KR20190015434A - Dielectric ceramic composition and electronic device using the same - Google Patents
Dielectric ceramic composition and electronic device using the same Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 239000000919 ceramic Substances 0.000 title claims abstract description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 17
- 239000003985 ceramic capacitor Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000006104 solid solution Substances 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000370 acceptor Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- 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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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
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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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Abstract
Description
본 발명은 유전체 자기조성물 및 이를 적용한 전자소자에 관한 것으로서, 보다 상세하게는 EIA 규격에서 명시한 X5R, X7R, 그리고 X8R 특성을 만족하는 유전체 자기조성물 및 이를 적용한 전자소자에 관한 것이다.
SUMMARY OF THE INVENTION [ The magnetic composition and This More particularly, to a dielectric ceramic composition satisfying the X5R, X7R, and X8R characteristics specified in the EIA standard, and an electronic device using the dielectric ceramic composition.
기존의 X5R, X7R 혹은 X8R등의 고용량 BME 적층세라믹캐패시터의 유전체재료의 조성 시스템은 주성분 재료인 BaTiO3 혹은 (Ba1 - xCax)(Ti1 - yCay)O3, 등의 모재에 대략 4부류 이상의 첨가제 부성분들을 필수적으로 포함한다. 첨가제 부성분 중에서 가장 큰 비율을 차지하는 것은 원자가고정 억셉터 (fixed-valence acceptor)인 Mg 등과 희토류 원소 (rare-earth elements)이며, 그 외에 원자가가변 억셉터 (variable-valence acceptor)가 이들 양보다 소량 첨가되고, 소결성 증진을 위해 소결조제(sintering aids)가 포함되게 된다. 이와 같은 기존의 조성시스템은 공통적으로 희토류원소 (rare-earth element) 및 원자가고정 억셉터 (fixed-valence acceptor)인 Mg 등이 BaTiO3와 반응하여 코어-쉘 구조를 형성하며, 이는 정상적인 적층세라믹캐패시터의 특성구현을 위해 필요하다. BaTiO3 모재를 적용하여 큐리온도를 상승시키기 위해서는 CaZrO3를 첨가하거나 과량의 희토류 원소를 첨가하여 큐리온도 이상에서 유전율의 감소정도를 완화시키는 방법이 알려져 있다.
The composition system of dielectric materials of high capacity BME multilayer ceramic capacitors such as X5R, X7R or X8R is composed of BaTiO 3 or (Ba 1 - x Ca x ) (Ti 1 - y Ca y ) O 3 which is the main component material. Essentially comprising at least four classes of additive subcomponents. The largest proportion of the additive subcomponents are Mg and rare-earth elements, which are fixed-valence acceptors, and variable-valence acceptors are added in smaller quantities than these quantities. And sintering aids are included for the sinterability enhancement. In such conventional composition systems, rare-earth elements and Mg, which are fixed-valence acceptors, react with BaTiO 3 to form a core-shell structure, which is a normal multilayer ceramic capacitor Is required for the characterization of In order to increase the Curie temperature by applying BaTiO 3 base material, it is known to add CaZrO 3 or excess rare earth element to relax the degree of decrease of the permittivity above the Curie temperature.
본 발명은 EIA 규격에서 명시한 X5R, X7R, 그리고 X8R 특성을 만족하는 유전체 자기조성물로서, 니켈을 내부전극으로 사용하고 1300℃ 이하에서 상기 니켈이 산화되지 않는 환원분위기에서 소성이 가능한 유전체 자기조성물과 이를 이용한 전자소자를 제공하는데 그 목적이 있다.
The present invention relates to a dielectric ceramic composition that satisfies the X5R, X7R, and X8R characteristics specified in the EIA standard and uses a nickel as an internal electrode and is capable of being fired in a reducing atmosphere in which the nickel is not oxidized at 1300 ° C or lower, And an electronic device using the same.
본 발명에서는 BaTiO3와 (Na,K)NbO3를 적정비율로 혼합하거나, 고용체를 형성하도록 하고, SiO2 및 MnO2를 소량 첨가하여 소결체를 제작함으로써 상온에서 1500 이상의 비교적 높은 유전율을 유지할 수 있도록 하고, 동시에 X8R 온도특성을 충족시킬 수 있도록 한다.
In the present invention, a sintered body is prepared by mixing BaTiO 3 and (Na, K) NbO 3 at a proper ratio or by forming a solid solution and adding a small amount of SiO 2 and MnO 2 so that a relatively high dielectric constant of 1500 or more can be maintained at room temperature And simultaneously satisfy the X8R temperature characteristics.
