JPH05306470A - Catalytic solution for selective electroless plating - Google Patents
Catalytic solution for selective electroless platingInfo
- Publication number
- JPH05306470A JPH05306470A JP32302591A JP32302591A JPH05306470A JP H05306470 A JPH05306470 A JP H05306470A JP 32302591 A JP32302591 A JP 32302591A JP 32302591 A JP32302591 A JP 32302591A JP H05306470 A JPH05306470 A JP H05306470A
- Authority
- JP
- Japan
- Prior art keywords
- electroless plating
- conductor pattern
- metal
- solution
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Manufacturing Of Printed Wiring (AREA)
- Chemically Coating (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、電子部品等の基板上の
導体パターン上のみに選択的無電解めっきを施すための
無電解めっき用触媒液に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst solution for electroless plating for selective electroless plating only on a conductor pattern on a substrate such as an electronic component.
【0002】[0002]
【従来の技術】ガラスエポキシ樹脂、紙フェノール樹
脂、ポリイミド樹脂等の合成樹脂基板上に銅(Cu)の
配線(導体)パターンを形成した後、更に導体パターン
上にニッケル(Ni)や金(Au)等の無電解めっきを
選択的に施す場合がある。その場合導体パターンを活性
化しなければならない。その活性化手段としては、一般
にPdを含む触媒液が用いられている。導体パターンの
金属とPdを置換させ、無電解めっき皮膜はこの金属P
d上に析出する。このようなPdの活性による無電解め
っきを選択的析出する第1の方法は、金属パターンの被
めっき部分以外をレジストで被覆し、導体パターン上の
みにPdを析出させる方法がある。この方法を無電解N
iめっきの例で、さらに詳細に説明すれば、導体パター
ンが設けられた基板を第1すず(Sn)イオンを含むセ
ンシタイジング液(SnCl2 −HCl)に浸漬した
後、Pdイオンを含む活性化液(PdCl2 −HCl)
に浸漬するか、あるいは第1SnイオンとPdイオンと
を含む活性化液に浸漬する。しかし、第1Snイオン、
Pdイオンは吸着性が強いため、結果的には基板全面に
Pdが析出するといわれている(特開平2−24027
1号参照)。従って、その後レジストを剥離し、導体パ
ターンに析出するPdのみを残存させ、Pdを触媒とし
て導体パターン上のみに無電解Niめっきの初期析出を
行うものである。また第2の方法として、特公昭61−
31188号公報に示されるように、導体パターンが設
けられた基板を触媒活性の大きいPd活性化を短時間行
うことと、触媒活性の小さいシアン化金による金活性と
の2段処理を行い、これら2つを併用する相乗効果によ
り、無電解めっきを行った段階で導体パターン間にブリ
ッヂを生じることなく無電解めっきを施す方法がある。
そして第3の方法では、特開昭62−238374号公
報に示されるように、導体パターンが設けられている基
板の一部をPd処理し、その後無電解めっき処理を行
う。するとPd処理をした部分からめっき析出が始まっ
てから数十秒後にPd未処理部分の導体パターン上に選
択的にめっき金属、例えばニッケル等を析出することが
できる。Pd処理部分においては、導体パターン外にも
無電解めっきが施されているので導体パターンは電気的
に短絡状態にある。従ってPd処理部分を除去(切断)
し、これより回路的に独立した所望の導体パターンが得
られる方法がある。さらに第4の方法として、特開平2
−101172号公報に示されているように、タングス
テン(W)やモリブデン(Mo)皮膜を有するセラミッ
ク部品を、シアニド水溶液とPdCl2 水溶液の2段処
理により、W、Mo膜上に選択的に金属Pdを析出さ
せ、その後、無電解ニッケルめっき液中に浸漬し、セラ
ミックス部分にはめっき析出せず、W、Mo膜上のみ無
電解めっき被覆を形成させる方法がある。第5の方法と
して、導体パターンを形成した基板をそのままレジスト
被覆することなく、水溶性Pd塩に無機酸を添加したP
d活性液に浸漬して導体パターン上を選択的に活性化す
る方法が従来ある。この方法は、Pdの吸着ではなく、
導体パターンの金属(例えばCu)とPdの置換反応に
基づくものであるため、Pdの吸着性が導体上と非導体
上とで差があることを利用するものであるといわれてい
る(特開平2−240271号参照)。2. Description of the Related Art After a wiring (conductor) pattern of copper (Cu) is formed on a synthetic resin substrate such as glass epoxy resin, paper phenol resin, or polyimide resin, nickel (Ni) or gold (Au) is further formed on the conductor pattern. ) Etc. may be selectively applied. In that case, the conductor pattern must be activated. As the activation means, a catalyst liquid containing Pd is generally used. The metal of the conductor pattern is replaced by Pd, and the electroless plating film is made of this metal Pd.
