KR101136004B1 - Non-reducing dielectric ceramic composite for low temperature co-fired ceramics and high frequency and multi layer ceramic capacitor using the same - Google Patents
Non-reducing dielectric ceramic composite for low temperature co-fired ceramics and high frequency and multi layer ceramic capacitor using the same Download PDFInfo
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- KR101136004B1 KR101136004B1 KR1020090113944A KR20090113944A KR101136004B1 KR 101136004 B1 KR101136004 B1 KR 101136004B1 KR 1020090113944 A KR1020090113944 A KR 1020090113944A KR 20090113944 A KR20090113944 A KR 20090113944A KR 101136004 B1 KR101136004 B1 KR 101136004B1
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- 239000000919 ceramic Substances 0.000 title claims abstract description 77
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title 1
- 239000011521 glass Substances 0.000 claims abstract description 49
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 105
- 230000009467 reduction Effects 0.000 claims description 25
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 239000004615 ingredient Substances 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 5
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 5
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 5
- 229910010346 TiF Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000002002 slurry Substances 0.000 abstract description 13
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- 238000005054 agglomeration Methods 0.000 abstract description 4
- 239000003990 capacitor Substances 0.000 abstract description 3
- -1 Dielectric Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000011575 calcium Substances 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 description 3
- 241000566146 Asio Species 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010344 co-firing Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
본 발명은 주성분에 망목 구조를 갖는 글라스 프릿을 혼합하여 저온 소성이 가능하며 슬러리 제작 공정 중 글라스 프릿을 안정적으로 형성되도록 하여 글라스 뭉침을 방지할 수 있는 내환원성 LTCC용 고주파 유전체 세라믹 조성물 및 이를 이용한 적층 세라믹 커패시터에 관한 것으로, (CaxSr1-x)(ZryTi1-y)O3계로 이루어지는 주성분 87~97 wt%와, 망목 구조를 갖는 글라스 프릿으로 이루어지는 제1부성분 1~10 wt%와, 고주파 품질계수를 향상시키는 Ni2Ta2O7로 이루어지는 제2부성분 1~5 wt%와, MoO3, V2O5 및 MnO3 중 하나 이상으로 이루어지는 제3부성분 1~3 wt%로 이루어지고, 주성분은 0.6 ≤ x ≤0.8, 0.95 ≤ y ≤0.97을 만족하도록 하는 것을 특징으로 한다.The present invention is capable of low-temperature firing by mixing a glass frit having a mesh structure in a main component and stably forming the glass frit during the slurry manufacturing process to prevent glass agglomeration. A ceramic capacitor, comprising: 87 to 97 wt% of a main component consisting of (CaxSr1-x) (ZryTi1-y) O 3 system, 1 to 10 wt% of a first subcomponent comprising a glass frit having a network structure, and a high frequency quality factor. and increase the second subcomponent is 1 ~ 5 wt% consisting of Ni 2 Ta 2 O 7 which, MoO 3, V 2 O 5 and MnO comprise a third sub-component 1 ~ 3 wt% consisting of one or more of the three main components are 0.6 X ≦ 0.8, 0.95 ≦ y ≦ 0.97.
적층, 세라믹, 커패시터, 유전체, 세라믹, 글라스, 프릿, LTCC Laminated, Ceramic, Capacitors, Dielectric, Ceramic, Glass, Frit, LTCC
Description
본 발명은 내환원성 LTCC용 고주파 유전체 세라믹 조성물 및 이를 이용한 적층 세라믹 커패시터에 관한 것으로, 더욱 상세하게는 주성분에 망목 구조를 갖는 글라스 프릿을 혼합하여 저온 소성이 가능하며 슬러리 제작 공정 중 글라스 프릿을 안정적으로 형성되도록 하여 글라스 뭉침을 방지할 수 있는 내환원성 LTCC용 고주파 유전체 세라믹 조성물 및 이를 이용한 적층 세라믹 커패시터에 관한 것이다. The present invention relates to a high frequency dielectric ceramic composition for reducing resistance LTCC and a multilayer ceramic capacitor using the same. More particularly, the glass frit may be mixed at a low temperature by mixing a glass frit having a mesh structure as a main component, and the glass frit is stably maintained during the slurry manufacturing process. The present invention relates to a high frequency dielectric ceramic composition for reduction-resistant LTCC and a multilayer ceramic capacitor using the same, which can be formed to prevent glass aggregation.
적층 세라믹 커패시터(multi layer ceramic capacitor: MLCC)는 다수개의 유전체 세라믹층, 다수개의 유전 세라믹층 사이에 형성되는 내부전극 및 내부전극을 연결하는 외부전극으로 이루어지다. The multilayer ceramic capacitor (MLCC) includes a plurality of dielectric ceramic layers, an internal electrode formed between the plurality of dielectric ceramic layers, and an external electrode connecting the internal electrodes.
외부전극으로 연결되는 내부전극은 Pd(팔라듐)-Ag(은) 합금과 같은 귀금속이나 Ni(니켈)을 사용하고 있다. Pd-Ag 합금은 고가로 제조원가을 상승시키는 문제점이 있으며, Ni은 강자성체이므로 적층 세라믹 커패시터를 고주파 대역에서 사용하 는 경우 Ni이 자화되어 손실을 증대시키거나 비저항이 높아지는 문제점이 있다. The internal electrode connected to the external electrode uses a noble metal such as Pd (palladium) -Ag (silver) alloy or Ni (nickel). Pd-Ag alloy has a problem of increasing the manufacturing cost at a high price, Ni is a ferromagnetic material, when using a multilayer ceramic capacitor in the high frequency band, there is a problem that Ni is magnetized to increase the loss or increase the specific resistance.
