JP2005116484A - Conductive paste - Google Patents
Conductive paste Download PDFInfo
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- JP2005116484A JP2005116484A JP2003352823A JP2003352823A JP2005116484A JP 2005116484 A JP2005116484 A JP 2005116484A JP 2003352823 A JP2003352823 A JP 2003352823A JP 2003352823 A JP2003352823 A JP 2003352823A JP 2005116484 A JP2005116484 A JP 2005116484A
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- conductive paste
- barium
- calcium
- green sheet
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- 239000002241 glass-ceramic Substances 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 29
- 150000001553 barium compounds Chemical class 0.000 claims abstract description 23
- 229940043430 calcium compound Drugs 0.000 claims abstract description 22
- 150000001674 calcium compounds Chemical class 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 239000004332 silver Substances 0.000 claims abstract description 11
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 239000011575 calcium Substances 0.000 claims abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011224 oxide ceramic Substances 0.000 claims abstract description 3
- 229910052574 oxide ceramic Inorganic materials 0.000 claims abstract description 3
- -1 barium fatty acid salts Chemical class 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 abstract description 23
- 239000000758 substrate Substances 0.000 description 27
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 21
- 238000010304 firing Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000004020 conductor Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- NKFIBMOQAPEKNZ-UHFFFAOYSA-N 5-amino-1h-indole-2-carboxylic acid Chemical compound NC1=CC=C2NC(C(O)=O)=CC2=C1 NKFIBMOQAPEKNZ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- PJUKKJYOSBWEQO-UHFFFAOYSA-L barium(2+);octanoate Chemical compound [Ba+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O PJUKKJYOSBWEQO-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- NDWWLJQHOLSEHX-UHFFFAOYSA-L calcium;octanoate Chemical compound [Ca+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O NDWWLJQHOLSEHX-UHFFFAOYSA-L 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- Conductive Materials (AREA)
Abstract
Description
本発明は、導電性ペースト、特に高周波共振器、集積回路、ハイブリッド回路などを構成する回路基板に採用されるセラミック多層基板に用いられる導電性ペーストに関する。 The present invention relates to a conductive paste, and more particularly to a conductive paste used for a ceramic multilayer substrate employed in a circuit substrate constituting a high frequency resonator, an integrated circuit, a hybrid circuit, or the like.
電子部品の小型化、高性能化が進むに伴って、回路基板には高密度化、低誘電率化、低熱膨張率化等が要求され、ガラスセラミックスグリーンシート上に導電性ペーストを印刷し、これを積み重ねて焼成されるセラミック多層基板が回路基板として使用されるようになってきた。 As electronic components become smaller and higher in performance, circuit boards are required to have higher density, lower dielectric constant, lower thermal expansion coefficient, etc., and conductive paste is printed on glass ceramic green sheets. Ceramic multilayer substrates that are stacked and fired have been used as circuit boards.
ガラスセラミックスグリーンシートは、アルミナ、ムライト、コーディライト、ジルコン、フォルステライト、ジルコニア、石英などのセラミックフィラーと、軟化点が５００〜８００℃程度の、アルミノ硼珪酸をベースに酸化鉛、アルカリ土類金属酸化物、アルカリ金属酸化物、酸化亜鉛等を含有したガラス粉とからなる組成物であり、ガラス粉末とセラミックス粉体を有機バインダと共に混練してスラリーを作り、これをドクターブレード法等によってシート状にされている。 Glass ceramics green sheets are lead oxides and alkaline earth metals based on ceramic fillers such as alumina, mullite, cordierite, zircon, forsterite, zirconia, quartz, and aluminoborosilicate with a softening point of about 500-800 ° C. It is a composition consisting of glass powder containing oxide, alkali metal oxide, zinc oxide, etc., and glass powder and ceramic powder are kneaded with an organic binder to make a slurry, which is formed into a sheet by doctor blade method etc. Has been.
