JP7410742B2 - Copper particle manufacturing method, copper paste and semiconductor device - Google Patents
Copper particle manufacturing method, copper paste and semiconductor device Download PDFInfo
- Publication number
- JP7410742B2 JP7410742B2 JP2020028425A JP2020028425A JP7410742B2 JP 7410742 B2 JP7410742 B2 JP 7410742B2 JP 2020028425 A JP2020028425 A JP 2020028425A JP 2020028425 A JP2020028425 A JP 2020028425A JP 7410742 B2 JP7410742 B2 JP 7410742B2
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- Prior art keywords
- copper
- acid
- group
- copper particles
- linear
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 124
- 229910052802 copper Inorganic materials 0.000 title claims description 123
- 239000010949 copper Substances 0.000 title claims description 123
- 239000002245 particle Substances 0.000 title claims description 93
- 239000004065 semiconductor Substances 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- -1 amine compound Chemical class 0.000 claims description 66
- 239000003960 organic solvent Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 16
- 150000004699 copper complex Chemical class 0.000 claims description 16
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 14
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 11
- 239000005749 Copper compound Substances 0.000 claims description 10
- 150000001880 copper compounds Chemical class 0.000 claims description 10
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 10
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 8
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000005750 Copper hydroxide Substances 0.000 claims description 5
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 4
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 32
- 239000011347 resin Substances 0.000 description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 23
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 13
- 125000001931 aliphatic group Chemical group 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 13
- 229920001187 thermosetting polymer Polymers 0.000 description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000005245 sintering Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 6
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 239000003822 epoxy resin Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 6
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 6
- 229920000647 polyepoxide Polymers 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
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- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 5
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910000431 copper oxide Inorganic materials 0.000 description 5
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 5
- 230000017525 heat dissipation Effects 0.000 description 5
- 239000002932 luster Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920005862 polyol Polymers 0.000 description 5
- 150000003077 polyols Chemical class 0.000 description 5
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical group CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
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- 150000003839 salts Chemical class 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
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- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 3
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
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- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical class [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- MUQNAPSBHXFMHT-UHFFFAOYSA-N tert-butylhydrazine Chemical compound CC(C)(C)NN MUQNAPSBHXFMHT-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- YHTQKJJDMAPMSS-UHFFFAOYSA-N undecylhydrazine Chemical compound CCCCCCCCCCCNN YHTQKJJDMAPMSS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JBCJMTUHAXHILC-UHFFFAOYSA-N zinc;octanoic acid Chemical compound [Zn+2].CCCCCCCC(O)=O JBCJMTUHAXHILC-UHFFFAOYSA-N 0.000 description 1
Description
本開示は、銅粒子の製造方法、銅ペースト及び半導体装置に関する。 The present disclosure relates to a method for manufacturing copper particles, a copper paste, and a semiconductor device.
半導体製品の大容量、高速処理化及び微細配線化に伴い半導体製品作動中に発生する熱の問題が顕著になってきており、半導体製品から熱を逃がす、いわゆるサーマルマネージメントがますます重要な課題となってきている。このため半導体製品にヒートスプレッダー、ヒートシンクなどの放熱部材を取り付ける方法などが一般的に採用されており、放熱部材を接着する材料自体の熱伝導率はより高いものが望まれてきている。
一方、半導体製品の形態によっては、サーマルマネージメントをより効率的なものとするため、半導体素子そのもの又は半導体素子を接着したリードフレームのダイパッド部にヒートスプレッダーを接着する方法及びダイパッド部をパッケージ表面に露出させることにより放熱板としての機能を持たせる方法などが採用されている(例えば、特許文献1参照)。
The issue of heat generated during semiconductor product operation has become more prominent as semiconductor products become larger in capacity, faster to process, and become finer in their wiring.So-called thermal management, which allows heat to escape from semiconductor products, is becoming an increasingly important issue. It has become to. For this reason, methods of attaching heat dissipating members such as heat spreaders and heat sinks to semiconductor products are commonly employed, and there is a growing desire for the material to which the heat dissipating members are bonded to have a higher thermal conductivity itself.
On the other hand, depending on the form of the semiconductor product, in order to make thermal management more efficient, there are methods of bonding a heat spreader to the semiconductor element itself or the die pad part of a lead frame to which the semiconductor element is attached, and exposing the die pad part to the package surface. A method has been adopted in which the heat dissipation plate is made to function as a heat sink (for example, see Patent Document 1).
また、さらには半導体素子をサーマルビアなどの放熱機構を有する有機基板などに接着する場合もある。この場合も半導体素子を接着する材料に高熱伝導性が要求される。また、近年の白色発光LEDの高輝度化により、フルカラー液晶画面のバックライト照明、シーリングライト、ダウンライト等の照明装置にも広く用いられるようになっている。ところで、発光素子の高出力化による高電流投入により、発光素子と基板とを接着する接着剤が熱及び光等で変色したり、電気抵抗値の経時変化が発生したりする問題があった。とりわけ発光素子と基板との接合を接着剤の接着力に完全に頼る方法では、電子部品のはんだ実装時に接合材料がはんだ溶融温度下に接着力を失い剥離し、不灯に至る致命的問題の懸念があった。また、白色発光LEDの高性能化は、発光素子チップの発熱量の増大を招くこととなり、これに伴いLEDの構造及びそれに使用する部材にも放熱性の向上が求められている。 Furthermore, there are cases where a semiconductor element is bonded to an organic substrate having a heat dissipation mechanism such as a thermal via. In this case as well, the material to which the semiconductor elements are bonded is required to have high thermal conductivity. In addition, due to the recent increase in the brightness of white light emitting LEDs, they have come to be widely used in lighting devices such as backlights for full-color liquid crystal screens, ceiling lights, and downlights. However, due to the high current input due to the increase in the output of light emitting elements, there have been problems such as discoloration of the adhesive that bonds the light emitting element and the substrate due to heat and light, and changes in electrical resistance over time. In particular, methods that rely entirely on the adhesive strength of adhesives to bond light-emitting elements and substrates can cause the fatal problem of the bonding material losing its adhesive strength and peeling off at the solder melting temperature when electronic components are soldered, leading to non-lighting. There were concerns. In addition, improving the performance of white light emitting LEDs results in an increase in the amount of heat generated by the light emitting element chip, and accordingly, the structure of the LED and the members used therein are also required to have improved heat dissipation.
特に、近年、電力損失の少ない炭化ケイ素(SiC)、窒化ガリウムのようなワイドバンドギャップ半導体を使用するパワー半導体装置の開発が盛んとなり、素子自身の耐熱性が高く、大電流による250℃以上の高温動作が可能となっている。しかし、その特性を発揮するためには、動作発熱を効率的に放熱する必要があり、導電性及び伝熱性に加え、長期高温耐熱性に優れた接合材料が求められている。 In particular, in recent years, the development of power semiconductor devices that use wide bandgap semiconductors such as silicon carbide (SiC) and gallium nitride with low power loss has become active, and the devices themselves have high heat resistance and High temperature operation is possible. However, in order to exhibit these characteristics, it is necessary to efficiently dissipate heat generated during operation, and there is a need for a bonding material that has excellent long-term high-temperature heat resistance in addition to electrical conductivity and heat conductivity.
このように半導体装置及び電気・電子部品の各部材の接着に用いられる材料(ダイアタッチペースト及び放熱部材接着用材料等)に高い熱伝導性が要求されている。また、これらの材料は、同時に製品の基板搭載時のリフロー処理に耐える必要もあり、さらには大面積の接着が要求される場合も多く、構成部材間の熱膨張係数の違いによる反りなどの発生を抑制するための低応力性も併せ持つ必要がある。 As described above, high thermal conductivity is required of materials used for bonding semiconductor devices and electrical/electronic components (die attach pastes, heat dissipation member bonding materials, etc.). In addition, these materials also need to withstand reflow processing when the product is mounted on a board, and are often required to be bonded over a large area, which can cause warping due to differences in thermal expansion coefficients between component parts. It is also necessary to have low stress properties to suppress this.
ここで、通常、高熱伝導性を有する接着剤を得るには、銀粉、銅粉などの金属フィラー及び窒化アルミニウム、窒化ボロンなどのセラミック系フィラーなどを充填剤として有機系のバインダーに高い含有率で分散させる必要がある(例えば、特許文献2参照)。しかし、その結果、硬化物の弾性率が高くなってしまい、良好な熱伝導性と良好なリフロー性(前記リフロー処理後に剥離が生じにくいこと)を併せ持つことは困難であった。 Generally, in order to obtain an adhesive with high thermal conductivity, metal fillers such as silver powder and copper powder, and ceramic fillers such as aluminum nitride and boron nitride are added to an organic binder at a high content. It is necessary to disperse it (for example, see Patent Document 2). However, as a result, the elastic modulus of the cured product becomes high, making it difficult to have both good thermal conductivity and good reflow properties (resistance to peeling after the reflow treatment).
ところで、銀粒子は導電性が非常に良好であるが、価格が高いこと及びマイグレーションの問題から、他の金属への代替が検討されている。そこで、現在、銀粒子と比較して安価で、マイグレーション耐性のある銅粒子に注目が集まっている。 Incidentally, silver particles have very good conductivity, but due to their high cost and migration problems, alternatives to other metals are being considered. Therefore, copper particles, which are cheaper than silver particles and have migration resistance, are currently attracting attention.
また、金属パターンの形成方法として、金、銀、銅等の金属粒子を含むペースト、インク等の導電材料をスクリーン印刷、インクジェット印刷等の手法で基材上に付与する工程と、基材上に付与した導電材料を加熱して金属粒子を融着させ、導電性を発現させる導体化工程とを有する、いわゆるプリンテッドエレクトロニクス法が知られている(例えば、特許文献3参照)。 In addition, as a method for forming a metal pattern, there is a process of applying a conductive material such as a paste or ink containing metal particles such as gold, silver, or copper onto a base material using methods such as screen printing or inkjet printing. A so-called printed electronics method is known, which includes a conductorization step of heating an applied conductive material to fuse metal particles and develop conductivity (for example, see Patent Document 3).
ところで、プリンテッドエレクトロニクス法で形成される金属パターンは、フォトリソグラフィ法で形成される金属パターンに比べて体積抵抗率が高く、基材との接着力が低くなる傾向にある。このため、低温焼結が可能で、且つ接着強度の良好なペーストが求められている。
しかしながら、銅粒子は、表面の保護分子によっては、該保護分子が銅表面に強く吸着することで保存安定性は良好となるものの、焼結温度が高くなる場合がある。
Incidentally, a metal pattern formed by a printed electronics method has a higher volume resistivity and tends to have lower adhesive strength with a base material than a metal pattern formed by a photolithography method. Therefore, there is a need for a paste that can be sintered at low temperatures and has good adhesive strength.
However, depending on the protective molecules on the surface of the copper particles, the protective molecules are strongly adsorbed to the copper surface, so that although the storage stability is good, the sintering temperature may be high.
本開示は、このような実情に鑑みてなされたものであり、低温焼結性に優れた銅粒子を得ることが可能な銅粒子の製造方法、該製造方法によって得られる銅粒子を含む銅ペースト並びに該銅ペーストを使用することで接合特性が良好であり信頼性に優れた半導体装置を提供することを目的とする。 The present disclosure has been made in view of the above circumstances, and provides a method for producing copper particles capable of obtaining copper particles having excellent low-temperature sinterability, and a copper paste containing copper particles obtained by the method. Another object of the present invention is to provide a semiconductor device with good bonding characteristics and excellent reliability by using the copper paste.
