KR920008104B1 - Ceramic material for capacitor - Google Patents
Ceramic material for capacitor Download PDFInfo
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- KR920008104B1 KR920008104B1 KR1019900012586A KR900012586A KR920008104B1 KR 920008104 B1 KR920008104 B1 KR 920008104B1 KR 1019900012586 A KR1019900012586 A KR 1019900012586A KR 900012586 A KR900012586 A KR 900012586A KR 920008104 B1 KR920008104 B1 KR 920008104B1
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- 239000003990 capacitor Substances 0.000 title claims description 5
- 229910010293 ceramic material Inorganic materials 0.000 title description 3
- 239000000919 ceramic Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 13
- 229910002113 barium titanate Inorganic materials 0.000 abstract description 7
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 2
- 229910011255 B2O3 Inorganic materials 0.000 abstract 2
- 229910002118 Bi2Ti2O7 Inorganic materials 0.000 abstract 2
- 229910004774 CaSnO3 Inorganic materials 0.000 abstract 2
- 229910003781 PbTiO3 Inorganic materials 0.000 abstract 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 2
- 239000003985 ceramic capacitor Substances 0.000 description 8
- 230000001747 exhibiting effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01G4/002—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
-
- 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
-
- 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
- C04B35/4682—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 based on BaTiO3 perovskite phase
- C04B35/4684—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 based on BaTiO3 perovskite phase containing lead compounds
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- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
제1도는 본 발명 세라믹 유전체 조성의 실시예에 대한 미세조직 확대사진.Figure 1 is an enlarged microstructure image of an embodiment of the ceramic dielectric composition of the present invention.
제2도는 본 발명 세라믹 유전체 조성의 실시예에 대한 유전율과 온도와의 관계를 보인 그래프.2 is a graph showing the relationship between dielectric constant and temperature for an embodiment of the ceramic dielectric composition of the present invention.
본 발명은 저온소결이 가능하고, 상온(常溫) 부근에서 비교적 높은 유전율을 나타내는 적층 캐패시터용 세라믹 유전체 조성에 관한 것이다.The present invention relates to a ceramic dielectric composition for multilayer capacitors capable of low-temperature sintering and exhibiting a relatively high dielectric constant near room temperature.
일반적으로 적층 세라믹 캐패시터(Multilayer ceramic capacitor)는 다수개의 얇은 판상형태로 이루어진 유전체층과 그 유전체층 사이에 위치하는 내부전극이 순차적층되어 구성되는데, 이같은 적층 칩 형태의 세라믹 캐패시터는 단위부피당 정전용량을 극대화할 수 있다는 점에서 다른 형태의 캐패시터에 비해 널리 사용되고 있다.In general, a multilayer ceramic capacitor is composed of a sequential layer of a plurality of thin plate-like dielectric layers and internal electrodes located between the dielectric layers. Such a multilayer chip-type ceramic capacitor may maximize capacitance per unit volume. It is widely used in comparison with other types of capacitors in that it can be.
이와 같은 적층 세라믹 캐패시터의 유전체층을 이루는 유전체 산화물 재료로는 높은 유전상수 및 절연저항을 갖는 티탄산바륨(BaTio3)이 가장 많이 사용되고 있다.As the dielectric oxide material constituting the dielectric layer of the multilayer ceramic capacitor, barium titanate (BaTio 3 ) having a high dielectric constant and insulation resistance is most frequently used.
그런데, 적층 세라믹 캐패시터의 주성분으로 사용되는 티탄산 바륨은 그 소결온도가 1300℃ 정도로 높기 때문에 적층 세라믹 캐패시터의 내부전극으로는 고온 반응성이 낮으면서도 고융점을 갖은 금속으로서 Pd/Ag, Pd/Au 또는 이와 유사한 고가의 금속 즉, 귀금속을 사용하여야만 하기 때문에 제조비용면에 있어 문제점을 지니고 있다.However, barium titanate, which is used as a main component of multilayer ceramic capacitors, has a high melting point and low melting point at high internal reactivity as Pd / Ag, Pd / Au, or the like. Similar expensive metals, ie precious metals, have to be used, which is problematic in terms of manufacturing cost.
이에따라, 고가의 내부전극 문제를 해결하기 위한 방편으로 티탄산 바륨을 주성분으로 하고 여기에 여러가지의 소결조제를 첨가하여 소결온도를 1100℃ 근처로 낮춘 세라믹캐패시터용 유전체 조성물이 미국특허 제4,283,753호, 제4,335,216호, 제4,530,031호에 나타나 있으나, 이들 유전체 조성물은 소결조제의 첨가에 의해 소결온도가 낮아진 반면 유전체에서 가장 중요한 특성인 유전율이 저하되는 결점이 있다.Accordingly, a dielectric composition for ceramic capacitors having barium titanate as a main component and adding various sintering aids to lower the sintering temperature to around 1100 ° C. as a way to solve the expensive internal electrode problem is disclosed in US Pat. Nos. 4,283,753, 4,335,216 4,530,031, these dielectric compositions have the disadvantage that the sintering temperature is lowered by the addition of a sintering aid, while the dielectric constant, which is the most important characteristic of the dielectric, is lowered.