Precipitates on d. A first method for selectively depositing the electroless plating based on the activity of Pd is a method of coating the portion other than the plated portion of the metal pattern with a resist and depositing Pd only on the conductor pattern. This method is electroless N
In more detail, an example of i plating will be described. After immersing the substrate on which the conductor pattern is provided in a sensitizing liquid (SnCl 2 —HCl) containing first tin (Sn) ions, an activity containing Pd ions is activated. Liquid (PdCl 2 -HCl)
Or an activation liquid containing first Sn ions and Pd ions. However, the first Sn ion,
Since Pd ions have strong adsorptivity, it is said that Pd eventually deposits on the entire surface of the substrate (JP-A-2-24027).
(See No. 1). Therefore, after that, the resist is peeled off to leave only Pd deposited on the conductor pattern, and the initial deposition of electroless Ni plating is performed only on the conductor pattern using Pd as a catalyst. The second method is as follows.
As disclosed in Japanese Patent No. 31188, the two-step treatment of performing Pd activation with high catalytic activity on a substrate provided with a conductor pattern for a short time and gold activation with gold cyanide with low catalytic activity is performed. Due to the synergistic effect of using the two together, there is a method of performing electroless plating without causing bridges between conductor patterns at the stage of electroless plating.
Then, in the third method, as shown in JP-A-62-238374, a part of the substrate on which the conductor pattern is provided is subjected to Pd treatment, and then electroless plating treatment is performed. Then, it is possible to selectively deposit a plating metal, such as nickel, on the conductor pattern of the Pd-untreated portion several tens of seconds after the plating deposition starts from the Pd-treated portion. In the Pd-treated portion, the electroless plating is also applied outside the conductor pattern, so the conductor pattern is in an electrically short-circuited state. Therefore, the Pd treated part is removed (cut)
However, there is a method of obtaining a desired conductor pattern which is circuit-independent from this. Further, as a fourth method, Japanese Patent Application Laid-Open No. Hei 2
As disclosed in Japanese Patent Application Laid-Open No. 101172, a ceramic part having a tungsten (W) or molybdenum (Mo) coating is selectively metallized on the W and Mo films by a two-step treatment with an aqueous cyanide solution and an aqueous PdCl 2 solution. There is a method of precipitating Pd and then immersing it in an electroless nickel plating solution so that plating is not deposited on the ceramic portion and an electroless plating coating is formed only on the W and Mo films. As a fifth method, it is possible to add P by adding an inorganic acid to a water-soluble Pd salt without directly coating the substrate on which the conductor pattern is formed with a resist.
Conventionally, there is a method of immersing in a d-active liquid to selectively activate the conductor pattern. This method is not the adsorption of Pd
Since it is based on the substitution reaction of Pd with the metal (for example, Cu) of the conductor pattern, it is said that the fact that the adsorptivity of Pd is different between on the conductor and on the non-conductor is used (Japanese Patent Laid-Open No. Hei 10 (1999) -135242) 2-240271).