Ni의 문제점을 해결하기 위해 내부전극으로 Cu(구리)를 적용하는 기술이 개발되었다. 내부전극으로 Cu를 사용하는 경우에 산화를 방지하기 위해 유전체를 환원성 분위기에서 소성온도를 1000℃이하로 낮추어 소성해야 한다. 이와 같이 Cu를 사용하는 경우에 저온 소성할 수 있도록 유전체 세라믹 조성물의 주성분에 글라스 프릿(glass frit)을 첨가하는 기술들이 공개되어 있다. In order to solve the problem of Ni, a technology of applying Cu (copper) as an internal electrode has been developed. When Cu is used as the internal electrode, the dielectric should be fired by reducing the firing temperature below 1000 ° C. in a reducing atmosphere to prevent oxidation. As described above, a technique of adding glass frit to the main component of the dielectric ceramic composition is disclosed to enable low-temperature firing when Cu is used.
유전체 세라믹 조성물의 주성분에 글라스 프릿을 첨가하는 기술은 일본 특개평11-283860호(공개일:1999년10월15일, 출원인: 쿄세라) 및 일본 특개2002-256371호(공개일: 2002년9월11일, 출원인: 다이호 공업)에 공개되어 있다. 일본 특개평11-283860호에 공개된 유전체 세라믹 조성물은 Ca(Zr1-yTiy)O3을 주성분으로 하고, 주성분 100중량부에 대해 부성분인 aSiO2-bB2O3-eCaO(25≤a≤45, 45≤b≤65, 5≤e≤20)계 조성물 프릿 0.5~2.5중량부와 부성분인 Mn화합물 1.0~3.0 중량부를 혼합하여 형성된다. 일본 특개 2002-256371호에 공개된 유전체 세라믹 조성물은 (Ca1-xMgx)(Zr1-yTiy)O3을 주성분으로 하고, 주성분 100중량부에 대해 aSiO2-bB2O3-cLi2O-eCaO-iBaO(0.1≤a≤0.7, 0.15≤b≤0.89, 0.01≤c≤0.5, 0<d≤0.4, 0<i≤0.4)계 조성물 프릿 0.5~2.5중량부와 MnO2를 혼합하여 이루어진다.Techniques for adding glass frit to the main components of dielectric ceramic compositions are disclosed in Japanese Patent Application Laid-Open No. 11-283860 (published October 15, 1999, by Kyocera) and Japanese Patent Application Laid-Open No. 2002-256371 (published: 20029). Applicant: Daiho Industries). The dielectric ceramic composition disclosed in Japanese Patent Laid-Open No. Hei 11-283860 has Ca (Zr1-yTiy) O 3 as a main component and aSiO 2 -bB 2 O 3 -eCaO (25 ≦ a ≦ 45, which is a subcomponent with respect to 100 parts by weight of the main component. And 45 ≤ b ≤ 65, 5 ≤ e ≤ 20) system composition frit is formed by mixing 1.0 to 3.0 parts by weight of the Mn compound as a minor component. The dielectric ceramic composition disclosed in Japanese Patent Laid-Open No. 2002-256371 has (Ca 1-x Mg x ) (Zr 1-y Ti y ) O 3 as a main component and aSiO 2 -bB 2 O 3 -based on 100 parts by weight of the main component. cLi 2 O-eCaO-iBaO (0.1≤a≤0.7, 0.15≤b≤0.89, 0.01≤c≤0.5, 0 <d≤0.4, 0 <i≤0.4) based composition frit 0.5-2.5 parts by weight and MnO 2 It is made by mixing.
종래와 같이 주성분에 글라스 프릿을 혼합하여 이루어지는 유전체 세라믹 조성물은 글라스 프릿의 일부 성분이 용출되거나 휘발에 따른 조성변경으로 인해 글라스 프릿의 유동성이 저하되어 소결체의 표면에서 글라스 뭉침(agglomeration)이 발생하는 문제점이 있다. 또한, 고주파 커패시터를 제작하기 위해서는 고주파 영역에서 높은 품질계수가 필요한 데 글라스 프릿을 첨가하면 품질계수가 급격히 저하된다. Dielectric ceramic composition by mixing the glass frit with the main component as in the prior art is a problem that the glass agglomeration occurs on the surface of the sintered body due to the flowability of the glass frit due to the elution of some components of the glass frit or the composition change due to volatilization There is this. In addition, in order to manufacture a high frequency capacitor, a high quality factor is required in the high frequency region, but when the glass frit is added, the quality factor is drastically reduced.
본 발명의 목적은 전술한 문제점을 해결하기 위한 것으로, 주성분에 망목 구조를 갖는 글라스 프릿을 혼합하여 저온 소성이 가능하고, 슬러리 제작공정 중 글라스 프릿을 안정적으로 형성되도록 하여 글라스 뭉침을 방지하며, 고주파 대역에서 품질계수를 증가시킬 수 있는 내환원성 LTCC용 고주파 유전체 세라믹 조성물 및 이를 이용한 적층 세라믹 커패시터를 제공함에 있다.An object of the present invention is to solve the above-mentioned problems, by mixing the glass frit having a mesh structure in the main component to enable low-temperature baking, to stably form the glass frit during the slurry manufacturing process to prevent glass aggregation, high frequency The present invention provides a high frequency dielectric ceramic composition for reduction resistant LTCC and a multilayer ceramic capacitor using the same which can increase the quality factor in a band.
