JP3505135B2 - Copper surface treatment method - Google Patents
Copper surface treatment methodInfo
- Publication number
- JP3505135B2 JP3505135B2 JP2000261069A JP2000261069A JP3505135B2 JP 3505135 B2 JP3505135 B2 JP 3505135B2 JP 2000261069 A JP2000261069 A JP 2000261069A JP 2000261069 A JP2000261069 A JP 2000261069A JP 3505135 B2 JP3505135 B2 JP 3505135B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- surface treatment
- treatment method
- treated
- group
- 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.)
- Expired - Fee Related
Links
Landscapes
- Chemical Treatment Of Metals (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Lead Frames For Integrated Circuits (AREA)
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 surface treatment method for copper, copper treated by the method, and a printed wiring board and a semiconductor device manufactured by 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 Bonding of copper and resin is carried out, for example, in the production of a copper clad laminate. However, the adhesion between copper and resin (polymer) is generally low. This is because copper or copper ions prevent the resin (polymer) from hardening,
This is because it serves as a decomposition catalyst for the resin (polymer). As a remedy for this, there is a method of increasing the copper surface roughness, or a method of oxidizing the copper surface or coating the copper surface with plating or chemical conversion treatment to shield the active copper surface. For example, the surface of the copper foil that adheres to the resin (matte surface) has a large surface roughness, copper particles are attached, and zinc, brass, or other metal is plated, and chemical conversion treatment such as chromate treatment is performed. 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, the surface that does not adhere to the resin (the shiny surface) is subjected to chemical conversion treatment such as chromate treatment for the purpose of preventing discoloration of the copper foil. However, such a method for improving the adhesive strength with a resin is complicated and cannot be processed without a special plating device 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。Further, copper foil or copper-plated copper wiring is used for the inner layer copper wiring of the multilayer wiring board. For example, when a copper foil is used, not only the matte surface but also the shiny surface is required to have adhesiveness with the resin (polymer). The copper surface (shiny surface) is a method of roughening the surface by soft etching or the like and then making the surface cuprous oxide or cupric oxide in order to improve the adhesion with resin (polymer) such as prepreg. (Blackening process) is common. However, this copper oxide film is easily corroded when immersed in hydrochloric acid or the like, resulting in 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 apply a polysiloxane film on a copper foil (JP-A-2-307294). This polysiloxane is disclosed in
According to the description on page (307) of JP-A-307294, it may have a linear, cyclic or network structure, and this polysiloxane does not have an organic group, and a part of H of OH of the substituent is It is said that it is substituted with Na and has a pH of 10.5-11.2 when dispersed in water to form a solution (the above-mentioned publication (2) page, upper left column, line 15 to upper right column, line 2). .
In this method, the surface of copper is made to be silica-like, and the adhesiveness with resin is improved. The surface treatment with a silane coupling agent or the like can further improve the adhesive strength. However, in this treatment method, when the treatment is performed using sodium silicate as the material for forming the polysiloxane film, followed by washing with water, the polysiloxane film is not formed on the copper surface. In general, sodium silicate corrodes metals such as Sn, Zn, and Al to form a film of polysiloxane and metal oxide on the newly appeared metal surface, but copper is difficult to react with sodium silicate and polysiloxane Difficult to form a film. That is, in order to form a polysiloxane film on the copper surface, a method of treating with sodium silicate and then drying without washing with water, or treating a material coated with a metal such as Sn, Zn, or Al with sodium silicate is used. I have to take it. However, the polysiloxane film obtained by treating copper with sodium silicate and then drying it without washing it with water does not have sufficient bonding between the copper and the polysiloxane film, and when the resin and copper are subsequently bonded, the resin and copper are highly The adhesiveness cannot be obtained. In addition, when the metal is coated, 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。As another example, there is a demand for improvement in adhesion between copper and resin, such as adhesion between a lead frame made of a copper material used in a semiconductor device and a sealing resin or paste (mount material). Is. Regarding this, each company is currently considering 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 Under these circumstances, 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 resin. In addition, copper foil treated by the treatment method, copper plating film,
It is an object of the present invention to provide a sputtered copper coating and a printed wiring board and a semiconductor device produced by 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 extensive studies, the present inventor oxidizes the copper surface first to form an oxide film,
The inventors have found that forming a polysiloxane film by subsequent treatment with an aqueous alkali silicate solution is effective in improving the adhesion of the copper surface to the resin, and arrived at the present invention. Although the mechanism of formation of the polysiloxane film is not clear, by forming an oxide film on the copper surface, the alkaline silicate aqueous solution erodes the oxide film,
It is considered that the polysiloxane film is formed at the same time. That is, when the oxide film is thin, the polysiloxane film is not sufficiently formed and the adhesiveness with the resin cannot be improved. The oxide film should preferably have a thickness of 50 Å or more.
