JPH0282408A - Metal powder for conductive paste - Google Patents
Metal powder for conductive pasteInfo
- Publication number
- JPH0282408A JPH0282408A JP23187588A JP23187588A JPH0282408A JP H0282408 A JPH0282408 A JP H0282408A JP 23187588 A JP23187588 A JP 23187588A JP 23187588 A JP23187588 A JP 23187588A JP H0282408 A JPH0282408 A JP H0282408A
- Authority
- JP
- Japan
- Prior art keywords
- conductive paste
- surface electrode
- weight
- metal powder
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000843 powder Substances 0.000 title claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000000919 ceramic Substances 0.000 abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 19
- 239000000758 substrate Substances 0.000 abstract description 19
- 239000011135 tin Substances 0.000 abstract description 19
- 229910052718 tin Inorganic materials 0.000 abstract description 17
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052709 silver Inorganic materials 0.000 abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 11
- 239000004332 silver Substances 0.000 abstract description 11
- 229910052759 nickel Inorganic materials 0.000 abstract description 10
- 229910052763 palladium Inorganic materials 0.000 abstract description 9
- 230000006866 deterioration Effects 0.000 abstract description 5
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000000452 restraining effect Effects 0.000 abstract 1
- 239000010944 silver (metal) Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 15
- 238000003878 thermal aging Methods 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229910000679 solder Inorganic materials 0.000 description 8
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 6
- 238000005476 soldering Methods 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000003247 decreasing effect 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
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
Landscapes
- Conductive Materials (AREA)
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は、低温焼成多層セラミック基板などに用いられ
る導電ペーストの導電性を付与するための金属粉に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a metal powder for imparting conductivity to a conductive paste used in low-temperature fired multilayer ceramic substrates and the like.
「従来の技術」
従来より、低温焼成多層セラミ−ツク基板を製造すると
きには、セラミック生シートの上に導電ペーストを用い
て電極回路を形成し、これらのセラミック生シートを積
層し真空加熱圧着を行ないセラミック生基板が形成され
る。圧着成形されたセラミック生基板は脱脂の後、９５
０℃、１５〜３０分間焼成される。この焼成後のセラミ
ック基板が、低温焼成多層セラミック基板である。この
低温焼成多層セラミック基板の表面にチップ部品等の電
子部品素子を半田付けすることにより、電子部品、ユニ
ット部品となる。``Prior art'' Conventionally, when manufacturing low-temperature firing multilayer ceramic substrates, electrode circuits are formed using conductive paste on raw ceramic sheets, and these raw ceramic sheets are laminated and bonded under vacuum heat and pressure. A ceramic green substrate is formed. After degreasing, the pressure-molded ceramic green substrate is heated to 95%.
Baked at 0°C for 15-30 minutes. This fired ceramic substrate is a low temperature fired multilayer ceramic substrate. By soldering electronic component elements such as chip components to the surface of this low-temperature fired multilayer ceramic substrate, it becomes an electronic component or a unit component.
第１図は、この低温焼成多層セラミック基板の断面図で
ある。図中符号ｌはセラミックであり、２は表面電極、
３は内部電極で、４がバイア電極を示す。ここに示す表
面電極２上に、チップ部品等の電子部品素子が半田付け
されるのである。第２図は、この表面電極２上に電子部
品素子の端子が半田付けされている状態を示す図で、図
中符号５はセラミックｌ上に電極とセラミックとを接着
する接合層である。その上に表面電極２があり、この表
面電極２に、半田６によってチップ部品等の端子７が半
田付けされているのである。FIG. 1 is a cross-sectional view of this low-temperature fired multilayer ceramic substrate. In the figure, the symbol l is ceramic, 2 is a surface electrode,
3 is an internal electrode, and 4 is a via electrode. Electronic component elements such as chip components are soldered onto the surface electrode 2 shown here. FIG. 2 is a diagram showing a state in which the terminals of an electronic component element are soldered onto the surface electrode 2, and reference numeral 5 in the figure is a bonding layer that adheres the electrode and the ceramic on the ceramic l. There is a surface electrode 2 thereon, and a terminal 7 of a chip component or the like is soldered to this surface electrode 2 with solder 6.
