JP2002069661A - Surface treatment method for copper - Google Patents
Surface treatment method for copperInfo
- Publication number
- JP2002069661A JP2002069661A JP2000261069A JP2000261069A JP2002069661A JP 2002069661 A JP2002069661 A JP 2002069661A JP 2000261069 A JP2000261069 A JP 2000261069A JP 2000261069 A JP2000261069 A JP 2000261069A JP 2002069661 A JP2002069661 A JP 2002069661A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- treatment method
- surface treatment
- treated
- oxide film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000010949 copper Substances 0.000 title claims abstract description 74
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004381 surface treatment Methods 0.000 title claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000011889 copper foil Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 8
- 238000007747 plating Methods 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- 125000005641 methacryl group Chemical group 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 22
- 239000011347 resin Substances 0.000 abstract description 22
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract 1
- -1 polysiloxane Polymers 0.000 description 21
- 229920001296 polysiloxane Polymers 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000004115 Sodium Silicate Substances 0.000 description 8
- 229910052911 sodium silicate Inorganic materials 0.000 description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 229960004643 cupric oxide Drugs 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000005751 Copper oxide Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 101100316860 Autographa californica nuclear polyhedrosis virus DA18 gene Proteins 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Lead Frames For Integrated Circuits (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銅の表面処理方
法、その方法で処理した銅、およびその方法で処理した
銅材を用いて作製したプリント配線板および半導体デバ
イスに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper surface treatment method, copper treated by the method, and a printed wiring board and a semiconductor device manufactured using the copper material treated by the method.
【０００２】[0002]
【従来の技術】銅と樹脂との接着は、たとえば、銅張積
層板などの製造において行われている。しかし、一般的
に銅と樹脂（ポリマー）との接着性は低い。これは銅ま
たは銅イオンが樹脂（ポリマー）の硬化を阻害したり、
樹脂（ポリマー）の分解触媒となるためである。その改
善策としては、銅表面粗さを大きくする方法、あるいは
銅表面を酸化させるか又はめっきや化成処理等で銅表面
を被覆することによって活性な銅表面を遮蔽する方法が
ある。例えば、銅箔の樹脂と接着する面（マット面）は
表面粗さを大きくし、銅の微粒子を付着させ、さらに亜
鉛や真鍮またはその他の金属等のめっきを施し、クロメ
ート処理等の化成処理を行っている。2. Description of the Related Art The bonding between copper and a resin is performed, for example, in the production of a copper-clad laminate. However, the adhesion between copper and a resin (polymer) is generally low. This is because copper or copper ions inhibit the curing of the resin (polymer),
This is because it serves as a decomposition catalyst for the resin (polymer). As a remedy, there is a method of increasing the copper surface roughness, or a method of oxidizing the copper surface or shielding the active copper surface by coating the copper surface with plating or chemical conversion treatment. For example, the surface (mat surface) of the copper foil that is to be bonded to the resin has a large surface roughness, adheres fine copper particles, and is further plated with zinc, brass, or other metal, and then subjected to a chemical treatment such as a chromate treatment. Is going.
【０００３】一方、樹脂と接着しない面（シャイニー
面）は銅箔の変色を防止する目的でクロメート処理等の
化成処理を行っている。しかしながら、このように樹脂
との接着強度を改善させるための方法は複雑であり、特
殊なめっき装置等がないと処理できないという欠点があ
る。On the other hand, a surface (shiny surface) that does not adhere to the resin is subjected to a chemical conversion treatment such as a chromate treatment in order to prevent discoloration of the copper foil. However, such a method for improving the adhesive strength with a resin is complicated, and has a drawback that it cannot be processed without a special plating apparatus or the like.