본 발명에 따르면, 모재 파우더에 환경에 유해한 납 (Pb)을 사용하지 않으면서도, 큐리온도 상승 및 고온부 유전율이 평탄해지는 특성을 구현할 수 있고, X8R 온도 특성 및 양호한 고온내전압 특성을 만족시킬 수 있다.
According to the present invention, it is possible to realize a characteristic in which the Curie temperature is elevated and the dielectric constant of the high temperature portion becomes flat without using lead (Pb) which is harmful to the environment in the base material powder, and X8R temperature characteristic and good high temperature withstand voltage characteristic can be satisfied.
이하, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 150도까지 온도 특성 및 신뢰성이 보증되는 X8R 특성을 충족시키는 신규 유전체 자기조성물에 관한 것이다. The present invention relates to a novel dielectric ceramic composition that satisfies the X8R characteristics of which temperature characteristics and reliability are guaranteed up to 150 degrees.
고용량 Ni-MLCC의 주 재료인 BaTiO3의 경우 큐리온도 (TC)가 125도 부근이며, 이 온도이상에서는 유전율이 급격하게 낮아지는 현상이 있으므로, 150도까지 용량 온도특성을 X8R 규격 ±15% 이내로 맞추기 위해서는 이에 맞는 조성이 요구된다. BaTiO 3 , which is the main material of high-capacity Ni-MLCC, has a Curie temperature (TC) of about 125 ° C. and above this temperature, the dielectric constant sharply decreases. In order to meet this, a composition is required.
예를 들면, BaTiO3 모재에 희토류 원소를 과량 첨가하여 큐리온도 이상에서 유전율 감소정도를 완화시키거나, CaZrO3를 적정량 첨가하면 큐리온도가 상승하여 고온부 TCC (Temperature Coefficient of Capacitance)가 개선될 수 있다는 보고가 있다 (일본공개특허 2001-279534, 2004-73856 등). 그러나 희토류를 과량 첨가하는 경우 Pyrochlore라는 이차상이 생성되어 신뢰성이 저하되는 문제가 있으며 (Yoon et al., J. Mater. Res., 22[9] 2539 (2007)), 큐리온도가 125도인 BaTiO3 모재에 희토류를 과량으로 첨가하거나, CaZrO3를 첨가하는 경우, X8R 특성을 만족한다고 하더라도 우수한 고온부 TCC 특성을 얻는데 한계가 있다.For example, if the rare earth element is added to the BaTiO 3 base material in an excessive amount to alleviate the degree of decrease in the dielectric constant above the Curie temperature, or if an appropriate amount of CaZrO 3 is added, the Curie temperature may rise and the TCC (Temperature Coefficient of Capacitance) (Japanese Patent Application Laid-Open No. 2001-279534, 2004-73856, etc.). However, when an excess amount of rare earth is added, a secondary phase called Pyrochlore is generated and reliability is degraded (Yoon et al., J. Mater. Res., 22 [9] 2539 (2007)), BaTiO 3 When rare earths are added to the base material in an excessive amount or when CaZrO 3 is added, there is a limit to obtaining excellent TCC characteristics at high temperature even when the X8R characteristics are satisfied.
또 다른 방법으로, 큐리 온도가 높은 파우더를 적용하여 고온부 TCC를 개선할 수 있다. Ca이 ABO3 Perovskite 구조의 A-site에 고용이 되면 큐리 온도가 올라가는 것으로 알려져 있으며, 이러한 Ca이 고용된 BaTiO3 (BCT) 파우더를 적용하면 고온부 TCC 특성을 향상시킬 수 있어 X8R 재료로서의 가능성이 제시된 바가 있다. (Yoon et al., J. Mater. Res., 25[11] 2135 (2010)). 고상법으로 공기 중에서 하소하여 BaTiO3를 합성하는 경우, 큐리온도를 높일 수 있는 원소로 현재까지 알려진 것은 앞서 말한 Ca 이외에 Pb도 있다. 그런데 Pb의 경우 유해물질로 분류되어 있고, Ni-적층세라믹 캐패시터와 같이 환원분위기에서 소성하는 경우 쉽게 휘발하는 문제가 발생하여 공정상 적용하기가 곤란하다.As another method, high temperature TCC can be improved by applying a powder having a high Curie temperature. It is known that when Ca is added to the A-site of the ABO 3 perovskite structure, the Curie temperature rises. When such Ba-TiO 3 (BCT) powder is used, the TCC characteristics at high temperature can be improved. There is a bar. (Yoon et al., J. Mater. Res., 25 [11] 2135 (2010)). When BaTiO 3 is synthesized by calcination in the air using the solid phase method, Pb is also known in addition to Ca as mentioned above as an element capable of raising the Curie temperature. However, Pb is classified as a harmful substance, and when it is fired in a reducing atmosphere such as a Ni-multilayer ceramic capacitor, it easily volatilizes and it is difficult to apply it to the process.