따라서, 본 발명은 낮은 온도에서 소결이 가능하면서도 티탄산바륨의 높은 유전율을 유지한채 낮은 유전손실을 나타내는 적층 세라믹 캐패시터용 유전체 조성물을 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a dielectric composition for multilayer ceramic capacitors capable of sintering at low temperature and exhibiting low dielectric loss while maintaining high dielectric constant of barium titanate.
본 발명의 유전체 조성물은 1130℃-1140℃의 온도범위에서 소결이 행해지기 때문에 Pd에 비해 저가인 Ag가 70％ 함유되고 Pd가 30％ 함유된 Pd/Ag 내부전극의 사용이 가능하다.Since the dielectric composition of the present invention is sintered at a temperature range of 1130 ° C.-1140 ° C., it is possible to use Pd / Ag internal electrodes containing 70% Ag and 30% Pd, which is cheaper than Pd.
이와 같은 본 발명 적층 세라믹 캐패시터용 유전체 조성은 중량비로 BaTiO382.603-88.118％, CaSnO37.267-8.715％, MnO20.130％, PbTiIO30.500-4.002％, Bi2Ti2O70.510-4.260％, ZnO 0.976-2.440％ 및 B2O30.304-0.760％으로 이루어진다.The dielectric composition for the multilayer ceramic capacitor of the present invention is BaTiO 3 82.603-88.118%, CaSnO 3 7.267-8.715%, MnO 2 0.130%, PbTiIO 3 0.500-4.002%, Bi 2 Ti 2 O 7 0.510-4.260%, ZnO 0.976-2.440% and B 2 O 3 0.304-0.760%.
세라믹 재료의 유전율은 큐리(Curie) 온도에서 최고치를 나타내므로 가능한 세라믹 재료의 큐리온도를 상온부근으로 유지하는 것이 바람직한 바, 본 발명은 티탄산바륨의 큐리 온도를 상온으로 낮추기 위하여 CaSnO3화합물이 첨가된다.Since the dielectric constant of the ceramic material exhibits the highest value at the Curie temperature, it is desirable to keep the Curie temperature of the ceramic material as close to room temperature as possible. In the present invention, a CaSnO 3 compound is added to lower the Curie temperature of barium titanate to room temperature. .
특히, CaSnO3는 소결조제 첨가량의 변화에 대하여 민감하지 않기 때문에 재조 공정상 어느정도의 조성불균질성에 대해서도 특성변화가 매우 적다는 특징이 있다.In particular, since CaSnO 3 is not sensitive to changes in the amount of sintering aid added, there is a characteristic that the characteristic change is very small even to some degree of composition heterogeneity in the remanufacturing process.
이같은 CaSnO3의 첨가에 의해 본 발명 세라믹 유전체 조성물의 큐리온도는 20-30℃ 사이에 존재하는데, CaSnO3의 첨가량이 증가됨에 따라 큐리온도는 저온으로 이동하고 CaSnO3와 BaTiO3의 몰비율이 0.1일 때 상온에서 큐리온도가 존재한다.By the addition of CaSnO 3 , the Curie temperature of the ceramic dielectric composition of the present invention is present between 20-30 ° C. As the amount of CaSnO 3 is increased, the Curie temperature moves to low temperature and the molar ratio of CaSnO 3 and BaTiO 3 is 0.1. Curie temperature is at room temperature.
한편, 본 발명은 PbTiIO3, Bi2Ti2O7, ZnO, B2O3계 소결조제가 사용되는데, 그 첨가량은 중량비로 4-10％가 바람직하며 유전율은 4700-5300, 유전손실은 2.0％ 이하를 나타낸다.Meanwhile, the present invention uses PbTiIO 3 , Bi 2 Ti 2 O 7 , ZnO, B 2 O 3 based sintering aid, the addition amount is preferably 4-10% by weight ratio, dielectric constant is 4700-5300, dielectric loss is 2.0 % Or less is shown.
이때 소결조제의 첨가량이 4％ 이하로 되는 경우에는 소결성이 저하되는 결과 유전손실이 증가하게 되며, 반대로 10％ 이상으로 되는 경우에는 유전율이 감소를 초래하게 된다.At this time, when the amount of the sintering aid is 4% or less, the dielectric loss increases as a result of the decrease in the sintering property. On the contrary, when the amount of the sintering aid is 10% or more, the dielectric constant decreases.
특히, 본 발명의 세라믹 유전체 조성은 10-85℃의 온도 범위에서 5000 이상의 유전율을 나타내는 한편 온도계수가 +10에서 -56％을 보임으로서 Z5U 규격을 만족하는 유전체조성에 속한다.In particular, the ceramic dielectric composition of the present invention belongs to a dielectric composition that satisfies the Z5U standard by exhibiting a dielectric constant of 5000 or more in a temperature range of 10-85 ° C and a temperature coefficient of -10 to -56%.
본 발명의 실시예는 다음과 같다.Embodiments of the present invention are as follows.
