JP3030114B2 - Electroless plating solution - Google Patents
Electroless plating solutionInfo
- Publication number
- JP3030114B2 JP3030114B2 JP3106572A JP10657291A JP3030114B2 JP 3030114 B2 JP3030114 B2 JP 3030114B2 JP 3106572 A JP3106572 A JP 3106572A JP 10657291 A JP10657291 A JP 10657291A JP 3030114 B2 JP3030114 B2 JP 3030114B2
- Authority
- JP
- Japan
- Prior art keywords
- plating solution
- gold
- deposited
- copper
- electroless plating
- 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 - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は、銅素地の微細回路基板
上へ長時間安定に厚付け金めつきを施すことが可能な無
電解金めつき液に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroless plating solution capable of stably applying a thick plating onto a fine circuit board made of copper base for a long time.
【０００２】[0002]
【従来の技術】これまで多くの自己触媒めつき液が報告
されているが、シアン化合物を含有し高アルカリ性で使
用するめつき液が多い。2. Description of the Related Art Many autocatalytic plating solutions have been reported so far, but there are many plating solutions containing a cyanide and used at high alkalinity.
【０００３】一方、シアン化合物を全く含まない中性無
電解金めつき液としては、特願平２−７０６３号に記載
されている水溶性亜硫酸金化合物、水溶性ポリアミノポ
リカルボン酸又はその塩、水溶性アミン又はその誘導
体、チオ硫酸塩、亜硫酸塩及びヒドラジン化合物を含有
する金めつき液がある。On the other hand, neutral electroless plating solutions containing no cyanide include water-soluble gold sulfite compounds, water-soluble polyaminopolycarboxylic acids or salts thereof described in Japanese Patent Application No. 2-7063. There is a plating solution containing a water-soluble amine or a derivative thereof, a thiosulfate, a sulfite and a hydrazine compound.
【０００４】[0004]
【発明が解決しようとする問題点】レジストを使用して
微細回路を形成した銅素地の微細回路基板上に例えば無
電解ニツケルめつきを施し続いて金めつきを行う場合、
レジストの金めつき液への溶解による微細回路の破壊が
なく、素地金属である銅のめつき液への溶け込みがな
く、銅の溶解に伴う金の異常析出がなく（膜厚のばらつ
きが小さい）、レジスト上及び微細回路間に金が析出し
て微細回路が短絡せず（以下これをパターン性が良いと
いう）、微細回路上に析出した金皮膜はムラ、ガスピツ
ト等の外観不良がない等の特性が要求される。For example, when performing electroless nickel plating and then gold plating on a copper-based fine circuit board on which a fine circuit is formed using a resist,
There is no breakage of microcircuits due to dissolution of the resist in the plating solution, no incorporation of the base metal, copper, into the plating solution, and no abnormal deposition of gold due to the dissolution of copper. ), Gold is deposited on the resist and between the fine circuits, and the fine circuit is not short-circuited (hereinafter referred to as having good patternability), and the gold film deposited on the fine circuit has no uneven appearance such as unevenness and gas pits. Characteristics are required.
【０００５】従来多くの無電解金めつき液は、シアン化
合物を含む高アルカリ性めつき液であるため、レジスト
を使用した微細回路をめつきした場合、基板上のレジス
トを溶解するため微細回路が破壊され、パターン性が悪
くなる。また、シアン化合物を含有するめつき液は、作
業時及び廃液処理時等において安全上問題がある。さら
にシアン化合物を含有する金めつき液は、銅、ニツケル
などの素地の溶け込みによる不純物金属の影響を敏感に
受けて自己分解を生じ連続使用できないなどの欠点を有
している。Conventionally, many electroless gold plating solutions are highly alkaline plating solutions containing a cyanide. Therefore, when a fine circuit using a resist is plated, the fine circuit is dissolved to dissolve the resist on the substrate. It is destroyed and the pattern becomes poor. Further, the plating solution containing a cyanide has a safety problem at the time of work and at the time of waste liquid treatment. Furthermore, the plating solution containing a cyanide has a disadvantage that it is sensitive to the influence of the impurity metal due to the dissolution of the base material such as copper and nickel, self-decomposes, and cannot be used continuously.
【０００６】したがつて、金めつき液がシアン化合物を
含むことなく、中性のめつき条件で使用できれば、かよ
うな金めつき液は、レジストを溶解することがなく、微
細回路基板上にパターン性良く金を析出することが可能
であり、また作業時、廃液処理時などにおいて有利であ
る。Accordingly, if the plating solution does not contain a cyanide and can be used under neutral plating conditions, such a plating solution does not dissolve the resist and can be used on a fine circuit board. It is possible to deposit gold with good patternability, and it is advantageous at the time of work, waste liquid treatment, and the like.
【０００７】一方、従来のシアン化合物を含まない中性
無電解金めつき液は、レジストを溶解することなくめつ
きできるが、めつき液に銅が溶解する欠点がある。たと
え銅素地にニツケルめつきを行つても、ニツケルめつき
の欠陥部分及びレジストと銅との界面部分などから素地
の銅が液中に溶解するため、溶解部分に金が異常析出し
膜厚が部分的に高くなる。さらに異常析出に伴いパター
ン性は悪くなる。On the other hand, a conventional neutral electroless plating solution containing no cyanide can be plated without dissolving the resist, but has a disadvantage that copper is dissolved in the plating solution. Even if nickel plating is performed on a copper substrate, the copper in the substrate dissolves in the liquid from the defective portion of the nickel plating and the interface between the resist and the copper, so that gold is abnormally deposited on the dissolved portion and the film thickness is reduced. Will be higher. Furthermore, the pattern property deteriorates with abnormal precipitation.
【０００８】また、銅の溶解濃度が高くなるとめつき液
は、自己分解を起こし易くなり連続使用できない傾向が
ある。In addition, when the concentration of dissolved copper increases, the plating solution tends to undergo self-decomposition and cannot be used continuously.