본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물은 (CaxSr1-x)(ZryTi1-y)O3계로 이루어지는 주성분 87~97 wt%와, 망목 구조를 갖는 글라스 프릿으로 이루어지는 제1부성분 1~10 wt%와, Ni2Ta2O7로 이루어지는 제2부성분 1~5 wt%와, MoO3, V2O5 및 MnO3 중 하나 이상으로 이루어지는 제3부성분 1~3 wt%로 이루어지고, 상기 주성분은 0.6 ≤ x ≤0.8, 0.95 ≤ y ≤0.97을 만족하며, 상기 망목 구조를 갖는 글라스 프릿은 aBa계 조성물-bSi계 조성물-cLi계 조성물-dB계 조성물-fRF계 조성물로 이루어지고, 상기 a+b+c+d+f=100 mol%로 3≤ a ≤25 mol%, 20≤ b ≤30 mol%, 5≤ c ≤20 mol%, 30≤ d ≤50 mol%, 1≤ f ≤10 mol%를 만족하며, 상기 Ba계 조성물은 BaO와 BaCO3 중 하나이고, 상기 Si계 조성물은 SiO2이며, 상기 Li계 조성물은 Li2O, Li2CO3 및 LiOH 중 하나이며, B계 조성물은 B2O3와 H3BO3 중 하나이며, RF계 조성물은 MgF2, CaF2, AlF3 및 TiF4 중 하나인 것을 특징으로 한다.The high frequency dielectric ceramic composition for reduction-resistant LTCC of the present invention is composed of (CaxSr1-x) (ZryTi1-y) O 3 based component, 87-97 wt%, and the first subcomponent composed of a glass frit having a network structure. And 1 to 5 wt% of a second subcomponent consisting of Ni 2 Ta 2 O 7 , and 1 to 3 wt% of a third subcomponent composed of one or more of MoO 3 , V 2 O 5, and MnO 3 . 0.6 ≤ x ≤ 0.8, 0.95 ≤ y ≤ 0.97, the glass frit having a network structure is composed of aBa composition-bSi composition-cLi composition-dB composition-fRF composition, the a + b + c + d + f = 100 mol% with 3 ≦ a ≦ 25 mol%, 20≤ b ≤30 mol%, 5≤ c ≤20 mol%, 30≤ d ≤50 mol%, 1≤ f ≤10 mol% Sa, the Ba-based composition is one of BaO and BaCO 3 , the Si-based composition is SiO 2 , the Li-based composition is one of Li 2 O, Li 2 CO 3 and LiOH, B-based composition is B optionally replaced with one 2 O 3 and H 3 BO 3 , RF-based composition is characterized in that one of MgF 2, CaF 2, AlF 3 and TiF 4.
본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물을 이용한 적층 세라믹 커패시터는 내환원성 LTCC(Low Temperature Co-fired Ceramics)용 고주파 유전체 세라믹 조성물로 이루어지는 다수개의 유전체 세라믹층과; 상기 다수개의 유전체 세라믹층 사이에 각각 형성되는 내부전극과; 상기 내부전극과 전기적으로 접속되도록 형성되는 외부전극으로 구성되며, 상기 내환원성 LTCC용 고주파 유전체 세라믹 조성물은 (CaxSr1-x)(ZryTi1-y)O3계로 이루어지는 주성분 87~97 wt%와, 망목 구조를 갖는 글라스 프릿으로 이루어지는 제1부성분 1~10 wt%와, Ni2Ta2O7로 이루어지는 제2부성분 1~5 wt%와, MoO3, V2O5 및 MnO3 중 하나 이상으로 이루어지는 제3부성분 1~3 wt%로 이루어지고, 상기 주성분은 0.6 ≤ x ≤0.8, 0.95 ≤ y ≤0.97을 만족하며, 상기 망목 구조를 갖는 글라스 프릿은 aBa계 조성물-bSi계 조성물-cLi계 조성물-dB계 조성물-fRF계 조성물로 이루어지고, 상기 a+b+c+d+f=100 mol%로 3≤ a ≤25 mol%, 20≤ b ≤30 mol%, 5≤ c ≤20 mol%, 30≤ d ≤50 mol%, 1≤ f ≤10 mol%를 만족하며, 상기 Ba계 조성물은 BaO와 BaCO3 중 하나이고, 상기 Si계 조성물은 SiO2이며, 상기 Li계 조성물은 Li2O, Li2CO3 및 LiOH 중 하나이며, B계 조성물은 B2O3와 H3BO3 중 하나이며, RF계 조성물은 MgF2, CaF2, AlF3 및 TiF4 중 하나인 것을 특징으로 한다.The multilayer ceramic capacitor using the high frequency dielectric ceramic composition for reducing LTCC of the present invention comprises a plurality of dielectric ceramic layers comprising a high frequency dielectric ceramic composition for reducing temperature resistant low temperature co-fired ceramics (LTCC); Internal electrodes formed between the plurality of dielectric ceramic layers, respectively; The high frequency dielectric ceramic composition for reduction resistant LTCC is composed of (CaxSr1-x) (ZryTi1-y) O 3 system with 87-97 wt% of main component and a mesh structure. 1 to 10 wt% of a first sub ingredient consisting of a glass frit having 1 to 5 wt% of a second sub ingredient consisting of Ni 2 Ta 2 O 7 and MoO 3 , V 2 O 5, and MnO 3 . It consists of 1-3 parts by weight of 3 parts by weight, and the main component satisfies 0.6 ≦ x ≦ 0.8, 0.95 ≦ y ≦ 0.97, and the glass frit having the network structure is aBa composition-bSi composition-cLi composition-dB System composition-fRF composition, wherein a + b + c + d + f = 100 mol%, 3 ≦ a ≦ 25 mol%, 20 ≦ b ≦ 30 mol%, 5 ≦ c ≦ 20 mol%, 30 Satisfies ≦ d ≦ 50 mol% and 1 ≦ f ≦ 10 mol%, wherein the Ba-based composition is one of BaO and BaCO 3 , the Si-based composition is SiO 2 , and the Li-based composition is Li 2 O, Li 2 CO 3 and LiOH, B-based composition is one of B 2 O 3 and H 3 BO 3 , RF-based composition is characterized in that one of MgF 2 , CaF 2 , AlF 3 and TiF 4 do.
