KR950000505B1 - Composite with high dielectricity - Google Patents
Composite with high dielectricity Download PDFInfo
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- KR950000505B1 KR950000505B1 KR1019910006979A KR910006979A KR950000505B1 KR 950000505 B1 KR950000505 B1 KR 950000505B1 KR 1019910006979 A KR1019910006979 A KR 1019910006979A KR 910006979 A KR910006979 A KR 910006979A KR 950000505 B1 KR950000505 B1 KR 950000505B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
Abstract
Description
본 발명은 반도체 바이패스(Bypass)용 고유전율계 자기조성물에 관한 것으로, 좀더 구체적으로는 BaTiO3, CeO2, TiO2로 구성되어지되, Ba1-XCe2X/3TiO3+X/3(0.02x0.035)의 조성비를 가지며 MnO2가 0.01∼0.09중량% 첨가되는 조성물로서 큐리(Curie) 온도가 60℃∼70℃이고, 큐리온도에서의 유전율이 6000∼8000인 반도체 바이패스용 고유전율계 자기조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high dielectric constant magnetic composition for semiconductor bypass, and more specifically, to BaTiO 3 , CeO 2 , TiO 2 , Ba 1-X Ce 2X / 3 TiO 3 + X / 3 (0.02 x A composition having a composition ratio of 0.035) and 0.01% to 0.09% by weight of MnO 2 , and has a Curie temperature of 60 ° C. to 70 ° C. and a dielectric constant of 6000 to 8000 at a Curie temperature. It is about.
종래에는 반도체 IC용 바이패스 콘덴서로 EIA(Electronic Industry Association) 규격의 Y5V(-30℃∼+85℃까지 25℃에서 유전율을 기준으로 유전율 변화율이 -82% 내지 +22%) 또는 Z5U(-25℃∼+85℃까지 25℃에서 유전율을 기준으로 유전율 변화율이 -56% 내지 +22%) 온도특성을 만족시키는 유전체 자기조성물이 주로 사용되었으나, Y5V 또는 Z5U 특성의 유전체 자기조성물은 큐리온도가 13℃∼35℃의 범위에 존재하게 되고, 이로 인하여 반도체 IC가 정상 작동하는 60℃∼70℃ 온도범위에서의 유전율이 4000∼5000 정도로 작아서 바이패스 특성, 즉 노이즈(Noise) 제거 특성이 저하되는 문제점이 있었다.Conventionally, as a bypass capacitor for semiconductor ICs, the dielectric constant change rate is -82% to + 22% based on the dielectric constant at 25 ° C from Y5V (-30 ° C to + 85 ° C) of the Electronic Industry Association (EIA) standard or Z5U (-25 Dielectric magnetic composition satisfying temperature characteristics of -56% to + 22% based on dielectric constant at 25 ° C from 25 ° C to + 85 ° C) was mainly used, but dielectric magnetic composition having Y5V or Z5U characteristics had a Curie temperature of 13 Present in the range of ℃ ~ 35 ℃, due to this the dielectric constant in the temperature range of 60 ℃ ~ 70 ℃ in which the semiconductor IC is operating normally is small to about 4000 ~ 5000, the bypass characteristics, that is, the noise removal characteristics is reduced There was this.
그러므로 전술한 문제점을 해결하기 위해서 유전체 자기조성물의 큐리온도가 60℃∼70℃에 위치하며 이때의 유전율이 비교적 높은 조성물의 개발이 요구되었다.Therefore, in order to solve the above problems, the Curie temperature of the dielectric magnetic composition is located at 60 ° C to 70 ° C, and development of a composition having a relatively high dielectric constant is required.
따라서, 본 발명의 목적은 반도체 IC가 정상 작동하는 60℃∼70℃ 범위에서 큐리온도가 존재하고 높은 유전율(6000∼8000)을 가지며 상온에서도 비교적 높은 유전율을(4000∼5000) 가지는 반도체 바이패스용 고유전율계 자기조성물을 제공하는데 있다.Accordingly, an object of the present invention is for a semiconductor bypass having a Curie temperature in the range of 60 ° C. to 70 ° C. in which the semiconductor IC operates normally, having a high dielectric constant (6000 to 8000) and a relatively high dielectric constant (4000 to 5000) even at room temperature. To provide a high dielectric constant magnetic composition.
