive which inhibits oxidation of the Ni electrode, it is possible to maintain insulation resistance even after sintering in a strong reducing atmosphere. It is an object of the present invention to provide a reducing resistant dielectric composition with little degradation.
본 발명은 내환원성 유전체 조성물에 있어서, 몰%로, BaTiO3:82-86%, CaZrO3:4-7%, SrZrO3:9-13%, SrCO3:2.5%이하로 이루어지는 기본조성에 MnO2:0.1-0.3wt% 및 SiO2:0.2-0.4wt%가 첨가되어 조성되는 내환원성 유전체 조성물에 관한 것을 그 요지로 한다.The present invention provides MnO in a basic composition comprising, in mol%, BaTiO 3 : 82-86%, CaZrO 3 : 4-7%, SrZrO 3 : 9-13%, SrCO 3 : 2.5% or less in mol%. The summary relates to a reducing-resistant dielectric composition comprising 2 : 0.1-0.3 wt% and SiO 2 : 0.2-0.4 wt% added.
Description
본 발명은 적층 세라믹 커퍼시터(Multi-Layer Ceramic Capacitor, 이하, MLCC라함)에 사용되는 유전체 조성물에 관한 것으로서, 보다 상세하게는 1㎌이상의 대용량 MLCC에 사용되는 내환원성 유전체 조성물에 관한 것이다.The present invention relates to a dielectric composition for use in a multilayer ceramic capacitor (hereinafter referred to as MLCC), and more particularly, to a reducing-resistant dielectric composition for use in a large capacity MLCC of 1 micron or more.
일반적으로 MLCC는 유전체를 이용하여 시트를 성형한 후 내부전극과 적층하여 대기중에서 소결하여 제조한다.In general, MLCC is manufactured by forming a sheet using a dielectric and laminating with an internal electrode and sintering in the air.
종래에는 MLCC의 유전체로서 BaTiO3계를 사용하고 내부전극으로서는 고가의 Pd를 사용하였으나, 1㎌이상의 대용량품에 있어서는 50층 이상으로 고적층이 되면서 전극면적이 커지므로 내부전극 재료의 코스트가 현격하게 높아지는 단점이 있었다.Conventionally, the BaTiO 3 system is used as the dielectric of MLCC and expensive Pd is used as the internal electrode. However, the cost of the internal electrode material is remarkably increased because the electrode area is increased to 50 layers or more for large-capacity products of 1 품 or more. There was a disadvantage of increasing.
이러한 내부전극에 대한 코스트절감을 위하여 여러가지 방법들이 제시되었는데, 그 대표적인 방안들은 다음과 같이 내부전극으로서 (1) 비교적 저가격의 Ag-Pd을 이용하여 저온소결하는 방법; (2) Ni, Cu등의 비금속(base metal)을 이용하는 방법; 및 (3) 내부전극부에 Pb등의 저융점 금속을 주입하는 방법 등이 연구되어 왔다.Various methods have been proposed to reduce the cost of such internal electrodes, and representative methods include (1) low temperature sintering using Ag-Pd of relatively low cost as internal electrodes; (2) a method of using base metals such as Ni and Cu; And (3) a method of injecting a low melting point metal such as Pb into the internal electrode portion.
상기 방법들 중 특히 Ni 내부전극을 이용하여 유전체와 전극을 동시에 소결하는 방법이 주목받고 있는데, 이때 Ni의 산화를 억제하는 저산소 분압하에서 소결하여도 절연저항의 열화가 일어나지 않는 내환원성 유전체의 개발이 요구되고 있다.Among the above methods, in particular, a method of simultaneously sintering a dielectric and an electrode using a Ni internal electrode has been attracting attention, and at this time, development of a reducing-resistant dielectric that does not cause deterioration of insulation resistance even when sintering under low oxygen partial pressure that suppresses oxidation of Ni It is required.