【０００４】また、多層配線板の内層の銅配線は銅箔や
銅めっきされたものが使用される。例えば銅箔を使用し
た場合、マット面のみでなく、シャイニー面も樹脂（ポ
リマー）との接着性を要求される。その銅表面（シャイ
ニー面）はプリプレグ等の樹脂（ポリマー）との密着性
を改善させるために、ソフトエッチング等で表面を粗化
した後、表面を酸化第一銅や酸化第二銅とする方法（黒
化処理）が一般的である。しかし、この酸化銅被膜は塩
酸等に浸漬した際、侵されやすく接着強度の低下を引き
起こす。[0004] Copper foil or copper-plated copper wiring in the inner layer of the multilayer wiring board is used. For example, when a copper foil is used, not only the matte surface but also the shiny surface is required to have adhesiveness to a resin (polymer). A method in which the copper surface (shiny surface) is roughened by soft etching or the like to improve adhesion to a resin (polymer) such as prepreg, and then the surface is changed to cuprous oxide or cupric oxide. (Blackening) is common. However, when this copper oxide film is immersed in hydrochloric acid or the like, it is easily eroded and causes a decrease in adhesive strength.
【０００５】その他の方法としては、銅箔上へのポリシ
ロキサン膜の付与（特開平２−３０７２９４）を行うこ
とも提案されている。このポリシロキサンは、特開平２
−３０７２９４号公報（２）頁の説明によれば、直鎖
状、環状、網状構造のいずれでもよく、またこのポリシ
ロキサンとしては有機基を有せず、置換基のＯＨのＨの
一部がＮａで置換しており、水に分散して溶液としたと
きｐＨが１０．５〜１１．２のものが好ましいとされて
いる（前記公報（２）頁左上欄１５行〜右上欄２行）。
この方法は銅の表面をシリカライクにし、樹脂との接着
性が向上するものである。シランカップリング剤等を表
面処理することによってさらに接着強度を向上させるこ
とができる。しかしながら、この処理方法では前記ポリ
シロキサン皮膜形成材料としてケイ酸ナトリウムを用い
て処理し、その後に水洗をすると銅表面にポリシロキサ
ン皮膜が形成されない。一般的に、ケイ酸ナトリウムは
Ｓｎ、Ｚｎ、Ａｌ等の金属を侵食し、新たに現れた金属
表面にポリシロキサンおよび金属酸化物の皮膜ができる
が、銅はケイ酸ナトリウムと反応しにくくポリシロキサ
ン皮膜を形成しずらい。すなわち、ポリシロキサンの皮
膜が銅表面上に形成するためにはケイ酸ナトリウム処理
後に水洗せず乾燥するか、またはＳｎ、Ｚｎ、Ａｌ等の
金属を被覆したものにケイ酸ナトリウムを処理する方法
をとらなければならない。しかし、銅をケイ酸ナトリウ
ム処理した後、水洗しないで乾燥して得られたポリシロ
キサン皮膜は、銅とポリシロキサン皮膜の結合が十分で
なく、その後樹脂と接着した場合に樹脂と銅との高い接
着性が得られない。また、金属を被覆する場合はめっき
工程が増え実際の操業上好ましくない。As another method, it has been proposed to provide a polysiloxane film on a copper foil (JP-A-2-307294). This polysiloxane is disclosed in
According to the description on page (2) of JP-A-307294, the polysiloxane may have any of a linear, cyclic or network structure, and this polysiloxane has no organic group and a part of H of OH of a substituent is It is said that those which have been replaced with Na and have a pH of 10.5-11.2 when dispersed in water to form a solution are described above (page (2), line 15 in the upper left column to line 2 in the upper right column). .
In this method, the surface of copper is made silica-like, and the adhesiveness with a resin is improved. By subjecting the silane coupling agent or the like to a surface treatment, the adhesive strength can be further improved. However, in this treatment method, when the treatment is carried out using sodium silicate as the material for forming the polysiloxane film, and then the substrate is washed with water, no polysiloxane film is formed on the copper surface. In general, sodium silicate erodes metals such as Sn, Zn, and Al, and forms a film of polysiloxane and metal oxide on the newly appearing metal surface, but copper is less likely to react with sodium silicate and polysiloxane. It is difficult to form a film. That is, in order to form a polysiloxane film on a copper surface, a method of drying without washing with sodium silicate after treatment with sodium silicate, or treating a material coated with a metal such as Sn, Zn, Al with sodium silicate. Must take. However, after the copper is treated with sodium silicate, the polysiloxane film obtained by drying without washing with water is not sufficiently bonded to the copper and polysiloxane film. Adhesiveness cannot be obtained. Further, when coating with metal, the number of plating steps increases, which is not preferable in actual operation.