この表面電極２のような低温焼成多層セラミッり基板の
電極用に用いられる導電ペーストは、従来より一般に、
アルミナ基板に用いられる厚膜ハイブリットＩＣ用導電
ペーストを転用しているのが現状である。Conventionally, conductive pastes used for electrodes of low-temperature fired multilayer ceramic substrates such as this surface electrode 2 are generally
Currently, conductive paste for thick film hybrid ICs used for alumina substrates is being reused.
「発明が解決しようとする課題」
上記表面電極に要求される基本特性として重要なしのに
、熱エージング特性がある。この熱ニーソング特性とは
、低温焼成多層セラミック基板の表面電極にチップ部品
等の電子部品素子の半田付けを行ない、この電子部品を
熱雰囲気下に放置し、セラミック部と表面電極部との接
着強度の経時変化を言うものである。熱エージング特性
の悪いもの、つまり熱雰囲気下におけろセラミック部と
表面電極部との接着強度が時間と共に大きく低下するら
のは、その電子部品としての信頼性の」−で大きな問題
となる。``Problem to be Solved by the Invention'' A basic characteristic required of the above-mentioned surface electrode is thermal aging characteristics, although it is not important. This thermal knee song characteristic refers to the strength of the bond between the ceramic part and the surface electrode by soldering an electronic component such as a chip component to the surface electrode of a low-temperature fired multilayer ceramic substrate and leaving the electronic component in a hot atmosphere. It refers to changes over time. Materials with poor thermal aging characteristics, such as the adhesive strength between the ceramic portion and the surface electrode portion decreasing significantly over time in a hot atmosphere, pose a major problem in terms of reliability as an electronic component.
厚膜ハイブリットｔＣ用導電ペーストにおいては、現在
多くの種類のものが市販されているが、一般に低温焼成
多層セラミック基板の表面電極用に転用されているのは
、コスト等の関係から銀パラジウム系の導電ペーストで
ある。ところが、この一般に最も多く転用されている銀
−パラジウム系の厚膜ハイブリットＩＣ用の導電ペース
トは、上記熱エージング特性に問題がある。この導電ペ
ーストの熱エージング特性の低下の機構については明ら
かではないが、予想される機構を第２図を用いて説明す
る。There are currently many types of conductive paste for thick film hybrid TC on the market, but silver-palladium-based conductive pastes are generally used for surface electrodes of low-temperature fired multilayer ceramic substrates due to cost considerations. It is a conductive paste. However, the silver-palladium-based conductive paste for thick film hybrid ICs, which is most commonly used, has a problem with the above-mentioned thermal aging characteristics. Although the mechanism of this decrease in thermal aging characteristics of the conductive paste is not clear, the expected mechanism will be explained using FIG. 2.
この銀−パラジウム系の導電ペーストを、第２図中の表
面電極２に用い熱雰囲気中に放置した場合、図中符号８
の矢印で示ｌ−ように半田６中のスズが、熱拡散し表面
電極２中に移行する。この移行したスズは、表面電極２
内に存在する銀と、銀スズ金属間化合物を形成ずろ。こ
の形成された銀−スズ金属間化合物の体積膨張率が接合
層５の膨張率と大きく異なることにより、接合ｊｎ５と
表面電極２との間において接着力の低下もしくは剥離が
起こる。これはつまり、表面電極とセラミック基数との
接着力の低下となる。When this silver-palladium based conductive paste is used as the surface electrode 2 in FIG. 2 and left in a hot atmosphere, the reference numeral 8 in the figure
Tin in the solder 6 is thermally diffused and transferred into the surface electrode 2 as shown by the arrow 1-. This transferred tin is transferred to the surface electrode 2.
With the silver present in the metal, a silver-tin intermetallic compound is formed. Since the volume expansion coefficient of the formed silver-tin intermetallic compound is significantly different from the expansion coefficient of the bonding layer 5, a decrease in adhesive force or separation occurs between the bond jn5 and the surface electrode 2. This means that the adhesive force between the surface electrode and the ceramic base is reduced.