본 발명의 내환원성 LTCC용 고주파 유전체 및 이를 이용한 적층 세라믹 커패시터는 주성분인 (CaxSr1-x)(ZryTi1-y)O3계에 망목 구조를 갖는 글라스 프릿을 혼합하여 저온 소성이 가능하고, 슬러리 제작 중 글라스 프릿을 안정적으로 형성되도록 하여 글라스 뭉침을 방지하는 이점이 있으며, 적층 칩 제조 시 수율을 향상 시킬 수 있다. 또한, Ni2Ta2O7과 MoO3, V2O5 및 MnO3 중 하나 이상을 첨가하여 고주파 대역에서 품질계수를 증가시킬 수 있는 이점을 제공한다. The high frequency dielectric for the reduction resistant LTCC of the present invention and the multilayer ceramic capacitor using the same are capable of low-temperature firing by mixing a glass frit having a mesh structure in the main component (CaxSr1-x) (ZryTi1-y) O 3 system, and during slurry production The glass frit can be stably formed to prevent glass agglomeration, and the yield can be improved when the laminated chip is manufactured. In addition, the addition of one or more of Ni 2 Ta 2 O 7 and MoO 3 , V 2 O 5 and MnO 3 provides the advantage of increasing the quality factor in the high frequency band.
본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물 및 이를 이용한 적 층 세라믹 커패시터의 실시예를 첨부된 도면을 참조하여 설명하면 다음과 같다.An embodiment of a high frequency dielectric ceramic composition for a reduced resistance LTCC of the present invention and a laminated ceramic capacitor using the same will be described with reference to the accompanying drawings.
먼저, 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물을 설명하면 다음과 같다.First, the high frequency dielectric ceramic composition for the reduction-resistant LTCC of the present invention will be described.
본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물은 (CaxSr1-x)(ZryTi1-y)O3계로 이루어지는 주성분 87~97 wt%와, 망목 구조를 갖는 글라스 프릿으로 이루어지는 제1부성분 1~10 wt%와, Ni2Ta2O7로 이루어지는 제2부성분 1~5 wt%와, MoO3(산화몰리브덴), V2O5(산화바나듐) 및 MnO3(산화망간) 중 하나 이상으로 이루어지는 제3부성분 1~3 wt%로 이루어진다. The high frequency dielectric ceramic composition for reduction-resistant LTCC of the present invention is composed of (CaxSr1-x) (ZryTi1-y) O 3 based component, 87-97 wt%, and the first subcomponent composed of a glass frit having a network structure. And a third subcomponent comprising 1 to 5 wt% of the second subcomponent composed of Ni 2 Ta 2 O 7 , and at least one of MoO 3 (molybdenum oxide), V 2 O 5 (vanadium oxide), and MnO 3 (manganese oxide). It consists of 1-3 wt%.
주성분인 (CaxSr1-x)(ZryTi1-y)O3계에서 x, x-1, y 및 y-1은 각각 0.6 ≤ x ≤0.8, 0.2 ≤ 1-x ≤0.4, 0.95 ≤ y ≤0.97, 0.03 ≤ 1-y ≤0.05를 각각 만족되도록 설정하여 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물을 이용하여 제조된 적층 세라믹 커패시터(10: 도 3에 도시됨)가 온도변화에 따른 오차와 동작 온도가 COG의 규격을 만족되도록 한다. COG의 규격은 온도 특성이 -55℃~125℃까지 동작하고 온도특성은 0±30 ppm/℃로 해당되도록 한다. 이러한 (CaxSr1-x)(ZryTi1-y)O3계는 소성 시 Ca(칼슘)의 일부가 Ti(티타늄)의 위치에 고용되어 억셉터(acceptor)로 작용하고, 같은 수의 산소 공공이 발생하기 때문에 환원작용이 어려워져 내환원성을 갖게 된다. 또한, Ni2Ta2O7을 첨가함으로서 글래스 프릿에 의한 산소공공의 발생을 최소화 할 수 있다.In the main component (CaxSr1-x) (ZryTi1-y) O 3 system, x, x-1, y and y-1 are 0.6 ≤ x ≤ 0.8, 0.2 ≤ 1-x ≤ 0.4, 0.95 ≤ y ≤ 0.97, 0.03, respectively. The multilayer ceramic capacitor (10: shown in FIG. 3) manufactured by using the high frequency dielectric ceramic composition for reduction-resistant LTCC of the present invention by setting ≤ 1-y ≤0.05 so as to satisfy the error and operating temperature Ensure that the specifications of the COG are met. The specification of COG ensures that the temperature characteristics operate from -55 ℃ to 125 ℃ and the temperature characteristics correspond to 0 ± 30 ppm / ℃. In the (CaxSr1-x) (ZryTi1-y) O 3 system, part of Ca (calcium) is dissolved at the position of Ti (titanium) during firing to act as an acceptor, and the same number of oxygen vacancies are generated. Because of this, the reduction is difficult, resulting in reduction resistance. In addition, by adding Ni 2 Ta 2 O 7 It is possible to minimize the generation of oxygen pores by the glass frit.