이와같은 유전체와 Ni 내부전극을 동시에 소결하는 유전체 제조에 관한 대표적인 기술로는 무라타(Murata)등이 제시한 일본공개특허공보 평 3-26378호에 의한 것을 들 수 있는데, 상기 유전체는 BaTiO3계에 SrZrO3를 5-30몰%, CaZrO3를 0.5-2.2몰% 첨가하여 [(Ba, Ca, Sr)O]m[(Ti, Zr)O2]를 기본 조성으로 하고 있다.In a typical description of the same dielectric as the dielectric of manufacturing a sintered Ni of the internal electrode at the same time, there can be mentioned that according to JP-A-3-26378 proposed a number such as Murata (Murata), the genome is based on BaTiO 3 and 5 to 30 mol% of SrZrO 3, CaZrO 3 was added 0.5-2.2 mol% and a [(Ba, Ca, Sr) O] m [(Ti, Zr) O 2] in the basic composition.
그러나, 상기 유전체는 내부전극과 동시 소결시 저산소 분압하에서 내환원성이 저하되는 단점이 있다.However, the dielectric has a disadvantage in that the reduction resistance under low oxygen partial pressure when co-sintering with the internal electrode is lowered.
따라서, 본 발명은 상기한 문제점을 해결하고자 제안된 것으로서, [(Ba, Ca, Sr)O]m[(Ti, Zr)O2]를 기본조성으로 하되, Ni 전극의 산화를 억제하는 첨가제를 첨가하므로서, 강한 환원성 분위기에서 소결후에도 절연저항의 열화가 거의 없는 내환원성 유전체 조성물을 제공하고자 하는데, 그 목적이 있다.Therefore, the present invention is proposed to solve the above problems, [[Ba, Ca, Sr) O] m [(Ti, Zr) O 2 ] as a basic composition, but the additive to suppress the oxidation of the Ni electrode It is an object of the present invention to provide a reducing-resistant dielectric composition with little degradation of insulation resistance even after sintering in a strong reducing atmosphere.
본 발명은 내환원성 유전체 조성물에 있어서, 몰%로, BaTiO3:82-86%, CaZrO3:4-7%, SrZrO3:9-13%, SrCO3:2.5%이하로 이루어지는 기본조성에 MnO2:0.1-0.3wt% 및 SiO2:0.2-0.4wt%가 첨가되어 조성되는 내환원성 유전체 조성물에 관한 것이다.The present invention provides MnO in a basic composition comprising, in mol%, BaTiO 3 : 82-86%, CaZrO 3 : 4-7%, SrZrO 3 : 9-13%, SrCO 3 : 2.5% or less in mol%. 2 : 0.1-0.3 wt% and SiO 2 : 0.2-0.4 wt% are added.
이하, 본 발명의 유전체 조성물에 대한 수치한정 이유에 대하여 상세히 설명한다.Hereinafter, the reason for numerical limitation of the dielectric composition of the present invention will be described in detail.
본 발명은 BaTiO3를 기본으로 하며 [(Ba, Ca, Sr)O]m[(Ti, Zr)O2] 형태의 기본조성으로 나타나지만, 상기 BaTiO3의 함유량이 82몰% 보다 적거나 86몰% 이상으로 되면 유전율이 저하되기 때문에 그 함유량을 82-86몰%로 제한함이 바람직하다.The present invention is based on BaTiO 3 and appears as a basic composition in the form of [(Ba, Ca, Sr) O] m [(Ti, Zr) O 2 ], but the content of BaTiO 3 is less than 82 mol% or 86 mol If it is more than%, the dielectric constant decreases, so the content is preferably limited to 82-86 mol%.
본 발명에서 Zr과 Sr은 큐리온도(Tc)를 이동시키는 역활을 하고, Ca는 일부가 Ti-Site로 치환되어 환원 분위기하에서 소결하여도 절연저항이 저하되지 않도록 하는 역활을 하는데, 상기 CaZrO3및 SrZrO3가 과잉으로 첨가되는 경우 큐리온도가 매우 저온으로 이동하여 상온 유전율이 7000 이하로 저하되며, 너무 적게 첨가되면 소결성이 저하되어 유전율이 감소하므로 상기 CaZrO3및 SrZrO3는 각각 4-7몰% 및 9-13몰%로 첨가함이 바람직하다.In the present invention, Zr and Sr plays a role of shifting the Curie temperature (Tc), and Ca is a part of Ti-Site is substituted to Ti-Site so as not to lower the insulation resistance even when sintered in a reducing atmosphere, the CaZrO 3 and When SrZrO 3 is added in excess, the Curie temperature moves to a very low temperature and the dielectric constant of room temperature is lowered to 7000 or less. If too little is added, the CaZrO 3 and SrZrO 3 are each 4-7 mol% because the sinterability decreases. And 9-13 mol%.
