JPH08291389A - Gold plating liquid not substituted with cyanide and gold plating method using this liquid - Google Patents
Gold plating liquid not substituted with cyanide and gold plating method using this liquidInfo
- Publication number
- JPH08291389A JPH08291389A JP9251795A JP9251795A JPH08291389A JP H08291389 A JPH08291389 A JP H08291389A JP 9251795 A JP9251795 A JP 9251795A JP 9251795 A JP9251795 A JP 9251795A JP H08291389 A JPH08291389 A JP H08291389A
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- Japan
- Prior art keywords
- gold
- gold plating
- salt
- concn
- 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.)
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- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、毒性が低く、めっきの
耐レジストに優れた、ニッケル皮膜上に優れた金皮膜が
形成可能な置換金めっき液とこの液を用いた金めっき方
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a displacement gold plating solution having low toxicity and excellent resistance to plating and capable of forming an excellent gold film on a nickel film, and a gold plating method using this solution.
【０００２】[0002]
【従来の技術】プリント配線板の金めっき処理は、電解
金めっき法と無電解金めっき法の２通りが行われている
が、コスト面から電解金めっきが主流である。しかしな
がら、近年の高密度実装化の要求の中で、電解めっきの
ためのリードに対する設計上の制約、独立パターンへの
めっき処理等の問題があり無電解めっき法が必要とされ
てきている。2. Description of the Related Art There are two types of gold plating treatments for printed wiring boards, an electrolytic gold plating method and an electroless gold plating method, but electrolytic gold plating is the mainstream in terms of cost. However, with the recent demand for high-density mounting, there are problems such as design restrictions on the leads for electrolytic plating and plating on an independent pattern, so that electroless plating has been required.
【０００３】独立した銅パターン上への無電解金めっき
方法は、まず銅パターンに置換パラジウムめっきが行わ
れ、その後、パラジウムを触媒として無電解ニッケルめ
っきが行われる。次にニッケルイオンとの置換反応を利
用した置換金めっきが行われ、最後に還元剤を含む厚付
け無電解金めっきが行われ、金めっき工程が終了する。
前記の金めっき工程の中で置換金めっき法は、置換金め
っき液に卑金属導体を浸漬することにより、液中の金が
卑金属導体上に置換析出するものであるが、置換反応で
あるため金が卑金属導体全面に析出したところで反応が
止まる。In an electroless gold plating method on an independent copper pattern, substitutional palladium plating is first performed on a copper pattern, and then electroless nickel plating is performed using palladium as a catalyst. Next, displacement gold plating utilizing a substitution reaction with nickel ions is performed, and finally thick electroless gold plating containing a reducing agent is performed, and the gold plating step is completed.
The displacement gold plating method in the gold plating step is one in which gold in the liquid is displacement-precipitated on the base metal conductor by immersing the base metal conductor in the displacement gold plating solution, but since it is a substitution reaction, gold The reaction stops when is deposited on the entire surface of the base metal conductor.
【０００４】[0004]
【発明が解決しようとする課題】置換金めっき法で使用
されている置換金めっき液は、今まで多くの液組成が報
告されているが、それらのほとんどにシアン化合物が含
まれており、毒性が強いことから環境上の問題点があっ
た。更にシアン化合物を含んだ置換金めっき液のほとん
どは高温で使用しているため、めっきレジストを溶解
し、パターンめっき性が悪くなる問題があった。The displacement gold plating solution used in the displacement gold plating method has been reported to have a large number of solution compositions up to now, but most of them contain a cyanide compound and are toxic. There was an environmental problem because it was strong. Further, since most of the displacement gold plating solutions containing cyanide compounds are used at high temperature, there is a problem that the plating resist is dissolved and the pattern plating property is deteriorated.
【０００５】特開平５−２８７５４１号公報に記載のシ
アン化合物を含んだ置換金めっき液は、処理温度を９０
℃以上としているため、上記と同様に問題があった。一
方、置換金めっき液中の金は高価な貴金属であるため、
基板処理の際、めっき液の持出しによる金の持出しを少
なくすることが望まれ、そのためには置換金めっき液中
の金濃度を極力低濃度にする必要性がある。現在報告さ
れている置換金めっき液中の金濃度は０．５g/l〜１０g
/lである。このように種々の問題の中、環境上の問題を
解決するために、シアン化合物を含まない毒性の低い置
換金めっき液について研究開発がされ、開示がなされて
いる。The displacement gold plating solution containing a cyanide compound described in JP-A-5-287541 has a treatment temperature of 90.