본 발명은 BaTiO3와 (Na,K)NbO3를 적정 비율로 혼합하거나 고용체를 형성하고, SiO2 및 MnO2를 소량 첨가하여 소결체를 제작함으로써, 유전율이 1500 이상이고 절연저항이 우수하며 X8R 온도특성을 구현할 수 있는 자기조성물을 제시한다. 즉, CaZrO3나 과량의 희토류 원소를 첨가하지 않아도 X8R 특성 구현이 가능하며 기존의 BaTiO3 모재를 적용한 경우에 비해 보다 양호한 고온부 TCC 특성 구현이 가능하다. The present invention relates to a method for producing a sintered body by mixing BaTiO 3 and (Na, K) NbO 3 in an appropriate ratio or forming a solid solution, and adding a small amount of SiO 2 and MnO 2 to produce a sintered body. ≪ RTI ID = 0.0 > characteristic. ≪ / RTI > In other words, it is possible to realize X8R characteristics without adding CaZrO 3 or excessive rare earth element, and it is possible to realize better TCC characteristics at high temperature compared with the case of using BaTiO 3 base material.
본 발명의 일 측면에 따르면, 제1 주성분 BaTiO3와 제2 주성분 (Na1-yKy)NbO3의 고용체인 (1-x)BaTiO3-x(Na1 - yKy)NbO3(0.005≤x≤0.5, 0.3≤y≤1.0)를 주성분으로 하고, Mn, V, Cr, Fe, Ni, Co, Cu 및 Zn로 이루어진 군에서 선택되는 원소를 포함하는 제1 부성분, 및 SiO2 또는 이를 포함하는 유리 형성 물질을 제2 부성분으로 포함하는 유전체 자기조성물이 제공된다. According to an aspect of the invention, first the main component BaTiO 3 and the second main component (Na1-yKy) NbO 3 employs chains (1-x) of the BaTiO 3 -x (Na 1 - y K y) NbO 3 (0.005≤x as a main component a ≤0.5, 0.3≤y≤1.0) and, Mn, V, Cr, Fe, Ni, Co, comprising a first sub-component, and SiO 2 or them containing an element selected from the group consisting of Cu and Zn There is provided a dielectric ceramic composition comprising a glass forming material as a second accessory ingredient.
상기에서 x 및 y의 범위는 상기 조성 및 본 발명의 실시예에 따라 도출된 표 1과 표 2의 실험결과를 바탕으로 하고 있다.The ranges of x and y in the above are based on the experimental results of Tables 1 and 2 derived in accordance with the above composition and embodiments of the present invention.
유전체 자기 조성물은, 제1주성분 BaTiO3와 제2주성분 (Na,K)NbO3를 혼합 고용하여 모재를 구성하고, 첨가제로는 제1부성분인 원자가가변 억셉터 (variable-valence acceptor) 원소 산화물 혹은 탄산염, 제2부성분인 SiO2를 포함한다. 상기 합성된 모재는 파우더의 형태로서, 그 입자크기는 1.0㎛ 이하가 바람직하다.The dielectric ceramic composition may be prepared by mixing the first main component BaTiO 3 and the second main component (Na, K) NbO 3 to form a base material. The additive may be a first subcomponent variable-valence acceptor element oxide or Carbonate, and SiO 2 as a second subcomponent. The synthesized base material is in the form of powder, and its particle size is preferably 1.0 탆 or less.
일 실시예에 있어서, 상기 제1 부성분은 Mn, V, Cr, Fe, Ni, Co, Cu 및 Zn로 이루어진 군에서 선택되는 원소의 산화물 또는 탄산염일 수 있다.In one embodiment, the first subcomponent may be an oxide or a carbonate of an element selected from the group consisting of Mn, V, Cr, Fe, Ni, Co, Cu and Zn.
일 실시예에 있어서, 상기 제1 부성분은 MnO2 또는 MnCO3일 수 있다.In one embodiment, the first subcomponent is MnO 2 Or MnCO be three days.
일 실시예에 있어서, 상기 제1 부성분의 함량은 0.1~5.0at%일 수 있다.In one embodiment, the content of the first accessory ingredient may be 0.1 to 5.0 at%.
일 실시예에 있어서, 상기 제2 부성분 중 SiO2의 함량이 0.1~5.0at%일 수 있다.In one embodiment, the content of SiO 2 in the second subcomponent may be 0.1 to 5.0 at%.