ガラスセラミックスグリーンシートは、これを焼成すると、１０〜２０％収縮し、一方ガラスセラミックスグリーンシート上に塗布された導電性ペーストも収縮するので、ガラスセラミックスグリーンシートと導電性ペーストの両者の熱収縮率に差があると、互いに収縮を拘束することになり収縮応力による歪みが生じ、焼成して得られたセラミック多層基板に反りや変形を与えることになる。 When the glass ceramic green sheet is fired, it shrinks by 10 to 20%, while the conductive paste applied on the glass ceramic green sheet also shrinks, so the thermal shrinkage rate of both the glass ceramic green sheet and the conductive paste. If there is a difference, the shrinkage is restrained and distortion due to the shrinkage stress is generated, which warps or deforms the ceramic multilayer substrate obtained by firing.
このセラミック多層基板の反りや変形をなくすために、例えば、銀粉体のペーストにガラスセラミック材料を加えたり、粒子径の異なる２種以上の銀粉体を混合して用いる方法〔特許文献１参照〕、導電性ペースト中の銀系粉末の比表面積を特定範囲にして、かつ特定の有機樹脂及び有機溶剤を加えて導電性ペーストの熱収縮をグリーンシートの収縮に合わせる方法〔特許文献２参照〕など焼結に伴うガラスセラミックス基板材料と金属導体の収縮率の差を小さくする方法が提案された。 In order to eliminate warpage and deformation of the ceramic multilayer substrate, for example, a method of adding a glass ceramic material to a paste of silver powder or using a mixture of two or more kinds of silver powders having different particle diameters [see Patent Document 1 ], A method in which the specific surface area of the silver-based powder in the conductive paste is within a specific range, and a specific organic resin and an organic solvent are added to adjust the thermal shrinkage of the conductive paste to the shrinkage of the green sheet [see Patent Document 2] A method has been proposed for reducing the difference in shrinkage between the glass ceramic substrate material and the metal conductor during sintering.
また、導電性ペーストとグリーンシートの粒径を変化させて導電性ペーストの収縮終了温度をグリーンシートの収縮終了温度より高くする方法〔特許文献３参照〕、導電性ペーストに用いる銀などの導電性粉末の表面に、予めＡｌ２Ｏ３、ＺｒＯ２、ＴｉＯ２、ＢａＯ、ＣａＯなどの高融点金属酸化物皮膜を形成させておいて、焼成時における導電性ペースト収縮開始温度をセラミック成形体の収縮終了温度より高くする方法〔特許文献４参照〕、高い結晶性の銀を導電性材料に用いて焼成時に起きる銀の収縮開始を遅らせて基板材料との燒結挙動を一致させる方法〔特許文献５参照〕など導電性ペーストとグリーンシートの収縮タイミングをずらして反りや変形を少なくする提案がある。 In addition, a method of changing the particle size of the conductive paste and the green sheet to make the shrinkage end temperature of the conductive paste higher than the shrinkage end temperature of the green sheet (see Patent Document 3), conductivity such as silver used for the conductive paste A refractory metal oxide film such as Al 2 O 3 , ZrO 2 , TiO 2 , BaO, and CaO is formed on the surface of the powder in advance, and the conductive paste shrinkage start temperature during firing is reduced by the shrinkage of the ceramic compact. A method of making the temperature higher than the end temperature (see Patent Document 4), a method of using highly crystalline silver as a conductive material, delaying the onset of shrinkage of silver that occurs during firing, and matching the sintering behavior with the substrate material (see Patent Document 5) There is a proposal to reduce warpage and deformation by shifting the contraction timing of the conductive paste and the green sheet.
その他、パラジウム含有率により導体膜のガラスセラミックス基板に対する密着強度が変ることに着目して導電性金属粉体にパラジウム、さらに酸化ビスマスと酸化銅を少量添加する方法〔特許文献６参照〕によりガラスセラミックスグリーンシートと導電性ペーストとの間の密着強度を弱めて熱収縮率の差を緩和する提案、さらに、焼成工程においてシートの収縮を実質的に生じさせないようにする、いわゆる無収縮プロセス〔特許文献７参照〕の提案もある。 In addition, focusing on the fact that the adhesion strength of the conductor film to the glass-ceramic substrate changes depending on the palladium content, glass ceramics is obtained by adding a small amount of palladium, bismuth oxide and copper oxide to the conductive metal powder [see Patent Document 6]. Proposal to reduce the difference in thermal shrinkage by weakening the adhesion strength between the green sheet and the conductive paste, and the so-called non-shrink process that prevents the sheet from shrinking substantially in the firing step [Patent Document 7)] is also proposed.