本発明者は、前記課題を解決するべく鋭意検討した結果、下記の発明により前記課題を解決できることを見出した。 As a result of intensive studies to solve the above problems, the inventors of the present invention found that the above problems could be solved by the following invention.
すなわち、本開示は、以下に関する。
[1](a)少なくとも2つ以上の3級窒素原子を有するアミン化合物及び(b)有機カルボン酸を配位子とする銅錯体(A)を還元することによる銅粒子の製造方法。
[2]前記(a)成分が、下記一般式(1)で表されるアミン化合物であり、前記(b)成分が、下記一般式(2)で表されるモノカルボン酸である上記[1]に記載の銅粒子の製造方法。
That is, the present disclosure relates to the following.
[1] A method for producing copper particles by reducing a copper complex (A) having (a) an amine compound having at least two or more tertiary nitrogen atoms and (b) an organic carboxylic acid as a ligand.
[2] The above [1] wherein the component (a) is an amine compound represented by the following general formula (1), and the component (b) is a monocarboxylic acid represented by the following general formula (2). ] The method for producing copper particles according to.
(式中、R1~R4は、それぞれ独立して直鎖状もしくは分岐状のアルキル基、または直鎖状もしくは分岐状のヒドロキシアルキル基を表し、Xは、下記一般式(i)または(ii)で示される基を表す。)
(In the formula, R 1 to R 4 each independently represent a linear or branched alkyl group or a linear or branched hydroxyalkyl group, and X represents the following general formula (i) or ( Represents the group shown in ii).)
(式中、nは0または1以上の自然数を表し、R5及びR6は、それぞれ独立して直鎖状または分岐状のアルキレン鎖を表す。*は結合部分を示す。)
(In the formula, n represents a natural number of 0 or 1 or more, and R 5 and R 6 each independently represent a linear or branched alkylene chain. * represents a bonding moiety.)
(式中、mは1以上の自然数を表し、R7及びR8は、それぞれ独立して直鎖状または分岐状のアルキレン鎖を表し、R9は、直鎖状もしくは分岐状のアルキル基、または直鎖状もしくは分岐状のヒドロキシアルキル基を表す。また、m=1のときR9とR1とは互いに結合して環を形成していてもよい。*は結合部分を示す。)
(In the formula, m represents a natural number of 1 or more, R 7 and R 8 each independently represent a linear or branched alkylene chain, R 9 represents a linear or branched alkyl group, or represents a linear or branched hydroxyalkyl group.Also, when m=1, R 9 and R 1 may be bonded to each other to form a ring. * indicates a bonding moiety.)
(式中、R10は水素原子または炭素数1~12の炭化水素基を表す。)
[3]前記銅錯体(A)が、水酸化銅、酸化銅(I)及び酸化銅(II)からなる群より選ばれる少なくとも一種の銅化合物と、前記(a)成分及び(b)成分とを反応させることにより得られる上記[1]又は[2]に記載の銅粒子の製造方法。
[4]上記[1]~[3]のいずれかに記載の銅粒子の製造方法によって得られる銅粒子を含む銅ペースト。
[5]上記[4]に記載の銅ペーストを用いて接合されてなる半導体装置。
(In the formula, R 10 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.)
[3] The copper complex (A) contains at least one copper compound selected from the group consisting of copper hydroxide, copper (I) oxide, and copper (II) oxide, and the (a) component and (b) component. The method for producing copper particles according to [1] or [2] above, which is obtained by reacting.
[4] A copper paste containing copper particles obtained by the method for producing copper particles according to any one of [1] to [3] above.
[5] A semiconductor device bonded using the copper paste described in [4] above.
本開示によれば、低温焼結性に優れた銅粒子を得ることが可能な銅粒子の製造方法、該製造方法によって得られる銅粒子を含む銅ペースト並びに該銅ペーストを使用することで接合特性が良好であり信頼性に優れた半導体装置を提供することができる。 According to the present disclosure, a method for manufacturing copper particles that can obtain copper particles with excellent low-temperature sinterability, a copper paste containing copper particles obtained by the manufacturing method, and a bonding property that can be obtained by using the copper paste. It is possible to provide a semiconductor device with good performance and excellent reliability.
以下、本開示について、一実施形態を参照しながら詳細に説明する。
なお、本明細書において、「(メタ)アクリル」とは、アクリル及び/又はメタクリルを意味し、また、「(メタ)アクリレート」とは、アクリレート及び/又はメタクリレートを意味する。
Hereinafter, the present disclosure will be described in detail with reference to one embodiment.
In addition, in this specification, "(meth)acrylic" means acrylic and/or methacryl, and "(meth)acrylate" means acrylate and/or methacrylate.
<銅粒子の製造方法>
本実施形態の銅粒子の製造方法は、(a)少なくとも2つ以上の3級窒素原子を有するアミン化合物及び(b)有機カルボン酸を配位子とする銅錯体(A)を還元する。
<Method for producing copper particles>
The method for producing copper particles of the present embodiment reduces (a) an amine compound having at least two or more tertiary nitrogen atoms and (b) a copper complex (A) having an organic carboxylic acid as a ligand.
前記銅錯体(A)は、銅化合物と、(a)少なくとも2つ以上の3級窒素原子を有するアミン化合物及び(b)有機カルボン酸とを反応させることにより得られる。また、前記銅錯体(A)を得る反応は、上記原料を混合して得られる混合物からの溶出によるものでもよい。 The copper complex (A) is obtained by reacting a copper compound with (a) an amine compound having at least two or more tertiary nitrogen atoms, and (b) an organic carboxylic acid. Moreover, the reaction for obtaining the copper complex (A) may be carried out by elution from a mixture obtained by mixing the above raw materials.
本実施形態で用いられる(a)成分のアミン化合物は、少なくとも2つ以上の3級窒素原子を有するアミン化合物である。前記(a)成分のアミン化合物は、該アミン化合物が有する窒素原子を通して金属原子に配位することができる。前記(a)成分のアミン化合物は、該アミン化合物が有する窒素原子が、炭素原子、ケイ素原子、酸素原子、イオウ原子のいずれかのみに直接結合している化合物であってもよい。 The amine compound of component (a) used in this embodiment is an amine compound having at least two or more tertiary nitrogen atoms. The amine compound of component (a) can be coordinated to a metal atom through the nitrogen atom of the amine compound. The amine compound of component (a) may be a compound in which the nitrogen atom of the amine compound is directly bonded to only one of a carbon atom, a silicon atom, an oxygen atom, and a sulfur atom.
アミン化合物中の窒素原子に炭素原子、ケイ素原子、酸素原子、イオウ原子のいずれかの原子以外の原子が直接結合している場合、例えば、水素原子が窒素原子に直接結合している場合には、アミン化合物の銅原子への吸着性が強くなりすぎるため、得られる銅粒子は焼結温度が高くなる。また、アミン化合物として1分子中に3級窒素原子が1つのアミン化合物を用いた場合には、銅錯体の形成性が悪く、銅粒子の製造性が低下する。 When an atom other than a carbon atom, silicon atom, oxygen atom, or sulfur atom is directly bonded to the nitrogen atom in the amine compound, for example, when a hydrogen atom is directly bonded to the nitrogen atom, , since the adsorption of the amine compound to copper atoms becomes too strong, the resulting copper particles have a high sintering temperature. Furthermore, when an amine compound having one tertiary nitrogen atom in one molecule is used as the amine compound, the formation of a copper complex is poor and the productivity of copper particles is reduced.
前記(a)成分のアミン化合物としては、少なくとも2つ以上の3級窒素原子を有すれば特に限定されず、例えば、脂肪族ポリアミン類、脂環式1,2-ジアミン類、置換もしくは非置換のフェニレンジアミン類、置換もしくは非置換の2,2’-ジピリジル誘導体、2-アミノアルキル置換ピリジン誘導体、1,10-フェナントロリン類、シッフ塩基化合物等が挙げられる。前記(a)成分のアミン化合物は、脂肪族ポリアミン類であってもよく、錯体形成性の観点から、下記一般式(1)で表されるアミン化合物であってもよい。 The amine compound of component (a) is not particularly limited as long as it has at least two or more tertiary nitrogen atoms, and includes, for example, aliphatic polyamines, alicyclic 1,2-diamines, substituted or unsubstituted Examples include phenylenediamines, substituted or unsubstituted 2,2'-dipyridyl derivatives, 2-aminoalkyl-substituted pyridine derivatives, 1,10-phenanthrolines, and Schiff base compounds. The amine compound of the component (a) may be an aliphatic polyamine, or from the viewpoint of complex formation, an amine compound represented by the following general formula (1).
一般式(1)中、R1~R4は、それぞれ独立して直鎖状もしくは分岐状のアルキル基、または直鎖状もしくは分岐状のヒドロキシアルキル基を表し、Xは、下記一般式(i)または(ii)で示される基を表す。 In the general formula (1), R 1 to R 4 each independently represent a linear or branched alkyl group or a linear or branched hydroxyalkyl group, and X represents the following general formula (i ) or (ii).
一般式(i)中、nは0または1以上の自然数を表し、R5及びR6は、それぞれ独立して直鎖状または分岐状のアルキレン鎖を表す。*は結合部分を示す。 In general formula (i), n represents a natural number of 0 or 1 or more, and R 5 and R 6 each independently represent a linear or branched alkylene chain. * indicates a bonding part.
一般式(ii)中、mは1以上の自然数を表し、R7及びR8は、それぞれ独立して直鎖状または分岐状のアルキレン鎖を表し、R9は、直鎖状もしくは分岐状のアルキル基、または直鎖状もしくは分岐状のヒドロキシアルキル基を表す。また、m=1のときR9とR1とは互いに結合して環を形成していてもよい。*は結合部分を示す。 In general formula (ii), m represents a natural number of 1 or more, R 7 and R 8 each independently represent a linear or branched alkylene chain, and R 9 represents a linear or branched alkylene chain. Represents an alkyl group or a linear or branched hydroxyalkyl group. Further, when m=1, R 9 and R 1 may be bonded to each other to form a ring. * indicates a bonding part.
前記R1~R4の直鎖状もしくは分岐状のアルキル基の炭素数は、1以上10以下であってもよく、1以上6以下あってもよい。アルキル基の具体例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基、ペンチル基、ヘキシル基、デシル基等が挙げられる。アルキル基は、メチル基、エチル基、であってもよく、メチル基であってもよい。 The number of carbon atoms in the linear or branched alkyl group of R 1 to R 4 may be 1 or more and 10 or less, or 1 or more and 6 or less. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, decyl group, and the like. The alkyl group may be a methyl group, an ethyl group, or a methyl group.