【０００６】またその他の例として、銅と樹脂の接着改
善が要求されているところとしては、半導体デバイスに
使用されている銅材のリードフレームと封止樹脂やペー
スト（マウント材料）との接着性である。これについて
は各社が樹脂の添加剤や銅の表面処理剤の開発を検討し
ている現状にある。[0006] As another example, there is a demand for improvement in the adhesion between copper and a resin. The adhesion between a lead frame made of a copper material used in a semiconductor device and a sealing resin or a paste (mount material) is required. It is. At this time, each company is currently studying the development of resin additives and copper surface treatment agents.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、こうした実
情の下に、銅と樹脂との接着性を向上するために、銅表
面を処理する方法を提供することを目的とするものであ
り、またその処理方法で処理した銅箔、銅めっき被膜、
スパッタ銅被膜およびその銅材を用いて作製したプリン
ト配線板および半導体デバイスを提供することを目的と
するものである。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for treating a copper surface in order to improve the adhesion between copper and a resin under such circumstances. In addition, copper foil, copper plating film,
It is an object of the present invention to provide a sputtered copper film and a printed wiring board and a semiconductor device manufactured using the copper material.
【０００８】[0008]
【課題を解決するための手段】本発明者は、鋭意検討し
た結果、銅表面をまず酸化して酸化皮膜を形成せしめ、
その後ケイ酸アルカリ水溶液で処理することにより、ポ
リシロキサン皮膜を形成することが、銅表面の樹脂との
接着性を向上する上で有効であることを知見し、本発明
に至った。ポリシロキサン皮膜の形成の機構については
明らかではないが、銅表面に酸化皮膜を形成することに
より、ケイ酸アルカリ水溶液がその酸化皮膜を侵食し、
それとともにポリシロキサン皮膜が形成されるものと考
えられる。すなわち、酸化皮膜が薄いとポリシロキサン
皮膜が十分に形成されず、樹脂との接着性が改善できな
い。酸化皮膜は好ましくは５０Å以上必要である。Means for Solving the Problems As a result of intensive studies, the present inventor first oxidized the copper surface to form an oxide film,
Thereafter, the present inventors have found that forming a polysiloxane film by treating with an aqueous alkali silicate solution is effective in improving the adhesiveness of the copper surface to the resin, and have reached the present invention. The mechanism of the formation of the polysiloxane film is not clear, but by forming an oxide film on the copper surface, the alkali silicate aqueous solution erodes the oxide film,
It is considered that a polysiloxane film is formed at the same time. That is, if the oxide film is thin, the polysiloxane film is not sufficiently formed, and the adhesion to the resin cannot be improved. The oxide film should preferably be at least 50 °.
【０００９】すなわち、本発明は、（１）銅を酸化して
酸化皮膜を形成した後、ケイ酸アルカリ溶液で処理する
ことを特徴とする銅の表面処理方法、（２）酸化皮膜が
５０Å以上であることを特徴とする前記（１）記載の銅
の表面処理方法、（３）銅を酸化性溶液と接触させるこ
とにより酸化皮膜を形成する前記（１）記載の銅の表面
処理方法、（４）前記（１）記載の方法で表面処理した
銅にさらにシランカップリング剤を塗布することを特徴
とする銅の表面処理方法、（５）シランカップリング剤
がエポキシ基、アミノ基、メルカプト基、ビニル基、メ
タクリル基、イミダゾール基、またはジメチルアミノ基
を有することを特徴とする前記（４）記載の銅の表面処
理方法、（６）前記（１）〜（５）のいずれかの表面処
理方法で処理した銅、（７）前記（１）〜（５）のいず
れかの表面処理方法で処理した銅箔、（８）前記（１）
〜（５）のいずれかの表面処理方法で処理した銅めっき
被膜、（９）前記（１）〜（５）のいずれかの表面処理
方法で処理したスパッタ銅被膜、（１０）前記（７）〜
（９）記載の銅材を用いて作製したプリント配線板、
（１１）前記（７）〜（９）記載の銅材を用いて作製し
た半導体デバイス、に関する。That is, the present invention provides (1) a copper surface treatment method, which comprises oxidizing copper to form an oxide film and then treating it with an alkali silicate solution; (3) the copper surface treatment method according to (1), wherein the copper surface is contacted with an oxidizing solution to form an oxide film; 4) A copper surface treatment method comprising further applying a silane coupling agent to copper surface-treated by the method described in (1) above, and (5) the silane coupling agent is an epoxy group, an amino group, or a mercapto group. A surface treatment method for copper according to the above (4), which has a vinyl group, a methacryl group, an imidazole group, or a dimethylamino group; and (6) a surface treatment according to any one of the above (1) to (5). Processed in the way , (7) the (1) to (5) copper foil treated with any surface treatment method, (8) the (1)
To (5) a copper plating film treated by any one of the surface treatment methods, (9) a sputtered copper film treated by any one of the surface treatment methods (1) to (5), and (10) the (7) ~
(9) A printed wiring board manufactured using the copper material according to (9),
(11) A semiconductor device manufactured using the copper material according to (7) to (9).