본 발명을 좀 더 구체적으로 설명하면 다음과 같다.The present invention is described in more detail as follows.
99.5% 이상 순도의 BaTiO3주성분에 소량의 TiO2, CeO2, MnO2를 첨가 혼합하여 소성해서 이루어진 유전체 자기조성물에 관한 것이다.The present invention relates to a dielectric magnetic composition obtained by baking by adding a small amount of TiO 2 , CeO 2 , MnO 2 to BaTiO 3 main components having a purity of 99.5% or more.
BaTiO3, CeO2및 TiO2는 Ba1-XCe2X/3TiO3+X/3(0.02x0.035)의 조성식이 되도록 혼합한다.BaTiO 3 , CeO 2 and TiO 2 are Ba 1-X Ce 2X / 3 TiO 3 + X / 3 (0.02 x 0.035) and the composition formula.
또한, 본 조성물에 절연저항 및 유전손실 계수를 향상시키기 위해 천이금속 Mn의 산화물 MnO2를 0.01∼0.09중량% 첨가하였다.Also, the oxide of the transition metal Mn was added MnO 2 0.01~0.09% by weight in order to improve the insulation resistance and dielectric loss factor in the composition.
이때 25℃, 1KHz에서의 유전율이 4000∼5000 정도이고, 큐리온도 범위인 60∼70℃에서의 유전율이 6000∼8000 정도이며, 1KHz, 50mV OSC(oscillation) Level에서 유전손실 계수의 값이 2.0% 미만의 손실을 가지므로 적층 자기콘덴서의 조성물로서 사용가능한 유전체 자기조성물이 얻어진다.At this time, the dielectric constant at 25 ℃ and 1KHz is about 4000 ~ 5000, the dielectric constant is about 6000 ~ 8000 at 60 ~ 70 ℃ which is Curie temperature range, and the value of dielectric loss coefficient is 2.0% at 1KHz, 50mV OSC (oscillation) level. With less loss, a dielectric magnetic composition is obtained that can be used as a composition of a laminated magnetic capacitor.
상기 조성물에 있어서 MnO2첨가량이 0.01∼0.09중량%를 벗어나면 저주파수에서의 유전손실 계수가 증가하며, 절연저항의 특성이 양호하지 못하게 된다.In the composition, when the amount of MnO 2 added exceeds 0.01 to 0.09% by weight, the dielectric loss coefficient at low frequency is increased, and the characteristics of insulation resistance are not good.
CeO2와 TiO2는 큐리온도를 조절하는 작용을 하는 것으로 상기 조성식중 CeO2및 TiO2가 상기 조성 범위 이하로 첨가되었을 경우에는 소결성이 나빠지게 되며, 상기 범위 이상에서는 유전율은 높아지지만 큐리 온도가 상온 이하로 낮아지게 되어 본 발명의 목적에 부합하지 않게 된다.CeO2 and TiO 2 act to control the Curie temperature. When CeO 2 and TiO 2 in the composition formula are added below the composition range, the sintering property is deteriorated. The dielectric constant is higher than the above range, but the Curie temperature is room temperature. It will be lowered below to not meet the purpose of the present invention.
특히, Ce와 Ti는 조성식과 같이 2/3의 비율을 유지하여 첨가되어야 하고 첨가량이 증가함에 따라 큐리온도는 저온부로 이동하게 된다.In particular, Ce and Ti should be added to maintain a ratio of 2/3 as in the formula, and the Curie temperature is moved to the low temperature portion as the amount of addition increases.
즉, 상기 조성물에 있어서 Ce/Ti의 비는 2/3를 유지하여야 하는데 Ce/Ti의 비가 2/3보다 클때는 큐리온도에서 높은 유전율을 얻을 수 없고, Ce/Ti의 비가 2/3보다 작을때는 절연저항이 감소하는 문제가 있다.That is, in the composition, the ratio of Ce / Ti should be maintained at 2/3. When the ratio of Ce / Ti is greater than 2/3, a high dielectric constant cannot be obtained at the Curie temperature, and the ratio of Ce / Ti is less than 2/3. In this case, there is a problem that the insulation resistance decreases.