「課題を解決するための手段」
本発明では、ニッケル（Ｎ ｉ）が３．６〜６．０重量
％、スズ（Ｓｎ）が０．９〜１．５ｆｆｉ爪％、パラジ
ウム（Ｐｄ）が４０〜５．０重量％、銀（Ａｇ）が８７
．５〜９１．５重量％からなる組成を有する金属粉を導
電ペースト用金属粉とすることで、その解決手段とした
。"Means for Solving the Problems" In the present invention, nickel (Ni) is 3.6 to 6.0% by weight, tin (Sn) is 0.9 to 1.5ffi%, and palladium (Pd) is 40% by weight. ~5.0% by weight, silver (Ag) 87
．． A solution to this problem was achieved by using metal powder having a composition of 5 to 91.5% by weight as metal powder for conductive paste.
「作用 」
銀、パラジウム、ニッケル、スズを上記の組成で含む本
発明の金属粉を分散した導電ペーストを表面電極に用い
ることにより、半田付は後の熱エノング時に半田に含ま
れるスズの表面電極内への拡散速度を、一般に使用され
ている銀−パラジウム系の導電ペーストを用いた場合と
比較して低下させることができる。これは、表面電極内
での銀−スズ金属間化合物の形成をおさえることになり
、この銀−スズ金属間化合物に起因する熱エージング時
の表面電極層と接合層との剥離もしくは接着力の低下を
防止することができる。"Function" By using the conductive paste in which the metal powder of the present invention containing silver, palladium, nickel, and tin in the above composition is dispersed for the surface electrode, the soldering can be carried out during the subsequent thermal enlongation to form the surface electrode of the tin contained in the solder. The rate of diffusion into the interior can be reduced compared to the case of using a commonly used silver-palladium-based conductive paste. This suppresses the formation of silver-tin intermetallic compounds within the surface electrode, resulting in peeling or decrease in adhesive strength between the surface electrode layer and the bonding layer during thermal aging due to this silver-tin intermetallic compound. can be prevented.
さらに、本発明の金属粉を分散させた導電ペーストから
なる表面電極層は、一般に使用されている銀−パラジウ
ム系導電ペーストからなる表面電極層に比較して、接合
層との熱膨張率の差が少ないため、これら熱エージング
時の表面電極層と接合層との剥離らしくは接着力の低下
の防止に寄与している。Furthermore, the surface electrode layer made of the conductive paste in which the metal powder of the present invention is dispersed has a difference in thermal expansion coefficient with the bonding layer compared to the surface electrode layer made of the commonly used silver-palladium-based conductive paste. This contributes to preventing deterioration in adhesive strength due to peeling between the surface electrode layer and the bonding layer during thermal aging.
以下、本発明の導電ペースト用金属粉について詳しく説
明ずろ。The metal powder for conductive paste of the present invention will be explained in detail below.
本発明の導電ペースト用金属粉は、ニッケルが３６〜６
０重量％、スズが０９〜１５重９％、パラジウムが４．
０〜５．０重量％、銀か８７．５〜９１．５重量％とい
う組成であることを特徴とする金属粉である。これらの
組成中ニッケルどスズは、前述したように熱エージング
時に半田からのスズの熱拡散速度の低下、接合層と表面
７Ｔｉ極層との熱膨張率の近似化に寄与するしので、ニ
ッケルにおいてはその組成か３６玉虫％未満であると上
記効果が発現せず、６０重量％を越えると焼成時に酸化
物が増加し半田の濡れが悪くなる。スズにおいてら同様
に０９重量％未満であると上記効果が発現せず、１５重
量％を越えろと焼成時に酸化物が増加し半田の濡れが悪
くなる。パラジウムにおいては、４．０重量％未満では
、９５０°Ｃでの焼成時に電極が溶解してしまい、５．
０重量％以上であるとコスト高になり好ましくない。銀
においては、その組成が８７．５重量％未満では、結果
的にニッケル、スズの組成が上記範囲を越え、半田の濡
れが悪くなる。また、９１．５重量％を越えると同様に
ニッケル、スズの組成が上記範囲未満となってしまい熱
エージング特性が低下すると共に、９５０℃でのセラミ
ック生基板の焼成時に電極が溶融する不具合が発生する
。The metal powder for conductive paste of the present invention has a nickel content of 36 to 6
0% by weight, tin 09-15% by weight, palladium 4.
