KR940011059B1 - Semiconductor condenser - Google Patents
Semiconductor condenser Download PDFInfo
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- KR940011059B1 KR940011059B1 KR1019920010785A KR920010785A KR940011059B1 KR 940011059 B1 KR940011059 B1 KR 940011059B1 KR 1019920010785 A KR1019920010785 A KR 1019920010785A KR 920010785 A KR920010785 A KR 920010785A KR 940011059 B1 KR940011059 B1 KR 940011059B1
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- 239000004065 semiconductor Substances 0.000 title description 5
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000003990 capacitor Substances 0.000 claims description 26
- 229910002367 SrTiO Inorganic materials 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 239000011810 insulating material Substances 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract 2
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 8
- -1 PbO Chemical class 0.000 description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000006247 magnetic powder Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
Classifications
-
- 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
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- Power Engineering (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Ceramic Capacitors (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
제 1 도는 본 발명의 입계형 반도성 자기콘덴서의 단면구조도.1 is a cross-sectional structure diagram of a grain boundary semiconducting magnetic capacitor of the present invention.
제 2 도는 본 발명의 입계형 반도성 자기콘덴서의 온도변화에 따른 유전상수의 변화율을 나타낸 도표.2 is a chart showing the rate of change of the dielectric constant according to the temperature change of the grain boundary semiconducting capacitor of the present invention.
본 발명은 SrTiO3를 주성분으로 하는 다결정 구조의 반도성 결정입자 사이에 입계절연층이 형성된 입계형 반도성 자기콘덴서에 관한 것으로, 특히 주성분으로 TiO2, Dy2O3, ZnO, MnO2및 Al2O3등을 소량 첨가하여 이루어진 조성물을 사용하여 환원분위기중에서 소결시킴으로써 미세구조의 치밀화와 결정성장의 촉진을 도모하여 우수한 전기적 특성을 나타내도록 한 입계형 반도성 자기콘덴서에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a grain boundary semiconducting magnetic capacitor having a grain boundary insulating layer formed between semiconducting crystal grains of polycrystalline structure mainly composed of SrTiO 3. Particularly, the present invention relates to TiO 2 , Dy 2 O 3 , ZnO, MnO 2 and Al. The present invention relates to a grain-shaped semiconducting magnetic capacitor which exhibits excellent electrical properties by sintering in a reducing atmosphere using a composition obtained by adding a small amount of 2 O 3 , to promote densification of microstructures and promotion of crystal growth.
BaTiO3나 SrTiO3를 주성분으로 하는 입계형 반도성 자기콘덴서는 반도성 결정입자 사이에 형성된 얇은 입계절연층을 유전체층으로 사용함으로써 두꺼운 자기층 전체를 유전체층으로 사용하는 종래의 일반적인 자기콘덴서에 비하여 겉보기 유전상수가 월등히 높아지게 되어 소형, 고용량화가 가능하게 된다는 장점을 지니고 있다.The grain boundary semiconducting magnetic capacitor mainly composed of BaTiO 3 or SrTiO 3 uses a thin grain boundary insulating layer formed between the semiconducting crystal grains as the dielectric layer, and has an apparent dielectric as compared with the conventional magnetic capacitor using the entire thick magnetic layer as the dielectric layer. Since the constant is much higher, it has the advantage of being capable of miniaturization and high capacity.
입계형 반도성 자기콘덴서중에서 특히 SrTiO3계 입계형 반도성 자기콘덴서의 경우에는 상온에서 상유전체인 SrTiO3를 주성분으로 하기 때문에 BaTiO3계에 비하여 유전손실(tan δ)이 낮고 유전상수의 온도 의존성이 월등히 우수한 것으로 알려지고 있다.Among the grain type semiconducting magnetic capacitors, especially SrTiO 3 type grain type semiconducting magnetic capacitors have low dielectric loss (tan δ) and temperature dependence of dielectric constants compared to BaTiO 3 type because they are mainly composed of SrTiO 3 which is a common dielectric at room temperature. This is known to be superior.