상기 조성물, Ba1-XCe2X/3TiO3+X/3에서 x가 0.02∼0.035인 범위일 경우에는 큐리온도는 60∼70℃에서 높은 유전율을 가진다.When x is in the range of 0.02 to 0.035 in the composition, Ba 1-X Ce 2X / 3 TiO 3 + X / 3 , the Curie temperature has a high dielectric constant at 60 to 70 ° C.
상술한 바와 같이 본 발명의 반도체 바이패스용 고유전율계 자기조성물은 6000∼8000 정도의 유전율을 가지므로 반도체 IC가 정상작동하는 60∼70℃ 온도범위에서 대용량의 (100000PF∼220000PF)적층 자기콘덴서의 조성물로 사용가능하다.As described above, the high dielectric constant magnetic composition for semiconductor bypass of the present invention has a dielectric constant of about 6000 to 8000. It can be used as a composition.
다음의 실시예 및 비교예는 본 발명의 고유전율계 자기조성물 및 이의 효과를 좀 더 구체적으로 설명하는 것이지만, 본 발명의 범주를 한정하는 것은 아니다.The following examples and comparative examples will be described in more detail the high dielectric constant magnetic composition of the present invention and its effects, but is not intended to limit the scope of the present invention.
[실시예 1]Example 1
출발원료로서 순도 99.5중량% 이상의 BaTiO3, TiO2, CeO2및 MnO2분말을 하기의 표 1의 기재와 같이 BaTiO398.274중량%, TiO20.987중량%, CeO20.688중량%, MnO20.051중량%가 되도록 평량한다.As a starting material, BaTiO 3 , TiO 2 , CeO 2 and MnO 2 powder having a purity of 99.5% by weight or more, as described in Table 1 below, 98.274% by weight of BaTiO 3, 0.987% by weight of TiO 2, 0.688% by weight of CeO 2 , and MnO 2 0.051 It is weighted to weight%.
그후 평량분말을 적정량의 결합제(아크릴계 바인더로 파우더 100g에 54g을 첨가함)와 혼합한 후 30㎛ 두께로 테이프 케스팅(Tape Casting)하여 시이트(Sheet)를 제조한다. 이러한 방법으로 제조된 시이트를 여러장 포개어 70℃ 온도에서 유니엑시얼 프레스(Uniaxial Press)로 10분간 압착한 후 1cm×1cm×0.1cm의 치수를 가지는 K-플레이트(Plate)를 제조한다.Thereafter, the basis weight powder is mixed with an appropriate amount of binder (adding 54 g to 100 g of powder with an acrylic binder), and then tape cast to a thickness of 30 μm to prepare a sheet. Sheets prepared in this manner are stacked and pressed for 10 minutes with a uniaxial press at a temperature of 70 ° C. to prepare a K-plate having a dimension of 1 cm × 1 cm × 0.1 cm.
K-플레이트를 1260℃∼1340℃ 온도 범위에서 1∼2시간 소성하고, Ag 전극을 도포하여 은소부하하였다.The K-plate was calcined for 1 to 2 hours at a temperature range of 1260 ° C to 1340 ° C, and an Ag electrode was applied to load the silver.
이에 대한 유전상수(K) 및 유전손실계수(tanδ)를 LCR Meter를 사용하며, 1KHz, 25℃, 0.05Vrms(Oscillation Level) 전계강도에서 측정하였고 온도특성은 항온 항습조에서 0∼85℃의 온도 범위에서 측정하고 그 결과를 표 1에 기재하였다.Dielectric constant (K) and dielectric loss coefficient (tanδ) were measured by LCR meter at 1KHz, 25 ℃ and 0.05Vrms (Oscillation Level) field strength, and the temperature characteristics were 0 ~ 85 ℃ in constant temperature and humidity It measured in the range and the result is shown in Table 1.
[실시예 2∼6]EXAMPLES 2-6
BaTiO3, TiO2, CeO2및 MnO2를 하기 표 1에 기재된 비율로 평량한 것을 제외하고는 실시예 1에 기재된 방법과 동일한 방법으로 실시하여 은소부 K-플레이트를 제조한 다음, 이에 대한 특성치를 실시예 1과 동일한 방법으로 측정하여 그 결과를 하기 표 1에 기재하였다.A silver calcined K-plate was prepared by the same method as described in Example 1 except that BaTiO 3 , TiO 2 , CeO 2, and MnO 2 were weighed in the proportions shown in Table 1 below, and then the characteristic values therefor Was measured in the same manner as in Example 1 and the results are shown in Table 1 below.