먼저, 평균입경 1.5μm를 유지하는 원료분말을 아래의 표 1과 같은 조성으로 평량하여 폴리에틸렌 자(Jar)중에서 증류수를 분산매로 사용하여 6시간 동안 습식분쇄한 후 120℃의 전기건조기에서 완전히 건조시켰다. 다음, 완전히 건조된 분말을 직경 1cm의 금형몰드를 사용하여 1500kg/cm의 압력으로 1축 가압성형한 후 1100-1140℃에서 소결을 행하였다. 이어서 소결된 시편의 양면에 Ag 전극을 도포하고 소부하여 세라믹 캐패시터를 제작하였다.First, a raw material powder having an average particle diameter of 1.5 μm was weighed into a composition as shown in Table 1 below, wet pulverized for 6 hours using distilled water as a dispersion medium in polyethylene jars, and then completely dried in an electric dryer at 120 ° C. . Next, the completely dried powder was uniaxially press-molded at a pressure of 1500 kg / cm using a mold mold having a diameter of 1 cm, and then sintered at 1100-1140 ° C. Subsequently, Ag electrodes were coated on both surfaces of the sintered specimens and baked to prepare ceramic capacitors.
[표 1]TABLE 1
위의 표 1과 같은 조성의 소결 및 전극 처리가 왼료된 각 실시예에 대해서 1KHz에서 유전특성을 측정하였으며, 그 유전특성(유전율, 유전손실, 온도계수 및 큐리온도)의 결과치는 아래의 표 2와 같다.Dielectric properties were measured at 1 KHz for each of the examples of the sintering and electrode treatment of the composition shown in Table 1 above, and the results of the dielectric properties (dielectric constant, dielectric loss, temperature coefficient and Curie temperature) are shown in Table 2 below. Same as
[표 2]TABLE 2
한편, 제1도는 1130℃에서 3시간 소결시킨 본 발명의 실시예 4에 대한 미세조직 확대사진으로서, 입자의 크기가 균일함을 알 수 있으며, 제2도의 유전율의 온도특성을 보인 그래프로부터는 실시예 4의 조성이 Z5U 규격을 만족시키고 있음을 알 수 있다.On the other hand, Figure 1 is an enlarged microstructure of Example 4 of the present invention sintered for 3 hours at 1130 ℃, it can be seen that the particle size is uniform, from the graph showing the temperature characteristics of the dielectric constant of FIG. It can be seen that the composition of Example 4 satisfies the Z5U standard.
이상과 같이 본 발명은 적층캐패시터용 세라믹 유전체의 조성으로서 고 유전율의 BaTiO3를 주성분으로 하고 여기에 CaSnO3, PbTiO3, BiTi2O7, ZnO 및 B2O3등을 첨가하여 소결온도를 저하시킴으로써 저온소결이 가능할 뿐만 아니라, Z5U 규격을 만족시킨다.As described above, the present invention has a high dielectric constant of BaTiO 3 as a main component of the ceramic dielectric for multilayer capacitors, and CaSnO 3 , PbTiO 3 , BiTi 2 O 7 , ZnO, and B 2 O 3 are added to lower the sintering temperature. This allows not only low temperature sintering but also meets the Z5U specification.
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019900012586A KR920008104B1 (en) | 1990-08-16 | 1990-08-16 | Ceramic material for capacitor |
| GB9101052A GB2247014B (en) | 1990-08-16 | 1991-01-17 | Ceramic dielectric composition for multilayer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019900012586A KR920008104B1 (en) | 1990-08-16 | 1990-08-16 | Ceramic material for capacitor |
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| Publication Number | Publication Date |
|---|---|
| KR920005190A KR920005190A (en) | 1992-03-28 |
| KR920008104B1 true KR920008104B1 (en) | 1992-09-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1019900012586A KR920008104B1 (en) | 1990-08-16 | 1990-08-16 | Ceramic material for capacitor |
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| KR (1) | KR920008104B1 (en) |
| GB (1) | GB2247014B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108588658A (en) * | 2018-04-20 | 2018-09-28 | 东莞理工学院 | A kind of CaSnO3/Ag/CaSnO3Multilayered structure flexible transparent conductive film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5067541B2 (en) | 2007-03-30 | 2012-11-07 | Ｔｄｋ株式会社 | Dielectric ceramic composition, composite electronic component and multilayer ceramic capacitor |
| JP7047526B2 (en) * | 2018-03-27 | 2022-04-05 | Tdk株式会社 | Multilayer ceramic electronic components |
-
1990
- 1990-08-16 KR KR1019900012586A patent/KR920008104B1/en not_active IP Right Cessation
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1991
- 1991-01-17 GB GB9101052A patent/GB2247014B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108588658A (en) * | 2018-04-20 | 2018-09-28 | 东莞理工学院 | A kind of CaSnO3/Ag/CaSnO3Multilayered structure flexible transparent conductive film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2247014A (en) | 1992-02-19 |
| GB2247014B (en) | 1994-04-27 |
| KR920005190A (en) | 1992-03-28 |
| GB9101052D0 (en) | 1991-02-27 |
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