【0003】[0003]
【発明が解決しようとする課題】従来技術の第1から第
4に示される方法では、工程数が多く、かつ複雑であ
り、作業能率が悪くなり、コストも高くなる。また、第
2、第4に示される方法は、最近、環境や作業者の健康
の点から非シアン化の要求が強まっているためあまり好
ましくない。従って、これらの問題を解決するものとし
ては、第5の方法が望ましく最近広く利用されている。
しかし、この方法は非導電性基板上へのPd吸着量をO
Kするのは難しく、このため導体パターン間に電気的な
短絡が発生し易い。触媒液への浸漬時間が長くなればな
るほどブリッヂが発生し易いので、触媒液の最適使用範
囲が狭く、作業管理が難しいといえる。そこで本発明
は、導体パターン上のみ選択的に金属Pdを析出させる
方法において、導体パターン間にブリッヂが生じること
なく、また触媒液の最適使用範囲が広く、作業管理が容
易である選択的無電解めっき用触媒を施すものである。In the methods shown in the first to fourth prior arts, the number of steps is large and complicated, the work efficiency is poor, and the cost is high. In addition, the methods shown in the second and fourth methods are not so preferable because the demand for non-cyanation has recently been increasing from the viewpoint of environment and health of workers. Therefore, as a solution to these problems, the fifth method is desirable and has been widely used recently.
However, this method reduces the amount of Pd adsorbed on the non-conductive substrate to O
It is difficult to perform K, and therefore an electrical short circuit is likely to occur between the conductor patterns. Since the longer the immersion time in the catalyst solution is, the more likely the bridge is to occur, the optimum use range of the catalyst solution is narrow, and it can be said that work management is difficult. Therefore, the present invention is a method of selectively depositing metal Pd only on a conductor pattern, in which no bridges are formed between conductor patterns, the optimum use range of the catalyst liquid is wide, and work management is easy, and selective electroless A plating catalyst is applied.
【0004】[0004]
【課題を解決するための手段】本発明では、上記の目的
を達成するために種々の検討を行った。その結果、水溶
性Pd塩とアンモニウム化合物とを1:750〜1:1
500のモル比に調整し、pHを2.5〜4.0に調整
し、この液で導体パターンの設けられている基板を処理
することにより、活性化工程を1回の処理で導体パター
ン上のみ選択的に金属Pdを析出させることができ、な
おかつ、最適使用条件範囲が広く、これにより工程管理
も容易にすることができることを見いだした。そこで、
この方法を詳しく説明すると、水溶性Pd塩とアンモニ
ウム化合物のモル比が1:750未満、あるいはpHが
2.5未満では、導体パターンの活性化を処理温度25
℃で5分間行い、更に無電解Niめっき処理した場合、
導体パターン間にNiブリッヂが発生し易く、処理時間
が長くなると更にNiブリッヂが発生し易くなることが
わかった。つまり、この条件では最適使用条件範囲が狭
く、これにより工程管理も難しいと言える。また、pH
が4を越えると、導体パターン上へのPd触媒活性が弱
まり、導体パターン上への無電解めっき析出開始時間が
遅くなる。そして、PdCl2 とNH4 Clのモル比が
1:1500を越えると、NH4 Clの溶解が困難にな
るため製造上で不備な点がある。水溶性Pd塩とアンモ
ニウム化合物とのモル比の割合が1:750から1:1
500の範囲でpHを2.5から4の範囲にすると、導
体パターン上のみ選択的に金属Pdを析出させることが
でき、活性化の処理時間が長くても無電解めっき後、導
体パターン間に金属ブリッヂは発生しない。よって最適
使用条件範囲が広く、これにより工程管理も容易である
といえる。以上のことより、導体パターン上のみ選択的
に金属Pdを析出させ、なお且つ最適使用条件範囲を広
くするためには、単に液中に生成しているPd塩のPd
イオンとアンモニウム化合物のアンモニウムイオンとの
パラジウムアンモニウム錯体の特性により、上記の目的
を達成するのではないことがわかった。むしろこの錯体
というのは、溶液中におけるPdイオンを安定にしてお
くという働きをするものであり、上記の目的を達成する
ためには、液中に含まれる過剰のアンモニウム化合物が
必要であるといえる。In the present invention, various studies have been made in order to achieve the above object. As a result, the water-soluble Pd salt and ammonium compound were mixed at 1: 750 to 1: 1.
By adjusting the molar ratio to 500, adjusting the pH to 2.5 to 4.0, and treating the substrate on which the conductor pattern is provided with this solution, the activation step can be performed on the conductor pattern in a single treatment. It has been found that the metal Pd can be selectively precipitated only, and the range of optimum use conditions is wide, which can facilitate process control. Therefore,
This method will be described in detail. When the molar ratio of the water-soluble Pd salt to the ammonium compound is less than 1: 750 or the pH is less than 2.5, activation of the conductor pattern is performed at a treatment temperature of 25.