【００１０】本発明の銅の表面処理方法における銅の酸
化法は、銅表面に酸化皮膜を形成し得るものであればよ
く、とくに制限されないが、銅表面を脱脂後、酸化性溶
液と接触させることによる方法が好ましい。この酸化性
溶液はたとえば過酸化水素−希硫酸水溶液、過マンガン
酸カリウム、過硫酸ナトリウム等が好ましく用いられ
る。酸化性溶液と銅との接触は、銅表面に５０Å以上、
より好ましくは１００Å以上の酸化皮膜が形成されるよ
うに行われる。酸化皮膜が５０Å未満であると後続のケ
イ酸アルカリによるポリシロキサン皮膜の形成が困難で
ある。The method for oxidizing copper in the method for treating a copper surface of the present invention is not particularly limited as long as it can form an oxide film on the copper surface, and is not particularly limited. Are preferred. As the oxidizing solution, for example, a hydrogen peroxide-dilute sulfuric acid aqueous solution, potassium permanganate, sodium persulfate and the like are preferably used. The contact between the oxidizing solution and the copper is 50 ° or more on the copper surface,
It is more preferably performed so that an oxide film of 100 ° or more is formed. When the thickness of the oxide film is less than 50 °, it is difficult to form a polysiloxane film by the subsequent alkali silicate.
【００１１】酸化皮膜を形成した後、銅はケイ酸アルカ
リ、好ましくはケイ酸ナトリウム水溶液で処理される。
この処理は、酸化皮膜を形成した銅をケイ酸アルカリ水
溶液に室温〜９０℃で５秒〜２０分間浸漬するかまたは
シャワーにより行われる。この処理により、銅酸化皮膜
表面上にポリシロキサン皮膜が形成され、このことによ
り、樹脂との接着性が向上する。ポリシロキサン皮膜は
１０Å以上の層厚で形成するのが好ましい。また、ポリ
シロキサン皮膜は形成後水洗してナトリウムイオンを除
去後乾燥することが樹脂との接着性を向上する上でより
好ましい。After forming the oxide film, the copper is treated with an aqueous solution of alkali silicate, preferably sodium silicate.
This treatment is performed by immersing the copper on which the oxide film has been formed in an aqueous alkali silicate solution at room temperature to 90 ° C. for 5 seconds to 20 minutes, or by showering. By this treatment, a polysiloxane film is formed on the surface of the copper oxide film, thereby improving the adhesiveness with the resin. The polysiloxane film is preferably formed with a layer thickness of 10 ° or more. Further, it is more preferable that the polysiloxane film is formed, washed with water to remove sodium ions, and then dried, in order to improve the adhesiveness with the resin.
【００１２】本発明の処理方法においては、銅表面にポ
リシロキサン皮膜を形成した上で、さらにこの皮膜上に
シランカップリング剤を塗布すると樹脂との接着性を一
層向上することができる。このようなシランカップリン
グ剤としては、公知のシランカップリング剤を用いるこ
とができるが、とくに好ましいものとして、その分子中
にエポキシ基、アミノ基、メルカプト基、ビニル基、メ
タクリル基、イミダゾール基、ジメチルアミノ基を含有
するものを挙げることができる。In the treatment method of the present invention, after forming a polysiloxane film on the copper surface, and further applying a silane coupling agent on the film, the adhesiveness with the resin can be further improved. As such a silane coupling agent, known silane coupling agents can be used, and particularly preferred are epoxy groups, amino groups, mercapto groups, vinyl groups, methacryl groups, imidazole groups, Those containing a dimethylamino group can be mentioned.