The metal powder is characterized by having a composition of 0 to 5.0% by weight and 87.5 to 91.5% by weight of silver. In these compositions, nickel and tin contribute to reducing the thermal diffusion rate of tin from the solder during thermal aging and approximating the coefficient of thermal expansion between the bonding layer and the surface 7Ti electrode layer. If the composition is less than 36% by weight, the above effects will not be exhibited, and if it exceeds 60% by weight, oxides will increase during firing and the solder wetting will be poor. Similarly to tin, if it is less than 0.9% by weight, the above effects will not be achieved, and if it exceeds 15% by weight, oxides will increase during firing and solder wetting will be poor. In case of palladium, if it is less than 4.0% by weight, the electrode will melt during firing at 950°C.
If it is 0% by weight or more, the cost will increase, which is not preferable. When the composition of silver is less than 87.5% by weight, the composition of nickel and tin ends up exceeding the above range, resulting in poor solder wetting. In addition, if it exceeds 91.5% by weight, the nickel and tin composition will fall below the above range, resulting in poor thermal aging properties and the problem of melting of the electrodes during firing of the raw ceramic substrate at 950°C. do.
本発明の導電ペースト用金属粉の作製方法の一例を以下
に示す。An example of the method for producing the metal powder for conductive paste of the present invention is shown below.
銀、ニッケル、スズ、パラジウムの各金属を上記組成に
なるように配合し、これらを不活性ガス（アルゴン、窒
素など）中で抵抗加熱、高周波加熱、アーク溶解等で溶
融し合金化する。この合金を真空中で微粉化したり、ま
たはアトマイズ法で微粉化する。このようにして微粉化
された金属粉末の粒径は、数μｍ以下に調整される。Metals such as silver, nickel, tin, and palladium are blended to have the above composition, and these are melted and alloyed by resistance heating, high-frequency heating, arc melting, etc. in an inert gas (argon, nitrogen, etc.). This alloy is pulverized in a vacuum or by an atomization method. The particle size of the metal powder thus pulverized is adjusted to several μm or less.
本発明の金属粉には、セラミック基板との接着性向上の
ため、酸化銅、酸化ビスマス、酸化マンガン、酸化クロ
ムなどの金属酸化物粉末、あるいはガラスフッリドなど
を必要に応じて添加する。To the metal powder of the present invention, metal oxide powder such as copper oxide, bismuth oxide, manganese oxide, chromium oxide, or glass fluoride is added as necessary to improve adhesion to the ceramic substrate.
これらの粉末は、Ｖ型混合機等の粉体混合装置にて十分
に混合される。These powders are thoroughly mixed in a powder mixing device such as a V-type mixer.
本発明の金属粉を分散させて導電ペーストとするビヒク
ルには、樹脂粘結体としては、エチルセルロース、ニト
ロセルロース、アクリル樹脂、フチラール樹脂の内少な
くとも１種類以上の樹脂を本発明の金属粉１００重量部
に対し０．５〜３゜０重量部程度用いるのが好適であり
、溶剤としては、ブチルカルピトール、ターピネオール
、ブチルカルピトールアセード等の内少なくとも１種類
以上の高沸点溶剤を９．０〜２８．５重量部程度用いる
のが好適である。さらにこのビヒクルには、必要に応じ
てパラフィンワックス、マイクロワックス等のワックス
類、ジオクチルフタレート等の可塑剤、ソルビタン酸モ
ノステアレート等の界面活性剤などを適宜添加してもよ
い。The vehicle in which the metal powder of the present invention is dispersed to form a conductive paste contains at least one resin selected from ethyl cellulose, nitrocellulose, acrylic resin, and phthalate resin as the resin caking body. It is preferable to use about 0.5 to 3.0 parts by weight per part, and as a solvent, at least one high boiling point solvent such as butyl carpitol, terpineol, butyl carpitol acede, etc. is used. It is preferable to use about 28.5 parts by weight. Further, waxes such as paraffin wax and microwax, plasticizers such as dioctyl phthalate, surfactants such as sorbitan acid monostearate, etc. may be added to this vehicle as appropriate.