上記のようにセラミック多層基板の反りや変形をなくすための導電性ペーストの改質は、導電性粉末そのものを変える方法と、添加剤を加える方法に大別されるが、導電性粉末そのものを変える方法は実施に多くのコストが必要であり、添加剤を加える方法は簡単に実施できるが導電性が損なわれることがある。 As described above, the modification of the conductive paste to eliminate warping and deformation of the ceramic multilayer substrate is roughly divided into a method of changing the conductive powder itself and a method of adding an additive, but the conductive powder itself is changed. The method is costly to implement and the method of adding additives is simple to implement, but conductivity may be compromised.
上記問題点を改善すべく本発明の目的は、導電性を損うことなく、ガラスセラミックスグリーンシートに印刷して焼成したときセラミック多層基板に生じる反りや変形が少ない導電性ペーストを提供することにある。 An object of the present invention to improve the above problems is to provide a conductive paste that is less warped and deformed in a ceramic multilayer substrate when printed on a glass ceramic green sheet and fired without impairing conductivity. is there.
かかる課題を解決すべく、請求項１の発明は導電性ペーストであり、ガラスと酸化物系セラミックスを主体としたグリーンシート上にパターンを形成するように塗布される銀を主成分とする導電性金属粉体を含む導電性ペーストであり、バリウム化合物とカルシウム化合物を組み合わせて添加されている。 In order to solve this problem, the invention of claim 1 is a conductive paste, which is a conductive material mainly composed of silver applied so as to form a pattern on a green sheet mainly composed of glass and oxide ceramics. A conductive paste containing metal powder, which is added in combination of a barium compound and a calcium compound.
請求項２の発明は請求項１記載の導電性ペーストであり、前記バリウム化合物は、バリウムの脂肪酸塩、酸化物、炭酸塩、水酸化物から選ばれる一種以上であり、前記カルシウム化合物は、カルシウムの脂肪酸塩、酸化物、炭酸塩、水酸化物から選ばれる一種以上である。 Invention of Claim 2 is the electrically conductive paste of Claim 1, and the said barium compound is 1 or more types chosen from the fatty-acid salt, oxide, carbonate, and hydroxide of barium, The said calcium compound is calcium. It is at least one selected from fatty acid salts, oxides, carbonates and hydroxides.
請求項３の発明は請求項１または２記載の導電性ペーストであり、前記バリウム化合物は、導電性金属粉体に対しバリウム金属を基準にして０．０３〜２重量％、前記カルシウム化合物は、導電性金属粉体に対しカルシウム金属を基準にして０．０３〜０．５重量％である。 Invention of Claim 3 is the electroconductive paste of Claim 1 or 2, The said barium compound is 0.03 to 2 weight% on the basis of barium metal with respect to electroconductive metal powder, The said calcium compound is It is 0.03-0.5 weight% on the basis of calcium metal with respect to electroconductive metal powder.
本発明の導電性ペーストは、導電性は良好であり、これをガラスセラミックスグリーンシートに印刷して焼成したときセラミック多層基板に反りや変形を少なくすることができ、製品歩留まり率を高くし、低下配線の不良、断線などをなくすことができ、信頼性を高めることができる。 The conductive paste of the present invention has good conductivity, and when this is printed on a glass ceramic green sheet and fired, the ceramic multilayer substrate can be less warped and deformed, and the product yield rate is increased and lowered. Wiring defects and disconnections can be eliminated, and reliability can be improved.
導電性ペーストは、グリーンシートと呼ばれる焼成前のガラスセラミックスシートに所定のパターンで印刷し、これを積層し、焼成してセラミック多層基板とする。 The conductive paste is printed in a predetermined pattern on a glass ceramic sheet before firing called a green sheet, laminated and fired to obtain a ceramic multilayer substrate.