[비교예 1]Comparative Example 1
BaTiO3, TiO2, CeO2및 MnO2를 표 1에 기재된 바와 같이 본 발명의 범주를 벗어난 비율로 혼합한 후 실시예 1∼6에 기재된 방법과 동일한 방법으로 유전체 자기조성물을 제조하고, 이에 대한 특정치를 실시예 1∼6에 기재된 방법과 동일한 방법으로 측정하여 그 결과를 표 1에 기재하였다.After mixing BaTiO 3 , TiO 2 , CeO 2 and MnO 2 at a ratio outside the scope of the present invention as shown in Table 1, a dielectric ceramic composition was prepared by the same method as described in Examples 1 to 6, and Specific values were measured by the same method as described in Examples 1 to 6, and the results are shown in Table 1.
이 비교예에 의해 x가 본 발명의 x의 범주(0.02∼0.35)보다 작은 0.015일때 큐리온도가 80℃로 증가하고, 이때 유전율은 5140으로 감소함을 알 수 있다.According to this comparative example, when x is 0.015 which is smaller than the range (0.02 to 0.35) of x of the present invention, the Curie temperature increases to 80 ° C., and the dielectric constant decreases to 5140.
[비교예 2]Comparative Example 2
BaTiO3, TiO2, CeO2및 MnO2를 표 1에 기재된 바와 같이 혼합한 후, 실시예 1∼6에 기재된 방법과 동일한 방법으로 유전체 자기조성물을 제조하고, 이에 대한 특성치도 동일한 방법으로 측정하여 그 결과를 표 1에 기재하였다.After mixing BaTiO 3 , TiO 2 , CeO 2 and MnO 2 as described in Table 1, a dielectric ceramic composition was prepared by the same method as described in Examples 1 to 6, and the characteristic values thereof were also measured by the same method. The results are shown in Table 1.
이 비교예에서 x가 본 발명의 x의 범주(0.02∼0.35)보다 높은 0.04일때 큐리온도는 50℃로 현저히 낮아지고, 이때 유전율은 4880으로 감소함을 알 수 있었다.In this comparative example, when x is 0.04 higher than the range (0.02 to 0.35) of x of the present invention, the Curie temperature is significantly lowered to 50 ° C., and the dielectric constant decreases to 4880.
상술한 바와 같이 BaTiO3, CeO2, TiO2로 구성되어지되 Ba1-XCe2X/3TiO3+X/3(0.02x0.035)의 조성식을 가지며 미량의 MnO2를 첨가한 본 발명의 고유전율계 자기조성물은 25℃, 1KHz에서 유전상수가 4000이상이고 60∼70℃ 범위에 큐리온도가 존재하며, 이때의 유전상수가 6000∼8000 정도이므로 반도체 IC 바이패스용 고유전율계 자기조성물로서 사용가능하다.As described above, BaTiO 3 , CeO 2 , TiO 2 , and Ba 1-X Ce 2X / 3 TiO 3 + X / 3 (0.02 x 0.035) and the high dielectric constant magnetic composition of the present invention to which a small amount of MnO 2 is added has a dielectric constant of 4000 or higher at 25 ° C and 1KHz and a Curie temperature in the range of 60 to 70 ° C. Since it is about 6000-8000, it can be used as a high dielectric constant magnetic composition for semiconductor IC bypass.
또한, 1KHz, 500mV OSC(Oscillation) Level에서 유전손실 계수의 값이 2.0% 미만의 손실을 가지므로 적층 자기콘덴서의 조성물로 사용가능하다.In addition, since the value of the dielectric loss coefficient is less than 2.0% at 1KHz, 500mV OSC (Oscillation) Level, it can be used as a composition of the multilayer magnetic capacitor.
[표 1](조성 및 전기적 특성)Table 1 (Composition and Electrical Characteristics)
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| KR1019910006979A KR950000505B1 (en) | 1991-04-30 | 1991-04-30 | Composite with high dielectricity |
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| KR1019910006979A KR950000505B1 (en) | 1991-04-30 | 1991-04-30 | Composite with high dielectricity |
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