前記R1~R4の直鎖状もしくは分岐状のヒドロキシアルキル基の炭素数は、1以上10以下であってもよく、1以上6以下あってもよい。ヒドロキシアルキル基の具体例としては、ヒドロキシメチル基、2-ヒドロキシエチル基、2-ヒドロキシプロピル基、3-ヒドロキシプロピル基、2-ヒドロキシブチル基、3-ヒドロキシブチル基、4-ヒドロキシブチル基等が挙げられる。ヒドロキシアルキル基は、ヒドロキシメチル基、2-ヒドロキシエチル基、2-ヒドロキシプロピル基であってもよい。 The number of carbon atoms in the linear or branched hydroxyalkyl group of R 1 to R 4 may be 1 or more and 10 or less, or 1 or more and 6 or less. Specific examples of hydroxyalkyl groups include hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. Can be mentioned. The hydroxyalkyl group may be a hydroxymethyl group, 2-hydroxyethyl group, or 2-hydroxypropyl group.
前記一般式(i)中のnは0または1以上の自然数を表し、0以上10以下であってもよく、0以上6以下であってもよい。 n in the general formula (i) represents 0 or a natural number of 1 or more, and may be 0 or more and 10 or less, or 0 or more and 6 or less.
前記R5及びR6の直鎖状または分岐状のアルキレン鎖の炭素数は、1以上12以下であってもよく、3以上6以下であってもよい。アルキレン鎖の具体例としては、メチレン鎖、エチレン鎖、プロピレン鎖等が挙げられる。アルキレン鎖は、エチレン鎖であってもよい。 The linear or branched alkylene chain of R 5 and R 6 may have 1 or more and 12 or less carbon atoms, or 3 or more and 6 or less. Specific examples of alkylene chains include methylene chains, ethylene chains, propylene chains, and the like. The alkylene chain may be an ethylene chain.
前記一般式(ii)中のmは1以上の自然数を表し、1以上10以下であってもよく、1以上6以下であってもよい。 m in the general formula (ii) represents a natural number of 1 or more, and may be 1 or more and 10 or less, or 1 or more and 6 or less.
前記R7及びR8の直鎖状または分岐状のアルキレン鎖の炭素数は、1以上12以下であってもよく、3以上6以下であってもよい。アルキレン鎖の具体例としては、前記R5及びR6で例示したものを挙げることができる。アルキレン鎖は、エチレン鎖であってもよい。 The linear or branched alkylene chain of R 7 and R 8 may have 1 or more and 12 or less carbon atoms, or 3 or more and 6 or less. Specific examples of the alkylene chain include those exemplified above for R 5 and R 6 . The alkylene chain may be an ethylene chain.
前記R9の直鎖状もしくは分岐状のアルキル基の炭素数は、1以上10以下であってもよく、1以上6以下あってもよい。アルキル基の具体例としては、前記R1~R4で例示したものを挙げることができる。アルキル基は、メチル基、エチル基であってもよい。
前記R9の直鎖状もしくは分岐状のヒドロキシアルキル基の炭素数は、1以上10以下であってもよく、1以上6以下あってもよい。ヒドロキシアルキル基の具体例としては、前記R1~R4で例示したものを挙げることができる。
The number of carbon atoms in the linear or branched alkyl group of R 9 may be 1 or more and 10 or less, or 1 or more and 6 or less. Specific examples of the alkyl group include those exemplified for R 1 to R 4 above. The alkyl group may be a methyl group or an ethyl group.
The number of carbon atoms in the linear or branched hydroxyalkyl group of R 9 may be 1 or more and 10 or less, or 1 or more and 6 or less. Specific examples of the hydroxyalkyl group include those exemplified for R 1 to R 4 above.
また、前記R9とR1とが互いに結合して環を形成する場合、環を構成する炭素原子と窒素原子の和は5以上20以下あってもよく、5以上10以下であってもよい。 Further, when R 9 and R 1 are combined with each other to form a ring, the sum of carbon atoms and nitrogen atoms constituting the ring may be 5 or more and 20 or less, or 5 or more and 10 or less. .
前記脂肪族ポリアミン類としては、例えば、N,N,N’,N’-テトラメチルエチレンジアミン、N,N,N’,N’-テトラエチルエチレンジアミン、N,N,N’,N”,N”-ペンタメチルジエチレントリアミン、N,N,N’,N’-テトラメチル-1,3-プロパンジアミン、1,1,2,2-テトラキス(ジメチルアミノ)エタン等の脂肪族ポリアルキレンポリアミン類;N,N,N’,N’-テトラキス(2-ヒドロキシプロピル)エチレンジアミン、ペントロール、1,3-ビス[トリス(ヒドロキシメチル)メチルアミノ]プロパン等のポリアルカノールポリアルキレンポリアミン類等が挙げられる。
前記脂肪族ポリアミン類は、反応の容易さ、高イオン伝導性の観点から、脂肪族ポリアルキレンポリアミン類であってもよく、N,N,N',N'-テトラメチルエチレンジアミン、N,N,N',N'-テトラエチルエチレンジアミンであってもよい。
Examples of the aliphatic polyamines include N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N',N",N"- Aliphatic polyalkylene polyamines such as pentamethyldiethylenetriamine, N,N,N',N'-tetramethyl-1,3-propanediamine, 1,1,2,2-tetrakis(dimethylamino)ethane; N,N , N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, pentrol, and polyalkanol polyalkylene polyamines such as 1,3-bis[tris(hydroxymethyl)methylamino]propane.
The aliphatic polyamines may be aliphatic polyalkylene polyamines from the viewpoint of ease of reaction and high ionic conductivity, and include N,N,N',N'-tetramethylethylenediamine, N,N, It may also be N',N'-tetraethylethylenediamine.
前記脂環式1,2-ジアミン類としては、例えば、N,N,N’,N’,-テトラメチル-1,2-ジアミノシクロヘキサン、N,N,N’,N’-テトラキス(2-ヒドロキシプロピル)-1,2-ジアミノシクロヘキサン等が挙げられる。
前記置換もしくは非置換のフェニレンジアミン類としては、例えば、N,N,N’,N’-テトラメチル-1,4-フェニレンジアミン等が挙げられる。
前記置換もしくは非置換の2,2’-ジピリジル誘導体としては、例えば、2,2’-ジピリジル、4,4’-ジメチル-2,2’-ジピリジル、2,2’:6’,2”-ターピリジン等が挙げられる。
前記2-アミノアルキル置換ピリジン誘導体としては、例えば、2-(2-ジメチルアミノエチル)ピリジン、2-(2-ピペリジノエチル)ピリジン、2-ジメチルアミノメチルピリジン、2,6-ジ(2-ジメチルアミノエチル)ピリジン等が挙げられる。
前記1,10-フェナントロリン類としては、例えば、1,10-フェナントロリン、4,7-ジメトキシ-1,10-フェナントロリン、2,9-ジメチル-1,10-フェナントロリン等が挙げられる。
前記シッフ塩基化合物としては、例えば、N,N’-ビス(サリチリデン)エチレンジアミン、N,N’-ビス(サリチリデン)-1,3-プロパンジアミン等が挙げられる。
Examples of the alicyclic 1,2-diamines include N,N,N',N',-tetramethyl-1,2-diaminocyclohexane, N,N,N',N'-tetrakis(2- (hydroxypropyl)-1,2-diaminocyclohexane and the like.
Examples of the substituted or unsubstituted phenylenediamines include N,N,N',N'-tetramethyl-1,4-phenylenediamine.
Examples of the substituted or unsubstituted 2,2'-dipyridyl derivatives include 2,2'-dipyridyl, 4,4'-dimethyl-2,2'-dipyridyl, 2,2':6',2''- Examples include terpyridine.
Examples of the 2-aminoalkyl-substituted pyridine derivatives include 2-(2-dimethylaminoethyl)pyridine, 2-(2-piperidinoethyl)pyridine, 2-dimethylaminomethylpyridine, 2,6-di(2-dimethylamino ethyl)pyridine, etc.
Examples of the 1,10-phenanthrolines include 1,10-phenanthroline, 4,7-dimethoxy-1,10-phenanthroline, and 2,9-dimethyl-1,10-phenanthroline.
Examples of the Schiff base compound include N,N'-bis(salicylidene)ethylenediamine, N,N'-bis(salicylidene)-1,3-propanediamine, and the like.
本実施形態で用いられる(b)成分の有機カルボン酸は、特に限定されず、モノカルボン酸、ジカルボン酸、トリカルボン酸等が挙げられる。(b)成分の有機カルボン酸は、例えば、下記一般式(2)で表されるモノカルボン酸であってもよい。また、(b)成分の有機カルボン酸は、飽和と不飽和とを問わない。 The organic carboxylic acid as the component (b) used in this embodiment is not particularly limited, and examples thereof include monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, and the like. The organic carboxylic acid of component (b) may be, for example, a monocarboxylic acid represented by the following general formula (2). Moreover, the organic carboxylic acid of component (b) may be saturated or unsaturated.
一般式(2)中、R10は水素原子または炭素数1~12の炭化水素基を表す。
前記R10の炭素数1~12の炭化水素基としては、炭素数1~12の飽和脂肪族炭化水素基、炭素数2~12の不飽和脂肪族炭化水素基等が挙げられる。前記飽和脂肪族炭化水素基及び不飽和脂肪族炭化水素基は、直鎖状であってもよく、分岐状であってもよい。また、前記炭化水素基は、置換基を有していてもよく、該置換基としては、例えば、水酸基、アシル基、アミノ基等が挙げられる。
In the general formula (2), R 10 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.
Examples of the hydrocarbon group having 1 to 12 carbon atoms for R 10 include saturated aliphatic hydrocarbon groups having 1 to 12 carbon atoms, unsaturated aliphatic hydrocarbon groups having 2 to 12 carbon atoms, and the like. The saturated aliphatic hydrocarbon group and unsaturated aliphatic hydrocarbon group may be linear or branched. Further, the hydrocarbon group may have a substituent, and examples of the substituent include a hydroxyl group, an acyl group, and an amino group.
前記炭素数1~12の飽和脂肪族炭化水素基としては、炭素数1~12のアルキル基が挙げられる。炭素数1~12のアルキル基としては、例えば、メチル基、エチル基、プロピル基、各種ブチル基、各種ペンチル基、各種ヘキシル基、各種ヘプチル基、各種オクチル基、各種ノニル基、各種デシル基、各種ドデシル基が挙げられる。また、前記炭素数1~12のアルキル基の1又は2以上の水素原子は、ハロゲン原子で置換されていてもよい。
前記炭素数2~12の不飽和脂肪族炭化水素基としては、例えば、ビニル基、各種ブテニル基、各種ヘキセニル基、各種ヘプテニル基、各種オクテニル基、各種ノネニル基、各種デセニル基、各種ドデセニル基等が挙げられる。
The saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms includes an alkyl group having 1 to 12 carbon atoms. Examples of alkyl groups having 1 to 12 carbon atoms include methyl groups, ethyl groups, propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, Examples include various dodecyl groups. Further, one or more hydrogen atoms of the alkyl group having 1 to 12 carbon atoms may be substituted with a halogen atom.
Examples of the unsaturated aliphatic hydrocarbon group having 2 to 12 carbon atoms include vinyl groups, various butenyl groups, various hexenyl groups, various heptenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, various dodecenyl groups, etc. can be mentioned.