한편, 상기 SrCO3는 [(Ba, Ca, Sr)O]m[(Ti, Zr)O2] 형태를 기본조성으로 하는 본 발명의 유전체에 첨가되어 Ba-사이트(Ba-site)에 치환되면서 Ba:Ti의 몰비를 1이상이 되도록 하여 유전체의 내환원성을 향상시키는 역할을 한다. 따라서, SrCO3이 첨가되지 않는 경우에는 내환원성이 없어 유전체가 환원되므로 바람직하지 않다. 그러나, 상기 SrCO3의 양이 2.5몰% 이상으로 첨가되면 유전율이 저하되므로 2.5몰% 이하로 첨가함이 바람직하다.On the other hand, the SrCO 3 is added to the dielectric material of the present invention based on the form of [(Ba, Ca, Sr) O] m [(Ti, Zr) O 2 ] form to be substituted for Ba-site (Ba-site) The molar ratio of Ba: Ti is set to 1 or more, which serves to improve the reduction resistance of the dielectric. Therefore, when SrCO 3 is not added, it is not preferable because there is no reduction resistance and the dielectric material is reduced. However, when the amount of SrCO 3 is added at 2.5 mol% or more, the dielectric constant is lowered, so it is preferable to add it at 2.5 mol% or less.
상기 MnO2는 유전체에 내환원성을 부여하는 역활을 하는 성분으로서, 그 첨가량은 기본조성에 대하여 0.1-0.3wt%로 첨가됨이 바람직한데, 그 이유는 상기 MnO2가 0.1wt% 이하로 첨가되면 유전체가 내환원성을 나타내지 않으며, 상기 MnO2가 0.3wt% 이상으로 첨가되면 유전율이 저하되기 때문이다.The MnO 2 is a component that imparts reduction resistance to the dielectric, and the amount of the MnO 2 is preferably added in an amount of 0.1-0.3 wt% with respect to the basic composition, because the MnO 2 is added in an amount of 0.1 wt% or less. This is because the dielectric material does not exhibit reduction resistance, and when the MnO 2 is added at 0.3 wt% or more, the dielectric constant decreases.
상기 SiO2는 소결온도를 하향화하는 소결조제의 역할을 하는데, 그 함유량이 0.2wt% 이하로 첨가되면 소결온도 감소효과가 미흡하고, 0.4wt% 이상이면 유전율이 저하되어 바람직하지 않다.The SiO 2 serves as a sintering aid to lower the sintering temperature, but when the content is added to 0.2wt% or less, the effect of reducing the sintering temperature is insufficient, and if it is 0.4wt% or more, the dielectric constant decreases, which is not preferable.
상기한 조성을 갖는 유전체 조성물은 [(Ba, Ca, Sr)O]m[(Ti, Zr)O2]를 기본조성하여, 여기에 MnO2및 SiO2등이 첨가되어 있어 강한 환원성 분위기에서 Ni 내부전극과 동시에 소결하여도 절연저항이 열화되지 않는 특징이 있다.The dielectric composition having the above-described composition basically forms [(Ba, Ca, Sr) O] m [(Ti, Zr) O 2 ], and MnO 2 and SiO 2 are added thereto to form Ni in a strong reducing atmosphere. Insulation resistance does not deteriorate even when sintered simultaneously with the electrode.
본 발명에 따른 유전체는 통상의 방법으로 소결해도 좋으나, 10-8-10-13atm의 산소분압하에서 1250-1350℃의 온도범위에서 소결함이 보다 바람직하다.The dielectric according to the present invention may be sintered by a conventional method, but more preferably sintered at a temperature range of 1250-1350 ° C. under an oxygen partial pressure of 10 −8 −10 −13 atm.