제1부성분은 망목 구조를 갖는 글라스 프릿이 사용된다. 망목 구조를 갖는 글라스 프릿은 aBa(바륨)계 조성물-bSi(실리콘)계 조성물-cLi(리튬)계 조성물-dB(보론)계 조성물-fRF(플루오르)계 조성물로 이루어지고, aBa계 조성물-bSi계 조성물-cLi계 조성물-dB계 조성물-fRF계 조성물에서 a, b, c, d, e, f는 a+b+c+d+f=100 mol%가 되도록 설정된다. a+b+c+d+f=100 mol%이 되도록 설치되는 경우에 각각의 a, b, c, d, e, f는 3≤ a ≤25 mol%, 20≤ b ≤30 mol%, 5≤ c ≤20 mol%, 30≤ d ≤50 mol%, 1≤ f ≤10 mol%를 만족되도록 한다. 망목 구조를 갖는 글라스 프릿에 F(플루오르)계 조성물을 첨가함으로써 저온 소성이 가능하고, 글라스 프릿의 안정적으로 형성할 수 있다. As the first subcomponent, a glass frit having a mesh structure is used. The glass frit having a mesh structure consists of aBa (barium) composition -bSi (silicon) composition -cLi (lithium) composition -dB (boron) composition -fRF (fluorine) composition, aBa composition -bSi In the composition-cLi composition-dB composition-fRF composition, a, b, c, d, e and f are set to be a + b + c + d + f = 100 mol%. When a + b + c + d + f = 100 mol%, each of a, b, c, d, e, and f is 3 ≦ a ≦ 25 mol%, 20 ≦ b ≦ 30 mol%, 5 C≤20 mol%, 30≤d≤50 mol%, and 1≤f≤10 mol%. By adding the F (fluorine) composition to the glass frit having a network structure, low-temperature baking is possible, and the glass frit can be stably formed.
제2부성분은 Ni2Ta2O7은 망목구조를 가지는 글라스 프릿 첨가에 따라 전자발생을 최소화하여 품질 계수(Q) 및 절연저항(IR)을 향상시킨다. The second accessory ingredient is Ni 2 Ta 2 O 7 is a glass frit having a network structure to minimize the generation of electrons to improve the quality factor (Q) and insulation resistance (IR).
제3부성분은 MoO3(산화몰리브덴), V2O5(산화바나듐) 및 MnO3(산화망간) 중 하나 이상이 사용되며, 적층 세라믹 커패시터(10: 도 3에 도시됨)의 품질계수(Q)를 개선시키기 위해 사용된다. 즉, 제3부성분은 첨가제로 MoO3(산화몰리브덴), V2O5(산화바나듐) 및 MnO3(산화망간) 중 하나나 하나 이상이 첨가된다. 이러한 MoO3, V2O5 및 MnO3은 각각 억셉터(acceptor)로 작용하여 환원분위기에서 소결함으로서 생성되는 자유전자를 흡수하여 고주파 대역에서 품질계수(Q) 값을 개선시키며 내환원성을 증진시킨다. 억셉터로 작용하는 제3부성분의 함량이 1~3 wt%의 조건을 만족하지 않고 작은 경우에 품질계수(Q) 값과 비저항값이 낮아지며, 큰 경우에는 고용이 잘 되지 않고 석출되어 소결성이 저하된다. As the third sub ingredient, at least one of MoO 3 (molybdenum oxide), V 2 O 5 (vanadium oxide) and MnO 3 (manganese oxide) is used, and the quality factor (Q) of the multilayer ceramic capacitor 10 (shown in FIG. Is used to improve the That is, the third sub ingredient is added with one or more of MoO 3 (molybdenum oxide), V 2 O 5 (vanadium oxide) and MnO 3 (manganese oxide) as additives. MoO 3 , V 2 O 5 and MnO 3 act as an acceptor, respectively, to absorb free electrons generated by sintering in a reducing atmosphere, thereby improving the quality factor (Q) in the high frequency band and enhancing the reduction resistance. . When the content of the third sub ingredient acting as an acceptor does not satisfy the condition of 1 to 3 wt%, the Q value and the specific resistance value are low, and when the content is large, it is precipitated without solid solution and the sinterability is reduced. do.
상기 구성 중 제1부성분을 이루는 aBa계 조성물-bSi계 조성물-cLi계 조성물-dB계 조성물-fRF계 조성물들을 상세히 설명하면 다음과 같다. The aBa composition, the bSi composition, the cLi composition, the dB composition, and the fRF composition constituting the first accessory ingredient will be described in detail as follows.
Ba계 조성물은 3 mol%~ 25 mol%가 바람직하며 BaO(산화바륨)와 BaCO3(탄산바륨) 중 하나가 사용된다. 이러한 Ba계 조성물은 글라스 프릿의 용융성을 개선하기 위해 첨가되어 유전체 세라믹 조성물을 이용하여 유전체 세라믹층(11: 도 3에 도시됨)를 제조한 후 유전체 세라믹층(11)을 적층한 후 소성 시 저온소성이 가능하도록 한다. The Ba-based composition is preferably 3 mol% to 25 mol%, and one of BaO (barium oxide) and BaCO 3 (barium carbonate) is used. The Ba-based composition is added to improve the meltability of the glass frit to produce a dielectric ceramic layer 11 (shown in FIG. 3) using the dielectric ceramic composition, and then laminate the dielectric