前記(b)成分の有機カルボン酸の具体例としては、ギ酸、酢酸、プロピオン酸、酪酸、イソ酪酸、吉草酸、イソ吉草酸、ヘキサン酸、4-メチル吉草酸、ヘプタン酸、ウンデカン酸、イコサン酸などの飽和脂肪族のモノカルボン酸;モノクロロ酢酸、ジクロロ酢酸、トリクロロ酢酸などのハロゲンを含有する飽和脂肪族のモノカルボン酸;アセトキシコハク酸、アセト酢酸、エトキシ酢酸、4-オキソ吉草酸、グリコール酸、グリシド酸、グリセリン酸、2-オキソ酪酸、グルタル酸などの置換基を含有する飽和脂肪族のモノカルボン酸;プロピオル酸、アクリル酸、クロトン酸、4-ペンテン酸、アリルマロン酸、イタコン酸、オキサロ酢酸などの不飽和脂肪族のモノカルボン酸;シュウ酸、マロン酸、コハク酸、アジピン酸、3-オキソグルタル酸、アゼライン酸、エチルマロン酸、3-オキソヘプタン酸、3-オキソグルタル酸などの飽和脂肪族のジカルボン酸;アセチレンジカルボン酸などの不飽和脂肪族のジカルボン酸;アコニット酸、イソカンホロン酸などのトリカルボン酸;アミノ酪酸、アラニンなどのアミノ酸;などが挙げられる。これらは単独で用いてもよく、2種以上を併用してもよい。
前記(b)成分の有機カルボン酸は、有機溶媒への分散しやすさ、及び形成された金属錯体の生成物の性状、の観点から、飽和脂肪族のモノカルボン酸であってもよく、ヘキサン酸、ヘプタン酸であってもよく、ヘキサン酸であってもよい。
Specific examples of the organic carboxylic acid of component (b) include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, hexanoic acid, 4-methylvaleric acid, heptanoic acid, undecanoic acid, and icosane. Saturated aliphatic monocarboxylic acids such as acids; halogen-containing saturated aliphatic monocarboxylic acids such as monochloroacetic acid, dichloroacetic acid, trichloroacetic acid; acetoxysuccinic acid, acetoacetic acid, ethoxyacetic acid, 4-oxovaleric acid, glycol saturated aliphatic monocarboxylic acids containing substituents such as glycidic acid, glyceric acid, 2-oxobutyric acid, glutaric acid; propiolic acid, acrylic acid, crotonic acid, 4-pentenoic acid, allylmalonic acid, itaconic acid, Unsaturated aliphatic monocarboxylic acids such as oxaloacetic acid; saturated such as oxalic acid, malonic acid, succinic acid, adipic acid, 3-oxoglutaric acid, azelaic acid, ethylmalonic acid, 3-oxoheptanoic acid, 3-oxoglutaric acid, etc. Aliphatic dicarboxylic acids; unsaturated aliphatic dicarboxylic acids such as acetylene dicarboxylic acid; tricarboxylic acids such as aconitic acid and isocamphoronic acid; amino acids such as aminobutyric acid and alanine; and the like. These may be used alone or in combination of two or more.
The organic carboxylic acid of component (b) may be a saturated aliphatic monocarboxylic acid from the viewpoint of ease of dispersion in an organic solvent and the properties of the formed metal complex product, and hexane The acid may be heptanoic acid or hexanoic acid.
本実施形態で用いられる銅化合物は、銅原子を含むものであれば特に限定されるものではない。銅化合物としては、例えば、カルボン酸銅、酸化銅、水酸化銅、窒化銅等が挙げられる。銅粒子の収率の観点から水酸化銅、酸化銅であってもよい。また、これらは単独で用いてもよく、2種以上を併用してもよい。 The copper compound used in this embodiment is not particularly limited as long as it contains copper atoms. Examples of the copper compound include copper carboxylate, copper oxide, copper hydroxide, copper nitride, and the like. From the viewpoint of the yield of copper particles, copper hydroxide or copper oxide may be used. Further, these may be used alone or in combination of two or more.
酸化銅としては、酸化銅(II)、酸化銅(I)が挙げられ、生産性の観点から酸化銅(I)であってもよい。また、水酸化銅としては、水酸化銅(II)、水酸化銅(I)が挙げられる。
これらは単独で用いてもよく、2種以上を併用してもよい。
Examples of copper oxide include copper (II) oxide and copper (I) oxide, and from the viewpoint of productivity, copper (I) oxide may be used. Further, examples of copper hydroxide include copper (II) hydroxide and copper (I) hydroxide.
These may be used alone or in combination of two or more.
前記銅化合物と、(a)少なくとも2つ以上の3級窒素原子を有するアミン化合物と、(b)有機カルボン酸とは、有機溶剤中で混合してもよい。
有機溶剤は、上述の各原料を混合して得られる混合物から生成する銅錯体(A)等の性質を阻害しない反応溶媒として用いることができるものであれば、特に限定されずに使用することができる。
The copper compound, (a) the amine compound having at least two or more tertiary nitrogen atoms, and (b) the organic carboxylic acid may be mixed in an organic solvent.
The organic solvent may be used without particular limitation as long as it can be used as a reaction solvent that does not inhibit the properties of the copper complex (A) etc. produced from the mixture obtained by mixing the above-mentioned raw materials. can.
銅錯体(A)の生成後、連続して該銅錯体(A)の還元を行う場合、有機溶剤は、後述する還元性化合物に対して相溶性を示すアルコールであってもよい。また、有機溶剤は、還元性化合物による銅イオンの還元反応が発熱反応であることから、還元反応中に揮発しない有機溶剤であってもよい。有機溶剤はその沸点が70℃以上であり、炭素、水素及び酸素から構成されていてもよい。 When the copper complex (A) is continuously reduced after the production of the copper complex (A), the organic solvent may be an alcohol that is compatible with the reducing compound described below. Moreover, since the reduction reaction of copper ions by a reducing compound is an exothermic reaction, the organic solvent may be an organic solvent that does not volatilize during the reduction reaction. The organic solvent has a boiling point of 70° C. or higher and may be composed of carbon, hydrogen, and oxygen.
有機溶剤として用いられる前記アルコールとしては、1-プロパノール、2-プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、エチレングリコール、1,3-プロパンジオール、1,2-プロパンジオール、ブチルカルビトール、ブチルカルビトールアセテート、エチルカルビトール、エチルカルビトールアセテート、ジエチレングリコールジエチルエーテル、ブチルセロソルブ等が挙げられる。これらは単独で用いてもよく、2種以上を併用してもよい。 The alcohols used as organic solvents include 1-propanol, 2-propanol, butanol, pentanol, hexanol, heptanol, octanol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, butyl carbitol, Examples include butyl carbitol acetate, ethyl carbitol, ethyl carbitol acetate, diethylene glycol diethyl ether, butyl cellosolve, and the like. These may be used alone or in combination of two or more.
銅化合物、(a)成分のアミン化合物及び(b)成分の有機カルボン酸の使用量は、銅化合物1molに対し、(a)成分のアミン化合物は1~100mol、(b)成分の有機カルボン酸は0.1~100molであってもよく、(a)成分のアミン化合物は2~10mol、(b)成分の有機カルボン酸は1~10molであってもよい。 The amounts of the copper compound, the amine compound as the component (a), and the organic carboxylic acid as the component (b) are 1 to 100 mol of the amine compound as the component (a) and the organic carboxylic acid as the component (b) per 1 mol of the copper compound. may be 0.1 to 100 mol, the amine compound as component (a) may be 2 to 10 mol, and the organic carboxylic acid as component (b) may be 1 to 10 mol.
前記混合は、加熱温度10~120℃で0.1~10時間の条件で行ってもよく、加熱温度80~110℃で0.1~4時間の条件で行ってもよい。 The mixing may be carried out at a heating temperature of 10 to 120°C for 0.1 to 10 hours, or may be carried out at a heating temperature of 80 to 110°C for 0.1 to 4 hours.
このようにして得られる銅錯体(A)を還元することで銅粒子を得ることができる。
前記銅錯体(A)を還元する還元性化合物としては、該銅錯体(A)を還元し、金属銅を遊離させる還元力を有するものであれば、特に限定されない。
還元性化合物としては、典型的には、ヒドラジン誘導体が挙げられる。ヒドラジン誘導体としては、例えば、ヒドラジン一水和物、メチルヒドラジン、エチルヒドラジン、n-プロピルヒドラジン、i-プロピルヒドラジン、n-ブチルヒドラジン、i-ブチルヒドラジン、sec-ブチルヒドラジン、t-ブチルヒドラジン、n-ペンチルヒドラジン、i-ペンチルヒドラジン、neo-ペンチルヒドラジン、t-ペンチルヒドラジン、n-ヘキシルヒドラジン、i-ヘキシルヒドラジン、n-ヘプチルヒドラジン、n-オクチルヒドラジン、n-ノニルヒドラジン、n-デシルヒドラジン、n-ウンデシルヒドラジン、n-ドデシルヒドラジン、シクロヘキシルヒドラジン、フェニルヒドラジン、4-メチルフェニルヒドラジン、ベンジルヒドラジン、2-フェニルエチルヒドラジン、2-ヒドラジノエタノール、アセトヒドラジン等が挙げられる。これらは単独で用いてもよく、2種以上を併用してもよい。
Copper particles can be obtained by reducing the copper complex (A) obtained in this way.
The reducing compound that reduces the copper complex (A) is not particularly limited as long as it has the reducing power to reduce the copper complex (A) and liberate metallic copper.
Typical reducing compounds include hydrazine derivatives. Examples of hydrazine derivatives include hydrazine monohydrate, methylhydrazine, ethylhydrazine, n-propylhydrazine, i-propylhydrazine, n-butylhydrazine, i-butylhydrazine, sec-butylhydrazine, t-butylhydrazine, n -Pentylhydrazine, i-pentylhydrazine, neo-pentylhydrazine, t-pentylhydrazine, n-hexylhydrazine, i-hexylhydrazine, n-heptylhydrazine, n-octylhydrazine, n-nonylhydrazine, n-decylhydrazine, n -undecylhydrazine, n-dodecylhydrazine, cyclohexylhydrazine, phenylhydrazine, 4-methylphenylhydrazine, benzylhydrazine, 2-phenylethylhydrazine, 2-hydrazinoethanol, acetohydrazine and the like. These may be used alone or in combination of two or more.
還元性化合物の使用量は、銅化合物1molに対し、0.5~10molであってもよく、0.6~4molであってもよい。 The amount of the reducing compound used may be 0.5 to 10 mol, or 0.6 to 4 mol, per 1 mol of the copper compound.
有機溶剤は前記各成分が十分に反応を行うことができる量であればよく、例えば、50~2000mL程度用いるようにすればよい。 The organic solvent may be used in an amount that allows each of the components to react sufficiently, and for example, about 50 to 2000 mL may be used.
前記銅錯体(A)の還元反応は、加熱温度10~120℃で0.1~24時間の条件で行ってもよく、加熱温度80~110℃で1~4時間の条件で行ってもよい。加熱温度が前記範囲内であると基質の残留がなく、かつ独立性の高い粒子を得ることができる。 The reduction reaction of the copper complex (A) may be carried out at a heating temperature of 10 to 120°C for 0.1 to 24 hours, or may be carried out at a heating temperature of 80 to 110°C for 1 to 4 hours. . When the heating temperature is within the above range, no substrate remains and particles with high independence can be obtained.