Since the temperature is set to ℃ or above, there was a problem similar to the above. On the other hand, the gold in the displacement gold plating solution is an expensive precious metal,
During substrate processing, it is desired to reduce the carry-out of gold due to carry-out of the plating solution. For that purpose, it is necessary to make the gold concentration in the displacement gold plating solution as low as possible. The gold concentration in the substitution gold plating solution currently reported is 0.5 g / l to 10 g.
/ l. As described above, in order to solve environmental problems among various problems, research and development and disclosure of a low toxicity substituted gold plating solution containing no cyanide compound have been made.
【０００６】特開平４−３１４８７０号公報に記載の金
めっき液は、水溶性亜硫酸金化合物と亜硫酸塩を主成分
とし、シアン化合物を含まない置換金めっき液であるた
め、毒性が低い点では優れている。しかし、処理温度が
８５℃以上であるため、レジストへの耐久性が低いとい
うのが課題である。また、めっき液中の金濃度は０．５
g/lから１０g/lであり、０．５g/l以下では金の置換反
応が遅いため、めっき外観が悪く、又は置換反応が起こ
らないという問題がある。The gold plating solution described in Japanese Patent Application Laid-Open No. 4-314870 is a substituted gold plating solution containing a water-soluble gold sulfite compound and a sulfite as main components and containing no cyanide compound, and is therefore excellent in low toxicity. ing. However, since the processing temperature is 85 ° C. or higher, the problem is that durability against resist is low. The gold concentration in the plating solution is 0.5
The amount is from 10 g / l to 10 g / l, and if the amount is 0.5 g / l or less, the gold substitution reaction is slow, so that there is a problem that the plating appearance is poor or the substitution reaction does not occur.
【０００７】本発明は、毒性が低く、レジストを溶解す
ることなくパターンめっき性に優れ、更に、金濃度０．
５g/l以下でもニッケル皮膜上に優れた金皮膜が形成可
能な置換金めっき液とこの液を用いた金めっき方法を提
供するものである。The present invention has low toxicity, is excellent in pattern plating property without dissolving resist, and has a gold concentration of 0.
Provided is a displacement gold plating solution capable of forming an excellent gold film on a nickel film even at 5 g / l or less, and a gold plating method using this solution.
【０００８】[0008]
【課題を解決するための手段】本発明の置換金めっき液
は、金イオンの供給源として、亜硫酸金塩もしくは塩化
金酸塩、金の錯化剤として、アンモニウム塩及びエチレ
ンジアミントリ酢酸塩を含む置換金めっき液において、
液安定剤として、テトラアルキルアンモニウム塩を含
み、ｐＨ調整剤でｐＨを６から７に調整することを特徴
とする。The displacement gold plating solution of the present invention comprises a gold sulfite gold salt or chloroauric acid salt as a source of gold ions, and an ammonium salt and ethylenediamine triacetate salt as a gold complexing agent. In the replacement gold plating solution,
The liquid stabilizer is characterized by containing a tetraalkylammonium salt and adjusting the pH to 6 to 7 with a pH adjuster.
【０００９】金イオンの供給源である亜硫酸金塩は、亜
硫酸金ナトリウム、亜硫酸金カリウム、亜硫酸金アンモ
ニウム、また塩化金酸塩は、塩化金酸ナトリウム、塩化
金酸カリウム、塩化金酸アンモニウムを使用する。Gold sulfite, which is a source of gold ions, is sodium gold sulfite, potassium gold sulfite, ammonium gold sulfite, and sodium chloroaurate is sodium chloroaurate, potassium chloroaurate, or ammonium chloroaurate. To do.
【００１０】このような構成にすることによって、金濃
度を０．１g/lから５g/lの範囲で使用することが可能で
あり、さらに低濃度での使用もできる。しかし、金濃度
が０．１g/l未満では、金の置換速度が著しく遅くなる
ため、めっき外観が悪く、５g/lを超えると自己分解を
起こし、液分解する。With such a constitution, it is possible to use the gold concentration in the range of 0.1 g / l to 5 g / l, and it is also possible to use it at a lower concentration. However, if the gold concentration is less than 0.1 g / l, the substitution rate of gold is remarkably slow, and the plating appearance is poor, and if it exceeds 5 g / l, autolysis occurs and liquid decomposition occurs.