상기에서 각 성분의 함량 범위는 하기 표 1 및 표 2의 실험결과를 바탕으로 한 것이다.The content ranges of the above components are based on the experimental results shown in Tables 1 and 2 below.
본 발명의 다른 측면에 따르면, 상기 유전체 자기조성물을 이용하여 형성된 유전체를 포함하는 전자소자가 제공될 수 있다.According to another aspect of the present invention, an electronic device including a dielectric formed using the dielectric ceramic composition may be provided.
일 실시예에 있어서, 상기 전자소자는 적층세라믹 캐패시터, 압전 소자, 칩인덕터, 칩 배리스터, 칩저항 및 PTCR (Positive Temperature Coefficient Resistor) 로 이루어진 군에서 선택되는 하나 이상일 수 있다.In one embodiment, the electronic device may be at least one selected from the group consisting of a multilayer ceramic capacitor, a piezoelectric device, a chip inductor, a chip varistor, a chip resistor, and a Positive Temperature Coefficient Resistor (PTCR).
특히 본 발명의 유전체 자기조성물은 적층형 유전체 제품, 내부 전극층, 예를 들면, Ni 내부 전극층과 유전체층이 교대로 적층되어진 제품에 사용이 가능하다. 너무 얇은 두께의 유전체층은 한층 내에 존재하는 결정립 수가 작아 신뢰성에 나쁜 영향을 미칠 수 있으므로, 유전체 층의 두께는 소성 후, 0.1㎛ 이상의 범위에서 사용하는 것이 바람직하다.
In particular, the dielectric ceramic composition of the present invention can be used for a laminated dielectric product, an internal electrode layer, for example, a product in which a Ni internal electrode layer and a dielectric layer are alternately laminated. Since the dielectric layer having too thin a thickness has a small number of crystal grains existing in one layer and may adversely affect the reliability, the thickness of the dielectric layer is preferably used in a range of 0.1 탆 or more after firing.
[실시예][Example]
모재파우더인 주성분 (1-x)BaTiO3-x(Na1 - yKy)NbO3 혼합 고용체 파우더는 다음과 같이 고상법을 적용하여 제조하였다. 출발원료는 BaCO3, TiO2, Na2O, K2O, Nb2O5 이다. 먼저 BaCO3와 TiO2를 볼밀로 혼합하고 900~1000℃ 범위에 하소하여 평균입자 크기 300nm의 BaTiO3 파우더를 준비하였다. 유사한 방법으로 Na2O, K2O, 그리고 Nb2O5 볼밀 혼합하고 800~900℃ 범위에서 하소하여 평균입자 크기 300nm의 (Na0.5K0.5)NbO3 파우더를 준비하였다. 하기 표 1에 명시된 조성비에 맞게 이들을 에탄올에 분산 및 혼합시켰다. 이 혼합된 파우더들을 공기 중 950~1050℃ 범위에서 하소하여 평균입자 크기 300 nm 정도의 모재파우더를 제작하였다. 이와 같은 주성분 모재파우더에 부성분 첨가제 MnO2와 SiO2 파우더를 표 1에 명시된 조성비에 맞게 첨가한 후, 주성분과 부성분이 포함된 원료 분말을 지르코니아 볼을 혼합/분산 메디아로 사용하고 에탄올/톨루엔과 분산제 및 바인더를 혼합한 후, 20 시간 동안 볼밀링 하였다. 제조된 슬러리는 닥터 블레이드 방식의 코터를 이용하여 10 ㎛의 두께로 성형시트를 제조하였다.A base material powder of the main component (1-x) BaTiO 3 -x (Na 1 - y K y) NbO 3 solid solution powder mixture is prepared by applying a conventional method and as follows. The starting material is BaCO 3, TiO 2, Na 2 O, K 2 O, Nb 2 O 5. First, BaCO 3 and TiO 2 were mixed with a ball mill and calcined in the range of 900 to 1000 ° C to prepare a BaTiO 3 powder having an average particle size of 300 nm. (Na 0.5 K 0.5 ) NbO 3 powder having an average particle size of 300 nm was prepared by mixing Na 2 O, K 2 O, and Nb 2 O 5 ball mills in a similar manner and calcining in the range of 800 to 900 ° C. They were dispersed and mixed in ethanol in accordance with the composition ratios shown in Table 1 below. The mixed powders were calcined in air at 950 ~ 1050 ℃ to prepare a base powder having an average particle size of 300 nm. MnO 2 and SiO 2 powder were added to the main component powder of the main component according to the composition ratios shown in Table 1, and then the raw material powder containing the main component and the subcomponent was mixed with zirconia balls as a mixing / dispersing medium and ethanol / And the binder were mixed and then ball-milled for 20 hours. The prepared slurry was formed into a molded sheet having a thickness of 10 탆 by using a doctor blade type coater.