【００１３】本発明の処理方法は、銅と樹脂との接着性
が問題となる分野において有用な技術であるから、銅の
使用形態についても特に制限はないが、とりわけ積層や
ビルドアップ等で多層板を作成する際に使用される銅箔
または銅めっき膜に適用してプリント配線板を作製する
場合や半導体デバイス用のリードフレームと封止材また
はマウント材との密着向上に有用である。The treatment method of the present invention is a useful technique in the field where the adhesion between copper and resin is a problem, and there is no particular limitation on the form of use of copper. It is useful for producing a printed wiring board by applying it to a copper foil or a copper plating film used for producing a board, or for improving adhesion between a lead frame for a semiconductor device and a sealing material or a mounting material.
【００１４】[0014]
【実施例】以下に実施例を示し、本発明をより詳細に説
明する。 実施例１ 硫酸銅水溶液中で回転ドラムを陰極として電気分解を行
い、そこに連続的に銅を電着するとともに、形成された
銅箔を連続的に剥離して厚み３５μｍの銅箔を得た。こ
の銅箔のシャイニー面にＵＤＹＬＩＴＥ ＰＢ−２４２
［荏原ユージライト（株）製］の１０倍希釈液を用い、
４０℃で５分間処理して脱脂した。脱脂後、５０℃１分
間湯洗した。オージエ分析により、この銅箔のシャイニ
ー面の酸化銅皮膜は約２５Å（ＳｉＯ2エッチング速度
換算）であることが確認された。The present invention will be described in more detail with reference to the following examples. Example 1 Electrolysis was performed in a copper sulfate aqueous solution using a rotating drum as a cathode, and copper was continuously electrodeposited thereon, and the formed copper foil was continuously peeled to obtain a copper foil having a thickness of 35 μm. . UDYLITE PB-242 on the shiny side of this copper foil
Using a 10-fold diluted solution of [EBARA Eugerite Co., Ltd.]
Treated at 40 ° C for 5 minutes to degrease. After degreasing, the plate was washed with hot water at 50 ° C. for 1 minute. An Auger analysis confirmed that the copper oxide film on the shiny surface of this copper foil was about 25 ° (in terms of SiO 2 etching rate).
【００１５】次いでこの銅箔のシャイニー面を、３０％
Ｈ2Ｏ2の６２ｍｌ／ｌ水溶液と９６％Ｈ2ＳＯ4の１０ｍ
ｌ／ｌ水溶液との混合液に室温で１分間浸漬して銅箔シ
ャイニー面を酸化した。オージエ分析により形成された
酸化銅皮膜は約１３０Å（ＳｉＯ2エッチング速度換
算）であることが確認された。Then, the shiny side of this copper foil is
10m of of H 2 O 2 62 ml / l aqueous solution and 96% H 2 SO 4
The copper foil shiny surface was oxidized by immersion in a mixed solution with a 1 / l aqueous solution at room temperature for 1 minute. It was confirmed by an Auger analysis that the formed copper oxide film was about 130 ° (in terms of SiO 2 etching rate).
【００１６】このようにして酸化皮膜を形成した銅箔の
シャイニー面を、４％二ケイ酸ナトリウム水溶液［関東
化学（株）製］に８０℃で５分間浸漬した。浸漬処理
後、銅箔を水洗し、１００℃で５分間乾燥した。The shiny surface of the copper foil on which the oxide film was formed was immersed in a 4% aqueous solution of sodium disilicate [manufactured by Kanto Chemical Co., Ltd.] at 80 ° C. for 5 minutes. After the immersion treatment, the copper foil was washed with water and dried at 100 ° C. for 5 minutes.
【００１７】実施例２ 実施例１において、二ケイ酸ナトリウム水溶液への銅箔
のシャイニー面浸漬を８０℃で１５秒とした以外は実施
例１と同様にして銅箔の処理を行った。Example 2 A copper foil was treated in the same manner as in Example 1 except that the shiny surface of the copper foil was immersed in an aqueous solution of sodium disilicate at 80 ° C. for 15 seconds.