【０００９】本発明は、従来の無電解金めつき液に於け
る上記の問題点を解決すべく開発された無電解金めつき
液である。即ち、本発明はシアン化合物を含むことな
く、中性のめつき条件で使用でき、微細回路基板上のレ
ジストを溶解することなく、パターン性良く金が析出
し、また部分的異常析出及びパターン性劣化の原因であ
る銅のめつき液への溶け込みがなく、ムラ、ガスピツト
等の外観不良を有しない金皮膜を析出することができる
無電解金めつき液を提供することを目的とするものであ
る。The present invention is an electroless plating solution developed to solve the above-mentioned problems in the conventional electroless plating solution. That is, the present invention does not contain a cyanide, can be used under neutral plating conditions, does not dissolve the resist on a fine circuit board, deposits gold with good patternability, and partially abnormal deposition and patternability It is an object of the present invention to provide an electroless gold plating solution capable of depositing a gold film having no appearance defect such as unevenness and gas pit without dissolving into copper plating solution which causes deterioration. is there.
【００１０】[0010]
【問題点を解決するための手段】本発明の無電解金めつ
き液は、上記の目的を達成させるものとして、シアン化
合物を含むことなく、中性のめつき条件で使用でき、微
細回路基板上のレジストを溶解することなく、パターン
性良く金が析出し、また部分的異常析出及びパターン性
劣化の原因である銅のめつき液への溶け込みがなく、ム
ラ、ガスピツト等の外観不良を有しない金皮膜を析出す
ることができる無電解金めつき液を開発すべく研究検討
を結果開発されたものである。The electroless gold plating solution of the present invention can be used under neutral plating conditions without containing a cyanide compound to achieve the above object. Gold is deposited with good patternability without dissolving the resist on top.Also, there is no partial abnormal deposition and dissolution into copper plating solution, which is a cause of pattern deterioration, and there are appearance defects such as unevenness and gas pits. It was developed as a result of research and study to develop an electroless plating solution capable of depositing a gold film that does not need to be deposited.
【００１１】本発明は、水溶性亜硫酸金化合物と、水溶
性ポリアミノポリカルボン酸又はその塩と、水溶性アミ
ン又はその誘導体と、チオ硫酸塩と、亜硫酸塩と、ヒド
ラジン化合物とベンゾトリアゾール系化合物とを含むこ
とを特徴とする無電解金めつき液である。The present invention relates to a water-soluble gold sulfite compound, a water-soluble polyaminopolycarboxylic acid or a salt thereof, a water-soluble amine or a derivative thereof, a thiosulfate, a sulfite, a hydrazine compound and a benzotriazole compound. And an electroless plating solution.
【００１２】以下、本発明の無電解金めつき液について
詳細に説明する。Hereinafter, the electroless plating solution of the present invention will be described in detail.
【００１３】本発明の無電解金めつき液は、水溶性亜硫
酸金化合物を含有する、水溶性亜硫酸金化合物として
は、例えば亜硫酸金アンモニウム、亜硫酸金カリウム、
亜硫酸金ナトリウムなどを挙げることができる。本発明
の無電解金めつき液は、これら水溶性亜硫酸金化合物を
金イオンとして１〜８ｇ／ｌ、好ましくは２〜５ｇ／ｌ
含有するものである。これら水溶性亜硫酸金化合物の含
有量が金イオンとして１ｇ／ｌ以下であるとめつき反応
の進行が遅いか又はほとんど起こらず、８ｇ／ｌ以上で
あると金めつき液が自己分解し、沈澱が生じ、パターン
性が悪くなる傾向がある。The electroless gold plating solution of the present invention contains a water-soluble gold sulfite compound. Examples of the water-soluble gold sulfite compound include ammonium gold sulfite, potassium gold sulfite,
Gold sodium sulfite and the like can be mentioned. The electroless gold plating solution of the present invention uses these water-soluble gold sulfite compounds as gold ions in an amount of 1 to 8 g / l, preferably 2 to 5 g / l.
It contains. When the content of these water-soluble gold sulfite compounds is 1 g / l or less as gold ions, the progress of the plating reaction is slow or hardly occurs, and when the content is 8 g / l or more, the plating solution is self-decomposed and precipitates. And the patternability tends to deteriorate.
【００１４】本発明の無電解金めつき液は、水溶性ポリ
アミノポリカルボン酸又はその塩を含有する。水溶性ポ
リアミノポリカルボン酸又はその塩としては、例えばエ
チレンジアミン四酢酸、エチレンジアミン四酢酸二ナト
リウム、エチレンジアミン四酢酸二カリウム、エチレン
ジアミン四酢酸二アンモニウム及びニトリロ三酢酸など
を挙げることができる。本発明の無電解金めつき液は、
これら水溶性ポリアミノポリカルボン酸又はその塩を１
０ｇ／ｌ〜１５０ｇ／ｌ、好ましくは５０ｇ／ｌ〜１０
０ｇ／ｌ含有するものである。これら水溶性ポリアミノ
ポリカルボン酸又はその塩の含有量が１０ｇ／ｌ以下で
あると金めつき液は銅、ニツケルなどの不純物の影響を
受け易くなり、めつき液の安定性が低下し、金めつき液
の自己分解が生じる。一方、これら水溶性ポリアミノポ
リカルボン酸又はその塩の含有量を１５０ｇ／ｌ以上と
してもそれに見合う効果はほとんど得られないことが多
く、経済的ではない。The electroless plating solution of the present invention contains a water-soluble polyaminopolycarboxylic acid or a salt thereof. Examples of the water-soluble polyaminopolycarboxylic acid or a salt thereof include ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, dipotassium ethylenediaminetetraacetate, diammonium ethylenediaminetetraacetate, and nitrilotriacetic acid. The electroless plating solution of the present invention,
These water-soluble polyaminopolycarboxylic acids or salts thereof are
0 g / l to 150 g / l, preferably 50 g / l to 10
It contains 0 g / l. When the content of these water-soluble polyaminopolycarboxylic acids or salts thereof is 10 g / l or less, the plating solution is easily affected by impurities such as copper and nickel, and the stability of the plating solution is reduced. Self-decomposition of the plating solution occurs. On the other hand, even if the content of the water-soluble polyaminopolycarboxylic acid or a salt thereof is 150 g / l or more, an effect corresponding to the content is often hardly obtained, which is not economical.