이같은 SrTiO3계 입계형 반도성 자기콘덴서의 조성물로는 SrTiO3를 주성분으로 하여 소량의 Nb2O5와 SiO2가 첨가되어 이루어진 형태가 알려져 있으며, 이같은 조성물을 이용한 자기콘덴서의 제조는 상기 유전체 자기를 환원분위기 중에서 소결한 후 PbO, Bi2O3, B2O3또는 CuO 등의 금속산화물로 구성된 절연물질을 반도성 자기의 결정입계로 확산시켜 입계절연층을 형성함으로써 이루어진다.As a composition of the SrTiO 3 -based intergranular semiconducting magnetic capacitor, a form in which a small amount of Nb 2 O 5 and SiO 2 are added with SrTiO 3 as a main component is known. After sintering in a reducing atmosphere, an insulating material composed of metal oxides such as PbO, Bi 2 O 3 , B 2 O 3, or CuO is diffused to grain boundaries of semiconducting porcelain to form a grain boundary insulating layer.
그러나, 상기 종래의 입계형 반도성 자기의 조성물은 그 유전상수가 40,000정도록 낮기 때문에 이같은 조성물을 사용하여 제조된 입계형 반도성 자기콘덴서는 단위면적당 얻을 수 있는 정전용량에 한계가 있어 자기콘덴서 크기의 소형화가 불가능하다는 단점을 지니고 있다.However, since the conventional grain boundary semiconducting ceramic composition has a low dielectric constant of 40,000 tablets, the grain boundary semiconducting magnetic capacitor manufactured using such a composition has a limit in the capacitance that can be obtained per unit area. It has the disadvantage that it is impossible to miniaturize.
따라서, 본 발명은 상기 종래의 SrTiO3계 입계형 반도성 자기콘덴서 조성물에서 문제점을 지적되고 있는 낮은 유전상수를 개선하기 위하여 부성분으로 TiO2, Dy2O3, ZnO, MnO2및 Al2O3를 첨가하여 높은 유전상수를 나타내도록 한 입계형 반도성 자기콘덴서 조성물을 제공하는데 발명의 목적이 있다.Accordingly, the present invention provides TiO 2 , Dy 2 O 3 , ZnO, MnO 2, and Al 2 O 3 as subcomponents to improve the low dielectric constant, which has been pointed out in the conventional SrTiO 3 based grain type semiconducting magnetic capacitor composition. It is an object of the present invention to provide a grain-shaped semiconducting magnetic capacitor composition which is added to exhibit a high dielectric constant.
본 발명의 다른 목적은 상기 본 발명의 입계형 반도성 자기콘덴서 조성물을 환원분위기 중에서 소결시켜 유전체 자기의 결정입자를 반도체화 시키고, 반도체화된 유전체자기의 양면에 절연물질을 도포하여 열처리함으로써 입계절연층의 형성된 입계형 반도성 자기콘덴서를 제공하는데 있다.Another object of the present invention is to sinter the grain-shaped semiconducting magnetic capacitor composition of the present invention in a reducing atmosphere to semiconductor crystal grains of dielectric porcelain, and to apply heat treatment by applying an insulating material to both sides of the semiconductor dielectric. An intergranular semiconducting magnetic capacitor formed of a soft layer is provided.
본 발명의 입계형 전도성 자기콘덴서 조성물은 주성분인 SrTiO31몰(mole)에, 부성분으로The grain boundary conductive magnetic condenser composition of the present invention is contained in 1 mole of SrTiO 3 as a main component and as a subcomponent.
TiO20.01∼0.04몰0.01 to 0.04 mol of TiO 2
Dy2O30.001∼0.010몰Dy 2 O 3 0.001-0.010 mol
ZnO 0.001∼0.007몰ZnO 0.001 to 0.007 mol
MnO20.002∼0.012몰MnO 2 0.002-0.012 mol
Al2O30.01∼0.07몰Al 2 O 3 0.01-0.07 mol
이 첨가된 조성으로서, 이같은 조성에 의해 SrTiO3유전체 자기의 환원분위기 소결중 결정입계에 액상을 형성시켜 미세구조의 치밀화 및 결정성장을 촉진시킴은 물론 반도성 결정입자의 전기전도성을 증가시키는 한편으로 결정입계의 전기절연성을 향상시키게 된다.This added composition forms a liquid phase at the grain boundaries during sintering of the SrTiO 3 dielectric porcelain, which promotes densification and crystal growth of the microstructure and increases the electrical conductivity of the semiconducting crystal grains. The electrical insulation of the grain boundary is improved.