상기 제조된 성형시트에는 Ni 내부전극을 인쇄하였다. 상하 커버는 커버용 시트를 25 층으로 적층하여 제작하였고, 21 층의 인쇄된 활성시트를 가압하며 적층하여 바(bar)를 제작하였다. 압착바는 절단기를 이용하여 3.2mm x 1.6mm 크기의 칩으로 절단하였다. 제작이 완료된 3216 크기의 적층세라믹 캐패시터 (MLCC) 칩은 가소를 행한 후 환원분위기 0.1%H2/99.9%N2 (H2O/H2/N2 분위기)에서 1200 ~ 1300℃의 온도에서 2 시간 소성 뒤, 1000℃에서 N2 분위기에서 재산화를 3 시간 동안 열처리하였다. 소성된 칩에 대해 Cu 페이스트로 터미네이션 공정 및 전극 소성을 거쳐 외부전극을 완성하였다. A Ni inner electrode was printed on the formed sheet. The upper and lower covers were prepared by laminating 25 sheets of cover sheets, and 21 sheets of printed active sheets were pressed and stacked to produce bars. The compression bar was cut into chips of 3.2 mm x 1.6 mm using a cutter. Production is completed 3216 size multilayer ceramic capacitor (MLCC) chip was 2 hours and baked at a temperature of 1200 ~ 1300 ℃ in was subjected to preliminary firing in a reducing atmosphere 0.1% H2 / 99.9% N2 ( H 2 O / H 2 / N 2 atmosphere) Then, the reoxidation was performed in an N 2 atmosphere at 1000 ° C for 3 hours. The fired chip was subjected to a termination process and electrode firing with Cu paste to complete an external electrode.
(1-x)BaTiO3 + x(Na1 - yKy)NbO3 Molar ratio of each component of base metal
(1-x) BaTiO 3 + x (Na 1 - y K y) NbO 3
각 첨가제의 몰 수Base material BT-NKN per 100 moles
The mole number of each additive
(1-x)BaTiO 3
(1-x)
(x) (Na 1 - y K y) NbO 3
(x)
상기 표 1과 같이 완성된 프로토타입 적층세라믹 캐패시터 시편에 대해 용량, DF, 절연저항, TCC, 고온 150℃에서 전압 스텝 (step) 증가에 따른 저항열화 거동 등을 평가하였다. 적층세라믹 캐패시터 칩의 상온 정전용량 및 유전손실은 LCR 미터를 이용하여 1 kHz, AC 0.2V/㎛ 조건에서 용량을 측정하였다. Capacitance, DF, insulation resistance, TCC, and resistance deterioration behavior with increasing voltage step at 150 ℃ were evaluated for the completed prototype multilayer ceramic capacitor specimen as shown in Table 1 above. The capacitance and dielectric loss of the multilayer ceramic capacitor chip were measured at 1 kHz, AC 0.2V / ㎛ using LCR meter.
정전용량과 적층세라믹 캐패시터 칩의 유전체 두께, 내부전극 면적, 적층수로부터 적층세라믹 캐패시터 칩 유전체의 유전율을 계산하였다. The dielectric constant of the multilayer ceramic capacitor chip dielectric was calculated from the capacitance, the dielectric thickness of the multilayer ceramic capacitor chip, the internal electrode area, and the number of layers.
상온 절연저항 (IR)은 10 개씩 샘플을 취하여 DC 10V/㎛ 을 인가한 상태에서 60 초 경과 후 측정하였다. 온도에 따른 정전용량의 변화는 -55℃에서 150℃의 온도 범위에서 측정되었다. The room temperature insulation resistance (IR) was measured after elapse of 60 seconds in a state where 10 samples were taken and DC 10 V / 탆 was applied. The change in capacitance with temperature was measured at a temperature range of -55 ° C to 150 ° C.
고온 IR 승압 실험은 150℃에서 전압 단계를 5V/㎛씩 증가시키면서 저항 열화거동을 측정하였는데, 각 단계의 시간은 10분이며 5초 간격으로 저항값을 측정하였다. 고온 IR 승압 실험으로부터 고온 내전압을 도출하였는데, 이는 소성 후 7㎛ 두께의 20층의 유전체를 가지는 3216 크기 칩에서 150℃에서 전압 스텝 (voltage step) dc 5V/㎛를 10분간 인가하고 이 전압 스텝을 계속 증가시키면서 측정할 때, IR이 105Ω 이상을 견디는 전압을 의미한다. In the high-temperature IR boosting test, the resistance deterioration behavior was measured while increasing the voltage step by 5 V / μm at 150 ° C. The resistance value was measured at intervals of 5 seconds for each step time of 10 minutes. A high voltage withstand voltage was obtained from a high-temperature IR boosting test, which was performed by applying a voltage step dc 5V / μm at 150 ° C. for 10 minutes in a 3216 size chip having a 20 μm dielectric layer of 7 μm thickness after firing, When measured continuously, it means that the IR will withstand more than 105 Ω.