このようにして得られる銅粒子の平均粒子径は、焼結性の観点から、1~1000nmであってもよく、20~800nmであってもよく、30~500nmであってもよい。
なお、前記銅粒子の平均粒子径は、走査電子顕微鏡(例えば、日本電子(株)製、商品名:JSM-7600F;SEM)の観察画像に基づく任意に選択した10個の銅粒子(n=10)の平均値として算出する。なお、平均値は算術平均値であり、その算出にあたっては10個以上の銅粒子を用いてもよい。
The average particle diameter of the copper particles thus obtained may be 1 to 1000 nm, 20 to 800 nm, or 30 to 500 nm from the viewpoint of sinterability.
Note that the average particle diameter of the copper particles is determined by the average particle diameter of 10 arbitrarily selected copper particles (n = Calculated as the average value of 10). Note that the average value is an arithmetic average value, and 10 or more copper particles may be used in calculating the average value.
<銅ペースト>
本実施形態の銅ペーストは、上述の銅粒子の製造方法によって得られる銅粒子を含むことから、低温焼結性及び接合強度に優れる。
<Copper paste>
The copper paste of this embodiment contains copper particles obtained by the above-described copper particle manufacturing method, and therefore has excellent low-temperature sinterability and bonding strength.
本実施形態の銅ペーストは、上述の銅粒子として、2つ以上の異なる平均粒子径の銅粒子を併用してもよい。例えば、第一の銅粒子の平均粒子径に対して、該第一の銅粒子よりも大きい平均粒子径を有する第二の銅粒子の平均粒子径は2~10倍程度であってもよい。また、第一の銅粒子の配合量に対して、第二の銅粒子の配合量は1.5~10倍程度であであってもよい。 In the copper paste of this embodiment, two or more copper particles having different average particle diameters may be used in combination as the above-mentioned copper particles. For example, the average particle size of the second copper particles having a larger average particle size than the first copper particles may be about 2 to 10 times the average particle size of the first copper particles. Furthermore, the amount of the second copper particles may be about 1.5 to 10 times the amount of the first copper particles.
本実施形態の銅ペーストは上述の銅粒子以外に、上述の銅粒子よりも粒径の大きい大粒径銅粒子、熱硬化性樹脂、有機溶剤、その他添加剤を含んでもよい。これにより、銅粒子の焼結収縮の影響を緩和し、さらに基板との接合強度を高めることができる。 In addition to the above-mentioned copper particles, the copper paste of this embodiment may also contain large-sized copper particles having a larger particle size than the above-mentioned copper particles, a thermosetting resin, an organic solvent, and other additives. Thereby, the influence of sintering shrinkage of the copper particles can be alleviated, and the bonding strength with the substrate can be further increased.
(大粒径銅粒子)
大粒径銅粒子は、平均粒子径が1μmよりも大きく30μm以下であってもよく、2~20μmであってもよい。また、形状は特に限定されず、球状、プレート型、フレーク状、鱗片状、樹枝状、ロッド状、ワイヤー状等が使用できる。
なお、前記大粒径銅粒子の平均粒子径は、レーザー回折散乱式粒度分布測定装置等を用いて測定することができる。
(Large diameter copper particles)
The large-sized copper particles may have an average particle size of more than 1 μm and 30 μm or less, or 2 to 20 μm. Further, the shape is not particularly limited, and spherical, plate-shaped, flake-shaped, scale-shaped, dendritic, rod-shaped, wire-shaped, etc. can be used.
The average particle size of the large-sized copper particles can be measured using a laser diffraction scattering particle size distribution analyzer or the like.
前記大粒径銅粒子は、滑材、防錆剤で処理されているものを使用してもよい。このような処理として典型的なものは、カルボン酸化合物による処理である。カルボン酸化合物としては、例えば、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、カプリル酸、オクチル酸、ノナン酸、カプリン酸、パルミチン酸、オレイン酸、ステアリン酸、イソステアリン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ジグリコール酸、安息香酸、フタル酸、イソフタル酸、テレフタル酸、サリチル酸、没食子酸、グリコール酸、乳酸、タルトロン酸、リンゴ酸、グリセリン酸、ヒドロキシ酪酸、酒石酸、クエン酸、イソクエン酸などが挙げられる。銅粒子との焼結性の観点から、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、カプリル酸、オクチル酸、ノナン酸、カプリン酸、パルミチン酸、オレイン酸、ステアリン酸、イソステアリン酸、シュウ酸、マロン酸、コハク酸、グルタル酸であってもよく、銅粒子の分散性および耐酸化性の観点から、カプロン酸、カプリル酸、オクチル酸、ノナン酸、カプリン酸、マロン酸、コハク酸、グルタル酸であってもよい。 The large-sized copper particles may be treated with a lubricant or a rust preventive agent. A typical example of such treatment is treatment with a carboxylic acid compound. Examples of carboxylic acid compounds include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, octylic acid, nonanoic acid, capric acid, palmitic acid, oleic acid, stearic acid, isostearic acid, oxalic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, diglycolic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, glycolic acid, lactic acid, Examples include tartronic acid, malic acid, glyceric acid, hydroxybutyric acid, tartaric acid, citric acid, and isocitric acid. From the viewpoint of sinterability with copper particles, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, octylic acid, nonanoic acid, capric acid, palmitic acid, oleic acid, stearic acid, isostearic acid, Oxalic acid, malonic acid, succinic acid, and glutaric acid may be used, and from the viewpoint of dispersibility and oxidation resistance of copper particles, caproic acid, caprylic acid, octylic acid, nonanoic acid, capric acid, malonic acid, and succinic acid. , glutaric acid.
本実施形態の銅ペーストが前記大粒径銅粒子を含有する場合、その含有量は、前記銅粒子100質量部に対し、20~80質量部であってもよく、40~60質量部であってもよい。 When the copper paste of the present embodiment contains the large-sized copper particles, the content may be 20 to 80 parts by mass, or 40 to 60 parts by mass, based on 100 parts by mass of the copper particles. It's okay.
(熱硬化性樹脂)
熱硬化性樹脂は、一般に接着剤用途として使用される熱硬化性樹脂であれば特に限定されずに使用できる。熱硬化性樹脂は、液状樹脂であってもよく、室温(25℃)で液状である樹脂であってもよい。前記熱硬化性樹脂としては、例えば、シアネート樹脂、エポキシ樹脂、ラジカル重合性のアクリル樹脂、マレイミド樹脂などが挙げられる。これらは単独で用いてもよく、2種以上を併用してもよい。
本実施形態の銅ペーストが熱硬化性樹脂を含むことで、適度な粘度を有する接着材料(ペースト)とすることができる。また、本実施形態の銅ペーストが熱硬化性樹脂を含むと、その硬化時の反応熱によって銅ペーストの温度が上昇し、銅粒子の焼結性を促進させる。
(thermosetting resin)
The thermosetting resin is not particularly limited and can be used as long as it is a thermosetting resin that is generally used for adhesives. The thermosetting resin may be a liquid resin or a resin that is liquid at room temperature (25° C.). Examples of the thermosetting resin include cyanate resin, epoxy resin, radically polymerizable acrylic resin, and maleimide resin. These may be used alone or in combination of two or more.
Since the copper paste of this embodiment contains a thermosetting resin, it can be an adhesive material (paste) having an appropriate viscosity. Moreover, when the copper paste of this embodiment contains a thermosetting resin, the temperature of the copper paste increases due to reaction heat during curing, promoting sinterability of the copper particles.
シアネート樹脂は、分子内に-NCO基を有する化合物であり、加熱により-NCO基が反応することで3次元的網目構造を形成し、硬化する樹脂である。具体的に例示すると、1,3-ジシアナトベンゼン、1,4-ジシアナトベンゼン、1,3,5-トリシアナトベンゼン、1,3-ジシアナトナフタレン、1,4-ジシアナトナフタレン、1,6-ジシアナトナフタレン、1,8-ジシアナトナフタレン、2,6-ジシアナトナフタレン、2,7-ジシアナトナフタレン、1,3,6-トリシアナトナフタレン、4,4’-ジシアナトビフェニル、ビス(4-シアナトフェニル)メタン、ビス(3,5-ジメチル-4-シアナトフェニル)メタン、2,2-ビス(4-シアナトフェニル)プロパン、2,2-ビス(3,5-ジブロモ-4-シアナトフェニル)プロパン、ビス(4-シアナトフェニル)エーテル、ビス(4-シアナトフェニル)チオエーテル、ビス(4-シアナトフェニル)スルホン、トリス(4-シアナトフェニル)ホスファイト、トリス(4-シアナトフェニル)ホスフェート、及びノボラック樹脂とハロゲン化シアンとの反応により得られるシアネート類などが挙げられる。また、これらの多官能シアネート樹脂のシアネート基を三量化することによって形成されるトリアジン環を有するプレポリマーも使用できる。該プレポリマーは、前記の多官能シアネート樹脂モノマーを、例えば、鉱酸、ルイス酸などの酸、ナトリウムアルコラート、第三級アミン類などの塩基、炭酸ナトリウムなどの塩類、を触媒として重合させることにより得られる。 Cyanate resin is a compound having an -NCO group in its molecule, and is a resin that forms a three-dimensional network structure by reacting the -NCO group when heated, and is cured. Specific examples include 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1, 6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis (4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane, 2,2-bis(3,5-dibromo -4-cyanatophenyl)propane, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, tris(4-cyanatophenyl)phosphite, Examples include tris(4-cyanatophenyl) phosphate and cyanates obtained by reacting a novolak resin with cyanogen halide. Furthermore, prepolymers having triazine rings formed by trimerizing the cyanate groups of these polyfunctional cyanate resins can also be used. The prepolymer is produced by polymerizing the polyfunctional cyanate resin monomer using, for example, an acid such as a mineral acid or a Lewis acid, a base such as sodium alcoholate or tertiary amines, or a salt such as sodium carbonate as a catalyst. can get.
シアネート樹脂の硬化促進剤としては、一般に公知のものが使用できる。例えば、オクチル酸亜鉛、オクチル酸錫、ナフテン酸コバルト、ナフテン酸亜鉛、アセチルアセトン鉄などの有機金属錯体、塩化アルミニウム、塩化錫、塩化亜鉛などの金属塩、トリエチルアミン、ジメチルベンジルアミンなどのアミン類が挙げられるが、これらに限定されるものではない。これらの硬化促進剤は1種又は2種以上混合して用いることができる。 Generally known cyanate resin curing accelerators can be used. Examples include organometallic complexes such as zinc octylate, tin octylate, cobalt naphthenate, zinc naphthenate, iron acetylacetonate, metal salts such as aluminum chloride, tin chloride, and zinc chloride, and amines such as triethylamine and dimethylbenzylamine. However, it is not limited to these. These curing accelerators can be used alone or in combination of two or more.