【０００９】（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し、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、
（２）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（１）記載の表面処理方法、
（３）前記（１）または（２）記載の表面処理方法で処
理した銅、
（４）前記（１）または（２）記載の表面処理方法で処
理した銅箔、
（５）前記（１）または（２）記載の表面処理方法で処
理した銅めっき被膜、
（６）前記（１）または（２）記載の表面処理方法で処
理したスパッタ銅被膜、
（７）前記（４）〜（６）のいずれかの銅材を用いて作
製したプリント配線板、
（８）前記（４）〜（６）のいずれかの銅材を用いて作
製した半導体デバイス、に関する。(1) A method for surface treatment of copper, characterized in that after copper is oxidized to form an oxide film, it is treated with an alkali silicate solution and further a silane coupling agent is applied, (2) Silane cup Ring agent is epoxy group, amino group,
It has a mercapto group, a vinyl group, a methacryl group, an imidazole group, or a dimethylamino group, (3) The surface treatment method described in (1) or (2) above. Treated copper, (4) copper foil treated by the surface treatment method described in (1) or (2), (5) copper plating film treated by the surface treatment method described in (1) or (2), 6) A sputtered copper coating processed by the surface treatment method according to the above (1) or (2), (7) a printed wiring board produced using the copper material according to any one of the above (4) to (6), (8) ) A semiconductor device produced by using the copper material according to any one of (4) to (6).
【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 copper oxidation method in the copper surface treatment method of the present invention is not particularly limited as long as it can form an oxide film on the copper surface, but the copper surface is degreased and then contacted with an oxidizing solution. The method by means is preferred. As the oxidizing solution, for example, hydrogen peroxide-dilute sulfuric acid aqueous solution, potassium permanganate, sodium persulfate and the like are preferably used. The contact between the oxidizing solution and copper is 50Å or more on the copper surface,
More preferably, it is performed so that an oxide film of 100 Å or more is formed. If the oxide film is less than 50Å, it is difficult to form a polysiloxane film with 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 carried out by immersing the copper having an oxide film 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, which improves the adhesiveness with the resin. The polysiloxane film is preferably formed with a layer thickness of 10 Å or more. Further, it is more preferable that the polysiloxane film is washed with water after formation to remove sodium ions and then dried 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, a polysiloxane film is formed on the copper surface, and then a silane coupling agent is applied to the film to further improve the adhesiveness with the resin. As such a silane coupling agent, a known silane coupling agent can be used, but as particularly preferable ones, an epoxy group, an amino group, a mercapto group, a vinyl group, a methacryl group, an imidazole group in the molecule, The thing 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。Since the treatment method of the present invention is a useful technique in the field in which the adhesion between copper and resin is a problem, there are no particular restrictions on the usage form of copper, but especially in the case of lamination or build-up, it is possible to use multiple layers. 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 and 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 off 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 dilution of [EBARA Eugelite Co., Ltd.],
It was degreased by treating at 40 ° C. for 5 minutes. After degreasing, it was washed with hot water at 50 ° C. for 1 minute. It was confirmed by Auger analysis that the copper oxide film on the shiny surface of this copper foil had a thickness of about 25 Å (SiO 2 etching rate conversion).