ガラスセラミックスグリーンシートは、８００〜１０００℃程度の低温で焼成できるので、導電性ペーストに銀を用いることができる利点がある。最近では、ガラスセラミックスグリーンシートの改良が多く提案されているが、本発明導電性ペーストは、ガラスとセラミックスとからなり、８００〜１０００℃程度の低温で焼成できるガラスセラミックスグリーンシートで、その表面に導電性ペーストによるパターンを形成させて焼成してセラミック多層基板とすることができるものであればよい。 Since the glass ceramic green sheet can be fired at a low temperature of about 800 to 1000 ° C., there is an advantage that silver can be used for the conductive paste. Recently, many improvements of glass ceramic green sheets have been proposed, but the conductive paste of the present invention is made of glass and ceramics, and is a glass ceramic green sheet that can be fired at a low temperature of about 800 to 1000 ° C. Any material can be used as long as it can be formed into a pattern with a conductive paste and fired to form a ceramic multilayer substrate.
本発明の導電性ペーストは、導電性金属粉体、添加剤、有機ビヒクル、溶剤、必要により界面活性剤、分散剤を加えて混練して製造され、さらにガラス粉体を混合することがあり、本発明は広くガラス粉体を混合した導電性ペーストも包含している。 The conductive paste of the present invention is produced by kneading a conductive metal powder, an additive, an organic vehicle, a solvent, and optionally adding a surfactant and a dispersant, and further mixing glass powder. The present invention broadly includes a conductive paste mixed with glass powder.
導電性金属粉体は、粒径５μｍ以下、代表的には１〜４μｍの銀粉体を主成分としており、セラミック多層基板の使用目的により一部白金、金などを混合することもある。 The conductive metal powder is mainly composed of silver powder having a particle size of 5 μm or less, typically 1 to 4 μm, and may be partially mixed with platinum, gold, etc. depending on the intended use of the ceramic multilayer substrate.
添加剤は、本発明が目的とする焼成後のセラミック多層基板に反りや変形を少なくする機能を有し、バリウム化合物とカルシウム化合物を組合せて用いる。ここで、バリウム化合物とカルシウム化合物は、導電性ペーストとしてガラスセラミックスグリーンシートに印刷した後で焼成する温度、すなわち空気中８００〜１０００℃で酸化物となっているものであればよく、酸化物、あるいはこれより低い温度で酸化物になる化合物、例えば、ナフテン酸塩、オクタン酸塩、ステアリン酸塩などの脂肪酸塩、水酸化物、炭酸塩、硫酸塩などである。具体的には、バリウム化合物として、酸化バリウムの他、ナフテン酸バリウム、オクタン酸バリウム、ステアリン酸バリウム、炭酸バリウム、水酸化バリウムであり、カルシウム化合物として酸化カルシウムの他、ナフテン酸カルシウム、オクタン酸カルシウム、ステアリン酸カルシウム、炭酸カルシウム、水酸化カルシウムである。本発明では、バリウム化合物とカルシウム化合物について、それぞれ任意に一種以上が選ばれる。 The additive has a function of reducing warpage and deformation in the fired ceramic multilayer substrate targeted by the present invention, and is used in combination of a barium compound and a calcium compound. Here, the barium compound and the calcium compound may be any oxide as long as it is an oxide at a temperature of 800 to 1000 ° C. in air, after being printed on a glass ceramic green sheet as a conductive paste. Alternatively, a compound that becomes an oxide at a lower temperature, for example, a fatty acid salt such as naphthenate, octanoate, stearate, hydroxide, carbonate, sulfate or the like. Specifically, barium compounds include barium oxide, barium naphthenate, barium octoate, barium stearate, barium carbonate, and barium hydroxide, and calcium compounds as well as calcium oxide, calcium naphthenate, and calcium octoate. , Calcium stearate, calcium carbonate, calcium hydroxide. In this invention, 1 or more types are each arbitrarily selected about a barium compound and a calcium compound.