상기와 같은 본 발명의 입계형 반도성 자기콘덴서 조성물을 이용한 자기콘덴서의 제조공정은 먼저 혼합이 완료된 자기콘덴서 조성물을 환원분위기 중에서 1400∼1470℃의 온도로 소결하여 유전체 자기의 결정입자를 반도체화 시킨다.The manufacturing process of the magnetic capacitor using the grain-type semiconducting magnetic capacitor composition of the present invention as described above first sinters the mixed magnetic capacitor composition at a temperature of 1400 to 1470 ° C. in a reducing atmosphere to semiconductorize the crystal grains of the dielectric porcelain. .
다음, 반도체화된 유전체 자기의 양면에 PbO, Bi2O3, B2O3또는 CuO와 같은 절연물질로 구성된 절연페이스트를 도포하여 대기중에서 1100∼1300℃의 온도로 열처리 함으로써 절연물질이 반도성 유전체의 결정입계에 선택적으로 확상되어 입계절연층을 형성하도록 한다.Next, an insulating paste made of an insulating material such as PbO, Bi 2 O 3 , B 2 O 3, or CuO is applied to both surfaces of the semiconductor ceramic and heat treated at a temperature of 1100 to 1300 ° C. in the air to make the insulating material semiconductive. It is selectively enlarged at grain boundaries of the dielectric to form a grain boundary insulating layer.
이후, 후속공정으로서 입계절연층이 형성된 소결체의 양면에 통상의 외부전극을 처리함으로써 본 발명의 입계형 반도성 자기콘덴서가 얻어지게 된다.Subsequently, the grain boundary semiconducting capacitor of the present invention is obtained by treating ordinary external electrodes on both surfaces of the sintered body in which the grain boundary insulating layer is formed as a subsequent step.
제 1 도는 본 발명의 자기콘덴서 조성물을 이용하여 상기 본 발명의 제조공정을 통하여 제조된 입계형 반도성 자기콘덴서의 단면 구조도로서 반도체화된 다결정 유전체 자기의 결정입자(1)사이의 입계에 절연물질이 확산되어 형성된 입계절연층(2)이 존재하게 되고 이같이 결정입자(1)와 입계절연층(2)으로 구성된 소결체의 양면에 외부전극(3)이 처리되어 이루어진 구조임을 알 수 있다.1 is a cross-sectional structural diagram of a grain-shaped semiconducting magnetic capacitor manufactured by the manufacturing process of the present invention using the magnetic capacitor composition of the present invention, the insulating material at the grain boundaries between the crystal grains of the semiconductor crystallized polycrystalline dielectric porcelain (1) The grain boundary insulating layer 2 formed by diffusion is present and the external electrode 3 is treated on both surfaces of the sintered body composed of the crystal grain 1 and the grain boundary insulating layer 2 as described above.
본 발명은 입계형 반도성 자기콘덴서는 유전상수 50,000 이상, 유전손실(tan δ) 1.5% 이하, 비저항 10 GΩ·cm 이상의 우수한 전기적 특성을 나타낸다.In the present invention, the grain boundary semiconducting magnetic capacitor exhibits excellent electrical properties of dielectric constant of 50,000 or more, dielectric loss (tan δ) of 1.5% or less, and resistivity of 10 GΩ · cm or more.
본 발명의 실시예는 다음과 같다.Embodiments of the present invention are as follows.