【００１５】本発明の無電解金めつき液は、水溶性アミ
ン又はその誘導体を含有する。水溶性アミン又はその誘
導体としては、例えばトリエタノールアミン、トリエチ
レンテトラミン、エチレンジアミン、ジメチルアミン、
トリメタノールアミン及び塩酸ヒドロキシルアミンなど
を挙げることができる。本発明の無電解金めつき液は、
これら水溶性アミン又はその誘導体を１ｇ／ｌ〜１０ｇ
／ｌ、好ましくは２ｇ／ｌ〜６ｇ／ｌ含有するものであ
る。これら水溶性アミン又はその誘導体の含有量が１ｇ
／ｌ以下であると、ガスピツトの抑制の効果がなく、１
０ｇ／ｌ以上であると、めつき物の外観が悪くなる傾向
がある。The electroless plating solution of the present invention contains a water-soluble amine or a derivative thereof. Examples of the water-soluble amine or a derivative thereof include triethanolamine, triethylenetetramine, ethylenediamine, dimethylamine,
Trimethanolamine and hydroxylamine hydrochloride can be mentioned. The electroless plating solution of the present invention,
1 g / l to 10 g of these water-soluble amines or derivatives thereof
/ L, preferably 2 g / l to 6 g / l. The content of these water-soluble amines or derivatives thereof is 1 g
/ L or less, there is no gas pit suppression effect, and
When it is 0 g / l or more, the appearance of the plated object tends to deteriorate.
【００１６】本発明の無電解金めつき液は、チオ硫酸塩
を含有する。チオ硫酸塩としては、例えばチオ硫酸アン
モニウム、チオ硫酸カリウム及びチオ硫酸ナトリウムな
どを挙げることができる。本発明の無電解金めつき液
は、これらチオ硫酸塩を１〜５０ｇ／ｌ、好ましくは５
〜３０ｇ／ｌ含有するものである。これらチオ硫酸塩の
含有量が１ｇ／ｌ以下または５０ｇ／ｌ以上であると、
めつき液が自己分解し、沈澱が生じ、パターン性が悪く
なる傾向がある。The electroless plating solution of the present invention contains a thiosulfate. Examples of the thiosulfate include ammonium thiosulfate, potassium thiosulfate, and sodium thiosulfate. The electroless plating solution of the present invention contains these thiosulfates in an amount of 1 to 50 g / l, preferably 5 to 50 g / l.
-30 g / l. When the content of these thiosulfate is 1 g / l or less, or 50 g / l or more,
The plating solution tends to self-decompose and precipitate, resulting in poor patternability.
【００１７】本発明の無電解金めつき液は、亜硫酸塩を
含有する。亜硫酸塩としては、例えば亜硫酸アンモニウ
ム、亜硫酸カリウム、及び亜硫酸ナトリウムなどを挙げ
ることができる。本発明の無電解金めつき液は、これら
亜硫酸塩を５〜１５０ｇ／ｌ、好ましくは３０〜１００
ｇ／ｌ含有するものである。これら亜硫酸塩の含有量が
５ｇ／ｌ以下であると金めつき液が自己分解し、沈澱が
生じ、パターン性が悪くなり、１５０ｇ／ｌ以上である
と、めつき反応の進行を遅くするか妨げることが多い。The electroless plating solution of the present invention contains a sulfite. Examples of the sulfite include ammonium sulfite, potassium sulfite, and sodium sulfite. The electroless plating solution of the present invention contains these sulfites in an amount of 5 to 150 g / l, preferably 30 to 100 g / l.
g / l. If the content of these sulfites is 5 g / l or less, the plating solution will self-decompose and precipitate, resulting in poor patterning. If it is 150 g / l or more, the progress of the plating reaction is slowed down. Often hinders.
【００１８】本発明の無電解金めつき液は、ヒドラジン
化合物を含有する。ヒドラジン化合物としては、例えば
ヒドラジン水和物、塩酸ヒドラジン、硫酸ヒドラジン、
一塩化ヒドラジン及び二塩化ヒドラジンなどを挙げるこ
とができる。本発明の無電解金めつき液は、これらヒド
ラジン化合物を５〜５０ｇ／ｌ、好ましくは１０〜３０
ｇ／ｌ含有するものである。これらヒドラジン化合物の
含有量が５ｇ／ｌ以下であると、めつき反応の進行がほ
とんど起こらず、５０ｇ／ｌ以上であると、めつき液が
自己分解し、沈澱が生じ、パターン性が悪くなる。The electroless plating solution of the present invention contains a hydrazine compound. As the hydrazine compound, for example, hydrazine hydrate, hydrazine hydrochloride, hydrazine sulfate,
Examples thereof include hydrazine monochloride and hydrazine dichloride. The electroless plating solution of the present invention contains the hydrazine compound in an amount of 5 to 50 g / l, preferably 10 to 30 g / l.
g / l. When the content of these hydrazine compounds is 5 g / l or less, the progress of the plating reaction hardly occurs. When the content is 50 g / l or more, the plating solution self-decomposes and precipitates, resulting in poor patternability. .
【００１９】本発明の無電解金めつき液は、上記の成分
に加えてベンゾトリアゾール系化合物をさらに含有す
る。ベンゾトリアゾール系化合物としては、例えばベン
ゾトリアゾールナトリウム、ベンゾトリアゾールカリウ
ム、テトラヒドロベンゾトリアソール、メチルベンゾト
リアゾール及びニトロベンゾトリアゾールなどを挙げる
ことができる。本発明の無電解金めつき液は、これらベ
ンゾトリアゾール系化合物を１〜２０ｇ／ｌ、好ましく
は３〜１０ｇ／ｌ含有するものである。これらベンゾト
リアゾール系化合物の含有量が１ｇ／ｌ以下であると、
銅のめつき液への溶解抑制に効果がなく、銅の溶解によ
る部分的異常析出が生じパターン性が悪くなるばかりで
なく、自己分解を生じ易くなり、２０ｇ／ｌ以上である
とめつき反応の進行が極端に遅くなる。The electroless plating solution of the present invention further contains a benzotriazole compound in addition to the above components. Examples of the benzotriazole-based compound include benzotriazole sodium, benzotriazole potassium, tetrahydrobenzotriazole, methylbenzotriazole, and nitrobenzotriazole. The electroless plating solution of the present invention contains these benzotriazole-based compounds in an amount of 1 to 20 g / l, preferably 3 to 10 g / l. When the content of these benzotriazole-based compounds is 1 g / l or less,
It has no effect on suppressing the dissolution of copper in the plating solution, and not only causes partial abnormal precipitation due to the dissolution of copper, resulting in poor patternability, but also tends to cause self-decomposition. Progression becomes extremely slow.