本発明のバリウム化合物とカルシウム化合物は、導電性ペーストの収縮開始温度を高くしてグリーンシートの収縮に近付け、かつ導電性ペーストとグリーンシートとの密着強度を適度に保つ作用がある。バリウム化合物は収縮開始温度を高くする効果が大きいが、密着強度を弱くすることがあり、従ってバリウム化合物を多くすると、反りを少なくする上では有利であるが密着強度の上では満足できなくなる。一方、カルシウム化合物は、バリウム化合物に比較して導電性ペーストの収縮開始温度を高くする効果は少ないが、導電性ペーストのグリーンシートとの密着強度を高める効果がある。本発明は、バリウム化合物とカルシウム化合物を組合せることで、密着強度をある程度維持しつつ、焼成後のセラミック多層基板に与える反りや変形を少なくすることにその特徴がある。 The barium compound and calcium compound of the present invention have an effect of increasing the shrinkage start temperature of the conductive paste to approach the shrinkage of the green sheet, and appropriately maintaining the adhesion strength between the conductive paste and the green sheet. Although the barium compound has a large effect of increasing the shrinkage start temperature, it may weaken the adhesion strength. Therefore, increasing the barium compound is advantageous in reducing warpage, but is not satisfactory in terms of adhesion strength. On the other hand, the calcium compound is less effective in increasing the shrinkage start temperature of the conductive paste than the barium compound, but has the effect of increasing the adhesion strength of the conductive paste with the green sheet. The present invention is characterized in that by combining a barium compound and a calcium compound, warping and deformation applied to the fired ceramic multilayer substrate are reduced while maintaining the adhesion strength to some extent.
バリウム化合物とカルシウム化合物は、金属粉体の量に合わせて加えられ、バリウム化合物は、金属粉体に対しバリウム金属を基準にして０．０３〜２重量％、好ましくは０．０５〜１重量％、カルシウム化合物は、金属粉体に対しカルシウム金属を基準にして０．０３〜０．５重量％、好ましくは０．０５〜０．２重量％である。バリウム化合物とカルシウム化合物におけるこの適正範囲は、焼成後のセラミック多層基板における反りや変形の面から選ばれたものであり、この範囲より少ないと添加剤としての効果が小さく反りや変形が大きくなり、またこの範囲を超えると極端に悪くなることがないが、反りや変形にそれ以上の効果がみられないことが多い。 The barium compound and the calcium compound are added according to the amount of the metal powder, and the barium compound is 0.03 to 2% by weight, preferably 0.05 to 1% by weight, based on the barium metal with respect to the metal powder. The calcium compound is 0.03 to 0.5% by weight, preferably 0.05 to 0.2% by weight, based on calcium metal with respect to the metal powder. This appropriate range in the barium compound and calcium compound is selected from the aspect of warping and deformation in the fired ceramic multilayer substrate, and if it is less than this range, the effect as an additive is small and warping and deformation are large, Moreover, although it does not become extremely worse if it exceeds this range, there is often no further effect on warpage or deformation.
上述したように、本発明のバリウム化合物、カルシウム化合物は、酸化物以外のものを用いたときには、グリーンシートの焼結が始まる温度より低い温度で分解が始まり、焼結が始まる温度では、実質的にそれぞれの酸化物となっている。従って、焼結温度では、ガラスセラミックスグリーンシート中のガラス成分は溶融し、その中に導電性ペースト中の酸化バリウム、酸化カルシウムが一部溶解していくことで界面で一部両者が一体化される。 As described above, when a barium compound or calcium compound of the present invention is used other than an oxide, decomposition begins at a temperature lower than the temperature at which the green sheet starts to be sintered, Each of these is an oxide. Therefore, at the sintering temperature, the glass component in the glass ceramic green sheet is melted, and barium oxide and calcium oxide in the conductive paste are partially dissolved therein, so that both are partially integrated at the interface. The
ガラスセラミックスグリーンシート上に印刷された導電性ペーストは、ガラスセラミックスグリーンシートに対して密着強度が強過ぎると、高温になったとき反りや変形となり易く、密着強度が弱過ぎると、反りや変形にはなり難いが多層基板上の導電性パターンとして不満足である。従って、ガラスセラミックスグリーンシートと導電性ペーストとの界面の密着強度を、ある程度緩和することが必要である。 The conductive paste printed on the glass ceramic green sheet is likely to warp or deform when the adhesive strength is too high for the glass ceramic green sheet, and warp or deform when the adhesive strength is too weak. Although it is difficult to peel, it is unsatisfactory as a conductive pattern on a multilayer substrate. Therefore, it is necessary to moderate the adhesion strength at the interface between the glass ceramic green sheet and the conductive paste to some extent.