[실시예]EXAMPLE
먼저, 순도 99%의 SrCO3와 TiO2를 혼합하여 1130℃의 온도에서 2시간 하소하여 SrTiO3를 합성한 후, SrTiO31몰에 대하여 부성분으로 TiO2, Dy2O3, ZnO, MnO2및 Al2O3를 아래의 표 1과 같은 조성으로 첨가하여 습식으로 혼합 및 분쇄하였다.First, SrCO 3 and TiO 2 with 99% purity were mixed and calcined at 1130 ° C. for 2 hours to synthesize SrTiO 3 , followed by TiO 2 , Dy 2 O 3 , ZnO, and MnO 2 as subcomponents for 1 mole of SrTiO 3. And Al 2 O 3 It was added to the composition shown in Table 1 below, and mixed and pulverized wet.
다음, 혼합이 완료된 자기분말을 1mm 두께의 원판형태로 가압 성형한 후 질소와 수소가스의 혼합가스(N2: H2= 10 : 1, 부피비)로 이루어지는 환원분위기중에서 1450℃의 온도로 2시간 소결하여 유전체자기를 반도체화 하였다.Next, the mixed magnetic powder was press-molded into a disk shape having a thickness of 1 mm, followed by 2 hours at a temperature of 1450 ° C. in a reducing atmosphere consisting of a mixed gas of nitrogen and hydrogen gas (N 2 : H 2 = 10: 1, volume ratio). By sintering, the dielectric magnetization was semiconductorized.
환원분위기 소결시 승온속도는 300℃/hr 이었으며, 냉각속도는 소결온도에서 1000℃까지는 200℃/hr이였고, 그 이후는 노냉하였다.The temperature increase rate during the sintering of the reducing atmosphere was 300 ° C / hr, the cooling rate was 200 ° C / hr up to 1000 ° C from the sintering temperature, after which the furnace was cooled.
이때, 소결전 자기분말의 제조방법으로 SrTiO31몰에 해당하는 순도 99% 이상의 SrCO3와 TiO2각 1몰에 표 1의 조성과 같은 부성분을 첨가하여 습식으로 잘 혼합해서 대기중에서 1130℃의 온도로 2시간 하소하는 것도 가능하다.At this time, before sintering by the auxiliary component, such as the composition of Table 1, the SrTiO 3 1 mol of purity of at least 99% SrCO 3 and TiO 2, each one mole for the method for producing the magnetic powder was added in 1130 ℃ in the air to mix well with liquid It is also possible to calcinate with temperature for 2 hours.
환원분위기에서 소결하여 반도성을 갖는 유전체 시편의 양면에 PbO, Bi2O3및 B2O3가 무게비(wt%)로 50 : 45 : 5로 구성되는 절연페이스트를 스크린 인쇄후, 대기중에서 1200℃에서 열처리하여 반도성 결정입자사이의 결정입계에 전기절연층을 형성하였다.PbO, Bi 2 O 3 and B 2 O 3 are 50: 45: 5 in weight ratio (wt%) on both sides of semiconductive dielectric specimen by sintering in reducing atmosphere, after screen printing Heat treatment at 占 폚 formed an electrical insulation layer at grain boundaries between semiconducting crystal grains.
입계 절연처리된 시편의 양면에 은 전극 페이스트를 스크린 인쇄하고 대기중에서 800℃의 온도로 10분간 열처리하여 외부전극을 형성한 후, 1KHz의 주파수에서 유전상수(ε)와 유전손실(tan δ)을 측정하고, 직류 전압 25V하에서의 비저항(ρ)을 측정하였는바 그 결과는 표 1에 나타나 있다.After screen printing silver electrode paste on both sides of grain boundary insulation specimen and heat-treating for 10 minutes at 800 ℃ in air, the dielectric constant (ε) and dielectric loss (tan δ) were measured at the frequency of 1KHz. The resistivity under the DC voltage of 25V was measured, and the results are shown in Table 1.