Si계 조성물은 20 mol% ~ 30 mol%가 바람직하며 SiO2(산화규소)가 사용된다. 이러한 Si계 조성물은 열팽창을 낮추고 강도, 화학적 내구성을 향상시키지만 용융조건 및 실투온도에 따라 조성함량이 제한된다. 즉, Si계 조성물은 망목형성제로 유전체 세라믹층(11)의 소결 조건에 큰 영향을 주게 된다. 이로 인해 산화규소의 첨가량이 상기 조건 보다 적은 경우에 유전체 세라믹층(11)의 소결성을 저하시킬 수 있는 반면에 첨가량이 큰 경우에 연화온도가 높아져 유전체 세라믹층(11)의 저온 소성용 소결제로 작용되지 않을 수 있다.Si-based composition is preferably 20 mol% to 30 mol%, and SiO 2 (silicon oxide) is used. The Si-based composition lowers thermal expansion and improves strength and chemical durability, but the composition content is limited according to melting conditions and devitrification temperature. That is, the Si-based composition has a great influence on the sintering conditions of the dielectric
Li계 조성물은 5 mol% ~ 20 mol%가 바람직하며, Li2O(산화 리튬), Li2CO3 및 LiOH 중 하나가 사용된다. 이러한 Li계 조성물은 내환원성이 매우 우수한 알카리금속 산화물로 내환원성을 가지면서 동시에 글래스의 개질제(modifier)로 작용하여 고온에서의 점도를 급격히 떨어뜨려 소결성을 향상시키는 역할을 하여 유전체 세라믹층(11)의 저온 소성을 위해 첨가되나 산화규소와 치환되어 유리전이온도, 연화온도 등의 온도 특성을 감소시킴으로 이를 보완하기 위해 B계 조성물이 첨가된다. The Li-based composition is preferably 5 mol% to 20 mol%, and one of Li 2 O (lithium oxide), Li 2 CO 3 and LiOH is used. The Li-based composition is an alkali metal oxide having excellent reduction resistance and at the same time serves as a modifier of glass, thereby rapidly decreasing the viscosity at high temperature to improve sinterability, thereby increasing the dielectric
B계 조성물은 30 mol% ~ 50 mol%가 바람직하며, B2O3(산화보론)와 H3BO3(붕산) 중 하나가 사용된다. 이러한 B계 조성물은 글라스의 화학적 내구성의 개선, 글라스에 결정에 발생된 부분에서 투명성을 잃는 실투경향을 억제, 용융온도의 저하를 위해 사용되어 Li계 조성물과 같이 유전체 세라믹층(11)의 저온 소성을 위해 첨가된다. 또한, B계 조성물은 글라스 프릿의 망목형성산화물로서 Si계 조성물의 SiO2와 치환되어 유리전이온도, 연화온도 등의 온도특성을 감소시켜, 상기 조건 보다 크거나 작은 경우에 연화온도가 높아지거나 글라스 구조를 약화시켜 기계적 강도를 저하시킨다.The B-based composition is preferably 30 mol% to 50 mol%, and one of B 2 O 3 (boron oxide) and H 3 BO 3 (boric acid) is used. The B-based composition is used to improve the chemical durability of the glass, to suppress the devitrification tendency of losing transparency in the portion generated in the crystal, and to lower the melting temperature, so that the low-temperature firing of the dielectric
RF계 조성물은 1 mol% ~ 10 mol%가 바람직하며, MgF2(블화마그네슘), CaF2(블화칼슘), AlF3(블화알루미늄) 및 TiF4(블화티탄늄) 중 하나가 사용된다. F계 조성물은 글라스 형성제로 사용되며, 해리에너지와 배위수로부터 단일결합에 대한 강도를 구하여 산화물처럼 유리형성불화물, 중간불화물, 수식불화물로 분류하며, Mg(마그네슘), Ca(칼슘), Al(알루미늄) 및 Ti(티탄늄)이 망목을 형성하여 글라스가 안정되게 형성되도록 한다.The RF-based composition is preferably 1 mol% to 10 mol%, and one of MgF 2 (magnesium fluoride), CaF 2 (calcium fluoride), AlF 3 (aluminum fluoride), and TiF 4 (titanium fluoride) is used. The F-based composition is used as a glass former, and the strength of a single bond is determined from the dissociation energy and the coordination water. The F-based composition is classified into a glass-forming fluoride, an intermediate fluoride, and a modified fluoride like an oxide. Aluminum) and Ti (titanium) form a mesh to allow the glass to be stably formed.
이와 같이 내환원성 LTCC용 고주파 유전체 세라믹 조성물은 고주파 대역에서 품질계수(Q) 값을 개선함으로써 1GHz 이상의 대역에서 낮은 ESR(Equivalent Series Resistance)이 요구되는 적층 세라믹 커패시터(10: 도 3에 도시됨)의 소결체(10a: 도 3에 도시됨)나 이동통신 관련 고주파 모듈 및 안테나에 적용되는 유전체(도시 않음)의 제조에 사용될 수 있다.As described above, the high frequency dielectric ceramic composition for reduction-resistant LTCC is a multilayer ceramic capacitor (10: shown in FIG. 3) requiring low ESR (Equivalent Series Resistance) in a band of 1 GHz or more by improving the quality factor (Q) value in the high frequency band. It can be used for the production of dielectrics (not shown) applied to the
고주파 대역에서 품질계수(Q) 값을 개선시킬 수 있는 내환원성 LTCC용 고주파 유전체 세라믹 조성물을 이용하여 적층 세라믹 커패시터(10)를 제조하는 방법을 설명하면 다음과 같다.Hereinafter, a method of manufacturing the multilayer
먼저, 그린 시트(green sheet)인 유전체 세라믹층(11: 도 3에 도시됨)을 제조하게 된다. 유전체 세라믹층(11)을 제조하는 과정은 먼저, 주성분인 (CaxSr1-x)(ZryTi1-y)O3계의 슬러리, 제1부성분인 글라스 프릿, 제2부성분인 Ni2Ta2O7 및 제3부성분인 MoO3, V2O5 및 MnO3 중 하나 이상이 준비되면 이를 볼 밀링(ball milling)방법을 이용하여 혼합한다. 볼 밀링방법으로 혼합되면 혼합원료를 동결건조방법이나 건식분무방법을 이용하여 건조한다. 혼합원료의 건조가 완료되면 결합제로 PVB와 에탄올/톨루엔 용애로 볼 밀링한 후닥터 블레이드 캐스팅(doctor blade casting)방법으로 혼합원료를 캐스팅하여 유전체 세라믹층(11)으로 제조한다. First, a dielectric ceramic layer 11 (shown in FIG. 3), which is a green sheet, is manufactured. The process of manufacturing the dielectric