【００２０】本発明の無電解金めつき液は、ｐＨ５.０
〜１０.０で使用可能であるが、ｐＨ６.０〜８.０で使
用することが好ましい。ｐＨが５.０より低い場合、め
つき反応の進行がほとんど起こらず、１０.０より高い
場合、めつき液は自己分解し易くなる。またｐＨが１
０.０より高い場合は、金めつき液がレジストを溶解す
るようになる。尚、ｐＨの調整剤としては、水酸化ナト
リウム、水酸化カリウム、水酸化アンモニウム及び亜硫
酸水などを使用することができる。The electroless plating solution of the present invention has a pH of 5.0.
Although it can be used at a pH of from 10.0 to 10.0, it is preferably used at a pH of 6.0 to 8.0. When the pH is lower than 5.0, the plating reaction hardly proceeds, and when the pH is higher than 10.0, the plating liquid is liable to self-decompose. PH 1
If it is higher than 0.0, the plating solution will dissolve the resist. In addition, as a pH adjuster, sodium hydroxide, potassium hydroxide, ammonium hydroxide, aqueous sulfite, or the like can be used.
【００２１】本発明の金めつき液は、液温３０℃〜９０
℃で使用可能であるが、５０℃〜８０℃で使用すること
が好ましい。金めつき液の液温が３０℃よりも低いと、
めつき反応の進行がほとんど起こらず、９０℃より高い
とめつき液が自己分解をし、沈澱を生じ、パターン性が
悪くなる傾向がある。The plating solution of the present invention has a liquid temperature of 30.degree.
Although it can be used at 0 ° C, it is preferable to use at 50 ° C to 80 ° C. If the liquid temperature of the plating solution is lower than 30 ° C,
The plating reaction hardly progresses, and if the temperature is higher than 90 ° C., the plating liquid tends to self-decompose and precipitate, resulting in poor patternability.
【００２２】本発明の無電解金めつき液は、シアンを含
有せず、水溶性亜硫酸金化合物及びヒドラジン化合物を
含有するものであり、中性のめつき条件で使用すること
ができ、微細回路基板上のレジストを溶解することな
く、パターン性良くめつきすることができる。The electroless gold plating solution of the present invention does not contain cyan, but contains a water-soluble gold sulfite compound and a hydrazine compound, and can be used under a neutral plating condition. It is possible to adhere with good patternability without dissolving the resist on the substrate.
【００２３】また、本発明の無電解金めつき液は、水溶
性ポリアミノポリカルボン酸又はその塩、水溶性アミン
又はその誘導体、チオ硫酸塩及び亜硫酸塩を含有するの
で、水溶性亜硫酸金化合物のめつき液中での自己分解が
抑制される。The electroless plating solution of the present invention contains a water-soluble polyaminopolycarboxylic acid or a salt thereof, a water-soluble amine or a derivative thereof, a thiosulfate and a sulfite. Self-decomposition in the plating solution is suppressed.
【００２４】上記水溶性ポリアミノポリカルボン酸又は
その塩及び水溶性アミン又はその誘導体は、素地金属の
銅、ニツケルなどの溶け込みによる金属不純物を隠ぺい
するため、本発明の無電解金めつき液は、沈澱を生じる
ことなく、パターン性良く、外観良好な金皮膜を析出す
ることができる。The water-soluble polyaminopolycarboxylic acid or salt thereof and the water-soluble amine or derivative thereof cover metal impurities caused by dissolution of a base metal such as copper and nickel. Therefore, the electroless plating solution of the present invention A gold film having good patternability and good appearance can be deposited without causing precipitation.
【００２５】さらにまた、ベンゾトリアゾール系化合物
を含有することにより素地の銅がめつき液に溶解しない
ようになるため、銅の溶解に伴う部分的異常析出が生じ
なくなり、膜厚のばらつきが小さく、パターン性の良い
金を析出することができる。本発明の無電解金めつき液
は、上記水溶性亜硫酸金化合物と、水溶性ポリアミノポ
リカルボン酸又はその塩と、水溶性アミン又はその誘導
体と、チオ硫酸塩と、亜硫酸塩と、ヒドラジン化合物及
びベンゾトリアゾール系化合物とを含む他に、ひ素化合
物、タリウム化合物及び鉛化合物の少なくとも一つとキ
ノリン類及びオキシカルボン酸塩を含有することによ
り、さらに金皮膜外観、パターン性、自己分解抑制性が
向上する。Furthermore, since the base copper does not dissolve in the plating solution by containing the benzotriazole-based compound, partial abnormal precipitation due to dissolution of copper does not occur, the variation in film thickness is small, and the Good gold can be deposited. The electroless gold plating solution of the present invention is the above-described water-soluble gold sulfite compound, a water-soluble polyaminopolycarboxylic acid or a salt thereof, a water-soluble amine or a derivative thereof, a thiosulfate, a sulfite, a hydrazine compound and In addition to containing a benzotriazole-based compound, an arsenic compound, a thallium compound and a lead compound and at least one of quinolines and oxycarboxylates further improve the gold film appearance, patternability, and self-decomposition inhibiting property. .
【００２６】[0026]
【００２７】[0027]
【実施例１】レジストを使用して線幅５０〜１０００μ
ｍの回路を形成した。大きさ５×５ｃｍの銅素地微細回
路基板上に、厚さ５μｍのニツケル皮膜を無電解めつき
法により形成させた。この基板を、市販の置換金めつき
液（エヌ・イー・ケムキヤツト（株）ＡＴＯＭＥＸ）に
つけて金めつきを行つた。１０分後にこの基板を取り出
し、ケイ光Ｘ線膜厚測定器により析出膜厚を測定した。
置換金めつきの膜厚は０.０５μｍであつた。以下この
置換金めつきを施した基板を試料１と称する。[Embodiment 1] Using a resist, a line width of 50 to 1000 μm
m circuits were formed. A nickel film having a thickness of 5 μm was formed on a copper base fine circuit board having a size of 5 × 5 cm by an electroless plating method. The substrate was immersed in a commercially available replacement plating solution (ATMEX Co., Ltd.). After 10 minutes, the substrate was taken out, and the deposited film thickness was measured by a fluorescent X-ray film thickness measuring device.
The thickness of the metal plating was 0.05 μm. Hereinafter, the substrate on which the replacement plating has been performed is referred to as Sample 1.