このようなビヒクル中に本発明の金属粉と金属酸化物粉
末等を混合した粉末を加え、少量ならば乳鉢等、多量な
らば万能混合撹拌機あるいはライカイ機等の混合機で良
く徂練りをする。さらに、三本ロールで良く混椋し粉体
の粒径を整えた後、導電ペーストとして使用に供する。A powder mixture of the metal powder of the present invention and metal oxide powder, etc. of the present invention is added to such a vehicle, and the mixture is thoroughly kneaded using a mortar or the like if the amount is small, or a mixer such as an all-purpose mixer or a Raikai machine if the amount is large. . Further, the powder is thoroughly mixed with three rolls to adjust the particle size of the powder, and then used as a conductive paste.
「実施例」 本発明の実施例を第１表に示す。"Example" Examples of the present invention are shown in Table 1.
（以下、余白）
第 １ 表
上記１０種類の実施例と１種類の比較例の金属粉に、セ
ラミック基板との接着性向上のため、金属粉１００重量
部に対してＣｕＯを１．０重量部、Ｍ ｎ Ｏｔを０．
３重量部、Ｂ ｉｔ Ｏ３を２７重量部加えそれぞれＶ
型混合機を用いて混合した。さらにこれを、樹脂粘結体
としてニトロセルロース樹脂を３．０重量部、溶剤とし
てプチルヵルヒトール、ターピネオールをそれぞれ１２
．０重量部、さらにソルビタン酸モノステアレートを０
．２重量部配合したビヒクル中に分散させ導電ペースト
とした。他の比較例としては、市販の銀−パラジウム系
導電ペースト２種類を比較例２、比較例３とした。(Hereinafter, blank spaces) Table 1 1.0 parts by weight of CuO was added to the metal powders of the above 10 examples and 1 comparative example to improve adhesion to the ceramic substrate per 100 parts by weight of the metal powder. , M n Ot is 0.
3 parts by weight and 27 parts by weight of B it O3, respectively.
Mixed using a mold mixer. Furthermore, this was mixed with 3.0 parts by weight of nitrocellulose resin as a resin caking body, and 12 parts each of butylcalcitol and terpineol as solvents.
．． 0 parts by weight, and 0 parts by weight of sorbitan monostearate
．． It was dispersed in a vehicle containing 2 parts by weight to form a conductive paste. As other comparative examples, two types of commercially available silver-palladium conductive pastes were used as Comparative Example 2 and Comparative Example 3.
これらの導電ペーストを用いて、２ｍｍＸ２ｍｍの電極
をセラミック生シートに印刷し、脱脂の後９５０℃にて
焼成を行なった。さらにスズ６２重量％、鉛３６重里％
、銀２重量％からなる半田にて半田付けを行ない、これ
を１５０℃の恒温層にて熱エージングを行なった後、そ
れぞれセラミック基板との接着強度を測定したのが第３
図である。Using these conductive pastes, electrodes of 2 mm x 2 mm were printed on green ceramic sheets, and after degreasing, they were fired at 950°C. In addition, 62% by weight of tin and 36% by weight of lead
In the third test, the adhesive strength with the ceramic substrate was measured after soldering with solder consisting of 2% silver by weight and heat aging in a constant temperature layer at 150°C.
It is a diagram.
図中符号Ａにて示す曲線は、実施例３の金属粉を用いた
導電ペーストによる表面電極と接合層との熱エージング
後の接着強度の変化を示す曲線である。他の実施例につ
いてもほぼ同じ曲線を示すので図中においては省略する
。曲線Ｂし同しく比較例１の金属粉を用いた導電ペース
トによる表面電極のらのである。曲線Ｃは市販の導電ペ
ーストである比較例２の乙ので、曲線りも同様に比較例
３の乙のである。The curve indicated by the symbol A in the figure is a curve showing the change in adhesive strength between the surface electrode and the bonding layer after thermal aging using the conductive paste using the metal powder of Example 3. Since almost the same curves are shown for other embodiments, their illustrations are omitted in the figure. Curve B corresponds to a surface electrode made of a conductive paste using the metal powder of Comparative Example 1. Curve C is that of Comparative Example 2, which is a commercially available conductive paste, and the curve C is also that of Comparative Example 3.