【００１８】実施例３ 実施例１において、二ケイ酸ナトリウム水溶液への銅箔
のシャイニー面浸漬を６０℃で５分とした以外は実施例
１と同様にして銅箔の処理を行った。Example 3 A copper foil was treated in the same manner as in Example 1 except that the shiny surface of the copper foil was immersed in an aqueous solution of sodium disilicate at 60 ° C. for 5 minutes.
【００１９】実施例４ 実施例１において、二ケイ酸ナトリウム水溶液への銅箔
のシャイニー面浸漬を室温で５分とした以外は実施例１
と同様にして銅箔の処理を行った。Example 4 Example 1 was repeated except that the shiny surface of the copper foil was immersed in an aqueous solution of sodium disilicate for 5 minutes at room temperature.
The treatment of the copper foil was performed in the same manner as described above.
【００２０】実施例５ 実施例１と同様に、二ケイ酸ナトリウム水溶液へ銅箔を
浸漬した後、イミダゾールと３−グリシドキシプロピル
トリメトキシシランを９５℃で１時間反応させて得たイ
ミダゾール系シランカップリング剤の０．５％水溶液
（酢酸でｐＨ５に調整）でさらに浸漬処理した。水洗す
ることなく１００℃で５分間乾燥した。Example 5 In the same manner as in Example 1, an imidazole system obtained by immersing a copper foil in an aqueous solution of sodium disilicate and then reacting imidazole and 3-glycidoxypropyltrimethoxysilane at 95 ° C. for 1 hour. Further immersion treatment was carried out with a 0.5% aqueous solution of silane coupling agent (adjusted to pH 5 with acetic acid). It was dried at 100 ° C. for 5 minutes without washing with water.
【００２１】実施例６ 実施例５においてカップリング剤による処理を信越化学
（株）製 ３−グリシドキシプロピルトリメトキシシラ
ンの０．５％水溶液（酢酸でｐＨ５に調整）を使用した
以外は実施例５と同様にして銅箔の処理を行った。Example 6 The procedure of Example 5 was repeated, except that a 0.5% aqueous solution of 3-glycidoxypropyltrimethoxysilane (adjusted to pH 5 with acetic acid) manufactured by Shin-Etsu Chemical Co., Ltd. was used. The copper foil was treated in the same manner as in Example 5.
【００２２】実施例７ 実施例５において、カップリング剤による処理を信越化
学（株）製 ３−アミノプロピルトリエトキシシランの
０．５％水溶液（酢酸でｐＨ５に調整）を使用した以外
は、実施例５と同様にして銅箔の処理を行った。Example 7 Example 5 was repeated except that the treatment with the coupling agent was performed using a 0.5% aqueous solution of 3-aminopropyltriethoxysilane (adjusted to pH 5 with acetic acid) manufactured by Shin-Etsu Chemical Co., Ltd. The copper foil was treated in the same manner as in Example 5.
【００２３】比較例１ 実施例１において、銅箔の酸化処理を実施しない以外は
実施例１と同様にして銅箔の処理を行った。Comparative Example 1 A copper foil was treated in the same manner as in Example 1 except that the copper foil was not oxidized.
【００２４】比較例２ 実施例１において、二ケイ酸ナトリウム水溶液への銅箔
の浸漬処理を実施しない以外は、実施例１と同様にして
銅箔の処理を行った。Comparative Example 2 A copper foil was treated in the same manner as in Example 1, except that the copper foil was not immersed in an aqueous solution of sodium disilicate.