本発明のガラスセラミックスグリーンシートと導電性ペーストの界面は、一部一体化されることで互いの熱収縮が近づくとともに、界面に作用する密着強度が緩和されるように機能し、反りや変形が少ないセラミック多層基板となる。 The interface between the glass ceramic green sheet of the present invention and the conductive paste is partly integrated so that the thermal contraction of each other approaches and the adhesion strength acting on the interface is relaxed, and warping and deformation are prevented. Fewer ceramic multilayer substrates.
有機ビヒクルは、導電性ペーストに適度の粘性を与えて印刷パターンを安定化させる働きがあり、本発明でその種類を限定するものではないが、例えばセルロース類、アクリル類、ポリビニルアルコール類などが使用される。 The organic vehicle has the function of stabilizing the printing pattern by imparting an appropriate viscosity to the conductive paste, and the type is not limited in the present invention. For example, celluloses, acrylics, polyvinyl alcohols, etc. are used. Is done.
溶剤は、導電性ペーストを用いる有機ビヒクルとの関連で決められるもので、本発明でその種類を限定するものではないが、アルコール系溶剤、エステル系溶剤、ケトン系溶剤、エーテル系溶剤、炭化水素系溶剤などが任意に選ばれる。 The solvent is determined in relation to the organic vehicle using the conductive paste, and the type of the solvent is not limited in the present invention, but the alcohol solvent, ester solvent, ketone solvent, ether solvent, hydrocarbon A system solvent or the like is arbitrarily selected.
導電性ペーストにおける各成分の構成比は、代表的には導電性金属粉体は７０〜９０重量％、好ましくは８０〜８５重量％であり、有機ビヒクルは１〜５重量％、好ましくは３〜５重量％であり、溶剤は５〜３０重量％、好ましくは１０〜１５重量％であり、その他界面活性剤、分散剤が１重量％以下である。添加剤であるバリウム化合物とカルシウム化合物は、上述したように金属粉体の量に合わせて加えられる。これらの成分は、ロールミルなど公知の方法によりよく混練されて、導電性ペーストとなる。 The constituent ratio of each component in the conductive paste is typically 70 to 90% by weight, preferably 80 to 85% by weight for the conductive metal powder, and 1 to 5% by weight, preferably 3 to 3% for the organic vehicle. 5 wt%, the solvent is 5 to 30 wt%, preferably 10 to 15 wt%, and other surfactants and dispersants are 1 wt% or less. As described above, the barium compound and calcium compound, which are additives, are added according to the amount of the metal powder. These components are well kneaded by a known method such as a roll mill to form a conductive paste.
セラミック多層基板は、厚さ１００〜２００μｍのガラスセラミックスグリーンシート上に、導電性ペーストを厚さ２０〜４０μｍで所定のパターンに印刷し、さらにパターン印刷したグリーンシートを所定の手続により積重ねて、これを焼成して製造される。 The ceramic multilayer substrate is formed by printing a conductive paste in a predetermined pattern with a thickness of 20 to 40 μm on a glass ceramic green sheet with a thickness of 100 to 200 μm, and further stacking the green sheets with pattern printing by a predetermined procedure. Is manufactured by firing.
焼成温度は、ガラスセラミックスグリーンシートの組成により異なるが、銀の融点が９６１℃であるので、銀が溶融しない温度にて行う必要があり、通常８５０〜９５０℃、好ましくは８８０〜９２０℃である。焼成時間は、４〜２４時間で任意に選ばれる。このように低温焼成基板では、銀粉体で構成されるペーストを使い、焼成が空気中でも行うことができるため、アルミナ基板と比較して低コストで製造することができる。さらに、ガラスとセラミックスの混合材料は、アルミナ基板よりも誘電率が低く、回路における信号遅延時間を低減できる特性があるため、電気的特性の向上も図れる特徴がある。 Although the firing temperature varies depending on the composition of the glass ceramic green sheet, since the melting point of silver is 961 ° C., it is necessary to carry out at a temperature at which silver does not melt, and is usually 850 to 950 ° C., preferably 880 to 920 ° C. . The firing time is arbitrarily selected from 4 to 24 hours. Thus, the low-temperature fired substrate can be manufactured at a lower cost than the alumina substrate because the paste composed of silver powder can be used and firing can be performed in the air. Furthermore, the mixed material of glass and ceramic has a characteristic that the dielectric constant is lower than that of an alumina substrate and the signal delay time in the circuit can be reduced, so that the electrical characteristics can be improved.