【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。Next, the shiny surface of this copper foil is
62 ml / l aqueous solution of H 2 O 2 and 10 m of 96% H 2 SO 4
The copper foil shiny surface was oxidized by immersing it in a mixed solution of 1 / l aqueous solution at room temperature for 1 minute. It was confirmed by Auger analysis that the copper oxide film formed had a thickness of about 130Å (SiO 2 etching rate conversion).
【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 thus formed with the oxide film was immersed in a 4% sodium disilicate aqueous solution [Kanto Chemical Co., Inc.] 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 The copper foil was treated in the same manner as in Example 1 except that the shiny surface of the copper foil was immersed in the aqueous sodium disilicate solution 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 the 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 the aqueous solution of sodium disilicate for 5 minutes at room temperature.
The copper foil was treated in the same manner as in.
【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 An imidazole system obtained by immersing a copper foil in an aqueous solution of sodium disilicate and reacting imidazole with 3-glycidoxypropyltrimethoxysilane at 95 ° C. for 1 hour in the same manner as in Example 1 Further immersion treatment was carried out with a 0.5% aqueous solution of a silane coupling agent (pH was adjusted to 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 treatment with the coupling agent in Example 5 was carried out 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 The procedure of Example 5 was repeated, except that the treatment with the coupling agent was carried out by 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 dipped in the 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 immersion treatment of the copper foil in the aqueous solution of sodium disilicate was not performed. The shiny side of the treated copper foil was heat-pressed with a prepreg in which a glass base material was impregnated with an epoxy resin to produce a copper-clad laminate. The normal peel strength of this 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. Note that almost no difference was observed 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 previously oxidized to form an oxide film on the surface thereof, and the copper is treated with an alkali silicate solution or further with a silane coupling agent. As a result, the adhesive strength between the resin and copper can be significantly improved.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭57−185986（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 22/52 C23C 22/83 H01L 23/50 H05K 3/38 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-57-185986 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C23C 22/52 C23C 22/83 H01L 23 / 50 H05K 3/38
Claims (8)
酸アルカリ溶液で処理し、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。1. A method for surface treatment of copper, comprising the steps of oxidizing copper to form an oxide film, treating it with an alkali silicate solution, and then applying a silane coupling agent.
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１記載の表面処理方法。2. The surface treatment method according to claim 1, 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.
理した銅。3. Copper treated by the surface treatment method according to claim 1.
理した銅箔。4. A copper foil treated by the surface treatment method according to claim 1.
理した銅めっき被膜。5. A copper plating film treated by the surface treatment method according to claim 1.
理したスパッタ銅被膜。6. A sputtered copper coating treated by the surface treatment method according to claim 1.
製したプリント配線板。7. A printed wiring board produced by using the copper material according to claim 4.
製した半導体デバイス。8. A semiconductor device manufactured by using the copper material according to claim 4.
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| JP3505135B2 true JP3505135B2 (en) | 2004-03-08 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006316300A (en) * | 2005-05-11 | 2006-11-24 | Hitachi Chem Co Ltd | Method for surface-treating copper, and copper surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4298943B2 (en) * | 2001-10-18 | 2009-07-22 | 日鉱金属株式会社 | Copper foil surface treatment agent |
| JP3883543B2 (en) | 2003-04-16 | 2007-02-21 | 新光電気工業株式会社 | Conductor substrate and semiconductor device |
| JP4911296B2 (en) * | 2005-10-14 | 2012-04-04 | 宇部興産株式会社 | 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 |
| WO2010073711A1 (en) * | 2008-12-26 | 2010-07-01 | キヤノンアネルバ株式会社 | Sputtering equipment, sputtering method and method for manufacturing an electronic device |
| JP2014138532A (en) | 2013-01-18 | 2014-07-28 | Fuji Electric Co Ltd | Electric power conversion system |
| JP2014146704A (en) | 2013-01-29 | 2014-08-14 | Fuji Electric Co Ltd | Semiconductor device |
| KR20190021827A (en) * | 2017-08-24 | 2019-03-06 | 전자부품연구원 | Copper based particle, conductive ink composition comprising the particle and electrode formed by the composition |
| 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 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006316300A (en) * | 2005-05-11 | 2006-11-24 | Hitachi Chem Co Ltd | Method for surface-treating copper, and copper surface |
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