JP6257356B2 - Conductive adhesive, semiconductor device, and method of manufacturing conductive adhesive - Google Patents
Conductive adhesive, semiconductor device, and method of manufacturing conductive adhesive Download PDFInfo
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- JP6257356B2 JP6257356B2 JP2014018243A JP2014018243A JP6257356B2 JP 6257356 B2 JP6257356 B2 JP 6257356B2 JP 2014018243 A JP2014018243 A JP 2014018243A JP 2014018243 A JP2014018243 A JP 2014018243A JP 6257356 B2 JP6257356 B2 JP 6257356B2
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- 239000000853 adhesive Substances 0.000 title claims description 99
- 230000001070 adhesive effect Effects 0.000 title claims description 99
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000004065 semiconductor Substances 0.000 title claims description 8
- 239000000843 powder Substances 0.000 claims description 89
- 229910017750 AgSn Inorganic materials 0.000 claims description 77
- 239000000956 alloy Substances 0.000 claims description 77
- 229910045601 alloy Inorganic materials 0.000 claims description 77
- 238000000034 method Methods 0.000 claims description 48
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 28
- 229960003540 oxyquinoline Drugs 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 18
- 238000009689 gas atomisation Methods 0.000 claims description 18
- 229920001187 thermosetting polymer Polymers 0.000 claims description 16
- 238000009692 water atomization Methods 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 238000004458 analytical method Methods 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
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- 229920000647 polyepoxide Polymers 0.000 description 20
- 239000002245 particle Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 230000008859 change Effects 0.000 description 10
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- -1 amine compound Chemical class 0.000 description 9
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- 239000005011 phenolic resin Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
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- 238000004544 sputter deposition Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 4
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- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
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- 150000003512 tertiary amines Chemical class 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical class C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
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- FNXKBSAUKFCXIK-UHFFFAOYSA-M sodium;hydrogen carbonate;8-hydroxy-7-iodoquinoline-5-sulfonic acid Chemical class [Na+].OC([O-])=O.C1=CN=C2C(O)=C(I)C=C(S(O)(=O)=O)C2=C1 FNXKBSAUKFCXIK-UHFFFAOYSA-M 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
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Description
本発明は、導電性接着剤、この導電性接着剤の硬化物を含む半導体装置、および導電性接着剤の製造方法に関する。 The present invention relates to a conductive adhesive, a semiconductor device including a cured product of the conductive adhesive, and a method for manufacturing the conductive adhesive.
抵抗器やコンデンサー等の部品を、基板に電気的に接着するハンダの代替品として、導電性接着剤が使用されている。従来、導電性接着剤には、Ａｇ粉末と熱硬化性樹脂を含むものが使用されていた。 A conductive adhesive is used as a substitute for solder for electrically bonding components such as resistors and capacitors to a substrate. Conventionally, a conductive adhesive containing Ag powder and a thermosetting resin has been used.
このＡｇ粉末と熱硬化性樹脂を含む導電性接着剤には、配線間に電圧を印加したときのマイグレーションという問題がある。このマイグレーションの抑制を目的として、Ａｇ粉末をＡｇＳｎ合金粉末に置き換えた導電性接着剤が検討されている。 The conductive adhesive containing the Ag powder and the thermosetting resin has a problem of migration when a voltage is applied between the wirings. For the purpose of suppressing this migration, a conductive adhesive in which Ag powder is replaced with AgSn alloy powder has been studied.
しかし、ＡｇＳｎ合金粉末と熱硬化性樹脂を含む導電性接着剤には、電気抵抗値が低くない、という新たな問題が発生してしまう。この問題を解決するために、ＡｇＳｎ合金を含む導電性粒子と、ヒドロキシキノリン類等の添加剤と、樹脂を含む導電性接着剤が知られている（特許文献１）。 However, the conductive adhesive containing AgSn alloy powder and thermosetting resin has a new problem that the electrical resistance value is not low. In order to solve this problem, a conductive adhesive containing AgSn alloy, an additive such as hydroxyquinolines, and a conductive adhesive containing a resin are known (Patent Document 1).
しかしながら、ＡｇＳｎ合金粉末と、ヒドロキシキノリン類である８−キノリノールと、熱硬化性樹脂であるエポキシ樹脂を含む導電性接着剤を作製すると、導電性接着剤のポットライフが短くなってしまう、という問題がある。この導電性接着剤のポットライフが短くなってしまう原因は、８−キノリノールの反応性が高いため、８−キノリノールとＡｇＳｎ合金粉末のＳｎとが錯体を形成し、この８−キノリノールとＳｎの錯体の触媒効果が熱硬化性樹脂の硬化を促進するため、導電性接着剤のポットライフが短くなってしまうからである、と考えられる。 However, when a conductive adhesive containing AgSn alloy powder, 8-quinolinol which is a hydroxyquinoline, and an epoxy resin which is a thermosetting resin, a pot life of the conductive adhesive is shortened. There is. The reason why the pot life of this conductive adhesive is shortened is that 8-quinolinol has high reactivity, so 8-quinolinol and Ag of the AgSn alloy powder form a complex, and this 8-quinolinol and Sn complex. This is because the pot life of the conductive adhesive is shortened because the catalytic effect of this promotes the curing of the thermosetting resin.
本発明は、ポットライフが長く、硬化後に電気抵抗が低い導電性接着剤を提供することを目的とする。本発明者らは鋭意研究を行い、ＡｇＳｎ合金粉末の表面に、特定の厚さの酸化膜が存在することにより、８−キノリノールとＡｇＳｎ合金粉末のＳｎとの錯体形成を抑制し、導電性接着剤のポットライフを長くすることができ、かつ硬化後の電気抵抗が低い導電性接着剤を提供することができることを見出した。 An object of the present invention is to provide a conductive adhesive having a long pot life and low electrical resistance after curing. The present inventors have intensively studied, and the presence of an oxide film having a specific thickness on the surface of the AgSn alloy powder suppresses complex formation between 8-quinolinol and Sn of the AgSn alloy powder, and conductive adhesion. It has been found that the pot life of the agent can be increased and a conductive adhesive having a low electrical resistance after curing can be provided.
本発明は、以下の構成を有することによって上記問題を解決した導電性接着剤、この導電性接着剤の硬化物を含む半導体装置、および導電性接着剤の製造方法に関する。
〔１〕（Ａ）Ｘ線光電子分光法の深さ方向分析で測定する表面酸化膜の厚さが、２０ｎｍ以上４０ｎｍ以下であるＡｇＳｎ合金粉末、（Ｂ）８−キノリノール、および（Ｃ）熱硬化性樹脂を含むことを特徴とする、導電性接着剤。
〔２〕（Ａ）成分の表面酸化膜が、ＡｇとＳｎとＯからなる、上記〔１〕記載の導電性接着剤。
〔３〕（Ａ）成分の少なくとも一部が鱗片状である、上記〔１〕または〔２〕記載の導電性接着剤。
〔４〕さらに、（Ｄ）インジウム粉末を含む、上記〔１〕〜〔３〕のいずれか記載の導電性接着剤。
〔５〕上記〔１〕〜〔４〕のいずれか記載の導電性接着剤の硬化物を含む、半導体装置。
〔６〕（Ａ）ガスアトマイズ法または水アトマイズ法で形成されたＸ線光電子分光法の深さ方向分析で測定する表面酸化膜の厚さが、２０ｎｍ以上４０ｎｍ以下であるＡｇＳｎ合金粉末、（Ｂ）８−キノリノール、および（Ｃ）熱硬化性樹脂を混合することを特徴とする、導電性接着剤の製造方法。
〔７〕（Ａ）成分として、ガスアトマイズ法または水アトマイズ法で形成した後、鱗片化されたＸ線光電子分光法の深さ方向分析で測定する表面酸化膜の厚さが、２０ｎｍ以上４０ｎｍ以下であるＡｇＳｎ合金粉末を用いる、上記〔６〕記載の導電性接着剤の製造方法。
〔８〕（Ａ）成分として、ガスアトマイズ法または水アトマイズ法で形成した後、さらに酸化された、Ｘ線光電子分光法の深さ方向分析で測定する表面酸化膜の厚さが、２０ｎｍ以上４０ｎｍ以下であるＡｇＳｎ合金粉末を用いる、上記〔６〕または〔７〕記載の導電性接着剤の製造方法。
The present invention relates to a conductive adhesive that has solved the above problems by having the following configuration, a semiconductor device including a cured product of the conductive adhesive, and a method for manufacturing the conductive adhesive.