実施例に示した焼成温度に対する収縮率を示す図１で分るように、銀粉体を含む導電性ペーストにバリウム化合物、カルシウム化合物を含む添加剤を加えることにより、収縮率をガラスセラミックスグリーンシートの収縮率に近付けることができる。しかしそれでも尚ガラスセラミックスグリーンシートとは差があり、この差があるに拘らず焼成後に反りが少ないのは導電性ペーストとグリーンシートとの界面の相互作用により密着強度が緩和された為と推定される。 As shown in FIG. 1 showing the shrinkage ratio with respect to the firing temperature shown in the examples, the shrinkage ratio can be reduced by adding an additive containing a barium compound and a calcium compound to a conductive paste containing silver powder. The shrinkage rate can be approached. However, there is still a difference from the glass ceramic green sheet. Despite this difference, the reason why there is little warpage after firing is presumed that the adhesion strength has been relaxed due to the interaction between the conductive paste and the green sheet. The
１．ガラスセラミックスグリーンシート
ホウケイ酸ガラス粉末とアルミナ粉からなる低温焼成ガラスセラミックを有機バインダと共に混練してスラリーを作り、ドクターブレード法等によって延伸し、厚さ１５０μｍとした。
1. Glass ceramic green sheet Low-temperature fired glass ceramic made of borosilicate glass powder and alumina powder was kneaded with an organic binder to form a slurry, and stretched by a doctor blade method or the like to a thickness of 150 μm.
２．導電性ペースト
導電性金属粉体として銀粉体（平均粒径：２〜４μｍ）を８４重量部、有機ビヒクルとしてエチルセルロースとポリメチルアクリレートを３．４重量部、分散剤０．４重量部、添加剤として表１記載の成分を所定量、そして溶剤としてブチルカルビトールアセテートを加えて全体を１００重量部とした。この混合物を、ロールミルにてよく混練して導電性ペーストとした。
2. Conductive paste 84 parts by weight of silver powder (average particle size: 2 to 4 μm) as conductive metal powder, 3.4 parts by weight of ethyl cellulose and polymethyl acrylate as organic vehicles, 0.4 part by weight of dispersant added A predetermined amount of the components shown in Table 1 were added as an agent, and butyl carbitol acetate was added as a solvent to make 100 parts by weight as a whole. This mixture was well kneaded with a roll mill to obtain a conductive paste.
３．焼成
３×３ｃｍの大きさのガラスセラミックスグリーンシート上に導電性ペーストを塗布し、乾燥後コンベア炉にて９００℃で４時間焼成〔焼成炉；光洋サーモシステム株式会社製、モデル「４７−ＭＹ−９１２０１−２０ＭＣ−３６」を使用した〕し、最終的に厚さ約２０μｍの導体膜を形成させた。
3. Firing A conductive paste was applied onto a 3 × 3 cm glass ceramic green sheet, dried and then fired at 900 ° C. for 4 hours in a conveyor furnace [firing furnace; Koyo Thermo System Co., Ltd., model “47-MY-” 9201-20MC-36 "was used], and finally a conductor film having a thickness of about 20 μm was formed.
４．評価
１）熱収縮測定：導電性ペーストを１２０℃で乾燥しペレット状にし、熱収縮挙動〔島津製作所製、モデル「ＴＭＡ−５０」を使用〕を測定した。
２）膜厚換算抵抗値：ガラスセラミックスグリーンシート上に０．５ｍｍ幅の導体膜を作成し、長さ２０ｍｍ部分の抵抗値〔横河電機（株）製、「モデル２５０１」を使用〕を（Ｒ１）とし、下記の式より１０μ換算シート抵抗値（Ｒ／□）を求めた。
４）密着強度：ガラスセラミックスグリーンシート上に四角形〔２（ｍｍ）×２（ｍｍ）〕に焼成膜を形成させ、その上に基板と水平に０．６ｍｍφのメッキ軟鋼線をはんだ付けし、該メッキ軟鋼線を垂直方向約９０°に折り曲げた後、基板と垂直な方向に引張り、密着強度〔アイコーエンジニアリング（株）製、「モデル２１５２」を使用〕を測定した。
4). Evaluation 1) Measurement of heat shrinkage: The conductive paste was dried at 120 ° C. into pellets, and the heat shrinkage behavior (manufactured by Shimadzu Corporation, using model “TMA-50”) was measured.