【００２８】亜硫酸金ナトリウムを金イオンとして４ｇ
／ｌ、エチレンジアミン４酢酸２ナトリウムを７０ｇ／
ｌ、トリエタノールアミンを５ｇ／ｌ、チオ硫酸ナトリ
ウムを２０ｇ／ｌ、亜硫酸アンモニウムを５０ｇ／ｌ、
ヒドラジン一水和物を１５ｇ／ｌ及びベンゾトリアゾー
ルカリウムを８ｇ／ｌ含有する無電解金めつき液を調製
した。この無電解金めつき液のｐＨをｐＨ調整試薬によ
り７.０に調整し、温度を８０℃とした中に、撹拌しな
がら上記試料１を１時間浸漬した。１時間後に試料１を
取り出しケイ光Ｘ線膜厚測定器により１０箇所の析出膜
厚を測定した。１時間後の析出膜厚は１０箇所平均で
１.３０μｍであつた。また１０箇所の測定値のうち最
大の膜厚から最小の膜厚の引いたもの（以下これを膜厚
のばらつきＲという）は０.０６μｍであり、部分的異
常析出は認められなかつた。目視及び実体顕微鏡により
観察したがレジストの溶解は認められず、パターン性良
く微細回路上に金が析出した。析出した金皮膜の外観は
ムラ、ガスピツトがなく良好な外観を示した。4 g of gold sodium sulfite as gold ion
/ L, disodium ethylenediaminetetraacetate 70 g /
l, triethanolamine 5 g / l, sodium thiosulfate 20 g / l, ammonium sulfite 50 g / l,
An electroless plating solution containing 15 g / l of hydrazine monohydrate and 8 g / l of potassium benzotriazole was prepared. The pH of the electroless plating solution was adjusted to 7.0 with a pH adjusting reagent, and the sample 1 was immersed in a temperature of 80 ° C. for 1 hour with stirring. One hour later, Sample 1 was taken out, and the deposited film thickness at 10 locations was measured by a fluorescent X-ray film thickness measuring instrument. The deposited film thickness after one hour was 1.30 μm on average at 10 locations. Further, the value obtained by subtracting the minimum film thickness from the maximum film thickness among the measured values at 10 locations (hereinafter referred to as the film thickness variation R) was 0.06 μm, and no partial abnormal deposition was observed. Observation with a visual microscope and a stereoscopic microscope revealed that the resist was not dissolved, and gold was deposited on the fine circuit with good patternability. The appearance of the deposited gold film was good with no unevenness or gas pit.
【００２９】さらに同様にして１０時間のめつきを行つ
たが、レジストの溶解及び部分的異常析出は認められ
ず、パターン性良く外観の良好な金皮膜を析出した。Further, plating was carried out for 10 hours in the same manner, but no dissolution of the resist or partial abnormal deposition was observed, and a gold film having a good pattern and good appearance was deposited.
【００３０】１０時間めつき後の無電解金めつき液中の
不純物金属濃度は、銅５ｐｐｍ以下、ニツケル５ｐｐｍ
以下であつた。The concentration of the impurity metal in the electroless plating solution after plating for 10 hours is 5 ppm or less for copper and 5 ppm for nickel.
It was the following.
【００３１】[0031]
【実施例２】亜硫酸金アンモニウムを金イオンとして
２.５ｇ／ｌ、エチレンジアミン４酢酸２カリウムを９
０ｇ／ｌ、エチレンジアミンを３ｇ／ｌ、チオ硫酸アン
モニウムを１０ｇ／ｌ、亜硫酸ナトリウムを７０ｇ／
ｌ、硫酸ヒドラジンを１０ｇ／ｌ及びメチルベンゾトリ
アゾールを４.０ｇ／ｌ含有する無電解金めつき液を調
製した。この無電解金めつき液のｐＨをｐＨ調整試薬に
より６.５に調整し、温度を７０℃とした中に、撹拌し
ながら上記実施例１と同様にして準備した試料１を１時
間浸漬した。一時間後に試料１を取り出しケイ光Ｘ線膜
厚測定器により１０箇所の析出膜厚を測定した。１時間
後の析出膜厚は１０箇所平均で１.１５μｍであつた。
また膜厚のばらつきＲは０.０４μｍであり、部分的異
常析出は認められなかつた。目視及び実体顕微鏡により
観察したがレジストの溶解は認められず、パターン性良
く微細回路上に金が析出した。析出した金皮膜の外観は
ムラ、ガスピツトがなく良好な外観を示した。Example 2 2.5 g / l of gold ammonium sulfite as gold ion, and 9 g of dipotassium ethylenediaminetetraacetate
0 g / l, ethylene diamine 3 g / l, ammonium thiosulfate 10 g / l, sodium sulfite 70 g / l
An electroless plating solution containing 10 g / l of hydrazine sulfate and 4.0 g / l of methylbenzotriazole was prepared. The pH of this electroless plating solution was adjusted to 6.5 with a pH adjusting reagent, and the sample 1 prepared in the same manner as in Example 1 was immersed for 1 hour while stirring at a temperature of 70 ° C. . One hour later, the sample 1 was taken out, and the deposited film thickness at 10 locations was measured by a fluorescent X-ray film thickness measuring device. The deposited film thickness after 1 hour was 1.15 μm on average at 10 locations.
The variation R of the film thickness was 0.04 μm, and no partial abnormal precipitation was observed. Observation with a visual microscope and a stereoscopic microscope revealed that the resist was not dissolved, and gold was deposited on the fine circuit with good patternability. The appearance of the deposited gold film was good with no unevenness or gas pit.
【００３２】さらに同様にして１０時間のめつきを行つ
たが、レジストの溶解及び部分的異常析出は認められ
ず、パターン性良く外観の良好な金皮膜を析出した。Further, plating was carried out for 10 hours in the same manner, but no dissolution or partial abnormal deposition of the resist was observed, and a gold film having a good pattern and good appearance was deposited.
【００３３】１０時間めつき後の無電解金めつき液中の
不純物金属濃度は、銅５ｐｐｍ以下、ニツケル５ｐｐｍ
以下であつた。The concentration of the impurity metal in the electroless plating solution after plating for 10 hours is 5 ppm or less for copper and 5 ppm for nickel.
It was the following.
【００３４】[0034]
【実施例３】亜硫酸金ナトリウムを金イオンとして３.