[1] (A) AgSn alloy powder, (B) 8-quinolinol, and (C) thermosetting whose surface oxide film thickness is 20 nm or more and 40 nm or less as measured by depth direction analysis of X-ray photoelectron spectroscopy A conductive adhesive comprising a conductive resin.
[2] The conductive adhesive according to [1], wherein the surface oxide film of the component (A) is made of Ag, Sn, and O.
[3] The conductive adhesive according to [1] or [2] above, wherein at least a part of the component (A) is scaly.
[4] The conductive adhesive according to any one of [1] to [3], further including (D) indium powder.
[5] A semiconductor device comprising a cured product of the conductive adhesive according to any one of [1] to [4].
[6] (A) AgSn alloy powder having a surface oxide film thickness measured by depth direction analysis of X-ray photoelectron spectroscopy formed by gas atomization method or water atomization method is 20 nm or more and 40 nm or less, (B) A method for producing a conductive adhesive, comprising mixing 8-quinolinol and (C) a thermosetting resin.
[7] As the component (A), the thickness of the surface oxide film measured by the depth direction analysis of the scaled X-ray photoelectron spectroscopy after being formed by the gas atomization method or the water atomization method is 20 nm or more and 40 nm or less. The method for producing a conductive adhesive according to the above [6], wherein a certain AgSn alloy powder is used.
[8] As the component (A), the thickness of the surface oxide film measured by the depth direction analysis of the X-ray photoelectron spectroscopy after being formed by the gas atomization method or the water atomization method is 20 nm or more and 40 nm or less The method for producing a conductive adhesive according to the above [6] or [7], wherein the AgSn alloy powder is used.
本発明〔１〕によれば、ポットライフが長く、硬化後に電気抵抗が低い導電性接着剤を提供することができる。 According to the present invention [1], a conductive adhesive having a long pot life and low electrical resistance after curing can be provided.
本発明〔５〕によれば、低抵抗な導電性接着剤で接着された半導体装置を提供することができる。 According to the present invention [5], a semiconductor device bonded with a low-resistance conductive adhesive can be provided.
本発明〔６〕によれば、ポットライフが長く、硬化後に低抵抗な導電性接着剤を簡便に製造することができる。 According to the present invention [6], a conductive adhesive having a long pot life and low resistance after curing can be easily produced.
〔導電性接着剤〕
本発明の導電性接着剤は、（Ａ）Ｘ線光電子分光法の深さ方向分析で測定する表面酸化膜の厚さが、２０ｎｍ以上４０ｎｍ以下であるＡｇＳｎ合金粉末、（Ｂ）８−キノリノール、および（Ｃ）熱硬化性樹脂を含むことを特徴とする。
[Conductive adhesive]
The conductive adhesive of the present invention comprises (A) an AgSn alloy powder having a surface oxide film thickness of 20 nm or more and 40 nm or less as measured by depth direction analysis of X-ray photoelectron spectroscopy, (B) 8-quinolinol, And (C) a thermosetting resin.
（Ａ）ＡｇＳｎ合金粉末は、Ｘ線光電子分光法の深さ方向分析で測定する表面酸化膜の厚さが、２０ｎｍ以上４０ｎｍ以下である。ＡｇＳｎ合金粉末の酸化膜の平均厚みが、２０ｎｍ未満では、酸化膜が薄い部分などで保管中に酸化膜が除去されてしまい、Ｓｎと８−キノリノールが反応して錯体を形成し、導電性接着剤のポットライフが短くなってしまう。一方、ＡｇＳｎ合金粉末の酸化膜の平均厚みが４０ｎｍを超えると、常温での保存安定性は良好になり、導電性接着剤のポットライフが長くなるが、導電性接着剤の加熱時に表面の酸化膜が十分に除去できず、硬化後の導電性接着剤に十分な電気伝導性が得られなくなってしまう。ここで、ＡｇＳｎ合金粉末の酸化膜厚の測定には、走査型Ｘ線光電子分光分析装置（ＸＰＳ、ＵＬＢＡＣ−ＰＨＩ製、装置名称：Ｑｕａｎｔｅｒａ ＳＸＭ）を使用し、Ｘ線源として単色化Ａｌ／Ｋα線を使用する。試料のスパッタリングレートは、ＳｉＯ２換算で１６．５２ｎｍ／ｍｉｎ．とし、得られた深さ方向に対する元素分布スペクトルから酸素濃度が９％超となるときの深さを酸化膜厚と定義する。これは、集束イオンビーム（ＦＩＢ）によって直接観察できた後述する比較例２のＡｇＳｎ合金粉末の酸化膜の膜厚が４５ｎｍであり、同試料をＸＰＳで測定したとき、４５ｎｍまでスパッタリングした際の酸素濃度が９％であり、酸素濃度９％以下がＡｇＳｎ合金粉末の内部酸素量であるためである。 (A) As for AgSn alloy powder, the thickness of the surface oxide film measured by the depth direction analysis of X-ray photoelectron spectroscopy is 20 nm or more and 40 nm or less. If the average thickness of the oxide film of the AgSn alloy powder is less than 20 nm, the oxide film is removed during storage at a portion where the oxide film is thin, Sn reacts with 8-quinolinol to form a complex, and conductive adhesion The pot life of the agent will be shortened. On the other hand, when the average thickness of the oxide film of the AgSn alloy powder exceeds 40 nm, the storage stability at room temperature is improved and the pot life of the conductive adhesive is increased. However, the surface oxidation occurs when the conductive adhesive is heated. The film cannot be removed sufficiently, and sufficient electrical conductivity cannot be obtained for the conductive adhesive after curing. Here, for the measurement of the oxide film thickness of the AgSn alloy powder, a scanning X-ray photoelectron spectrometer (XPS, manufactured by ULBAC-PHI, apparatus name: Quantera SXM) is used, and the monochromatic Al / Kα is used as the X-ray source. Use lines. Sputtering rate of the sample, 16.52nm / min in terms of SiO 2. And the depth at which the oxygen concentration exceeds 9% is defined as the oxide film thickness from the obtained element distribution spectrum in the depth direction. This is because the film thickness of the oxide film of the AgSn alloy powder of Comparative Example 2 to be described later that can be directly observed by a focused ion beam (FIB) is 45 nm, and when the sample is measured by XPS, the oxygen when sputtering to 45 nm is observed. This is because the concentration is 9% and the oxygen concentration of 9% or less is the internal oxygen amount of the AgSn alloy powder.