[표 1] 입계형 반도성 자기콘덴서의 재료의 조성 및 특성[Table 1] Composition and Characteristics of Grain-type Semiconducting Magnetic Capacitors
위의 표 1의 시편중 시편번호 1 내지 3과 시편번호 37은 본 발명의 반도성 자기콘덴서 조성물 범위 밖의 비교시편이고, 그 외는 본 발명의 실시예 시편으로서, 본 발명의 실시예 시편, 즉 시편 4∼36은 50,000 이상의 유전상수, 1.5% 이하의 유전손실과 10GΩ·cm 이상의 비저항을 나타내고 있다.Specimen Nos. 1 to 3 and Specimen No. 37 among the specimens in Table 1 above are comparative specimens outside the range of the semiconducting magnetic capacitor composition of the present invention, and others are the exemplary specimens of the present invention. 4 to 36 show a dielectric constant of 50,000 or more, a dielectric loss of 1.5% or less, and a resistivity of 10 GΩ · cm or more.
그러나, 본 발명의 조성범위 밖의 비교시편의 경우에는 상기 본 발명 시편에서와 같은 전기적특성을 나타내고 있지 못함을 알 수 있다.However, it can be seen that the comparative specimens outside the composition range of the present invention do not exhibit the same electrical characteristics as the specimens of the present invention.
또한, 제 2 도의 온도변화에 따른 유전상수의 변화율을 나타낸 도표에서와 같이 본 발명의 조성범위의 재료에서는 -25∼85℃ 사이의 온도범위에서 온도변화에 따른 유전상수의 변화율도 15% 이하로 우수하였다.In addition, in the material of the composition range of the present invention, as shown in the chart showing the rate of change of dielectric constant according to the temperature change of FIG. 2, the rate of change of dielectric constant according to temperature change is less than 15% in the temperature range of -25 to 85 ° C. Excellent.
특히, 본 발명의 실시예 시편중 SrTiO31몰에 부성분으로 TiO20.01∼0.02몰, Dy2O30.002∼0.004몰, ZnO 0.001∼0.007몰, MnO20.005∼0.009몰, Al2O30.02∼0.04몰이 첨가된 조성의 시편(시편번호 : 6∼8, 13∼15, 20∼24, 27∼29, 34, 35)의 경우에 유전상수 80,000 이상, 비저항 10GΩ·cm 이상의 우수한 전기적 특성을 나타냈다.In particular, in an embodiment of the present invention, 1 mole of SrTiO 3 as a secondary component, 0.01 to 0.02 moles of TiO 2 , 0.002 to 0.004 moles of Dy 2 O 3 , 0.001 to 0.007 moles of ZnO, 0.005 to 0.009 moles of MnO 2 , and 0.02 moles of Al 2 O 3. The specimens with the added composition of ~ 0.04 mol (Sample Nos. 6-8, 13-15, 20-24, 27-29, 34, 35) showed excellent electrical properties of over 80,000 dielectric constants and over 10GΩcm resistivity. .
Claims (3)
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019920010785A KR940011059B1 (en) | 1992-06-20 | 1992-06-20 | Semiconductor condenser |
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| KR1019920010785A KR940011059B1 (en) | 1992-06-20 | 1992-06-20 | Semiconductor condenser |
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| KR940001211A KR940001211A (en) | 1994-01-11 |
| KR940011059B1 true KR940011059B1 (en) | 1994-11-22 |
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| KR1019920010785A KR940011059B1 (en) | 1992-06-20 | 1992-06-20 | Semiconductor condenser |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11358904B2 (en) | 2017-03-10 | 2022-06-14 | Samsung Electronics Co., Ltd. | Dielectric material, method of manufacturing thereof, and dielectric devices and electronic devices including the same |
| US11823838B2 (en) | 2017-03-31 | 2023-11-21 | Samsung Electronics Co., Ltd. | Two-dimensional perovskite material, dielectric material and multi-layered capacitor including the same |
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1992
- 1992-06-20 KR KR1019920010785A patent/KR940011059B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11358904B2 (en) | 2017-03-10 | 2022-06-14 | Samsung Electronics Co., Ltd. | Dielectric material, method of manufacturing thereof, and dielectric devices and electronic devices including the same |
| US11823838B2 (en) | 2017-03-31 | 2023-11-21 | Samsung Electronics Co., Ltd. | Two-dimensional perovskite material, dielectric material and multi-layered capacitor including the same |
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| KR940001211A (en) | 1994-01-11 |
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