In case of performing electroless Ni plating treatment at 5 ° C for 5 minutes,
It was found that Ni bridges are likely to occur between the conductor patterns, and Ni bridges are more likely to occur as the treatment time becomes longer. In other words, under these conditions, the range of optimum use conditions is narrow, which makes it difficult to control the process. Also, the pH
When the value exceeds 4, the Pd catalytic activity on the conductor pattern is weakened, and the time for starting the electroless plating deposition on the conductor pattern is delayed. If the molar ratio of PdCl 2 and NH 4 Cl exceeds 1: 1,500, it is difficult to dissolve NH 4 Cl, which is a defect in production. The molar ratio of the water-soluble Pd salt to the ammonium compound is 1: 750 to 1: 1.
When the pH is adjusted to the range of 2.5 to 4 in the range of 500, the metal Pd can be selectively deposited only on the conductor pattern, and even if the activation treatment time is long, after the electroless plating, a space between the conductor patterns is formed. No metal bridge is generated. Therefore, it can be said that the range of optimum use conditions is wide and process control is easy. From the above, in order to selectively deposit the metal Pd only on the conductor pattern and to widen the range of the optimum use condition, the Pd salt Pd formed in the liquid is simply added.
It has been found that the properties of the palladium ammonium complex of the ion with the ammonium ion of the ammonium compound do not achieve the above objectives. Rather, this complex functions to stabilize Pd ions in the solution, and it can be said that an excess amount of ammonium compound contained in the solution is necessary to achieve the above object. ..
【0005】[0005]
【実施例】第一表に示す組成の無電解めっき用触媒液を
調整した。(但し、pHはNaOHで調整した。)次
に、Cuパターンが形成されたガラスエポキシ基板を第
二表に示す工程により無電解ニッケル(Ni)めっきを
施した。その時の無電解めっき用触媒液の各基板処理時
間に対する無電解Niめっきの析出状態を第一表に併記
する。Example An electroless plating catalyst solution having the composition shown in Table 1 was prepared. (However, pH was adjusted with NaOH.) Next, the glass epoxy substrate on which the Cu pattern was formed was subjected to electroless nickel (Ni) plating by the steps shown in Table 2. Table 1 also shows the deposition state of the electroless Ni plating for each substrate treatment time of the electroless plating catalyst solution at that time.
【0006】[0006]
【表1】 [Table 1]
【0007】[0007]
【表2】 [Table 2]
【0008】第一表より、本発明の無電解めっき用触媒
液で処理したガラスエポキシ基板は確実に導体パターン
上のみ選択的に金属Pdを析出させ、そして無電解Ni
めっきを被覆させることができた。From Table 1, the glass epoxy substrate treated with the electroless plating catalyst solution of the present invention surely selectively deposits metal Pd only on the conductor pattern, and the electroless Ni
The plating could be coated.
【0009】比較例 第三表に示す組成の無電解めっき用触媒液を調整した
(但し、pHはNaOHで調整した。)。次に、第三表
に示す無電解めっき用触媒液を実施例と同様に行った。
その時の無電解めっき用触媒液の各基板処理時間に対す
る無電解Niめっきの析出状態を第三表に併記する。Comparative Example A catalyst solution for electroless plating having the composition shown in Table 3 was prepared (however, the pH was adjusted with NaOH). Next, the catalyst solutions for electroless plating shown in Table 3 were applied in the same manner as in the examples.
Table 3 also shows the deposition state of the electroless Ni plating for each substrate treatment time of the electroless plating catalyst solution at that time.
【0010】[0010]
【表3】 [Table 3]
【0011】第三表より、PdCl2 −HCl系無電解
めっき用触媒液では処理時間が30秒で、pHが3以上
ならば導体パターン間にNiブリッヂは発生しなかっ
た。しかし、処理時間が30秒を超えるとどのpHでも
Niブリッヂが発生した。またPdCl2 /NH4 Cl
>1/750で、なお且つpH<2.5の無電解めっき
用触媒液では、処理時間が長くなるとNiブリッヂが発
生した。From Table 3, with the PdCl 2 --HCl system electroless plating catalyst solution, when the treatment time was 30 seconds and the pH was 3 or more, Ni bridges did not occur between the conductor patterns. However, when the treatment time exceeded 30 seconds, Ni bridges were generated at any pH. Also PdCl 2 / NH 4 Cl
With the catalyst liquid for electroless plating of> 1/750 and pH <2.5, Ni bridges were generated when the treatment time was long.