（Ａ）ＡｇＳｎ合金粉末は、硬化後の導電性接着剤の耐マイグレーション性と接続抵抗値の観点からＡｇとＳｎの合計１００質量部に対して、Ａｇが６０〜７０質量部であると好ましい。また、ＡｇＳｎ合金粉末の平均粒径は、塗布作業性の観点から、１〜２０μｍであると好ましく、２〜１０μｍであるとより好ましい。ここで、平均粒径は、レーザー回折法によって測定した体積基準のメジアン径をいう。 (A) AgSn alloy powder is preferable in that Ag is 60 to 70 parts by mass with respect to a total of 100 parts by mass of Ag and Sn from the viewpoint of migration resistance and connection resistance value of the conductive adhesive after curing. The average particle size of the AgSn alloy powder is preferably 1 to 20 μm and more preferably 2 to 10 μm from the viewpoint of coating workability. Here, the average particle diameter refers to a volume-based median diameter measured by a laser diffraction method.
（Ａ）ＡｇＳｎ合金粉末の表面酸化膜は、ＡｇとＳｎとＯからなると好ましい。図１に、後述する実施例で使用したＡｇＳｎ合金粉末３）のＸ線光電子分光法の深さ方向分析結果を示す。図１において酸素濃度が９％を超える、スパッタ時間（Ｓｐｕｔｔｅｒ Ｔｉｍｅ）が０〜１．３分の範囲で、ＡｇとＳｎとＯが存在しており、この範囲が表面酸化膜である。 (A) The surface oxide film of the AgSn alloy powder is preferably composed of Ag, Sn, and O. FIG. 1 shows the results of depth direction analysis of the X-ray photoelectron spectroscopy of AgSn alloy powder 3) used in Examples described later. In FIG. 1, Ag, Sn, and O are present in the range where the oxygen concentration exceeds 9% and the sputtering time is 0 to 1.3 minutes, and this range is the surface oxide film.
（Ａ）ＡｇＳｎ合金粉末は、導電性接着剤がディスペンサーで塗布されるときのチキソ性の観点から、少なくとも一部が鱗片状であると好ましい。（Ａ）成分は、単独で用いてもよく、２種以上併用してもよい。 (A) The AgSn alloy powder is preferably at least partially scaly from the viewpoint of thixotropy when the conductive adhesive is applied with a dispenser. (A) A component may be used independently and may be used together 2 or more types.
（Ｂ）８−キノリノールは、ＡｇＳｎ合金粉末表面および被着物のＳｎメッキ電極の酸化膜を除去し、硬化後の導電性接着剤とＳｎメッキ電極との接続抵抗値を小さくする。しかし、８−キノリノールは、反応性が高いため、（Ａ）ＡｇＳｎ合金粉末のＳｎと錯体を形成し、このＳｎ錯体の触媒効果が熱硬化性樹脂（エポキシ樹脂等）の硬化を促進してしまう。本発明では、（Ａ）ＡｇＳｎ合金粉末の表面を酸化しているため、Ｓｎ錯体の形成を抑制できる。この結果、導電性接着剤のポットライフを長くできる。 (B) 8-Quinolinol removes the oxide film of the Sn-plated electrode on the surface of the AgSn alloy powder and the adherend, and decreases the connection resistance value between the cured conductive adhesive and the Sn-plated electrode. However, since 8-quinolinol has high reactivity, it forms a complex with Sn of the (A) AgSn alloy powder, and the catalytic effect of this Sn complex promotes the curing of the thermosetting resin (epoxy resin or the like). . In this invention, since the surface of (A) AgSn alloy powder is oxidized, formation of Sn complex can be suppressed. As a result, the pot life of the conductive adhesive can be lengthened.
（Ｃ）熱硬化性樹脂としては、例えば、エポキシ樹脂を用いるのが好ましい。エポキシ樹脂は、１分子中に２個以上のエポキシ基を有し、硬化して樹脂状になるエポキシ化合物であれば、特に、限定されない。エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、３官能エポキシ樹脂、ノボラック型エポキシ樹脂、脂環式エポキシ樹脂、ナフタレン型エポキシ樹脂、エーテル系又はポリエーテル系エポキシ樹脂、オキシラン環含有ポリブタジエン、シリコーンエポキシコポリマー樹脂等が挙げられる。また、これらの樹脂は、単独で用いてもよく、２種以上併用してもよい。 (C) As the thermosetting resin, for example, an epoxy resin is preferably used. The epoxy resin is not particularly limited as long as it is an epoxy compound that has two or more epoxy groups in one molecule and is cured and becomes resinous. Epoxy resins include bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, trifunctional epoxy resins, novolac type epoxy resins, alicyclic epoxy resins, and naphthalene type epoxy resins. , Ether-based or polyether-based epoxy resins, oxirane ring-containing polybutadiene, silicone epoxy copolymer resins, and the like. Moreover, these resin may be used independently and may be used together 2 or more types.
熱硬化性樹脂としてエポキシ樹脂を用いる場合の硬化剤としては、フェノール樹脂、酸無水物、又は、アミン系化合物等を用いることができる。 As a curing agent when an epoxy resin is used as the thermosetting resin, a phenol resin, an acid anhydride, an amine compound, or the like can be used.
フェノール樹脂としては、フェノールノボラック樹脂、クレゾールノボラック樹脂、ナフトール変性フェノール樹脂、ジシクロペンタジエン変性フェノール樹脂、ｐ―キシレン変性フェノール樹脂、ジシクロペンタジエン変性フェノール樹脂、ｐ―キシレン変性フェノール樹脂等が挙げられるが、これらに限定されるものではなく、導電性接着剤に通常用いられるものであればよい。エポキシ樹脂中のエポキシ基：１当量当たり、フェノール樹脂中のＯＨ当量が、０．１〜１．０当量となることが好ましく、０．２〜０．６当量となることがより好ましい。 Examples of the phenol resin include phenol novolac resin, cresol novolac resin, naphthol modified phenol resin, dicyclopentadiene modified phenol resin, p-xylene modified phenol resin, dicyclopentadiene modified phenol resin, p-xylene modified phenol resin and the like. However, the present invention is not limited to these, and any material that is usually used for conductive adhesives may be used. Epoxy groups in the epoxy resin: The OH equivalent in the phenol resin is preferably 0.1 to 1.0 equivalent, more preferably 0.2 to 0.6 equivalent, per equivalent.
酸無水物としては、メチルテトラヒドロフタル酸無水物、メチルヘキサヒドロフタル酸無水物、アルキル化テトラヒドロフタル酸無水物、ヘキサヘドロフタル酸無水物、無水メチルハイミック酸、無水ドデセニルコハク酸、無水メチルナジック酸等が挙げられるが、これらに限定されるものではない。エポキシ樹脂と酸無水化物の配合割合は、エポキシ樹脂中のエポキシ基：１当量当たり、酸無水化物の当量が０．１〜１．０当量となることが好ましい。 Examples of acid anhydrides include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahedrophthalic anhydride, methyl hymic anhydride, dodecenyl succinic anhydride, methyl nadic anhydride However, it is not limited to these. As for the compounding ratio of the epoxy resin and the acid anhydride, the equivalent of the acid anhydride is preferably 0.1 to 1.0 equivalent per 1 equivalent of epoxy group in the epoxy resin.