エポキシ樹脂は、グリシジル基を分子内に1つ以上有する化合物であり、加熱によりグリシジル基が反応することで3次元的網目構造を形成し、硬化する樹脂である。グリシジル基は1分子に2つ以上含まれていてもよい。これはグリシジル基が1つの化合物のみでは反応させても十分な硬化物特性を示すことができないからである。グリシジル基を1分子に2つ以上含む化合物は、2つ以上の水酸基を有する化合物をエポキシ化して得ることができる。このような化合物としては、ビスフェノールA、ビスフェノールF、ビフェノールなどのビスフェノール化合物又はこれらの誘導体、水素添加ビスフェノールA、水素添加ビスフェノールF、水素添加ビフェノール、シクロヘキサンジオール、シクロヘキサンジメタノール、シクロヘキサンジエタノールなどの脂環構造を有するジオール又はこれらの誘導体、ブタンジオール、ヘキサンジオール、オクタンジオール、ノナンジオール、デカンジオールなどの脂肪族ジオール又はこれらの誘導体などをエポキシ化した2官能のもの、トリヒドロキシフェニルメタン骨格、アミノフェノール骨格を有する化合物などをエポキシ化した3官能のもの、フェノールノボラック樹脂、クレゾールノボラック樹脂、フェノールアラルキル樹脂、ビフェニルアラルキル樹脂、ナフトールアラルキル樹脂などをエポキシ化した多官能のものなどが挙げられるが、これらに限定されるわけではない。また、前記エポキシ樹脂は、銅ペーストとして室温(25℃)でペースト状とするため、単独で又は混合物として室温(25℃)で液状のものでもよい。通常行われるように反応性希釈剤を使用することも可能である。反応性希釈剤としては、フェニルグリシジルエーテル、クレジルグリシジルエーテルなどの1官能の芳香族グリシジルエーテル類、脂肪族グリシジルエーテル類などが挙げられる。 Epoxy resin is a compound that has one or more glycidyl groups in its molecule, and is a resin that forms a three-dimensional network structure and cures when the glycidyl groups react with heat. Two or more glycidyl groups may be contained in one molecule. This is because a compound having only one glycidyl group cannot exhibit sufficient cured properties even if reacted. A compound containing two or more glycidyl groups per molecule can be obtained by epoxidizing a compound having two or more hydroxyl groups. Such compounds include bisphenol compounds such as bisphenol A, bisphenol F, and biphenol, or derivatives thereof, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, and alicyclic compounds such as cyclohexanediol, cyclohexanedimethanol, and cyclohexanediethanol. diols having a structure or derivatives thereof, difunctional diols obtained by epoxidizing aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol, decanediol, or derivatives thereof, trihydroxyphenylmethane skeleton, aminophenol These include trifunctional compounds made by epoxidizing compounds with skeletons, and multifunctional compounds made by epoxidizing phenol novolac resins, cresol novolac resins, phenol aralkyl resins, biphenylaralkyl resins, naphthol aralkyl resins, etc. It is not limited. Further, the epoxy resin may be in a liquid state at room temperature (25° C.) alone or as a mixture in order to form the copper paste into a paste form at room temperature (25° C.). It is also possible to use reactive diluents as is customary. Examples of the reactive diluent include monofunctional aromatic glycidyl ethers such as phenyl glycidyl ether and cresyl glycidyl ether, and aliphatic glycidyl ethers.
このとき、エポキシ樹脂を硬化させる目的で硬化剤を使用するが、エポキシ樹脂の硬化剤としては、例えば、脂肪族アミン、芳香族アミン、ジシアンジアミド、ジヒドラジド化合物、酸無水物、フェノール樹脂などが挙げられる。ジヒドラジド化合物としては、アジピン酸ジヒドラジド、ドデカン酸ジヒドラジド、イソフタル酸ジヒドラジド、p-オキシ安息香酸ジヒドラジドなどのカルボン酸ジヒドラジドなどが挙げられ、酸無水物としては、フタル酸無水物、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、エンドメチレンテトラヒドロフタル酸無水物、ドデセニルコハク酸無水物、無水マレイン酸とポリブタジエンの反応物、無水マレイン酸とスチレンの共重合体などが挙げられる。 At this time, a curing agent is used for the purpose of curing the epoxy resin, and examples of curing agents for epoxy resin include aliphatic amines, aromatic amines, dicyandiamide, dihydrazide compounds, acid anhydrides, and phenolic resins. . Examples of dihydrazide compounds include carboxylic acid dihydrazides such as adipic acid dihydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, and p-oxybenzoic acid dihydrazide, and examples of acid anhydrides include phthalic acid anhydride, tetrahydrophthalic anhydride, and hexahydrazide. Examples include phthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, a reaction product of maleic anhydride and polybutadiene, and a copolymer of maleic anhydride and styrene.
さらに、硬化を促進するために硬化促進剤を配合でき、エポキシ樹脂の硬化促進剤としては、イミダゾール類、トリフェニルホスフィン又はテトラフェニルホスフィン及びそれらの塩類、ジアザビシクロウンデセンなどのアミン系化合物及びその塩類などが挙げられる。硬化促進剤は、2-メチルイミダゾール、2-エチルイミダゾール、2-フェニルイミダゾール、2-フェニル-4-メチルイミダゾール、2-フェニル-4-メチル-5-ヒドロキシメチルイミダゾール、2-フェニル-4,5-ジヒドロキシメチルイミダゾール、2-C11H23-イミダゾール、2-メチルイミダゾールと2,4-ジアミノ-6-ビニルトリアジンとの付加物などのイミダゾール化合物を用いてもよい。硬化促進剤の融点が180℃以上のイミダゾール化合物であってもよい。 Furthermore, a curing accelerator can be added to accelerate curing, and examples of curing accelerators for epoxy resins include imidazoles, triphenylphosphine or tetraphenylphosphine and their salts, amine compounds such as diazabicycloundecene, and Examples include salts thereof. The curing accelerator is 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5 Imidazole compounds such as -dihydroxymethylimidazole, 2-C 11 H 23 -imidazole, and an adduct of 2-methylimidazole and 2,4-diamino-6-vinyltriazine may also be used. The curing accelerator may be an imidazole compound having a melting point of 180° C. or higher.
ラジカル重合性のアクリル樹脂とは、分子内に(メタ)アクリロイル基を有する化合物であり、(メタ)アクリロイル基が反応することで3次元的網目構造を形成し、硬化する樹脂である。(メタ)アクリロイル基は分子内に1つ以上含まれていてもよい。 A radically polymerizable acrylic resin is a compound having a (meth)acryloyl group in the molecule, and is a resin that forms a three-dimensional network structure by reacting with the (meth)acryloyl group and is cured. One or more (meth)acryloyl groups may be included in the molecule.
ここで、アクリル樹脂としては、例えば、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、3-ヒドロキシブチル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、1,2-シクロヘキサンジオールモノ(メタ)アクリレート、1,3-シクロヘキサンジオールモノ(メタ)アクリレート、1,4-シクロヘキサンジオールモノ(メタ)アクリレート、1,2-シクロヘキサンジメタノールモノ(メタ)アクリレート、1,3-シクロヘキサンジメタノールモノ(メタ)アクリレート、1,4-シクロヘキサンジメタノールモノ(メタ)アクリレート、1,2-シクロヘキサンジエタノールモノ(メタ)アクリレート、1,3-シクロヘキサンジエタノールモノ(メタ)アクリレート、1,4-シクロヘキサンジエタノールモノ(メタ)アクリレート、グリセリンモノ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、トリメチロールプロパンモノ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、ペンタエリスリトールモノ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ネオペンチルグリコールモノ(メタ)アクリレートなどの水酸基を有する(メタ)アクリレート及びこれら水酸基を有する(メタ)アクリレートとジカルボン酸又はその誘導体とを反応させて得られるカルボキシル基を有する(メタ)アクリレートなどが挙げられる。ここで使用可能なジカルボン酸としては、例えばシュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、マレイン酸、フマル酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸及びこれらの誘導体等が挙げられる。 Here, as the acrylic resin, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,2-cyclohexanediol mono(meth)acrylate, 1,3-cyclohexanediol mono(meth)acrylate, 1,4-cyclohexanediol mono(meth)acrylate, 1,2-cyclohexanedimethanol mono(meth)acrylate, 1,3-cyclohexanedimethanol mono(meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 1,2-cyclohexanedimethanol mono(meth)acrylate , 1,3-cyclohexane diethanol mono(meth)acrylate, 1,4-cyclohexane diethanol mono(meth)acrylate, glycerin mono(meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane mono(meth)acrylate, trimethylol (Meth)acrylates with hydroxyl groups such as propane di(meth)acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, neopentyl glycol mono(meth)acrylate, and these Examples include (meth)acrylates having carboxyl groups obtained by reacting (meth)acrylates having hydroxyl groups with dicarboxylic acids or derivatives thereof. Examples of dicarboxylic acids that can be used here include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, and tetrahydrophthalic acid. , hexahydrophthalic acid and derivatives thereof.
また、アクリル樹脂としては、分子量が100~10,000のポリエーテル、ポリエステル、ポリカーボネート、ポリ(メタ)アクリレートで(メタ)アクリル基を有する化合物、ヒドロキシル基を有する(メタ)アクリレート、ヒドロキシル基を有する(メタ)アクリルアミド、等が挙げられる。 In addition, acrylic resins include polyethers, polyesters, polycarbonates, and poly(meth)acrylates with a molecular weight of 100 to 10,000 and compounds having (meth)acrylic groups, (meth)acrylates having hydroxyl groups, and compounds having hydroxyl groups. (meth)acrylamide, etc.
マレイミド樹脂は、1分子内にマレイミド基を1つ以上含む化合物であり、加熱によりマレイミド基が反応することで3次元的網目構造を形成し、硬化する樹脂である。例えば、N,N’-(4,4’-ジフェニルメタン)ビスマレイミド、ビス(3-エチル-5-メチル-4-マレイミドフェニル)メタン、2,2-ビス[4-(4-マレイミドフェノキシ)フェニル]プロパンなどのビスマレイミド樹脂が挙げられる。マレイミド樹脂は、ダイマー酸ジアミンと無水マレイン酸の反応により得られる化合物、マレイミド酢酸、マレイミドカプロン酸といったマレイミド化アミノ酸とポリオールの反応により得られる化合物であってもよい。マレイミド化アミノ酸は、無水マレイン酸とアミノ酢酸又はアミノカプロン酸とを反応させることで得られる。ポリオールとしては、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリ(メタ)アクリレートポリオールであってもよく、芳香族環を含まないものであってもよい。 A maleimide resin is a compound containing one or more maleimide groups in one molecule, and is a resin that forms a three-dimensional network structure and cures when the maleimide groups react with heat. For example, N,N'-(4,4'-diphenylmethane)bismaleimide, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 2,2-bis[4-(4-maleimidophenoxy)phenyl ] Examples include bismaleimide resins such as propane. The maleimide resin may be a compound obtained by the reaction of dimer acid diamine and maleic anhydride, or a compound obtained by the reaction of a maleimidated amino acid such as maleimidoacetic acid or maleimidocaproic acid with a polyol. Maleimidated amino acids can be obtained by reacting maleic anhydride with aminoacetic acid or aminocaproic acid. The polyol may be a polyether polyol, a polyester polyol, a polycarbonate polyol, a poly(meth)acrylate polyol, or may not contain an aromatic ring.