표 2는 표 1 에 명시된 조성에 해당하는 프로토타입 적층세라믹 캐패시터 칩의 특성을 나타낸다.Table 2 shows the characteristics of the prototype multilayer ceramic capacitor chip corresponding to the composition shown in Table 1.
시
예room
city
Yes
(유전율/DF 측정조건: AC 0.2V/um, 1kHz)
(상온비저항: DC 10V/um)Ni-laminated ceramic capacitor prototype SPL characteristics
(Dielectric constant / DF measuring condition: AC 0.2 V / um, 1 kHz)
(Room temperature resistivity: DC 10 V / m)
(℃)Firing temperature
(° C)
유전율Room temperature
permittivity
(Ohm-cm)Room temperature resistivity
(Ohm-cm)
(-55℃)TCC (%)
(-55 ° C)
(125℃)TCC (%)
(125 DEG C)
(150℃)TCC (%)
(150 DEG C)
(150℃)
내전압(V/um)*High temperature
(150 DEG C)
Withstanding voltage (V / um) *
표 1의 실시예 1~12는 제2 주성분 (Na1 - yKy)NbO3에서 y=0.5 이고 제1 부성분 MnO2 및 제2 부성분 SiO2의 함량이 모재 파우더 (1-x)BaTiO3-x(Na1 - yKy)NbO3 대비 각각 0.5 at% 및 0.5 at% 일 때, 제1 주성분 BT의 함량 1-x 및 제2 주성분 (Na1 -yKy)NbO3의 함량 x 변화에 따른 프로토타입 칩의 특성을 나타낸다. x의 함량이 0 (실시예1)에서 0.6 (실시예12)으로 점점 증가함에 따라 유전율은 점점 감소하게 되는데, x가 0인 경우에는 (실시예1) 유전율이 3156으로 매우 높으나 TCC(150도)가 -35.2%로 ±15% X8R 규격을 벗어나는 문제가 있으며, x가 0.6인 경우에는 (실시예12) 상온유전율이 1500 미만으로 지나치게 낮아지는 문제가 있다. Carried out in Table 1 Examples 1 to 12 is the second main component (Na 1 - y K y) y = 0.5 , and the first subcomponent MnO 2 and the content of the second subcomponent SiO 2 base material powder (1-x) BaTiO 3 in NbO 3 -x (Na 1 - y K y ) NbO 3 , respectively compared to 0.5 at% and 0.5% at one time, the first principal component content of the BT-1 x and a second main component (Na y 1 -y K) content of 3 NbO x The characteristics of the prototype chip according to the change are shown. As the content of x gradually increases from 0 (Example 1) to 0.6 (Example 12), the dielectric constant gradually decreases. When x is 0 (Example 1), the dielectric constant is as high as 3156, ) Is -35.2%, which is outside the ± 15% X8R standard. When x is 0.6 (Example 12), there is a problem that the room temperature dielectric constant is excessively lowered to less than 1,500.
실시예 2~11의 시편에서 상온유전율 1500 이상, 고온내전압 50V/um 이상, TCC(150도)≤±15% 의 X8R 온도특성을 만족하므로 적정 x의 범위는 0.005≤x≤0.5라고 기술할 수 있다.
The specimen of Examples 2 to 11 satisfies the X8R temperature characteristic of a room temperature dielectric constant of 1500 or more, a high temperature withstand voltage of 50 V / um or more, and a TCC (150 degrees) of 賊 15%, so that the range of the titration x can be described as 0.005? X? have.
표 1의 실시예 13~19는 제2 주성분 (Na1 - yKy)NbO3에서 y=0.5 이고 이것의 함량 x=0.05 이고, 제2 부성분 SiO2의 함량이 모재 파우더 대비 0.5at% 일 때, 제1 부성분 MnO2 함량 변화에 따른 프로토타입 칩의 특성을 나타낸다. Mn의 함량이 0인 경우 (실시예13) 상온 비저항값이 8.480E7으로 매우 낮으며, Mn 함량이 0.1at% (실시예14) 이상부터는 1E11 이상의 절연특성이 구현됨을 확인할 수 있다. Mn의 함량이 증가함에 따라 유전율 및 상온비저항은 계속 감소하여 Mn 함량이 7at% 로 커지는 경우(실시예19), 유전율은 1365로 감소하여, 1500 미만이 되며, 상온비저항이 1E11 미만이 되는 문제가 발생한다.