０ｇ／ｌ、エチレンジアミン４酢酸２カリウムを６０ｇ
／ｌ、ジメチルアミンを６ｇ／ｌ、チオ硫酸アンモニウ
ムを１５ｇ／ｌ、亜硫酸カリウムを４０ｇ／ｌ、硫酸ヒ
ドラジンを２５ｇ／ｌ、テトラヒドロベンゾトリアゾー
ルを６.０ｇ／ｌ、酢酸鉛を８ｍｇ／ｌ、２−クロロキ
ノリンを３０ｍｇ／ｌ及びクエン酸ナトリウムを２５ｇ
／ｌ含有する無電解金めつき液を調製した。この無電解
金めつき液のｐＨをｐＨ調整試薬により７.５に調整
し、温度を６０℃とした中に、撹拌をしながら上記実施
例１と同様にして準備した試料１を１時間浸漬した。一
時間後に試料１を取り出しケイ光Ｘ線膜厚測定器により
１０箇所の析出膜厚を測定した。１時間後の析出膜厚は
１０箇所平均で１.０３μｍであつた。また膜厚のばら
つきＲは０.０２μｍであり、部分的異常析出は認めら
れなかつた。目視及び実体顕微鏡により観察したがレジ
ストの溶解は認められず、パターン性良く微細回路上に
金が析出した。析出した金皮膜の外観はムラ、ガスピツ
トがなく良好な外観を示した。Example 3 Gold sodium ion as gold ion 3.
0 g / l, 60 g of dipotassium ethylenediaminetetraacetate
/ G, dimethylamine 6 g / l, ammonium thiosulfate 15 g / l, potassium sulfite 40 g / l, hydrazine sulfate 25 g / l, tetrahydrobenzotriazole 6.0 g / l, lead acetate 8 mg / l, 2- 30 mg / l chloroquinoline and 25 g sodium citrate
/ L containing an electroless plating solution. The pH of the electroless plating solution was adjusted to 7.5 with a pH adjusting reagent, and the sample 1 prepared in the same manner as in Example 1 was immersed for 1 hour while stirring at a temperature of 60 ° C. did. One hour later, the sample 1 was taken out, and the deposited film thickness at 10 locations was measured by a fluorescent X-ray film thickness measuring device. The deposited film thickness after one hour was 1.03 μm on average at 10 points. The variation R of the film thickness was 0.02 μm, and no partial abnormal precipitation was observed. Observation with a visual microscope and a stereoscopic microscope revealed that the resist was not dissolved, and gold was deposited on the fine circuit with good patternability. The appearance of the deposited gold film was good with no unevenness or gas pit.
【００３５】さらに同様にして１０時間のめつきを行つ
たが、レジストの溶解及び部分的異常析出は認められ
ず、パターン性良く外観の良好な金皮膜を析出した。Further, plating was carried out for 10 hours in the same manner, but no dissolution or partial abnormal deposition of the resist was observed, and a gold film having a good pattern and good appearance was deposited.
【００３６】１０時間めつき後の無電解金めつき液中の
不純物金属濃度は、銅５ｐｐｍ以下、ニツケル５ｐｐｍ
以下であつた。The concentration of the impurity metal in the electroless plating solution after plating for 10 hours is 5 ppm or less for copper and 5 ppm for nickel.
It was the following.
【００３７】[0037]
【実施例４】レジストを使用して線幅５０〜１０００μ
ｍの回路を形成した、大きさ５×５ｃｍの銅素地微細回
路基板を、市販の置換金めつき液（エヌ・イー・ケムキ
ヤツト（株）ＡＴＯＭＥＸ）に浸漬して金めつきを行つ
た。１０分後にこの基板を取り出し、ケイ光Ｘ線膜厚測
定器により析出膜厚を測定した。置換金めつき膜厚は
０.０５μｍであつた。以下この置換金めつきを施した
基板を試料２と称する。[Embodiment 4] A line width of 50 to 1000 μm using a resist
The copper base fine circuit board having a size of 5 × 5 cm, on which a circuit of m was formed, was immersed in a commercially available replacement plating solution (ATMEX Co., Ltd.) to perform the plating. After 10 minutes, the substrate was taken out, and the deposited film thickness was measured by a fluorescent X-ray film thickness measuring device. The thickness of the replacement plating was 0.05 μm. Hereinafter, the substrate on which the replacement plating is performed is referred to as Sample 2.
【００３８】実施例１において、試料１の代わりに試料
２を用いた以外は、実施例１と同様にして、１時間後に
試料２を取り出しケイ光Ｘ線膜厚測定器により１０箇所
の析出膜厚を測定した。１時間後の析出膜厚は１０箇所
平均で１.５１μｍであつた。また膜厚のばらつきＲは
０.０９μｍであり、部分的異常析出は認められなかつ
た。目視及び実体顕微鏡により観察したがレジストの溶
解は認められず、パターン性良く微細回路上に金が析出
した。析出した金皮膜の外観はムラ、ガスピツトがなく
良好な外観を示した。In the same manner as in Example 1 except that Sample 2 was used in place of Sample 1, Sample 2 was taken out after 1 hour, and 10 deposited films were measured with a fluorescent X-ray film thickness meter. The thickness was measured. The deposited film thickness after 1 hour was 1.51 μm on average at 10 locations. The variation R of the film thickness was 0.09 μm, and no partial abnormal precipitation was observed. Observation with a visual microscope and a stereoscopic microscope revealed that the resist was not dissolved, and gold was deposited on the fine circuit with good patternability. The appearance of the deposited gold film was good with no unevenness or gas pit.
【００３９】さらに同様にして１０時間のめつきを行つ
たが、レジストの溶解及び部分的異常析出は認められ
ず、パターン性良く外観の良好な金皮膜を析出した。Further, plating was carried out for 10 hours in the same manner, but no dissolution of the resist or partial abnormal deposition was observed, and a gold film having a good pattern and good appearance was deposited.
【００４０】１０時間めつき後の無電解金めつき液中の
不純物金属濃度は、銅５ｐｐｍ以下であつた。The concentration of the impurity metal in the electroless plating solution after plating for 10 hours was 5 ppm or less of copper.
【００４１】[0041]
【実施例５】実施例２において、試料１の代わりに試料
２を用いた以外は、実施例２と同様にして、１時間後に
試料２を取り出しケイ光Ｘ線膜厚測定器により１０箇所
の析出膜厚を測定した。１時間後の析出膜厚は１０箇所
平均で１.３３μｍであつた。また膜厚のばらつきＲは
０.０６μｍであり、部分的異常析出は認められなかつ
た。目視及び実体顕微鏡により観察したがレジストの溶
解は認められず、パターン性良く微細回路上に金が析出
した。析出した金皮膜の外観はムラ、ガスピツトがなく
良好な外観を示した。Fifth Embodiment In the same manner as in the second embodiment except that the second sample is used in place of the first sample in the second embodiment, the sample 2 is taken out after 1 hour, and 10 places are measured with a fluorescent X-ray film thickness measuring device. The deposited film thickness was measured. The deposited film thickness after 1 hour was 1.33 μm on average at 10 locations. The variation R of the film thickness was 0.06 μm, and no partial abnormal precipitation was observed. Observation with a visual microscope and a stereoscopic microscope revealed that the resist was not dissolved, and gold was deposited on the fine circuit with good patternability. The appearance of the deposited gold film was good with no unevenness or gas pit.