ここで、熱硬化性樹脂を含有させる場合は、前記銅粒子および大粒径銅粒子の総量を100質量部としたとき、1~20質量部となるように含有させてもよい。熱硬化性樹脂が1質量部以上であると熱硬化性樹脂による接着効果を十分に得ることができ、熱硬化性樹脂が20質量部以下であると銅成分の割合が低下するのを抑制し、高熱伝導性を十分に確保することができ、熱放散性を向上させることができる。また、有機成分が多くなる過ぎず、光及び熱による劣化を抑え、その結果、発光装置の寿命を高めることができる。 Here, when a thermosetting resin is contained, it may be contained in an amount of 1 to 20 parts by mass when the total amount of the copper particles and large-sized copper particles is 100 parts by mass. When the thermosetting resin is 1 part by mass or more, the adhesive effect of the thermosetting resin can be sufficiently obtained, and when the thermosetting resin is 20 parts by mass or less, a decrease in the proportion of the copper component can be suppressed. , high thermal conductivity can be sufficiently ensured, and heat dissipation performance can be improved. In addition, the amount of organic components does not increase too much, and deterioration due to light and heat is suppressed, and as a result, the life of the light emitting device can be extended.
(有機溶剤)
有機溶剤は、還元剤として機能する溶剤であれば公知の溶剤を用いることができる。
前記有機溶剤としては、アルコールであってもよく、例えば、脂肪族多価アルコールを挙げることができる。脂肪族多価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロビレングリコール、1,4-ブタンジオール、グリセリン、ポリエチレングリコールなどのグリコール類などを挙げることができる。これらの有機溶剤は、単独で用いてもよく、2種以上を併用してもよい。
(Organic solvent)
As the organic solvent, any known solvent can be used as long as it functions as a reducing agent.
The organic solvent may be an alcohol, such as an aliphatic polyhydric alcohol. Examples of the aliphatic polyhydric alcohol include glycols such as ethylene glycol, diethylene glycol, propylene glycol, diprobylene glycol, 1,4-butanediol, glycerin, and polyethylene glycol. These organic solvents may be used alone or in combination of two or more.
有機溶剤として、アルコールを用いることにより、ペースト硬化(焼結)時の熱処理により高温となることでアルコールの還元力を増大させ、銅粒子中に一部存在している酸化銅及び金属基板上の酸化金属(例えば、酸化銅)がアルコールによって還元され、純粋な金属となり、結果としてより緻密で導電性が高く、基板との密着性の高い硬化膜の形成ができると考えられる。また、半導体素子と金属基板に挟まれていることでペースト硬化時の熱処理中にアルコールが一部還流状態となり、溶剤であるアルコールが揮発により系中から直ちに失われることがなく、沸点以上のペースト硬化温度で酸化金属がより効率的に還元されるようになる。 By using alcohol as an organic solvent, the reducing power of alcohol is increased by increasing the temperature during heat treatment during paste hardening (sintering), and the copper oxide partially present in the copper particles and on the metal substrate are increased. It is believed that the metal oxide (for example, copper oxide) is reduced by alcohol and becomes a pure metal, resulting in the formation of a cured film that is denser, more conductive, and has higher adhesion to the substrate. In addition, because it is sandwiched between the semiconductor element and the metal substrate, some of the alcohol is refluxed during the heat treatment during paste curing, and the solvent alcohol is not immediately lost from the system due to volatilization. The curing temperature allows the metal oxide to be reduced more efficiently.
有機溶剤の沸点は、具体的には、100~300℃であってもよく、150~290℃であってもよい。有機溶剤の沸点が100℃以上であると、常温であっても揮発性が高くなり過ぎず、分散媒の揮発による還元能力の低下を制御することができ、安定した接着強度を得ることができる。また、有機溶剤の沸点が300℃以下であると、硬化膜(導電膜)の焼結が生じやすく、緻密性に優れた膜を形成することができる。また、沸点が300℃以下の有機溶剤は、焼結時の揮発により容易に除去される。 Specifically, the boiling point of the organic solvent may be 100 to 300°C, or 150 to 290°C. When the boiling point of the organic solvent is 100°C or higher, the volatility does not become too high even at room temperature, it is possible to control the decrease in reducing ability due to volatilization of the dispersion medium, and it is possible to obtain stable adhesive strength. . Moreover, when the boiling point of the organic solvent is 300° C. or less, sintering of the cured film (conductive film) easily occurs, and a film with excellent density can be formed. Further, organic solvents having a boiling point of 300° C. or lower are easily removed by volatilization during sintering.
有機溶剤を含有させる場合、その含有量は、前記銅粒子および大粒径銅粒子の総量を100質量部としたとき、7~20質量部であってもよい。有機溶剤の含有量が、7質量部以上であると粘度が高くなり過ぎず、作業性を向上させることができ、20質量部以下であると粘度低下が抑制され、銅ペースト中の銅粒子の沈下が制御され、信頼性を高めることができる。 When an organic solvent is contained, the content may be 7 to 20 parts by mass when the total amount of the copper particles and large-sized copper particles is 100 parts by mass. When the content of the organic solvent is 7 parts by mass or more, the viscosity does not become too high and workability can be improved, and when the content is 20 parts by mass or less, the decrease in viscosity is suppressed and the copper particles in the copper paste are Subsidence can be controlled and reliability can be increased.
本実施形態の銅ペーストには、以上の各成分の他、本実施形態の効果を阻害しない範囲で、この種の組成物に一般に配合される、硬化促進剤、ゴム、シリコーン等の低応力化剤、カップリング剤、消泡剤、界面活性剤、着色剤(顔料、染料)、各種重合禁止剤、酸化防止剤、溶剤、その他の各種添加剤を、必要に応じて配合することができる。これらの各添加剤はいずれも1種を使用してもよく、2種以上を混合して使用してもよい。 In addition to the above-mentioned components, the copper paste of this embodiment also contains stress-lowering agents, such as hardening accelerators, rubber, and silicone, which are generally added to this type of composition, to the extent that they do not impede the effects of this embodiment. Agents, coupling agents, antifoaming agents, surfactants, colorants (pigments, dyes), various polymerization inhibitors, antioxidants, solvents, and other various additives can be blended as necessary. Each of these additives may be used alone or in combination of two or more.
本実施形態の銅ペーストは、上述した銅粒子、及び必要に応じて配合される大粒径銅粒子、熱硬化性樹脂、有機溶剤、カップリング剤等の添加剤等を十分に混合した後、さらにディスパース、ニーダー、3本ロールミル等により混練処理を行い、次いで、脱泡することにより、調製することができる。 The copper paste of this embodiment is produced by sufficiently mixing the above-mentioned copper particles and additives such as large-sized copper particles, a thermosetting resin, an organic solvent, and a coupling agent, which are blended as necessary. Further, it can be prepared by performing a kneading process using a disperser, a kneader, a three-roll mill, etc., and then defoaming.
本実施形態の銅ペーストの焼結温度は、200℃以下であってもよく、150℃以下であってもよい。
なお、前記焼結温度は、実施例に記載の方法により測定することができる。
The sintering temperature of the copper paste of this embodiment may be 200°C or lower, or may be 150°C or lower.
Note that the sintering temperature can be measured by the method described in Examples.
本実施形態の銅ペーストの接合強度は、30MPa以上であってもよく、40MPa以上であってもよい。
なお、前記接合強度は、実施例に記載の方法により測定することができる。
The bonding strength of the copper paste of this embodiment may be 30 MPa or more, or may be 40 MPa or more.
Note that the bonding strength can be measured by the method described in Examples.
<半導体装置>
本実施形態の半導体装置は、上述の銅ペーストを用いて接合されてなることから、信頼性に優れる。
<Semiconductor device>
The semiconductor device of this embodiment has excellent reliability because it is bonded using the above-described copper paste.
本実施形態の半導体装置は、上述の銅ペーストを用いて、半導体素子を素子支持部材となる基板上に接着してなるものである。すなわち、ここで銅ペーストはダイアタッチペーストとして使用され、このペーストを介して半導体素子と基板とが接着し、固定される。 The semiconductor device of this embodiment is formed by bonding a semiconductor element onto a substrate serving as an element support member using the above-described copper paste. That is, the copper paste is used here as a die attach paste, and the semiconductor element and the substrate are bonded and fixed via this paste.
ここで、半導体素子は、公知の半導体素子であればよく、例えば、トランジスタ、ダイオード等が挙げられる。さらに、この半導体素子としては、LED等の発光素子が挙げられる。また、発光素子の種類は特に制限されるものではなく、例えば、MOBVC法等によって基板上にInN、AlN、GaN、InGaN、AlGaN、InGaAlN等の窒化物半導体を発光層として形成させたものも挙げられる。
また、素子支持部材としては、銅、銅メッキ銅、PPF(プリプレーティングリードフレーム)、ガラスエポキシ、セラミックス等の材料で形成された支持部材が挙げられる。
Here, the semiconductor element may be any known semiconductor element, such as a transistor, a diode, etc. Further, examples of this semiconductor element include light emitting elements such as LEDs. Further, the type of light emitting element is not particularly limited, and examples include those in which a nitride semiconductor such as InN, AlN, GaN, InGaN, AlGaN, InGaAlN, etc. is formed as a light emitting layer on a substrate by MOBVC method etc. It will be done.
Examples of the element support member include support members made of materials such as copper, copper-plated copper, PPF (preplating lead frame), glass epoxy, and ceramics.
次に実施例により、本開示を具体的に説明するが、本開示は、これらの例によってなんら限定されるものではない。 Next, the present disclosure will be specifically explained with reference to Examples, but the present disclosure is not limited in any way by these Examples.
(銅粒子の製造)
[合成例1]
銅化合物として酸化銅(I)(古河ケミカルズ(株)製、商品名:FRC-10A)20mmolと、(a)少なくとも2つ以上の3級窒素原子を有するアミン化合物としてN,N,N’,N’-テトラメチルエチレンジアミン(東京化成工業(株)製)40mmolと、(b)有機カルボン酸としてヘキサン酸(東京化成工業(株)製)40mmolと、有機溶剤として1-プロパノール(東京化成工業(株)製)10mLとを50mLのサンプルビンに入れ、アルミブロック式加熱撹拌機中、100℃で10分間撹拌し、室温(25℃)まで冷却した。10分後、サンプルビン内に濃青色のヘキサン酸銅テトラメチルエチレンジアミン錯体の生成を確認した。その後、ヒドラジン一水和物(東京化成工業(株)製)15mmolを加え、室温(25℃)で2時間、次いで100℃で1時間撹拌した。5分後、エタノール(関東化学(株)製、特級)2mLを加え、遠心分離(4000rpm(1分間))により、固体物を得た。得られた固体物を減圧乾燥し、銅光沢をもつ粉体状の銅粒子1(平均粒子径120nm、収率98.0%)を得た。
(Manufacture of copper particles)
[Synthesis example 1]
20 mmol of copper (I) oxide (manufactured by Furukawa Chemicals Co., Ltd., trade name: FRC-10A) as a copper compound; and (a) N, N, N', as an amine compound having at least two or more tertiary nitrogen atoms; 40 mmol of N'-tetramethylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 40 mmol of hexanoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) as the (b) organic carboxylic acid, and 1-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) as an organic solvent. Co., Ltd.) into a 50 mL sample bottle, stirred for 10 minutes at 100°C in an aluminum block heating stirrer, and cooled to room temperature (25°C). After 10 minutes, formation of a dark blue copper hexanoate tetramethylethylenediamine complex was confirmed in the sample bottle. Thereafter, 15 mmol of hydrazine monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at room temperature (25°C) for 2 hours and then at 100°C for 1 hour. After 5 minutes, 2 mL of ethanol (manufactured by Kanto Kagaku Co., Ltd., special grade) was added, and a solid substance was obtained by centrifugation (4000 rpm (1 minute)). The obtained solid material was dried under reduced pressure to obtain powdery copper particles 1 (average particle size: 120 nm, yield: 98.0%) with copper luster.