2) Resistance value in terms of film thickness: A conductor film having a width of 0.5 mm was prepared on a glass ceramic green sheet, and a resistance value of 20 mm in length [using “Model 2501” manufactured by Yokogawa Electric Corporation] ( R 1 ), and a 10 μ-converted sheet resistance value (R / □) was determined from the following formula.
4) Adhesive strength: a fired film is formed in a square [2 (mm) × 2 (mm)] on a glass ceramic green sheet, and a 0.6 mmφ plated mild steel wire is soldered horizontally on the substrate; The plated mild steel wire was bent in a vertical direction of about 90 °, and then pulled in a direction perpendicular to the substrate, and the adhesion strength (“Model 2152” manufactured by Aiko Engineering Co., Ltd.) was measured.
５．結果
１）膜厚換算抵抗値（ｍΩ／□／１０μｍ）、反り量（ｍｍ）、密着強度（Ｎ）の結果を表１〜２に示した。
5). Results 1) The results of the film thickness converted resistance value (mΩ / □ / 10 μm), the warpage amount (mm), and the adhesion strength (N) are shown in Tables 1-2.
２）ガラスセラミックスグリーンシート、銀粉体を含む導電性ペースト、および銀粉体に本発明の添加剤を含む導電性ペーストそれぞれについて焼成温度に対する収縮率を図１に示した。 2) The shrinkage ratio with respect to the firing temperature for each of the glass ceramic green sheet, the conductive paste containing silver powder, and the conductive paste containing the additive of the present invention in silver powder is shown in FIG.
この結果から、ガラスセラミックスグリーンシートは８００℃から急速に収縮を始め、焼成終了時には最大２０％の収縮カーブを描く。一方、銀粉体の導電性ペーストは、４００℃から徐々に収縮が進行している。銀粉体を含む導電性ペーストに添加剤を加えると、熱収縮の始まりが６２０℃と上り、そこから収縮が進行していく。このように、銀粉体の導電性ペーストにバリウム化合物とカルシウム化合物を組合せた添加剤を加えることによりガラスセラミックスグリーンシートの収縮曲線に近付けることができることがわかる。 From this result, the glass ceramic green sheet starts to shrink rapidly from 800 ° C., and draws a shrinkage curve of a maximum of 20% at the end of firing. On the other hand, the silver powder conductive paste gradually contracts from 400 ° C. When an additive is added to the conductive paste containing silver powder, the beginning of heat shrinkage rises to 620 ° C., and shrinkage proceeds from there. Thus, it can be seen that the shrinkage curve of the glass ceramic green sheet can be approximated by adding an additive that combines a barium compound and a calcium compound to the conductive paste of silver powder.
本発明の導電性ペーストにより反りや変形が少ないセラミック多層基板が得られ、外部導体膜のパターンや位置と高い精度で接続することができて回路基板としての信頼性を高め、回路の微細化が可能になる。 The conductive paste of the present invention provides a ceramic multilayer substrate with less warping and deformation, and can be connected to the pattern and position of the outer conductor film with high accuracy, improving the reliability as a circuit substrate and miniaturizing the circuit. It becomes possible.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003352823A JP4126698B2 (en) | 2003-10-10 | 2003-10-10 | Conductive paste |
Applications Claiming Priority (1)
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| JP2003352823A JP4126698B2 (en) | 2003-10-10 | 2003-10-10 | Conductive paste |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013080927A (en) * | 2011-10-04 | 2013-05-02 | Samsung Electro-Mechanics Co Ltd | Multilayered ceramic substrate and method for manufacturing the same |
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| JP2013080927A (en) * | 2011-10-04 | 2013-05-02 | Samsung Electro-Mechanics Co Ltd | Multilayered ceramic substrate and method for manufacturing the same |
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