アミン系化合物としては、脂肪族ポリアミン、芳香族アミン、及び、ポリアミノアミド、ポリアミノイミド、ポリアミノエステル、ポリアミノ尿素等の変性ポリアミンが挙げられるが、これらに限定されるものではない。エポキシ樹脂とアミン系化合物の配合割合は、エポキシ樹脂中のエポキシ基：１当量当たり、アミン系化合物の当量が０．１〜１．０当量となることが好ましく、０．２〜０．７当量となることがより好ましい。さらに、第三級アミン系、イミダゾール系、ヒドラジド系、ジシアンジアミド系、メラミン系の化合物を用いることができる。また、これらの硬化剤は、単独で用いてもよく、２種以上併用してもよい。 Examples of amine compounds include, but are not limited to, aliphatic polyamines, aromatic amines, and modified polyamines such as polyaminoamides, polyaminoimides, polyaminoesters, and polyaminoureas. The blending ratio of the epoxy resin and the amine compound is preferably such that the equivalent of the amine compound is 0.1 to 1.0 equivalent per epoxy group in the epoxy resin: 0.2 to 0.7 equivalent. More preferably. Furthermore, tertiary amine, imidazole, hydrazide, dicyandiamide, and melamine compounds can be used. Moreover, these hardening | curing agents may be used independently and may be used together 2 or more types.
熱硬化性樹脂は、さらに、硬化触媒を含むと、導電性接着剤の硬化速度の観点から好ましい。硬化性触媒としては、第三級アミン系、イミダゾール系、ヒドラジド系、ジシアンジアミド系のものが挙げられる。また、硬化触媒は、単独で用いてもよく、２種以上併用してもよい。 When the thermosetting resin further contains a curing catalyst, it is preferable from the viewpoint of the curing rate of the conductive adhesive. Examples of the curable catalyst include tertiary amine-based, imidazole-based, hydrazide-based, and dicyandiamide-based catalysts. Moreover, a curing catalyst may be used independently and may be used together 2 or more types.
（Ａ）成分は、導電性接着剤：１００質量部に対して、７５〜８８質量部であると好ましい。図２に、（Ａ）成分の含有量を変化させたときの接続抵抗値の変化を示す。図２では、導電性接着剤から反応性希釈剤を除いた組成物１００質量％に対して、（Ｂ）成分を、２．７０質量％にし、（Ａ）成分は、表面酸化膜の厚さが２１．５ｎｍのＡｇＳｎ合金粉末（Ａｇ：６５質量％、Ｓｎ：３５質量％）を図２に示す質量％にした。具体的な組成は、図２のＡｇＳｎ合金粉末が約８３質量％（図２で左から３つめのプロット）である場合が、後述する実施例２である。図２の（Ａ）ＡｇＳｎ合金粉末が約８３質量％以外の場合は、（Ａ）ＡｇＳｎ合金粉末を図２に示す質量％にし、（Ａ）成分以外の成分は、実施例２での（Ｂ）成分、（Ｃ）成分、（Ｄ）成分および添加剤の割合を保ったまま、導電性接着剤中での含有量を変化させた。接続抵抗値の測定方法は、後述する。図２からわかるように、（Ａ）成分の含有量による接続抵抗値には、大きな変化はみられない。これは、還元剤である（Ｂ）成分の８−キノリノールは、被着部品のＳｎメッキ電極に対して還元効果を発揮すると同時に、（Ａ）成分のＡｇＳｎ合金粉末に対しても還元効果を発揮するため、ＡｇＳｎ合金粉末の配合量を増やすと、被着部品への単位面積あたりの還元効果が薄れる等の理由で、粉末含有量の変化によるメリットとデメリットとが相殺されるためである、と考えられる。 (A) A component is preferable in it being 75-88 mass parts with respect to 100 mass parts of conductive adhesives. FIG. 2 shows a change in connection resistance value when the content of the component (A) is changed. In FIG. 2, the component (B) is 2.70% by mass with respect to 100% by mass of the composition obtained by removing the reactive diluent from the conductive adhesive, and the component (A) is the thickness of the surface oxide film. 21.5 nm AgSn alloy powder (Ag: 65 mass%, Sn: 35 mass%) was adjusted to the mass% shown in FIG. As a specific composition, the case where the AgSn alloy powder of FIG. 2 is about 83% by mass (third plot from the left in FIG. 2) is Example 2 described later. When (A) AgSn alloy powder of FIG. 2 is other than about 83 mass%, (A) AgSn alloy powder is mass% shown in FIG. 2, and components other than (A) component are (B ) Component, (C) component, (D) component, and the content in an electrically conductive adhesive were changed, keeping the ratio of an additive. A method for measuring the connection resistance value will be described later. As can be seen from FIG. 2, there is no significant change in the connection resistance value depending on the content of the component (A). This is because (B) component 8-quinolinol, which is a reducing agent, exhibits a reducing effect on the Sn-plated electrode of the adherend, and at the same time, also exhibits a reducing effect on the (A) component AgSn alloy powder. Therefore, if the amount of AgSn alloy powder is increased, the advantages and disadvantages due to the change in the powder content are offset, for example, because the reduction effect per unit area on the adherend part is reduced. Conceivable.
（Ｂ）成分は、導電性接着剤：１００質量部に対して、１．５〜３．９質量部であると好ましく、２．０〜３．０質量部であると、より好ましい。１．５質量部未満では、ＡｇＳｎ合金粉末の酸化膜を十分に除去することができず、硬化後の導電性接着剤の接続抵抗値が高くなる場合があり、３．９質量部を超えると、導電性接着剤に含有される樹脂の濃度が減少するため、硬化後の導電性接着剤の硬度が不足する場合があり、また、（Ｂ）成分が、導電性接着剤の硬化工程で揮発するため、ボイドが発生する場合がある。図３に、（Ｂ）成分の含有量を変化させたときの接続抵抗値の変化を示す。図３では、導電性接着剤から反応性希釈剤を除いた組成物１００質量％に対して、（Ａ）成分として、表面酸化膜の厚さが２１．５ｎｍのＡｇＳｎ合金粉末（Ａｇ：６５質量％、Ｓｎ：３５質量％）を８３質量％とし、（Ｂ）成分は、図３に示す質量％とした。具体的な組成は、図３の（Ｂ）８−キノリノールが２．７質量％である場合（図３で左から４つめのプロット）が、後述する実施例２である。図３の（Ｂ）８−キノリノールが２．７質量％以外の場合は、（Ｂ）８−キノリノールを図３に示す質量％にし、（Ｂ）成分以外の成分は、実施例２での（Ａ）成分、（Ｃ）成分、（Ｄ）成分および添加剤の割合を保ったまま、導電性接着剤中での含有量を変化させた。図３からわかるように、（Ｂ）成分の８−キノリノールが増加すると、接続抵抗値が減少する。接続抵抗値は、２５ｍΩ以下であると好ましいため、図３から（Ｂ）成分の８−キノリノールは、１．５質量％以上であると、接続抵抗値の観点から好ましい。図３では、（Ｂ）成分の８−キノリノールは、１．５質量％のとき、接続抵抗値が２１ｍΩと低い。次に、図４に、（Ｂ）成分の含有量を変化させたときの接着強度の変化を示す。図４では、導電性接着剤から反応性希釈剤を除いた組成物１００質量％に対して、（Ａ）成分として表面酸化膜の厚さが２１．５ｎｍのＡｇＳｎ合金粉末（Ａｇ：６５質量％、Ｓｎ：３５質量％）を、８３質量％にし、（Ｂ）成分は、図４に示す質量％とした。図３と同様に、具体的な組成は、図４の（Ｂ）８−キノリノールが２．７質量％である場合（図４で左から４つめのプロット）が、後述する実施例２である。図４の（Ｂ）８−キノリノールが２．７質量％以外の場合は、（Ｂ）８−キノリノールを図４に示す質量％にし、（Ｂ）成分以外の成分は、実施例２での（Ａ）成分、（Ｃ）成分、（Ｄ）成分および添加剤の割合を保ったまま、導電性接着剤中での含有量を変化させた。図４では、（Ｂ）成分の８−キノリノールが、１．５質量％のとき、接着硬度が２５Ｎ；３質量％のとき、接着硬度が１７Ｎ；３．６質量％のとき、接着硬度が１３Ｎ；３．９質量％のとき、接着硬度が１１Ｎ；４．５質量％のとき、接着硬度が８Ｎである。接着強度の測定方法は、後述する。接着強度は、１０Ｎ以上であると好ましいので、図４から、（Ｂ）成分の８−キノリノールは、３．９質量％以下であると好ましいことがわかる。 (B) A component is preferable in it being 1.5-3.9 mass parts with respect to 100 mass parts of conductive adhesives, and it is more preferable in it being 2.0-3.0 mass parts. If the amount is less than 1.5 parts by mass, the oxide film of the AgSn alloy powder cannot be sufficiently removed, and the connection resistance value of the conductive adhesive after curing may increase. If the amount exceeds 3.9 parts by mass Since the concentration of the resin contained in the conductive adhesive decreases, the hardness of the conductive adhesive after curing may be insufficient, and the component (B) is volatilized in the curing process of the conductive adhesive. Therefore, voids may occur. FIG. 3 shows a change in the connection resistance value when the content of the component (B) is changed. In FIG. 3, AgSn alloy powder (Ag: 65 mass) having a surface oxide film thickness of 21.5 nm as component (A) with respect to 100 mass% of the composition obtained by removing the reactive diluent from the conductive adhesive. %, Sn: 35 mass%) was 83 mass%, and the component (B) was mass% shown in FIG. The specific composition is Example 2 described later when (B) 8-quinolinol in FIG. 3 is 2.7 mass% (the fourth plot from the left in FIG. 3). When (B) 8-quinolinol in FIG. 3 is other than 2.7 mass%, (B) 8-quinolinol is changed to mass% shown in FIG. 3, and components other than the component (B) are The content in the conductive adhesive was changed while maintaining the proportions of component A), component (C), component (D) and additives. As can be seen from FIG. 3, when 8-quinolinol as the component (B) increases, the connection resistance value decreases. Since the connection resistance value is preferably 25 mΩ or less, the component (B) 8-quinolinol in FIG. 3 is preferably 1.5% by mass or more from the viewpoint of connection resistance value. In FIG. 3, 8-quinolinol as component (B) has a low connection resistance value of 21 mΩ at 1.5 mass%. Next, FIG. 4 shows a change in adhesive strength when the content of the component (B) is changed. In FIG. 4, the AgSn alloy powder (Ag: 65 mass%) whose surface oxide film thickness is 21.5 nm as component (A) with respect to 100 mass% of the composition obtained by removing the reactive diluent from the conductive adhesive. , Sn: 35 mass%) was 83 mass%, and the component (B) was mass% shown in FIG. Similar to FIG. 3, the specific composition is Example 2 described later when (B) 8-quinolinol in FIG. 4 is 2.7 mass% (the fourth plot from the left in FIG. 4). . When (B) 8-quinolinol in FIG. 4 is other than 2.7 mass%, (B) 8-quinolinol is changed to mass% shown in FIG. 4, and components other than the component (B) are ( The content in the conductive adhesive was changed while maintaining the proportions of component A), component (C), component (D) and additives. In FIG. 4, when 8-quinolinol of the component (B) is 1.5% by mass, the adhesion hardness is 25N; when 3% by mass, the adhesion hardness is 17N; when 3.6% by mass, the adhesion hardness is 13N. When 3.9% by mass, the adhesion hardness is 11N; when 4.5% by mass, the adhesion hardness is 8N. A method for measuring the adhesive strength will be described later. Since the adhesive strength is preferably 10 N or more, FIG. 4 shows that 8-quinolinol of the component (B) is preferably 3.9% by mass or less.
導電性接着剤は、さらに、（Ｄ）インジウム粉末を含むと好ましい。（Ｄ）成分は、導電性接着剤の硬化時に溶融するため、硬化後の導電性接着剤の電気抵抗を安定化させることができる。（Ｄ）成分の平均粒径は、塗布作業性の観点から、４５μｍ以下であると好ましい。 The conductive adhesive preferably further contains (D) indium powder. Since the component (D) melts when the conductive adhesive is cured, the electrical resistance of the cured conductive adhesive can be stabilized. The average particle diameter of the component (D) is preferably 45 μm or less from the viewpoint of coating workability.
（Ｄ）成分は、導電性接着剤：１００質量部に対して、２〜８質量部であると好ましく、３〜５質量部であるとより好ましい。 The component (D) is preferably 2 to 8 parts by mass, more preferably 3 to 5 parts by mass with respect to 100 parts by mass of the conductive adhesive.
導電性接着剤は、本発明の目的を損なわない範囲で、更に必要に応じ、作業性改善を目的とした微粉シリカ、分散剤、柔軟性付与を目的としたアクリロニトリルゴム等のエラストマー、密着性付与を目的としたシランカップリング剤、低粘度化を目的とした反応性希釈剤等を含有することができる。 The conductive adhesive is within the range that does not impair the purpose of the present invention, and if necessary, finely divided silica for the purpose of improving workability, a dispersant, an elastomer such as acrylonitrile rubber for the purpose of imparting flexibility, and imparting adhesion. A silane coupling agent for the purpose of, a reactive diluent for the purpose of reducing the viscosity, and the like can be contained.
本発明の導電性接着剤は、ディスペンス用途、スクリーン印刷用途等、様々な分野で好適に用いることができるため、非常に有用である。 The conductive adhesive of the present invention is very useful because it can be suitably used in various fields such as dispensing and screen printing.
〔半導体装置〕
本発明の半導体装置は、上記導電性接着剤の硬化物を含む。上記導電性接着剤は、従来品と比べポットライフが長いので、部品と基板の接着工程での作業性が安定する。また、部品と基板の接着工程の作業時間を延長することができる。すなわち、導電性接着剤の可使時間が延び、導電性接着剤のシリンジ交換回数を減少できるため、生産性が向上する。被着体である部品や基板の電極としては、Ｓｎメッキ電極、Ｎｉメッキ電極、貴金属電極が挙げられる。部品としては、抵抗器、コンデンサー、ＩＣチップ等が挙げられる。
[Semiconductor device]
The semiconductor device of this invention contains the hardened | cured material of the said conductive adhesive. Since the conductive adhesive has a longer pot life than conventional products, the workability in the bonding process between the component and the substrate is stabilized. In addition, it is possible to extend the working time of the component and substrate bonding process. That is, the pot life of the conductive adhesive is extended and the number of times the conductive adhesive is replaced with a syringe can be reduced, so that productivity is improved. Examples of the electrode of the part to be adhered and the substrate include a Sn plating electrode, a Ni plating electrode, and a noble metal electrode. Examples of components include resistors, capacitors, and IC chips.