[合成例2]
(a)少なくとも2つ以上の3級窒素原子を有するアミン化合物としてN,N,N’,N’-テトラメチルエチレンジアミンの代わりにN,N,N’,N’-テトラエチルエチレンジアミン(東京化成工業(株)製)を用いた以外は合成例1と同様にして、銅光沢をもつ粉体状の銅粒子2(平均粒子径110nm、収率98.5%)を得た。
[Synthesis example 2]
(a) N,N,N',N'-tetraethylethylenediamine (Tokyo Kasei Kogyo Co., Ltd.) instead of N,N,N',N'-tetramethylethylenediamine as an amine compound having at least two or more tertiary nitrogen atoms Powder-like copper particles 2 (average particle diameter 110 nm, yield 98.5%) with copper luster were obtained in the same manner as in Synthesis Example 1, except that Powder Copper Particles 2 (average particle diameter 110 nm, yield 98.5%) were used.
[合成例3]
(a)少なくとも2つ以上の3級窒素原子を有するアミン化合物を使用せず、代わりにn-ブチルアミン(東京化成工業(株)製)を用いた以外は合成例1と同様にして、銅光沢をもつ粉体状の銅粒子3(平均粒子径120nm、収率98.1%)を得た。
[Synthesis example 3]
(a) Copper luster was obtained in the same manner as in Synthesis Example 1 except that the amine compound having at least two or more tertiary nitrogen atoms was not used and n-butylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead. Powder-like copper particles 3 (average particle diameter 120 nm, yield 98.1%) were obtained.
[合成例4]
(a)少なくとも2つ以上の3級窒素原子を有するアミン化合物を使用せず、代わりにジブチルアミン(東京化成工業(株)製)を用いた以外は合成例1と同様にして、銅光沢をもつ粉体状の銅粒子4(平均粒子径120nm、収率98.9%)を得た。
[Synthesis example 4]
(a) Copper luster was obtained in the same manner as Synthesis Example 1 except that the amine compound having at least two or more tertiary nitrogen atoms was not used and dibutylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead. Powder-like copper particles 4 (average particle diameter 120 nm, yield 98.9%) were obtained.
[合成例5]
(a)少なくとも2つ以上の3級窒素原子を有するアミン化合物を使用せず、代わりにトリブチルアミン(東京化成工業(株)製)を用いた以外は合成例1と同様にして、銅光沢をもつ粉体状の銅粒子5(平均粒子径160nm、収率97.8%)を得た。
[Synthesis example 5]
(a) Copper luster was obtained in the same manner as in Synthesis Example 1, except that tributylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of an amine compound having at least two or more tertiary nitrogen atoms. Powder-like copper particles 5 (average particle diameter 160 nm, yield 97.8%) were obtained.
(実施例1)
合成例1で得られた銅粒子1が100質量部、有機溶剤としてジエチレングリコール(東京化成工業(株)製)が15質量部となるように調製し、ロールで混練し、銅ペーストを得た。
(Example 1)
100 parts by mass of copper particles 1 obtained in Synthesis Example 1 and 15 parts by mass of diethylene glycol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as an organic solvent were prepared and kneaded with a roll to obtain a copper paste.
(実施例2、比較例1~3)
表1に記載の種類及び配合量の各成分に変更した以外は、実施例1と同様にして銅ペーストを得た。
(Example 2, Comparative Examples 1 to 3)
A copper paste was obtained in the same manner as in Example 1, except that the types and amounts of each component listed in Table 1 were changed.
各実施例及び比較例で得られた銅ペーストを用いて以下の方法で評価した。その結果を表1に示す。 The copper paste obtained in each Example and Comparative Example was evaluated by the following method. The results are shown in Table 1.
<銅ペーストの評価方法>
[焼結温度]
示差走査型熱量計(DSC)(TAインスツルメント社製、商品名:DSC Q2000)を用いて、銅ペーストを昇温速度10℃/minで加熱し、発熱挙動を観測しピークトップを焼結温度とした。
<Evaluation method of copper paste>
[Sintering temperature]
Using a differential scanning calorimeter (DSC) (manufactured by TA Instruments, product name: DSC Q2000), the copper paste was heated at a heating rate of 10°C/min, the exothermic behavior was observed, and the peak top was sintered. Temperature.
<半導体装置の評価方法>
[接合強度]
2mm×2mmの接合面に金蒸着層を設けたシリコンチップを、銅ペーストを用いて無垢の銅フレーム及びPPF(Ni-Pd/Auめっきした銅フレーム)にマウントし、窒素(3%水素)雰囲気下、200℃、60分間で硬化した。硬化後及び吸湿処理(85℃、相対湿度85%、72時間)後、それぞれについてDAGE 4000Plus(製品名、ノードソン(株)製)を用い、室温(25℃)におけるダイシェア強度を測定した。
<Evaluation method of semiconductor device>
[Joining strength]
A silicon chip with a gold vapor deposited layer on the bonding surface of 2 mm x 2 mm was mounted on a solid copper frame and a PPF (Ni-Pd/Au plated copper frame) using copper paste, and placed in a nitrogen (3% hydrogen) atmosphere. It was cured at 200°C for 60 minutes. After curing and moisture absorption treatment (85° C., relative humidity 85%, 72 hours), the die shear strength at room temperature (25° C.) was measured using DAGE 4000Plus (product name, manufactured by Nordson Corporation).
以上の結果より、本開示の、(a)少なくとも2つ以上の3級窒素原子を有するアミン化合物及び(b)有機カルボン酸を配位子とする銅錯体(A)を還元する製造方法で得られる銅粒子を含む銅ペーストは、焼結温度が100℃であり低温焼結性に優れる。また、該銅ペーストは、硬化後及び吸湿処理後の接合強度がいずれも45MPa以上と高く、信頼性に優れた半導体装置を得ることができる。 From the above results, it can be seen that the production method of the present disclosure involves reducing (a) an amine compound having at least two or more tertiary nitrogen atoms and (b) a copper complex (A) having an organic carboxylic acid as a ligand. The copper paste containing the copper particles has a sintering temperature of 100° C. and has excellent low-temperature sinterability. Further, the copper paste has a high bonding strength of 45 MPa or more after curing and after moisture absorption treatment, and a semiconductor device with excellent reliability can be obtained.
Claims (6)
(式中、R 1 ~R 4 は、それぞれ独立して直鎖状もしくは分岐状のアルキル基、または直鎖状もしくは分岐状のヒドロキシアルキル基を表し、Xは、下記一般式(i)または(ii)で示される基を表す。)
(式中、nは0または1以上の自然数を表し、R 5 及びR 6 は、それぞれ独立して直鎖状または分岐状のアルキレン鎖を表す。*は結合部分を示す。)
(式中、mは1以上の自然数を表し、R 7 及びR 8 は、それぞれ独立して直鎖状または分岐状のアルキレン鎖を表し、R 9 は、直鎖状もしくは分岐状のアルキル基、または直鎖状もしくは分岐状のヒドロキシアルキル基を表す。また、m=1のときR 9 とR 1 とは互いに結合して環を形成していてもよい。*は結合部分を示す。)
(式中、R 10 は水素原子または炭素数1~12の炭化水素基を表す。) In the method for producing copper particles by reducing (a) an amine compound having at least two or more tertiary nitrogen atoms and (b) a copper complex (A) having an organic carboxylic acid as a ligand, The component is an amine compound represented by the following general formula (1), and the component (b) is a monocarboxylic acid represented by the following general formula (2), and the average particle size is 110 nm to 1000 nm. Method for producing copper particles.
(In the formula, R 1 to R 4 each independently represent a linear or branched alkyl group or a linear or branched hydroxyalkyl group, and X represents the following general formula (i) or ( Represents the group shown in ii).)
(In the formula, n represents a natural number of 0 or 1 or more, and R 5 and R 6 each independently represent a linear or branched alkylene chain. * represents a bonding moiety.)
(In the formula, m represents a natural number of 1 or more, R 7 and R 8 each independently represent a linear or branched alkylene chain, R 9 represents a linear or branched alkyl group, or represents a linear or branched hydroxyalkyl group.Also, when m=1, R 9 and R 1 may be bonded to each other to form a ring. * indicates a bonding moiety.)
(In the formula, R 10 represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms.)
(式中、R1~R4は、それぞれ独立して直鎖状もしくは分岐状のアルキル基を表し、Xは、直鎖状もしくは分岐状のアルキレン基を表す。)
(式中、R10は水素原子または炭素数6~12の炭化水素基を表す。) 2. The method according to claim 1, wherein the component (a) is an amine compound represented by the following general formula (1), and the component (b) is a monocarboxylic acid represented by the following general formula (2). Method for producing copper particles.
(In the formula, R 1 to R 4 each independently represent a linear or branched alkyl group , and X represents a linear or branched alkylene group .)
(In the formula, R 10 represents a hydrogen atom or a hydrocarbon group having 6 to 12 carbon atoms.)
ン酸である請求項1又は2に記載の銅粒子の製造方法。The method for producing copper particles according to claim 1 or 2, wherein the copper particles are phosphoric acid.
る少なくとも一種の銅化合物と、前記(a)成分及び(b)成分とを反応させることによ
り得られる請求項1~3のいずれかに記載の銅粒子の製造方法。 The copper complex (A) causes the (a) component and the (b) component to react with at least one copper compound selected from the group consisting of copper hydroxide, copper (I) oxide, and copper (II) oxide. The method for producing copper particles according to any one of claims 1 to 3, which is obtained by.
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JP2016160456A (en) | 2015-02-27 | 2016-09-05 | 日立化成株式会社 | Copper-containing particle, conductor forming composition, method for producing conductor, conductor and device |
JP2019002054A (en) | 2017-06-16 | 2019-01-10 | 三井金属鉱業株式会社 | Copper particle |
WO2019093121A1 (en) | 2017-11-13 | 2019-05-16 | 京セラ株式会社 | Paste composition, semiconductor device, and electrical/electronic component |
JP2019527770A (en) | 2016-07-18 | 2019-10-03 | リード, ケネスREED, Kenneth | Method for producing metal nanoparticle colloidal dispersion |
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JP2016160456A (en) | 2015-02-27 | 2016-09-05 | 日立化成株式会社 | Copper-containing particle, conductor forming composition, method for producing conductor, conductor and device |
JP2019527770A (en) | 2016-07-18 | 2019-10-03 | リード, ケネスREED, Kenneth | Method for producing metal nanoparticle colloidal dispersion |
JP2019002054A (en) | 2017-06-16 | 2019-01-10 | 三井金属鉱業株式会社 | Copper particle |
WO2019093121A1 (en) | 2017-11-13 | 2019-05-16 | 京セラ株式会社 | Paste composition, semiconductor device, and electrical/electronic component |
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