유전체 세라믹층(11)이 제조되면 각각의 유전체 세라믹층(11)에 내부전극(12: 도 3에 도시됨)을 형성한 후 각각을 순차적으로 적층하여 소결한다. 내부전극(12)이 형성되는 유전체 세라믹층(11)이 적층되어 소결되면 유전체(부재번호 미도시)를 형성하게 된다. 유전체가 형성되면 내부전극(12)을 전기적으로 연결하기 위한 외부전극(13: 도 3에 도시됨)을 형성하여 적층 세라믹 커패시터(10: 도 3에 도시됨)를 제조하게 된다. When the dielectric
본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물을 이용하여 제조되는 적층 세라믹 커패시터(10)를 첨부된 도 3을 이용하여 보다 구체적으로 설명하면 다음과 같다.The multilayer
도 3에서와 같이 본 발명의 적층 세라믹 커패시터(10)는 다수개의 유전체 세라믹층(11), 내부전극(12) 및 외부전극(13)으로 구성된다. As shown in FIG. 3, the multilayer
다수개의 유전체 세라믹층(11)은 각각 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물을 이용하여 제조되며, 내부전극(12)은 다수개의 유전체 세라믹층(11) 사이에 각각 형성된다. 이러한 내부전극(12)은 Cu가 사용된다. 내부전극(12)은 Cu가 사용되는 경우에도 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물을 이용하여 제조된 유전체 세라믹층(11)은 내부전극(12)과 저온 동시 소성을 할 수 있다. 즉, 유전체 세라믹층(11)은 LTCC(Low Temperature Co-fired Ceramics)로 1000℃ 이하로 소성할 수 있어 내부전극(12)으로 Cu가 사용되는 경우에 동시에 저온 소성할 수 있다. 즉, 내부전극(12)이 형성된 다수개의 유전체 세라믹층(11)이 적층되어 저온 소성되면 소결체(10a)로 형성되고, 이 소결체(10a)에 내부전극(12)이 삽입된 형상으로 제조된다. Each of the plurality of dielectric
유전체 세라믹층(11)과 내부전극(12)이 1000℃ 이하로 소성되면 외부전극(13)은 내부전극(12)과 전기적으로 접속되도록 형성된다. 여기서, 외부전극(13)은Cu, Al, Ni, Ag(은), Pd(팔라듐) 및 Pt(백금) 중 하나가 사용된다. When the dielectric
상기 구성 중 다수개의 유전체 세라믹층(11)은 각각 내환원성 LTCC용 고주파 유전체 세라믹 조성물로 이루어진다. 내환원성 LTCC용 고주파 유전체 세라믹 조성물은 (CaxSr1-x)(ZryTi1-y)O3계로 이루어지는 주성분 87~97 wt%와, 망목 구조를 갖는 글라스 프릿으로 이루어지는 제1부성분 1~10 wt%와, Ni2Ta2O7로 이루어지는 제2부성분 1~5 wt%와, MoO3, V2O5 및 MnO3 중 하나 이상으로 이루어지는 제3부성분 1~3 wt%로 이루어지고, 상기 주성분은 0.6 ≤ x ≤0.8, 0.95 ≤ y ≤0.97을 만족한다. The plurality of dielectric
제1부성분인 망목 구조를 갖는 글라스 프릿은 aBa계 조성물-bSi계 조성물-cLi계 조성물-dB계 조성물-fRF계 조성물로 이루어지고, a+b+c+d+f=100 mol%로 상기 3≤ a ≤25 mol%, 20≤ b ≤30 mol%, 5≤ c ≤20 mol%, 30≤ d ≤50 mol%, 1≤ f ≤10 mol%를 만족한다. The glass frit having the mesh structure as the first subcomponent is composed of aBa composition-bSi composition-cLi composition-dB composition-fRF composition, and a + b + c + d + f = 100 mol%. Satisfies? A? 25 mol%, 20? B? 30 mol%, 5? C? 20 mol%, 30? D? 50 mol%, and 1? F? 10 mol%.
이와 같이 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물을 이용하여 제조되는 적층 세라믹 커패시터(10)의 제조 시 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물의 주성분인 (CaxSr1-x)(ZryTi1-y)O3계는 소성 시 Ca(칼슘)의 일부가 Ti(티타늄)의 위치에 고용되어 억셉터(acceptor)로 작용하고, 같은 수의 산소 공공이 발생하기 때문에 환원작용이 어려워져 내환원성을 갖게 된다.As described above, when the multilayer
이와 같이 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물을 이용하여 제조된 유전체 세라믹층(11)과 유전체 세라믹층(11)을 이용하여 제조된 적층 세라믹 커패시터(11)의 특성을 첨부된 도면을 참조하여 설명하면 다음과 같다. As described above, referring to the accompanying drawings, the characteristics of the dielectric
도 1은 유전체 세라믹층(11)을 형성하기 위한 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물 중 제1부성분인 글라스 프릿 조성비의 실시예를 나타 낸다. 도 1에서와 같이 Ba계 조성물, Si계 조성물, Li계 조성물, B계 조성물 및 F계 조성물의 조성비를 다르게 설정한 제1부성분을 A 내지 F로 명칭하여 분류하였다.FIG. 1 shows an embodiment of the glass frit composition ratio as the first subcomponent of the high frequency dielectric ceramic composition for reducing resistance LTCC of the present invention for forming the dielectric
도 2는 주성분인 (CaxSr1-x)(ZryTi1-y)O3계에서 x, 1-x, y 및 1-y를 각각 0.6 ≤ x ≤0.8, 0.2 ≤ 1-x ≤0.4, 0.95 ≤ y ≤0.97, 0.03 ≤ 1-y ≤0.05 범위를 만족하도록 변화시키면서 A 내지 F로 명칭하여 분류된 제1부성분인 글라스 프릿을 첨가하였으며 Ni2Ta2O7로 이루어지는 제2부성분 1~5 wt% 과 제3부성분인 MoO3, V2O5 및 MnO3을 하나 이상 첨가하여 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물을 제조하여 슬러리 특성을 테스트하였다. FIG. 2 shows x, 1-x, y, and 1-y of 0.6 ≤ x ≤ 0.8, 0.2 ≤ 1-x ≤ 0.4, 0.95 ≤ y ≤ in the main component (CaxSr1-x) (ZryTi1-y) O 3 system, respectively. 1 to 5 wt% of the second subcomponent consisting of Ni 2 Ta 2 O 7 was added, adding glass frit, the first subcomponent classified as A to F, changing to satisfy the range of 0.97, 0.03 ≤ 1-y ≤ 0.05. At least one triparticulate of MoO 3 , V 2 O 5, and MnO 3 was added to prepare a high frequency dielectric ceramic composition for reduction-resistant LTCC of the present invention, and the slurry characteristics were tested.