【００４２】さらに同様にして１０時間のめつきを行つ
たが、レジストの溶解及び部分的異常析出は認められ
ず、パターン性良く外観の良好な金皮膜を析出した。Further, plating was carried out for 10 hours in the same manner, but no dissolution of the resist or partial abnormal deposition was observed, and a gold film having a good pattern and good appearance was deposited.
【００４３】１０時間めつき後の無電解金めつき液中の
不純物金属濃度は、銅５ｐｐｍ以下であつた。The concentration of the impurity metal in the electroless plating solution after plating for 10 hours was 5 ppm or less of copper.
【００４４】[0044]
【実施例６】実施例３において、試料１の代わりに試料
２を用いた以外は、実施例３と同様にして、１時間後に
試料２を取り出しケイ光Ｘ線膜厚測定器により１０箇所
の析出膜厚を測定した。１時間後の析出膜厚は１０箇所
平均で１.２９μｍであつた。また膜厚のばらつきＲは
０.０４μｍであり、部分的異常析出は認められなかつ
た。目視及び実体顕微鏡により観察したがレジストの溶
解は認められず、パターン性良く微細回路上に金が析出
した。析出した金皮膜の外観はムラ、ガスピツトがなく
良好な外観を示した。Embodiment 6 In the same manner as in Embodiment 3 except that Sample 2 was used instead of Sample 1, Sample 2 was taken out after one hour, and 10 places were measured with a fluorescent X-ray film thickness meter. The deposited film thickness was measured. The deposited film thickness after 1 hour was 1.29 μm on average at 10 locations. The variation R of the film thickness was 0.04 μm, and no partial abnormal precipitation was observed. Observation with a visual microscope and a stereoscopic microscope revealed that the resist was not dissolved, and gold was deposited on the fine circuit with good patternability. The appearance of the deposited gold film was good with no unevenness or gas pit.
【００４５】さらに同様にして１０時間のめつきを行つ
たが、レジストの溶解及び部分的異常析出は認められ
ず、パターン性良く外観の良好な金皮膜を析出した。Further, plating was carried out for 10 hours in the same manner, but no dissolution or partial abnormal deposition of the resist was observed, and a gold film having a good pattern and good appearance was deposited.
【００４６】１０時間めつき後の無電解金めつき液中の
不純物金属濃度は、銅５ｐｐｍ以下であつた。The concentration of the impurity metal in the electroless plating solution after plating for 10 hours was 5 ppm or less of copper.
【００４７】比較例１ 亜硫酸金ナトリウムを金イオンとして４ｇ／ｌ、エチレ
ンジアミン４酢酸２ナトリウムを７０ｇ／ｌ、トリエタ
ノールアミンを５ｇ／ｌ、チオ硫酸ナトリウムを２０ｇ
／ｌ、亜硫酸アンモニウムを５０ｇ／ｌ及びヒドラジン
一水和物を１５ｇ／ｌ含有する無電解金めつき液を調製
した。この無電解金めつき液のｐＨをｐＨ調整試薬によ
り７.０に調整し、温度を７５℃とした中に撹拌しなが
ら上記実施例１と同様にして準備した試料１を１時間浸
漬した。１時間後に試料１を取り出しケイ光Ｘ線膜厚測
定器により１０箇所の析出膜厚を測定した。１時間後の
析出膜厚は１０箇所平均で１.３６μｍであつた。また
膜厚のばらつきＲは０.８９μｍであり、部分的異常析
出が認められた。Comparative Example 1 4 g / l of gold sodium sulfite as gold ion, 70 g / l of disodium ethylenediaminetetraacetate, 5 g / l of triethanolamine and 20 g of sodium thiosulfate
/ L, 50 g / l of ammonium sulfite and 15 g / l of hydrazine monohydrate were prepared. The pH of the electroless plating solution was adjusted to 7.0 with a pH adjusting reagent, and the sample 1 prepared in the same manner as in Example 1 was immersed for 1 hour while stirring at a temperature of 75 ° C. One hour later, Sample 1 was taken out, and the deposited film thickness at 10 locations was measured by a fluorescent X-ray film thickness measuring instrument. The deposited film thickness after 1 hour was 1.36 μm on average at 10 locations. The variation R of the film thickness was 0.89 μm, and partial abnormal precipitation was observed.
【００４８】目視及び実体顕微鏡により観察した結果、
レジストの溶解は認められず、微細回路上に金が析出し
たが、素地の銅の溶解により異常析出した部分の金皮膜
の外観はムラ、ピンホールなどの外観不良が生じてい
た。As a result of visual observation and observation with a stereoscopic microscope,
No dissolution of the resist was observed, and gold was deposited on the fine circuit. However, the appearance of the gold film in the portion where the copper was abnormally deposited due to the dissolution of the copper in the base had poor appearance such as unevenness and pinholes.
【００４９】さらに同様にして１０時間のめつきを行つ
た。その結果、レジストの溶解は認められなかつたが、
素地の銅の溶解による異常析出部分のパターン性は悪く
なつた。Further, plating was performed for 10 hours in the same manner. As a result, dissolution of the resist was not observed, but
The pattern property of the abnormally precipitated portion due to the dissolution of copper in the substrate became poor.
【００５０】１０時間めつき後の無電解金めつき液中の
不純物金属濃度は、銅３０ｐｐｍ、ニツケル５ｐｐｍ以
下であつた。The concentration of the impurity metal in the electroless plating solution after plating for 10 hours was 30 ppm for copper and 5 ppm or less for nickel.
【００５１】比較例２ 比較例１において、試料１の代わりに試料２を用いた以
外は、比較例１と同様にして、１時間後に試料２を取り
出しケイ光Ｘ線膜厚測定器により１０箇所の析出膜厚を
測定した。１時間後の析出膜厚は１０箇所平均で２.６
８μｍであつた。また膜厚のばらつきＲは１.６９μｍ
であり、部分的異常析出が認められた。Comparative Example 2 In the same manner as in Comparative Example 1, except that Sample 2 was used instead of Sample 1, one hour later, Sample 2 was taken out and 10 places were measured with a fluorescent X-ray film thickness meter. Was measured. The deposition thickness after 1 hour is 2.6 on average at 10 locations.