第３図より明らかであるように、実施例は比較例と比−
・て熱エージング中の接着強度の低下率が小さい。As is clear from FIG. 3, the example is comparable to the comparative example.
・The rate of decrease in adhesive strength during heat aging is small.
「発明の効果」
以上説明したように、本発明の導電ペースト用金属粉は
、ニッケルか３６〜６０重量％、スズが０．９〜１．５
重１％、パラジウムか４．０〜５０重量％、銀が８７．
５〜９１５重１％の組成を有するものであるので、この
金属粉を分散させた導電ペーストをセラミック基板等の
表面電極に用いると、半田付けされた状態での熱エージ
ング時において、表面電極と接合層との熱膨張率を近似
化させることができ、接合層と表面電極との接着強度の
熱劣化が抑制され、熱エージング特性が改良される。こ
れにより、本発明の金属粉を分散させた導電ペーストを
表面電極に用いろことにより、電子部品の熱雰囲気下に
おける信頼性が向上し、さらには溶融樹脂による実装樹
脂封止時などにおける実装部品の信頼性、歩どまりが向
上し、また自動車部品等の高温にて使用される基板部品
への応用が可能になるなどの効果も何ろ。"Effects of the Invention" As explained above, the metal powder for conductive paste of the present invention contains 36 to 60% by weight of nickel and 0.9 to 1.5% of tin.
1% by weight, 4.0-50% by weight of palladium, 87% by weight of silver.
Since it has a composition of 5 to 915% by weight, when a conductive paste containing this metal powder dispersed is used for the surface electrode of a ceramic substrate, etc., the surface electrode will not change during thermal aging in the soldered state. The thermal expansion coefficient can be approximated to that of the bonding layer, thermal deterioration of the adhesive strength between the bonding layer and the surface electrode is suppressed, and thermal aging characteristics are improved. As a result, by using the conductive paste in which the metal powder of the present invention is dispersed as a surface electrode, the reliability of electronic components in a hot atmosphere can be improved, and furthermore, the reliability of electronic components can be improved when the mounting resin is sealed with molten resin. Its reliability and yield are improved, and it can also be applied to substrate parts used at high temperatures such as automobile parts.
また、本発明の金属粉は、銀、パラジウムといった貴金
属の含有率か低いため、導電ペーストのコストダウンに
らなる。Further, since the metal powder of the present invention has a low content of noble metals such as silver and palladium, the cost of the conductive paste can be reduced.
【図面の簡単な説明】
第１図は低温焼成多層セラミック堰板を示す概略断面図
、第２図は表面電極での１４田付けの状態を示す概略断
面図、第３図は実施例における表面電極と接着層との熱
エージング時間に対する接着強度の変化を示すグラフで
ある。
第１図
？[Brief Description of the Drawings] Fig. 1 is a schematic cross-sectional view showing a low-temperature fired multilayer ceramic dam plate, Fig. 2 is a schematic cross-sectional view showing the state of 14 soldering with surface electrodes, and Fig. 3 is a schematic cross-sectional view showing the state of 14 soldering with surface electrodes. 2 is a graph showing changes in adhesive strength between an electrode and an adhesive layer with respect to thermal aging time. Figure 1?
Claims (1)
金属粉。[Claims] It is characterized by having a composition consisting of 3.6 to 6.0% by weight of Ni, 0.9 to 1.5% by weight of Sn, 4.0 to 5.0% by weight of Pd, and 87.5 to 91.5% by weight of Ag. Metal powder for conductive paste.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23187588A JPH0282408A (en) | 1988-09-16 | 1988-09-16 | Metal powder for conductive paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23187588A JPH0282408A (en) | 1988-09-16 | 1988-09-16 | Metal powder for conductive paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0282408A true JPH0282408A (en) | 1990-03-23 |
Family
ID=16930393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23187588A Pending JPH0282408A (en) | 1988-09-16 | 1988-09-16 | Metal powder for conductive paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0282408A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019067828A (en) * | 2017-09-28 | 2019-04-25 | Tdk株式会社 | Multilayer ceramic electronic component |
-
1988
- 1988-09-16 JP JP23187588A patent/JPH0282408A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019067828A (en) * | 2017-09-28 | 2019-04-25 | Tdk株式会社 | Multilayer ceramic electronic component |
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