〔導電性接着剤の製造方法〕
本発明の導電性接着剤の製造方法は、（Ａ）ガスアトマイズ法または水アトマイズ法で形成されたＸ線光電子分光法の深さ方向分析で測定する表面酸化膜の厚さが、２０ｎｍ以上４０ｎｍ以下であるＡｇＳｎ合金粉末、（Ｂ）８−キノリノール、および（Ｃ）熱硬化性樹脂を混合することを特徴とする。
[Method for producing conductive adhesive]
In the method for producing a conductive adhesive of the present invention, (A) the thickness of the surface oxide film measured by the depth direction analysis of X-ray photoelectron spectroscopy formed by gas atomization method or water atomization method is 20 nm or more and 40 nm or less. The AgSn alloy powder, (B) 8-quinolinol, and (C) a thermosetting resin are mixed.
（Ａ）表面酸化膜の厚さが、２０ｎｍ以上４０ｎｍ以下であるＡｇＳｎ合金粉末は、ガスアトマイズ法または水アトマイズ法で形成することができる。ガスアトマイズ法で使用されるガスとしては、アルゴンガスまたは窒素ガスが挙げられる。ガスアトマイズ法で形成されるＡｇＳｎ合金粉末は、球状であり、水アトマイズ法で形成されるＡｇＳｎ合金粉末は、不定形である。 (A) AgSn alloy powder having a surface oxide film thickness of 20 nm or more and 40 nm or less can be formed by a gas atomization method or a water atomization method. Examples of the gas used in the gas atomization method include argon gas and nitrogen gas. The AgSn alloy powder formed by the gas atomization method is spherical, and the AgSn alloy powder formed by the water atomization method is indefinite.
ガスアトマイズ法で形成されたＡｇＳｎ合金粉末は、酸化処理することにより、２０ｎｍ以上４０ｎｍ以下の表面酸化膜を形成することができる。酸化処理の条件の一例は、温度：８５℃、湿度：８５％ＲＨであり、この条件でＡｇＳｎ合金粉末（Ａｇ：６５質量％、Ｓｎ：３５質量％）を酸化したときの処理時間と酸化膜の厚さとの関係を、図５に示す。図５は、ガスアトマイズ法で形成されたＡｇＳｎ合金粉末の酸化処理が０、２、４８、９６時間での酸化膜の厚さを示しており、各処理時間での酸化膜の厚さは、８．３、３３．０、３８．０、４４．６ｎｍであった。ここで、酸化処理時間が０時間での酸化膜の厚さ：８．３ｎｍは、自然酸化膜の厚さである、と考えられる。また、図５には、水アトマイズ法で形成されたＡｇＳｎ合金粉末の酸化膜の厚さを示しており、水アトマイズ法で形成されたＡｇＳｎ合金粉末の酸化膜の厚さは、２１．５ｎｍであった。よって、水アトマイズ法で形成されたＡｇＳｎ合金粉末は、そのままでも使用可能であるが、場合により付加的な酸化処理により、２０ｎｍ以上４０ｎｍ以下の表面酸化膜を形成することができる。 The AgSn alloy powder formed by the gas atomization method can be oxidized to form a surface oxide film having a thickness of 20 nm or more and 40 nm or less. An example of the conditions for the oxidation treatment is temperature: 85 ° C., humidity: 85% RH, and the treatment time and oxide film when the AgSn alloy powder (Ag: 65 mass%, Sn: 35 mass%) is oxidized under these conditions. FIG. 5 shows the relationship with the thickness. FIG. 5 shows the thickness of the oxide film when the oxidation treatment of the AgSn alloy powder formed by the gas atomization method is 0, 2, 48, and 96 hours. The thickness of the oxide film at each treatment time is 8 3, 33.0, 38.0, 44.6 nm. Here, the thickness of the oxide film when the oxidation treatment time is 0 hour: 8.3 nm is considered to be the thickness of the natural oxide film. FIG. 5 shows the thickness of the oxide film of the AgSn alloy powder formed by the water atomization method. The thickness of the oxide film of the AgSn alloy powder formed by the water atomization method is 21.5 nm. there were. Therefore, although the AgSn alloy powder formed by the water atomization method can be used as it is, a surface oxide film of 20 nm or more and 40 nm or less can be formed by additional oxidation treatment depending on the case.
ガスアトマイズ法または水アトマイズ法で形成されたＡｇＳｎ合金粉末は、鱗片化されていると、好ましい。ＡｇＳｎ合金粉末を鱗片化する方法としては、ビーズミル、ポットミル等が挙げられる。 The AgSn alloy powder formed by the gas atomization method or the water atomization method is preferably scaled. Examples of the method for scaling the AgSn alloy powder include a bead mill and a pot mill.
ガスアトマイズ法または水アトマイズ法で形成されたＡｇＳｎ合金粉末は、鱗片化された後、さらに酸化されていると、表面酸化膜の膜厚の観点から、より好ましい。 The AgSn alloy powder formed by the gas atomization method or the water atomization method is more preferably oxidized after being scaled, from the viewpoint of the thickness of the surface oxide film.
本発明の導電性接着剤は、例えば、（Ａ）成分〜（Ｃ）成分およびその他の添加剤等を同時にまたは別々に、必要により加熱処理を加えながら、撹拌、溶融、混合、分散させることにより得ることができる。これらの混合、撹拌、分散等の装置としては、特に限定されるものではないが、撹拌、加熱装置を備えたライカイ機、３本ロールミル、ボールミル、プラネタリーミキサー、ビーズミル等を使用することができる。また、これら装置を適宜組み合わせて使用してもよい。 The conductive adhesive of the present invention can be prepared by, for example, stirring, melting, mixing, and dispersing the components (A) to (C) and other additives simultaneously or separately, with heat treatment as necessary. Can be obtained. The mixing, stirring, dispersing and the like devices are not particularly limited, and a raikai machine equipped with a stirring and heating device, a three-roll mill, a ball mill, a planetary mixer, a bead mill and the like can be used. . Moreover, you may use combining these apparatuses suitably.
導電性接着剤を塗布する方法は、特に限定されず、ディスペンサーディスペンス、印刷、ポッティング、スプレー、スピンコート等の当業者に公知の方法で行うことができる。 The method for applying the conductive adhesive is not particularly limited, and can be performed by methods known to those skilled in the art such as dispenser dispensing, printing, potting, spraying, spin coating and the like.
導電性接着剤の硬化条件の一例は、１２０〜１８０℃で、１０〜６０分間である。 An example of the curing conditions for the conductive adhesive is 120 to 180 ° C. and 10 to 60 minutes.
次に、硬化後の導電性接着剤の接続抵抗値の測定方法を説明する。搭載部品として３２１６サイズのＳｎメッキ積層コンデンサーを、基板としてＡｇ焼成厚膜を用い、本発明の導電性接着剤で接合し、１５０℃×３０分で硬化させたものを試験片とする。作製した試験片を４端子法で測定し（ｎ＝１６）、その平均値が１０ｍΩ以下のものを合格とする。 Next, a method for measuring the connection resistance value of the conductive adhesive after curing will be described. A 3216 sized Sn-plated multilayer capacitor is used as a mounting component, an Ag-fired thick film is used as a substrate, the conductive adhesive of the present invention is joined, and the test piece is cured at 150 ° C. for 30 minutes. The produced test piece is measured by a four-terminal method (n = 16), and an average value of 10 mΩ or less is accepted.