【００２５】比較例３ 実施例５において、二ケイ酸ナトリウム水溶液への銅箔
の浸漬処理を実施しない以外は実施例５と同様にして銅
箔の処理を行った。上記処理した銅箔のシャイニー面側
をガラス基材にエポキシ樹脂が含浸されたプリプレグと
加熱プレスし、銅張積層板を作製した。この銅張積層板
をＪＩＳ６４８１に規定する方法により常態ピール強度
を測定した。その結果を銅箔に形成されたポリシロキサ
ン皮膜厚とともに表１に示す。なお、各銅箔表面粗さに
はほとんど違いが見られなかった。Comparative Example 3 A copper foil was treated in the same manner as in Example 5 except that the copper foil was not immersed in an aqueous solution of sodium disilicate. The shiny side of the treated copper foil was hot-pressed with a prepreg in which a glass substrate was impregnated with an epoxy resin, to produce a copper-clad laminate. The normal peel strength of the copper clad laminate was measured by the method specified in JIS6481. The results are shown in Table 1 together with the thickness of the polysiloxane film formed on the copper foil. In addition, there was hardly any difference in the surface roughness of each copper foil.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】以上説明したように、本発明により銅を
あらかじめ酸化してその表面に酸化皮膜を形成してお
き、この銅をケイ酸アルカリ溶液で処理、あるいはさら
にシランカップリング剤で処理することにより、樹脂と
銅との接着強度を著しく向上することができる。As described above, according to the present invention, copper is oxidized in advance to form an oxide film on its surface, and this copper is treated with an alkali silicate solution or further treated with a silane coupling agent. Thereby, the adhesive strength between the resin and the copper can be significantly improved.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 赤瀬 文彰 茨城県北茨城市華川町臼場187番地４ 株 式会社日鉱マテリアルズ磯原工場内 Ｆターム(参考） 4K026 AA06 AA22 BA01 BA02 BA08 BA12 BB06 BB10 CA16 CA27 CA33 CA35 CA37 DA16 EB02 EB07 5E343 BB15 BB24 BB67 CC33 CC43 CC55 EE52 EE54 EE56 GG01 GG04 5F067 AA04 BA00 DE01 EA04 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Fumiaki Akase 187-4 Usaba, Hanakawa-cho, Kitaibaraki-shi, Ibaraki F-term in Nikko Materials Isohara Plant (reference) 4K026 AA06 AA22 BA01 BA02 BA08 BA12 BB06 BB10 CA16 CA27 CA33 CA35 CA37 DA16 EB02 EB07 5E343 BB15 BB24 BB67 CC33 CC43 CC55 EE52 EE54 EE56 GG01 GG04 5F067 AA04 BA00 DE01 EA04
Claims (11)
イ酸アルカリ溶液で処理することを特徴とする銅の表面
処理方法。1. A copper surface treatment method, comprising oxidizing copper to form an oxide film, and then treating with an alkali silicate solution.
とする請求項１記載の銅の表面処理方法。2. The copper surface treatment method according to claim 1, wherein the oxide film has a thickness of 50 ° or more.
酸化皮膜を形成する請求項１記載の銅の表面処理方法。3. The method of claim 1, wherein the oxide film is formed by bringing the copper into contact with an oxidizing solution.
さらにシランカップリング剤を塗布することを特徴とす
る銅の表面処理方法。4. A copper surface treatment method, further comprising applying a silane coupling agent to copper surface-treated by the method according to claim 1.
ミノ基、メルカプト基、ビニル基、メタクリル基、イミ
ダゾール基、またはジメチルアミノ基を有することを特
徴とする請求項４記載の銅の表面処理方法。5. The copper surface treatment method according to claim 4, wherein the silane coupling agent has an epoxy group, an amino group, a mercapto group, a vinyl group, a methacryl group, an imidazole group, or a dimethylamino group.
で処理した銅。6. Copper treated by the surface treatment method according to claim 1.
で処理した銅箔。7. A copper foil treated by the surface treatment method according to claim 1.
で処理した銅めっき被膜。8. A copper plating film treated by the surface treatment method according to claim 1.
で処理したスパッタ銅被膜。9. A sputtered copper film treated by the surface treatment method according to claim 1.
したプリント配線板。10. A printed wiring board manufactured using the copper material according to claim 7.
した半導体デバイス。11. A semiconductor device manufactured using the copper material according to claim 7.