【0012】[0012]
【発明の効果】本発明の無電解めっき用触媒液で導体パ
ターンが設けられている基板を処理することにより、導
体パターン上のみ選択的に金属Pdを析出させ、選択的
に無電解めっきを施すことができる。また、本触媒液は
最適使用範囲が広く、よって作業管理も容易である。EFFECTS OF THE INVENTION By treating a substrate provided with a conductor pattern with the electroless plating catalyst solution of the present invention, metal Pd is selectively deposited only on the conductor pattern, and electroless plating is selectively performed. be able to. Further, the catalyst liquid has a wide optimum use range, and therefore work management is easy.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成4年6月2日[Submission date] June 2, 1992
【手続補正1】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0010[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0010】[0010]
【表3】 [Table 3]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山本 弘 茨城県下館市大字森添島1245番地 日立ボ ーデン株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Yamamoto 1245 Morisoejima, Shimodate-shi, Ibaraki Hitachi Boden Co., Ltd.
Claims (3)
ンの錯化剤としてアンモニウム化合物、無機酸、pH調
整剤を必須成分とする無電解めっき用触媒液。1. A catalyst solution for electroless plating, which comprises a water-soluble palladium (Pd) salt, an ammonium compound as a complexing agent for Pd ions, an inorganic acid, and a pH adjuster as essential components.
モル比が1:750から1:1500の範囲であること
を特徴とする特許請求範囲第1項記載の無電解めっき用
触媒液。2. The catalyst solution for electroless plating according to claim 1, wherein the molar ratio of the water-soluble Pd salt to the ammonium compound is in the range of 1: 750 to 1: 1500.
とを特徴とする特許請求範囲第1項及び第2項記載の無
電解めっき用触媒液。3. The catalyst solution for electroless plating according to claim 1, wherein the pH is in the range of 2.5 to 4.0.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP32302591A JPH05306470A (en) | 1991-12-06 | 1991-12-06 | Catalytic solution for selective electroless plating |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP32302591A JPH05306470A (en) | 1991-12-06 | 1991-12-06 | Catalytic solution for selective electroless plating |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH05306470A true JPH05306470A (en) | 1993-11-19 |
Family
ID=18150284
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP32302591A Pending JPH05306470A (en) | 1991-12-06 | 1991-12-06 | Catalytic solution for selective electroless plating |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH05306470A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002241951A (en) * | 2001-02-16 | 2002-08-28 | C Uyemura & Co Ltd | Method for depositing electroless zinc oxide film |
KR101220327B1 (en) * | 2010-11-18 | 2013-01-09 | 한국기계연구원 | Preparation of the Pd catalytic ink, method for forming metal pattern using the same and method for the surface modification of substrate |
JP2013019044A (en) * | 2011-07-14 | 2013-01-31 | Toray Eng Co Ltd | Palladium catalyst-imparting solution comprising palladium ammine complex salt aqueous solution and electroless nickel plating method for copper wiring substrate using the same |
-
1991
- 1991-12-06 JP JP32302591A patent/JPH05306470A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002241951A (en) * | 2001-02-16 | 2002-08-28 | C Uyemura & Co Ltd | Method for depositing electroless zinc oxide film |
JP4600623B2 (en) * | 2001-02-16 | 2010-12-15 | 上村工業株式会社 | Method for forming electroless zinc oxide film |
KR101220327B1 (en) * | 2010-11-18 | 2013-01-09 | 한국기계연구원 | Preparation of the Pd catalytic ink, method for forming metal pattern using the same and method for the surface modification of substrate |
JP2013019044A (en) * | 2011-07-14 | 2013-01-31 | Toray Eng Co Ltd | Palladium catalyst-imparting solution comprising palladium ammine complex salt aqueous solution and electroless nickel plating method for copper wiring substrate using the same |
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