硬化後の導電性接着剤の接着強度（ダイシェア強度）の測定方法を説明する。３２１６サイズのＳｎメッキ積層コンデンサーを、基板としてＡｇ焼成厚膜を用い、本発明の導電性接着剤で接合し、１５０℃×３０分で硬化させたものを試験片とする。硬化後、アイコーエンジニアリング製強度試験機（型番：Ｍｏｄｅｌ １６０５ＨＴＰ）を用いて、室温（２５℃）で測定したダイシェア強度値である。 A method for measuring the adhesive strength (die shear strength) of the conductive adhesive after curing will be described. A test piece is obtained by bonding a 3216-size Sn-plated multilayer capacitor using an Ag fired thick film as a substrate, bonding it with the conductive adhesive of the present invention, and curing it at 150 ° C. for 30 minutes. It is the die shear strength value measured at room temperature (25 ° C.) using an Aiko Engineering strength tester (model number: Model 1605HTP) after curing.
本発明について、実施例により説明するが、本発明はこれらに限定されるものではない。なお、以下の実施例において、部、％はことわりのない限り、質量部、質量％を示す。
得られたＡｇＳｎ合金粉末の酸化膜厚の測定には、走査型Ｘ線光電子分光分析装置（ＸＰＳ、ＵＬＢＡＣ−ＰＨＩ製、装置名称：Ｑｕａｎｔｅｒａ ＳＸＭ）を使用し、Ｘ線源として単色化Ａｌ／Ｋα線を使用した。試料のスパッタリングレートは、ＳｉＯ２換算で１６．５２ｎｍ／ｍｉｎ．とし、得られた深さ方向に対する元素分布スペクトルから酸素濃度が９％超となるときの深さを酸化膜厚と定義した。これは、ＦＩＢによって直接観察できた比較例２のＡｇＳｎ合金粉末の酸化膜の膜厚が４５ｎｍであり、同試料をＸＰＳで測定したとき、４５ｎｍまでスパッタリングした際の酸素濃度が９％であり、酸素濃度９％以下がＡｇＳｎ合金粉末の内部酸素量であるためである。図１に、実施例で使用したＡｇＳｎ合金粉末３）のＸ線光電子分光法の深さ方向分析結果を示す。図１において酸素濃度が９％を超える、スパッタ時間（Ｓｐｕｔｔｅｒ Ｔｉｍｅ）が０〜１．３分の範囲（深さ：０〜２１．５ｎｍに相当する）で、ＡｇとＳｎとＯが存在しており、この範囲が表面酸化膜である。
The present invention will be described with reference to examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by mass and mass% unless otherwise specified.
For the measurement of the oxide film thickness of the obtained AgSn alloy powder, a scanning X-ray photoelectron spectroscopic analyzer (XPS, manufactured by ULBAC-PHI, apparatus name: Quantera SXM) was used, and the monochromatic Al / Kα was used as the X-ray source. A line was used. Sputtering rate of the sample, 16.52nm / min in terms of SiO 2. And the depth at which the oxygen concentration exceeds 9% was defined as the oxide film thickness from the obtained element distribution spectrum in the depth direction. This is because the film thickness of the oxide film of the AgSn alloy powder of Comparative Example 2 that can be directly observed by FIB is 45 nm, and when the sample is measured by XPS, the oxygen concentration when sputtered to 45 nm is 9%, This is because the oxygen concentration of 9% or less is the internal oxygen amount of the AgSn alloy powder. FIG. 1 shows the results of depth direction analysis of the X-ray photoelectron spectroscopy of AgSn alloy powder 3) used in the examples. In FIG. 1, Ag, Sn, and O are present in the range where the oxygen concentration exceeds 9% and the sputtering time is 0 to 1.3 minutes (corresponding to depth: 0 to 21.5 nm). This range is the surface oxide film.
〔ＡｇＳｎ合金粉末の作製〕
（Ａ）ＡｇＳｎ合金粉末１）
ガスアトマイズ法により得たＡｇＳｎ合金粉末（Ａｇ：６５質量％、Ｓｎ：３５質量％、平均粒径：５〜１０μｍの球状粉）を、温度：８５℃、湿度：８５％ＲＨの大気雰囲気下で２時間処理して、厚さ：３３ｎｍの表面酸化膜を有するＡｇＳｎ合金粉末を得た。
[Preparation of AgSn alloy powder]
(A) AgSn alloy powder 1)
An AgSn alloy powder (Ag: 65% by mass, Sn: 35% by mass, average particle size: 5 to 10 μm spherical powder) obtained by the gas atomization method was heated in an air atmosphere at a temperature of 85 ° C. and a humidity of 85% RH. Time treatment was performed to obtain an AgSn alloy powder having a surface oxide film with a thickness of 33 nm.
（Ａ）ＡｇＳｎ合金粉末２）
ガスアトマイズ法により得たＡｇＳｎ合金粉末（Ａｇ：６５質量％、Ｓｎ：３５質量％、平均粒径：５〜１０μｍの球状粉）を、温度：８５℃、湿度：８５％ＲＨの大気雰囲気下で４８時間処理して、厚さ：３８ｎｍの表面酸化膜を有するＡｇＳｎ合金粉末を得た。
(A) AgSn alloy powder 2)
An AgSn alloy powder (Ag: 65% by mass, Sn: 35% by mass, average particle size: 5 to 10 μm spherical powder) obtained by the gas atomization method is 48 in an air atmosphere at a temperature of 85 ° C. and a humidity of 85% RH. Time treatment was performed to obtain an AgSn alloy powder having a surface oxide film with a thickness of 38 nm.
（Ａ）ＡｇＳｎ合金粉末３）
水アトマイズ法により、厚さ：２１．５ｎｍの表面酸化膜を有するＡｇＳｎ合金粉末（Ａｇ：６５質量％、Ｓｎ：３５質量％、平均粒径：２〜５μｍの不定形粉）を得た。
(A) AgSn alloy powder 3)
An AgSn alloy powder (Ag: 65% by mass, Sn: 35% by mass, average particle size: 2 to 5 μm of amorphous powder) having a surface oxide film with a thickness of 21.5 nm was obtained by a water atomization method.
（Ａ）ＡｇＳｎ合金粉末４）
水アトマイズ法により、厚さ：２１．５ｎｍの表面酸化膜を有するＡｇＳｎ合金粉末（Ａｇ：６５質量％、Ｓｎ：３５質量％、平均粒径：２〜５μｍの不定形粉）に、ビーズミルを用いて、鱗片加工を行い、ＡｇＳｎ合金粉末（平均粒径：２〜７μｍの鱗片状粉）を得た。
(A) AgSn alloy powder 4)
A bead mill was used for AgSn alloy powder (Ag: 65% by mass, Sn: 35% by mass, average particle size: 2 to 5 μm of irregular shaped powder) having a surface oxide film with a thickness of 21.5 nm by a water atomization method. Then, scale processing was performed to obtain an AgSn alloy powder (scaled powder having an average particle diameter of 2 to 7 μm).
（Ａ）ＡｇＳｎ合金粉末５）
ガスアトマイズ法により得たＡｇＳｎ合金粉末（Ａｇ：６５質量％、Ｓｎ：３５質量％、平均粒径：５〜１０μｍの球状粉）をそのまま用いた。ＡｇＳｎ合金粉末の表面酸化膜の厚さは、８ｎｍであった。
(A) AgSn alloy powder 5)
The AgSn alloy powder (Ag: 65 mass%, Sn: 35 mass%, average particle diameter: 5-10 micrometers spherical powder) obtained by the gas atomization method was used as it was. The thickness of the surface oxide film of the AgSn alloy powder was 8 nm.