Carried out in Table 1 Examples 13-19 are the second main component (Na 1 - y K y) NbO y = 0.5 eseo 3 and a content of x = 0.05 of this, compared to the base metal powder is 0.5at% content of the second subcomponent SiO 2 il , The characteristics of the prototype chip according to the change of the MnO 2 content of the first subcomponent are shown. It can be seen that when the Mn content is 0 (Example 13), the room temperature specific resistance value is as low as 8.480E7 and when the Mn content is 0.1 at% (Example 14) or more, the insulating property of 1E11 or more is realized. As the Mn content increases, the dielectric constant and the room temperature resistivity continue to decrease, and when the Mn content increases to 7 at% (Example 19), the permittivity decreases to 1365 and becomes less than 1500 and the room temperature resistivity becomes less than 1E11 Occurs.
실시예 14~18의 시편에서 유전율, 고온내전압, TCC 특성이 본 발명의 목표특성을 만족하므로 Mn의 함량은 0.1 ~ 5.0at% 범위로 선정할 수 있다.Since the dielectric constant, high-temperature withstand voltage, and TCC characteristics of the specimens of Examples 14 to 18 satisfy the target characteristics of the present invention, the content of Mn can be selected within the range of 0.1 to 5.0 at%.
표 1의 실시예 20~25는 제2 주성분 (Na1 - yKy)NbO3에서 y=0.5, x=0.05이고, 제1 부성분 MnO2의 함량이 모재 파우더 대비 0.5at% 일 때, 제2 부성분 SiO2 함량 변화에 따른 프로토타입 칩의 특성을 나타낸다. SiO2의 함량이 0인 경우(실시예20), 적정 소성온도가 1300도 정도로 소성온도가 올라가고, SiO2가 첨가된 경우 (실시예 21~24) 소결성이 개선되는 효과가 있다. SiO2 함량이 7at% 인 경우(실시예25), 소결성 개선효과가 거의 없어지고 고온내전압 특성이 50V/um 미만으로 나빠지게 된다. 따라서, 실시예 20~25의 결과로부터 유전율, 고온내전압, TCC 특성, 그리고 소결성을 고려시 바람직한 SiO2의 함량은 0.1 ~ 5. 0 at% 범위로 선정할 수 있다.Carried out in Table 1 Examples 20 to 25 are the second main component - when the (Na y K 1 y) and y = 0.5, x = 0.05 in the NbO 3, the content of the first subcomponent MnO 2 0.5at% compared to the base metal powder, the 2 shows the characteristics of the prototype chip according to the change in the content of SiO 2 . When the content of SiO 2 is 0 (Example 20), the sintering property is improved when the sintering temperature is raised to about 1300 ° C and the SiO 2 is added (Examples 21 to 24). When the SiO 2 content is 7 at% (Example 25), the effect of improving the sinterability is hardly obtained and the high-temperature withstand voltage characteristic is deteriorated to less than 50 V / μm. Therefore, from the results of Examples 20 to 25, it is preferable to select SiO 2 content in the range of 0.1 to 5.0 at% in consideration of the dielectric constant, high-temperature withstand voltage, TCC characteristics, and sintering ability.
표 1의 실시예 26~29는 제2 주성분 (Na1 - yKy)NbO3 함량 x=0.05 이고, 제1 부성분 MnO2 및 제2 부성분 SiO2의 함량이 모재 파우더 대비 각각 0.5at% 및 0.5at% 일 때, 제2 주성분 (Na1 - yKy)NbO3 에서 K 함량 y 및 Na 함량 1-y에 따른 프로토타입 칩의 특성을 나타낸다. 제2 주성분 (Na1 - yKy)NbO3 에서 K 함량인 y=0.5를 기준으로 0.3 (실시예27) 내지 0.2 (실시예26)으로 감소함에 따라 유전율이 감소하고 고온내전압 특성이 나빠지게 됨을 알 수 있고, y=0.2 (실시예26) 인 경우에는 고온내전압 특성이 50V/um 미만인 문제가 발생함을 알 수 있다. K 함량 y=0.5를 기준으로 0.7 (실시예28) 내지 1.0 (실시예29)으로 증가함에 따라 유전율 및 고온내전압 특성이 다소 낮아지기는 하지만 유전율, 고온내전압, TCC 특성이 본 발명의 목표특성을 만족한다. 따라서 실시예 26~29의 결과로부터 유전율, 고온내전압, 상온비저항값을 고려시 바람직한 K의 함량 y의 범위는 0.3≤y≤1.0로 선정할 수 있다.Carried out in Table 1 Examples 26 to 29 are the second main component, wherein each 0.5at% (Na 1 y K y ) NbO 3 content of x = 0.05, and the powder preform is first subcomponent and the second subcomponent MnO 2 content of SiO 2 and compared (Na 1 - y Ky) NbO 3 , the K content y and the Na content 1-y of the second main component (Na 1 - y Ky) at 0.5 at%. A second main component (Na 1 - y K y) in NbO 3, based on the K content of y = 0.5 0.3 (Example 27) to 0.2 (Example 26) to decrease as the dielectric constant decreases and a high temperature withstand voltage characteristic deteriorates , And when y = 0.2 (Example 26), the problem that the high withstand voltage characteristic is less than 50 V / um occurs. Although the dielectric constant and high-temperature withstand voltage characteristics are somewhat lowered as the K content increases from 0.7 (Example 28) to 1.0 (Example 29) based on y = 0.5, the dielectric constant, high-temperature withstand voltage and TCC characteristics satisfy the target characteristics of the present invention do. From the results of Examples 26 to 29, therefore, it is preferable that the range of the content y of K is 0.3? Y? 1.0 when considering the dielectric constant, the high-temperature withstand voltage and the room temperature resistivity.