It was 8 μm. The variation R of the film thickness is 1.69 μm.
And partial abnormal precipitation was observed.
【００５２】素地の銅の溶解により異常析出した部分の
パターン性は悪くなつた。また、異常析出した部分の金
皮膜の外観はムラ、ピンホールなどの外観不良が生じて
いた。The pattern property of the portion where abnormal precipitation was caused by the dissolution of copper in the base material was deteriorated. In addition, the appearance of the gold film in the portion where the abnormal deposition occurred was uneven and pinholes and other appearance defects occurred.
【００５３】さらに同様にして１０時間のめつきを行つ
た。その結果、レジストの溶解は認められなかつたが、
素地の銅の溶解による異常析出部分のパターン性はさら
に悪くなつた。更にまためつき液は自己分解による沈澱
が生じた。Further, plating was performed for 10 hours in the same manner. As a result, dissolution of the resist was not observed, but
The patterning of the abnormally precipitated portion due to the dissolution of copper in the substrate became worse. Further, the accumulated solution was precipitated by autolysis.
【００５４】１０時間めつき後の無電解金めつき液中の
不純物金属濃度は、銅１００ｐｐｍであつた。The concentration of the impurity metal in the electroless plating solution after plating for 10 hours was 100 ppm of copper.
【００５５】[0055]
【本発明の効果】以上説明したように本発明の無電解金
めつき液は、シアン化合物を含むことがないので毒性が
低く安全上有利であり、中性のめつき条件で使用できる
ので微細回路基板上のレジストを溶解することなく、パ
ターン性良く金が析出することができる。As described above, the electroless plating solution of the present invention does not contain a cyanide compound, has low toxicity and is advantageous in safety, and can be used under neutral plating conditions, so that it can be used in fine conditions. Gold can be deposited with good patternability without dissolving the resist on the circuit board.
【００５６】また素地の銅のめつき液への溶け込みがな
いため、部分的異常析出及びパターン性の劣化を生じる
ことなくムラ、ガスピツト等の外観不良を有しない金皮
膜を析出することができる。Further, since the base material does not dissolve into the plating solution of copper, it is possible to deposit a gold film having no appearance defects such as unevenness and gas pits without causing partial abnormal deposition and deterioration of patternability.
【００５７】また本発明の無電解金めつき液は、金めつ
き液の安定性を劣化させる銅の溶け込みがないために、
自己分解を生じることなく長時間安定に使用することが
可能である。Further, the electroless plating solution of the present invention has no melting of copper which degrades the stability of the plating solution.
It can be used stably for a long time without causing self-decomposition.
【００５８】よつて本発明の無電解金めつき液は、銅素
地のレジストを用いたＩＣフレーム、プリント基板、セ
ラミツク基板などの微細回路上の金めつきが必要となる
製品に金めつきを施すのに最適である。Thus, the electroless plating solution of the present invention can be used for plating products on fine circuits such as IC frames, printed circuit boards, and ceramic substrates using a copper-based resist. Perfect for applying.
フロントページの続き (56)参考文献 特開 平１−191782（ＪＰ，Ａ) 特開 昭62−86171（ＪＰ，Ａ) 特開 平３−210171（ＪＰ，Ａ) 特開 平２−305984（ＪＰ，Ａ) 特開 平３−66496（ＪＰ，Ａ) 特開 平１−261888（ＪＰ，Ａ) 特開 平３−72084（ＪＰ，Ａ) 東ドイツ特許150762（ＤＤ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 18/42 - 18/44 Continuation of the front page (56) References JP-A-1-117882 (JP, A) JP-A-62-86171 (JP, A) JP-A-3-210171 (JP, A) JP-A-2-305984 (JP, A) JP-A-3-66496 (JP, A) JP-A-1-261888 (JP, A) JP-A-3-72084 (JP, A) East German Patent 150762 (DD, A) (58) (Int.Cl. 7 , DB name) C23C 18/42-18/44
Claims (1)
５０〜１００ｇ／ｌの水溶性ポリアミノポリカルボン酸
又はその塩、２〜６ｇ／ｌの水溶性アミン又はその誘導
体、５〜３０ｇ／ｌのチオ硫酸塩、３０〜１００ｇ／ｌ
の亜硫酸塩、１０〜３０ｇ／ｌのヒドラジン化合物、３
〜１０ｇ／ｌのベンゾトリアゾール系化合物及び必要量
のｐＨ調整剤からなることを特徴とする、５０℃〜８０
℃のめっき条件で使用される中性の無電解金めっき液。1 to 5 g / l of a water-soluble gold sulfite compound,
50-100 g / l water-soluble polyaminopolycarboxylic acid or salt thereof, 2-6 g / l water-soluble amine or derivative thereof, 5-30 g / l thiosulfate, 30-100 g / l
Sulfites, hydrazine compounds of 10 to 30 g / l, 3
Benzotriazole compound of 10 g / l and required amount
Characterized by comprising the pH-adjusting agent, 50 ° C. to 80
Neutral electroless gold plating solution used under plating conditions of ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3106572A JP3030114B2 (en) | 1991-04-12 | 1991-04-12 | Electroless plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3106572A JP3030114B2 (en) | 1991-04-12 | 1991-04-12 | Electroless plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04314871A JPH04314871A (en) | 1992-11-06 |
| JP3030114B2 true JP3030114B2 (en) | 2000-04-10 |
Family
ID=14436963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3106572A Expired - Lifetime JP3030114B2 (en) | 1991-04-12 | 1991-04-12 | Electroless plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3030114B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010031312A (en) * | 2008-07-28 | 2010-02-12 | Ne Chemcat Corp | Pattern plating film, and forming method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5318621A (en) * | 1993-08-11 | 1994-06-07 | Applied Electroless Concepts, Inc. | Plating rate improvement for electroless silver and gold plating |
-
1991
- 1991-04-12 JP JP3106572A patent/JP3030114B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010031312A (en) * | 2008-07-28 | 2010-02-12 | Ne Chemcat Corp | Pattern plating film, and forming method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04314871A (en) | 1992-11-06 |
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