（Ａ）ＡｇＳｎ合金粉末６）
ガスアトマイズ法により得たＡｇＳｎ合金粉末（Ａｇ：６５質量％、Ｓｎ：３５質量％、平均粒径：５〜１０μｍの球状粉）を、温度：８５℃、湿度：８５％ＲＨの大気雰囲気下で９６時間処理して、厚さ：４５ｎｍの表面酸化膜を有するＡｇＳｎ合金粉末を得た。
(A) AgSn alloy powder 6)
An AgSn alloy powder (Ag: 65% by mass, Sn: 35% by mass, average particle size: 5 to 10 μm spherical powder) obtained by the gas atomization method is 96 in an air atmosphere at a temperature of 85 ° C. and a humidity of 85% RH. Time treatment was performed to obtain an AgSn alloy powder having a surface oxide film with a thickness of 45 nm.
〔導電性接着剤の作製〕
表１に示す割合で、（Ｂ）８−キノリノール、（Ｃ）熱硬化性樹脂、および添加剤を混合し、３本ロールにより、大粒径が１０μｍ以下となるまで分散し（ＪＩＳ−Ｋ５６００−２−５を適用）、樹脂混合物を得た。作製した樹脂混合物と（Ａ）ＡｇＳｎ合金粉末、（Ｄ）Ｉｎ粉末を混合し、遊星式ミキサーで均一に攪拌した。分散後、反応性希釈剤（ダイセル製、品名：セロキサイド３０００）で粘度調整し、適切な粘度の導電性接着剤を得た。導電性接着剤を、真空状態にして、導電性接着剤内部の気泡を除去した。
[Preparation of conductive adhesive]
In the ratio shown in Table 1, (B) 8-quinolinol, (C) thermosetting resin, and additives are mixed and dispersed by a three roll until the large particle size becomes 10 μm or less (JIS-K5600- 2-5 was applied) to obtain a resin mixture. The prepared resin mixture, (A) AgSn alloy powder, and (D) In powder were mixed and stirred uniformly with a planetary mixer. After dispersion, the viscosity was adjusted with a reactive diluent (manufactured by Daicel, product name: Celoxide 3000) to obtain a conductive adhesive having an appropriate viscosity. The conductive adhesive was evacuated to remove bubbles inside the conductive adhesive.
〔導電性接着剤の評価〕
導電性接着剤の粘度を測定した。まず、得られた導電性接着剤を、ＤＶ−１型粘度計／１４号スピンドルを用いて、２５℃、１ｒｐｍで１分間回転させたときの粘度（表１には、１ｒｐｍでの粘度と記載した）を測定した。次に、導電性接着剤を、ＤＶ−１型粘度計／１４号スピンドルを用いて、２５℃、１０ｒｐｍで１分間回転させたときの粘度（表１には、１０ｒｐｍでの粘度と記載した）を測定した。得られた（１ｒｐｍでの粘度）／１０ｒｐｍでの粘度）からＴＩ（チキソトロピック指数、表１には、ＴＩ〔１ｒｐｍ／１０ｒｐｍ〕と記載した）を求めた。ＴＩは、２〜８であると好ましい。表１に、これらの結果を示す。
[Evaluation of conductive adhesive]
The viscosity of the conductive adhesive was measured. First, the viscosity obtained when the obtained conductive adhesive was rotated at 25 ° C. and 1 rpm for 1 minute using a DV-1 type viscometer / No. 14 spindle (in Table 1, described as the viscosity at 1 rpm). Measured). Next, the viscosity when the conductive adhesive was rotated at 25 ° C. and 10 rpm for 1 minute using a DV-1 type viscometer / 14 spindle (described in Table 1 as viscosity at 10 rpm) Was measured. From the obtained (viscosity at 1 rpm) / 10 viscosity at 10 rpm, TI (thixotropic index, described as TI [1 rpm / 10 rpm] in Table 1) was obtained. TI is preferably 2 to 8. Table 1 shows these results.
導電性接着剤のポットライフの評価を行った。導電性接着剤を２５℃で放置し、４８時間後、ＤＶ−１型粘度計／１４号スピンドルを用いて、２５℃、１０ｒｐｍで１分間回転させたときの粘度を測定した。４８時間後の粘度変化率（単位：％、（〔４８時間後の１０ｒｐｍでの粘度〕−〔放置前の１０ｒｐｍでの粘度〕）／〔放置前の１０ｒｐｍでの粘度〕×１００−１）を求めた。この粘度変化率が、１５％未満のものが合格である。表１に、ポットライフの評価結果を示す。 The pot life of the conductive adhesive was evaluated. The conductive adhesive was allowed to stand at 25 ° C., and after 48 hours, the viscosity when rotated at 25 ° C. and 10 rpm for 1 minute was measured using a DV-1 type viscometer / No. 14 spindle. Viscosity change rate after 48 hours (unit:%, ([viscosity at 10 rpm after 48 hours] − [viscosity at 10 rpm before leaving]) / [viscosity at 10 rpm before leaving] × 100 −1 )] Asked. A viscosity change rate of less than 15% is acceptable. Table 1 shows the pot life evaluation results.
硬化後の導電性接着剤の接続抵抗値を測定方法した。搭載部品として３２１６サイズのＳｎメッキ積層コンデンサーを、基板としてＡｇ焼成厚膜を用い、本発明の導電性接着剤で接合し、１５０℃×３０分で硬化させたものを試験片とした。作製した試験片を４端子法で測定し（ｎ＝１６）、その平均値が１０ｍΩ以下のものが合格である。表１に、接続抵抗値の結果を示す。 The connection resistance value of the conductive adhesive after curing was measured. A test piece was obtained by bonding a 3216-size Sn-plated multilayer capacitor as a mounted component, using an Ag-fired thick film as a substrate, bonding with the conductive adhesive of the present invention, and curing at 150 ° C. for 30 minutes. The produced test piece was measured by a four-terminal method (n = 16), and the average value thereof was 10 mΩ or less. Table 1 shows the results of connection resistance values.
表１からわかるように、実施例１〜６の全てにおいて、粘度、ＴＩ、ポットライフ、接続抵抗値の全てで良好な結果であった。鱗片状の（Ａ）成分を用いた実施例４は、水アトマイズ粉をそのまま用いた実施例２より、ＴＩが高く、接続抵抗値が低かった。これに対して、表面酸化膜の厚さが８ｎｍと本発明に係る（Ａ）成分より薄過ぎる比較例１では、４８時間後に粘度が上昇しすぎ、ポットライフが不合格であった。一方、表面酸化膜の厚さが厚過ぎる比較例２では、接続抵抗値が不合格であった。 As can be seen from Table 1, in all of Examples 1 to 6, good results were obtained in all of the viscosity, TI, pot life, and connection resistance value. Example 4 using the scale-like (A) component had a higher TI and a lower connection resistance value than Example 2 using the water atomized powder as it was. On the other hand, in Comparative Example 1 in which the thickness of the surface oxide film was 8 nm which was too thinner than the component (A) according to the present invention, the viscosity increased too much after 48 hours, and the pot life was unacceptable. On the other hand, in Comparative Example 2 where the thickness of the surface oxide film was too thick, the connection resistance value was unacceptable.
Claims (8)
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