상기와 같이 제조되는 본 발명의 유전체는 절연저항(IR)이 109Ω.㎝ 이상, 상온 유전상수가 8,000 이상, 상온 유전손실이 2.0% 이하의 우수한 특성을 얻을 수 있다.The dielectric of the present invention prepared as described above can obtain excellent characteristics of insulation resistance (IR) of 10 9 Ω.cm or more, room temperature dielectric constant of 8,000 or more, room temperature dielectric loss of 2.0% or less.
이하, 본 발명을 실시예를 통하여 구체적으로 설명한다.Hereinafter, the present invention will be described in detail through examples.
[실시예]EXAMPLE
하기 표1과 같은 조성을 갖도록 1um 이하의 분말원료를 약 50g 정도 배합하고, 1150℃의 온도에서 2시간정도 하소한 다음, 직경 10㎜, 두께 1㎜ 이하의 디스크 형태로 성형하였다.About 50 g of a powder raw material of 1 μm or less was blended to have a composition as shown in Table 1, and then calcined at a temperature of 1150 ° C. for about 2 hours, and then molded into a disk shape having a diameter of 10 mm and a thickness of 1 mm or less.
이후, 성형된 디스크를 약 200℃/hr의 승온속도로 승온시켜 10-8-10-13atm의 산소분위기에서 하기표 과 같은 소결온도에서 2시간정도 소결한 다음, 동일한 속도로 냉각시키고, 제조된 유전체 디스크에 대하여 절연저항, 상온 유전상수, 상온유전손실을 측정하고, 그 결과를 하기 표2에 나타내었다.Thereafter, the molded disk was heated at a heating rate of about 200 ° C./hr, sintered at an sintering temperature of about 10 hours in an oxygen atmosphere of 10 −8 −10 −13 atm, and then cooled at the same rate, and manufactured. Insulation resistance, room temperature dielectric constant, and dielectric loss at room temperature were measured for the prepared dielectric disk, and the results are shown in Table 2 below.
상기 표2에 나타난 바와같이 본 발명에 따른 조성범위를 만족하는 유전체는 저산소 분위기하에서 소결하여도 통상의 유전체가 갖는 절연저항인 108보다 큰 절연저항을 갖으므로서, 내환원성이 우수한 유전체로 사용이 가능함을 알 수 있다.As shown in Table 2, the dielectric satisfying the composition range according to the present invention has an insulation resistance greater than 10 8 , which is an insulation resistance of a conventional dielectric even when sintered in a low oxygen atmosphere, and thus is used as a dielectric having excellent reduction resistance. It can be seen that this is possible.
상술한 바와같이, 본 발명에 따른 유전체는 비금속(base metal)인 Ni 내부전극과 함께 환원분위기 하에서 동시 소결하여도 Ni 전극의 산화를 억제할 뿐만아니라 유전체 바디의 절연저항의 열화가 없는 MLCC를 제조할 수 있는 효과가 있다.As described above, the dielectric according to the present invention not only suppresses oxidation of the Ni electrode but also deteriorates the insulation resistance of the dielectric body even when simultaneously sintered together with a base metal of Ni internal electrode under a reducing atmosphere. It can work.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019940017807A KR0119124B1 (en) | 1994-07-22 | 1994-07-22 | Reducing Resistance Dielectric Composition |
| KR1019970022939A KR100224928B1 (en) | 1997-06-03 | 1997-06-03 | RF-IC Card Offline Parking Management System |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1019940017807A Division KR0119124B1 (en) | 1994-07-22 | 1994-07-22 | Reducing Resistance Dielectric Composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115985684A (en) * | 2022-08-01 | 2023-04-18 | 上海火炬电子科技集团有限公司 | Ceramic dielectric material with stable temperature of copper inner electrode and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115985684A (en) * | 2022-08-01 | 2023-04-18 | 上海火炬电子科技集团有限公司 | Ceramic dielectric material with stable temperature of copper inner electrode and preparation method thereof |
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