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|---|---|---|---|
| JP2000261069A JP3505135B2 (en) | 2000-08-30 | 2000-08-30 | Copper surface treatment method |
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|---|---|---|---|
| JP2000261069A JP3505135B2 (en) | 2000-08-30 | 2000-08-30 | Copper surface treatment method |
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|---|---|
| JP2002069661A true JP2002069661A (en) | 2002-03-08 |
| JP3505135B2 JP3505135B2 (en) | 2004-03-08 |
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ID=18748982
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|---|---|---|---|
| JP2000261069A Expired - Fee Related JP3505135B2 (en) | 2000-08-30 | 2000-08-30 | Copper surface treatment method |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003035930A1 (en) * | 2001-10-18 | 2003-05-01 | Nikko Materials Co., Ltd. | Surface treatment for copper foil |
| JP2006316300A (en) * | 2005-05-11 | 2006-11-24 | Hitachi Chem Co Ltd | Copper surface treatment method and copper surface |
| JP2007134695A (en) * | 2005-10-14 | 2007-05-31 | Ube Ind Ltd | Manufacturing method of metal wiring heat-resistant resin substrate |
| JP2009084652A (en) * | 2007-10-01 | 2009-04-23 | Hitachi Chem Co Ltd | Oxidation treatment method and oxidation treatment liquid for metal |
| US7524702B2 (en) | 2003-04-16 | 2009-04-28 | Shinko Electric Industries Co., Ltd. | Conductor substrate, semiconductor device and production method thereof |
| WO2009082005A1 (en) * | 2007-12-26 | 2009-07-02 | Denki Kagaku Kogyo Kabushiki Kaisha | Surface reactive support body, wiring board that uses same, and fabrication method therefor |
| JP4739464B2 (en) * | 2008-12-26 | 2011-08-03 | キヤノンアネルバ株式会社 | Sputtering apparatus, sputtering method, and electronic device manufacturing method |
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| JP2023107101A (en) * | 2022-01-21 | 2023-08-02 | ナミックス株式会社 | copper material |
| KR20230131453A (en) * | 2017-08-24 | 2023-09-13 | 한국전자기술연구원 | Copper based particle, conductive ink composition comprising the particle and electrode formed by the composition |
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2000
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003035930A1 (en) * | 2001-10-18 | 2003-05-01 | Nikko Materials Co., Ltd. | Surface treatment for copper foil |
| US6835241B2 (en) | 2001-10-18 | 2004-12-28 | Nikko Materials Co., Ltd. | Surface treatment for copper foil |
| US7524702B2 (en) | 2003-04-16 | 2009-04-28 | Shinko Electric Industries Co., Ltd. | Conductor substrate, semiconductor device and production method thereof |
| JP2006316300A (en) * | 2005-05-11 | 2006-11-24 | Hitachi Chem Co Ltd | Copper surface treatment method and copper surface |
| JP2007134695A (en) * | 2005-10-14 | 2007-05-31 | Ube Ind Ltd | Manufacturing method of metal wiring heat-resistant resin substrate |
| JP2009084652A (en) * | 2007-10-01 | 2009-04-23 | Hitachi Chem Co Ltd | Oxidation treatment method and oxidation treatment liquid for metal |
| WO2009082005A1 (en) * | 2007-12-26 | 2009-07-02 | Denki Kagaku Kogyo Kabushiki Kaisha | Surface reactive support body, wiring board that uses same, and fabrication method therefor |
| JP4739464B2 (en) * | 2008-12-26 | 2011-08-03 | キヤノンアネルバ株式会社 | Sputtering apparatus, sputtering method, and electronic device manufacturing method |
| US9178448B2 (en) | 2013-01-18 | 2015-11-03 | Fuji Electric Co., Ltd. | Power conversion device |
| US9355943B2 (en) | 2013-01-29 | 2016-05-31 | Fuji Electric Co., Ltd. | Manufacturing and evaluation method of a semiconductor device |
| KR20230131453A (en) * | 2017-08-24 | 2023-09-13 | 한국전자기술연구원 | Copper based particle, conductive ink composition comprising the particle and electrode formed by the composition |
| KR102650451B1 (en) | 2017-08-24 | 2024-03-22 | 한국전자기술연구원 | Copper based particle, conductive ink composition comprising the particle and electrode formed by the composition |
| CN113755829A (en) * | 2021-08-16 | 2021-12-07 | 深圳市志凌伟业光电有限公司 | Blackening-treated copper film surface anticorrosion protective liquid medicine |
| CN113755829B (en) * | 2021-08-16 | 2024-05-07 | 深圳市志凌伟业技术股份有限公司 | Blackening-treated copper film surface anti-corrosion protection liquid medicine |
| JP2023107101A (en) * | 2022-01-21 | 2023-08-02 | ナミックス株式会社 | copper material |
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