슬러리 특성 이외에 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물을 이용하여 제조된 본 발명의 적층 세라믹 커패시터(10: 도 3에 도시됨)를 이용하여 전기적인 특성 및 소성 온도 특성을 테스트하였다. In addition to the slurry properties, the electrical properties and the firing temperature characteristics were tested using the multilayer ceramic capacitor of the present invention (10: shown in FIG. 3) prepared using the high frequency dielectric ceramic composition for the reduction resistant LTCC of the present invention.
본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물의 슬러리 특성은 슬러리 안정화 시간으로 나타냈다. 슬러리 안정화 시간은 슬러리의 응집에 따른 슬러리 안정도를 시간으로 나타냈으며, 최소한 48시간 이상 안정화되어야 하며, 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물의 슬러리 안정화 시간은 도 2에서와 같이 75 내지 300 시간(hr) 동안 안정화되는 것으로 나타났다.The slurry properties of the high frequency dielectric ceramic composition for reduction resistant LTCC of the present invention are represented by slurry stabilization time. Slurry stabilization time represents the stability of the slurry according to the agglomeration of the slurry, and should be stabilized for at least 48 hours or more, the slurry stabilization time of the high frequency dielectric ceramic composition for reducing resistance LTCC of the present invention is 75 to 300 hours as shown in FIG. It appeared to stabilize during (hr).
전기적인 특성과 소성 온도 특성은 본 발명의 적층 세라믹 커패시터(10)를 이용하여 테스트하였으며, 전기적인 특성은 유전율, 절연저항(IR: Insulation Resistance) 및 품질계수(Q)를 이용하여 테스트하였다. 도 2에서와 같이 본 발명의 적층 세라믹 커패시터(10)의 전기적인 특성은 유전율 18 내지 28, 절연저항 1.9 × 1011 내지 7.2 × 1012Ω 및 품질계수(Q) 105 내지 1758로 나타나고 있으며, 소성 온도는 890 내지 1080℃로 나타나고 있다.Electrical and firing temperature characteristics were tested using the multilayer
상기와 같은 전기적인 특성을 갖는 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물을 이용한 적층 세라믹 커패시터(10)의 임피던스 특성(Cu-COG Z) 및 ESR(Cu-COG ESR)은 도 4에 도시되고 있다. 도 4에서와 같이 본 발명의 적층 세라믹 커패시터(10)의 임피던스 특성(Cu-COG Z) 및 ESR 특성(Cu-COG ESR)은 각각 고주파 대역에서 종래의 적층 세라믹 커패시터(도시 안음)의 임피던스 특성(Ni-COG Z) 및 ESR(Ni-COG ESR) 보다 개선되는 것으로 나타나고 있다. Impedance characteristics (Cu-COG Z) and ESR (Cu-COG ESR) of the multilayer
본 발명의 내환원성 LTCC용 고주파 유전체 및 이를 이용한 적층 세라믹 커패시터는 이동통신 관련 고주파 모듈이나 안테나 또는 초고주파 대용량의 고압 적층 커패시터 분야에 적용할 수 있다. The high-frequency dielectric material for the reduction-resistant LTCC and the multilayer ceramic capacitor using the same of the present invention can be applied to the field of mobile communication-related high-frequency modules or antennas or high-frequency high-capacity multilayer capacitors.
도 1은 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물 중 제1부성분인 글라스 프릿 조성비를 나타낸 표,1 is a table showing the composition ratio of the glass frit as the first minor component of the high frequency dielectric ceramic composition for reducing resistance LTCC of the present invention,
도 2는 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물의 조성비에 따른 전기적 특성을 나타낸 표,Figure 2 is a table showing the electrical properties according to the composition ratio of the high frequency dielectric ceramic composition for reduction resistant LTCC of the present invention,
도 3은 본 발명의 내환원성 LTCC용 고주파 유전체 세라믹 조성물을 이용한 적층 세라믹 커패시터의 단면도. 3 is a cross-sectional view of a multilayer ceramic capacitor using the high frequency dielectric ceramic composition for reduction-resistant LTCC of the present invention.
도 4는 도 3에 도시된 적층 세라믹 커패시터의 임피던스 및 ESR 특성을 나타낸 그래프.4 is a graph illustrating impedance and ESR characteristics of the multilayer ceramic capacitor illustrated in FIG. 3.
* 도면의 주요 부분에 대한 부호 설명 *Description of the Related Art [0002]
10: 적층 세라믹 커패시터 11: 유전체 10: multilayer ceramic capacitor 11: dielectric
12: 내부전극 13: 외부전극12: internal electrode 13: external electrode
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