본 발명은 유전체 자기조성물 및 이를 적용한 전자소자에 관한 것으로서, 보다 상세하게는 EIA 규격에서 명시한 X5R, X7R, 그리고 X8R 특성을 만족하는 유전체 자기조성물 및 이를 적용한 전자소자에 관한 것이다. 본 발명에 따르면, 모재 파우더에 환경에 유해한 납(Pb)을 사용하지 않으면서도, 큐리온도 상승 및 고온부 유전율이 평탄해지는 특성을 구현할 수 있고, X8R 온도 특성 및 양호한 고온내전압 특성을 만족시킬 수 있다.
SUMMARY OF THE INVENTION [ The magnetic composition and This More particularly, to a dielectric ceramic composition satisfying the X5R, X7R, and X8R characteristics specified in the EIA standard, and an electronic device using the dielectric ceramic composition. According to the present invention, it is possible to realize a characteristic in which the Curie temperature is elevated and the dielectric constant of the high temperature portion becomes flat without using lead (Pb) which is harmful to the environment in the base material powder, and X8R temperature characteristic and good high temperature withstand voltage characteristic can be satisfied.
이상으로 본 발명 내용의 특정한 부분을 상세히 기술하였는 바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적 기술은 단지 바람직한 실시 양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항 들과 그것들의 등가물에 의하여 정의된다고 할 것이다.While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.
Claims (7)
The first main component BaTiO 3 and the second main component (Na 1 - y K y) NbO employment chain (1-x) BaTiO 3 -x (Na 1 -y K y) of 3 NbO 3 (0.005≤x≤0.3, 0.3≤ a first subcomponent including an element selected from the group consisting of Mn, V, Cr, Fe, Ni, Co, Cu and Zn, and SiO 2 or a glass- As a subcomponent.
The dielectric ceramic composition according to claim 1, wherein the first subcomponent is an oxide or carbonate of an element selected from the group consisting of Mn, V, Cr, Fe, Ni, Co, Cu and Zn.
The method according to claim 1, wherein the first subcomponent is MnO 2 MnCO 3 or the dielectric ceramic composition.
The dielectric ceramic composition according to claim 1, wherein the content of the first subcomponent is 0.1-5.0 moles per 100 moles of the solid solution.
The method of claim 1 wherein the second content of the SiO 2 solid solution, 100 mol of 0.1 to 5.0 moles of the sub-component dielectric ceramic composition.
An electronic device comprising a dielectric formed using the dielectric ceramic composition of any one of claims 1 to 5.
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| JP2008011254A (en) | 2006-06-29 | 2008-01-17 | Sanyo Electric Co Ltd | Terrestrial digital broadcasting receiver |
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| KR20140125000A (en) * | 2013-04-17 | 2014-10-28 | 삼성전기주식회사 | Dielectric composition, multilayer ceramic capacitor using the same, and method for preparing multilayer ceramic capacitor |
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| JP2008011254A (en) | 2006-06-29 | 2008-01-17 | Sanyo Electric Co Ltd | Terrestrial digital broadcasting receiver |
| JP2013028478A (en) * | 2011-07-27 | 2013-02-07 | Tdk Corp | Dielectric ceramic composition and electronic component |
| KR20140125000A (en) * | 2013-04-17 | 2014-10-28 | 삼성전기주식회사 | Dielectric composition, multilayer ceramic capacitor using the same, and method for preparing multilayer ceramic capacitor |
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