【００１１】金の錯化剤であるアンモニウム塩は、塩化
アンモニウム、硫酸アンモニウム、またエチレンジアミ
ンテトラ酢酸塩は、エチレンジアミンテトラ酢酸、エチ
レンジアミンテトラ酢酸ナトリウム、エチレンジアミン
テトラ酢酸カリウム、エチレンジアミンテトラ酢酸アン
モニウムを使用する。アンモニウム塩の濃度は、７×１
０-3mol/lから０．４mol/lの範囲で使用することが好ま
しく、アンモニウム塩の濃度が７×１０-3mol/l未満で
も０．４ｍｏｌ／ｌを超えてもめっき液が不安定になり
液分解する。エチレンジアミンテトラ酢酸塩の濃度は、
２×１０−３ｍｏｌ／ｌから０．２mol/lの範囲で使用
することが好ましく、エチレンジアミンテトラ酢酸塩の
濃度が２×１０-3mol/l未満ではめっき液が不安定にな
り液分解し、０．２mol/lを超えると完全に溶解せずめ
っき液が白濁する。Ammonium chloride and ammonium sulfate, which are complexing agents for gold, are used, and ethylenediaminetetraacetic acid salts are ethylenediaminetetraacetic acid, sodium ethylenediaminetetraacetate, potassium ethylenediaminetetraacetate, and ammonium ethylenediaminetetraacetate. The concentration of ammonium salt is 7 x 1
It is preferable to use in the range of 0 -3 mol / l to 0.4 mol / l, and the plating solution is unstable even when the concentration of ammonium salt is less than 7 × 10 -3 mol / l or more than 0.4 mol / l And the liquid decomposes. The concentration of ethylenediamine tetraacetate is
It is preferable to use it in the range of 2 × 10 −3 mol / l to 0.2 mol / l. When the concentration of ethylenediaminetetraacetate is less than 2 × 10 −3 mol / l, the plating solution becomes unstable and liquid decomposition occurs. , If it exceeds 0.2 mol / l, the solution is not completely dissolved and the plating solution becomes cloudy.
【００１２】液安定剤であるテトラアルキルアンモニウ
ム塩は、塩化テトラメチルアンモニウム、塩化テトラエ
チルアンモニウム、塩化テトラプロピルアンモニウム、
塩化テトラブチルアンモニウムを使用する。テトラアル
キルアンモニウム塩の濃度は、９×１０-4mol/lから９
×１０-2mol/lの範囲で使用することが好ましく、９×
１０-4mol/l未満では、めっき液が不安定になり液分解
し、９×１０-2mol/lを超えると、置換反応が抑制され
るため、置換速度が遅くなりめっき外観が悪くなる。The tetraalkylammonium salt which is a liquid stabilizer includes tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride,
Tetrabutylammonium chloride is used. The concentration of tetraalkylammonium salt ranges from 9 × 10 -4 mol / l to 9
It is preferable to use in the range of × 10 -2 mol / l, 9 ×
If it is less than 10 -4 mol / l, the plating solution becomes unstable and is decomposed, and if it exceeds 9 × 10 -2 mol / l, the substitution reaction is suppressed, so that the substitution rate becomes slow and the plating appearance deteriorates. .
【００１３】ｐＨ調整剤としてｐＨを下げる場合には、
塩酸あるいは硫酸を使用するのが好ましい。また、ｐＨ
を上げる場合には、水酸化ナトリウム、水酸化カリウ
ム、アンモニア水を使用することが好ましい。このよう
な調整によってｐＨを６から７に調整することが好まし
く、ｐＨが６未満では、めっき液が不安定になり、液分
解し、ｐＨが７を超えると置換速度が遅くなり、めっき
外観が悪くなる。When lowering the pH as a pH adjuster,
Preference is given to using hydrochloric acid or sulfuric acid. Also, the pH
When raising the temperature, it is preferable to use sodium hydroxide, potassium hydroxide or aqueous ammonia. It is preferable to adjust the pH from 6 to 7 by such an adjustment. When the pH is less than 6, the plating solution becomes unstable and the solution decomposes, and when the pH exceeds 7, the replacement rate becomes slow and the plating appearance becomes poor. Deteriorate.
【００１４】本発明の置換金めっき液は、液温３０℃か
ら８０℃で使用することが好ましく、液温３０℃未満で
は、置換速度が遅くなりめっき外観が悪くなり、８０℃
を超えるとめっき液が不安定になり液分解する。The displacement gold plating solution of the present invention is preferably used at a solution temperature of 30 ° C. to 80 ° C. When the solution temperature is lower than 30 ° C., the replacement rate becomes slow and the plating appearance becomes poor, so
If it exceeds, the plating solution will become unstable and the solution will decompose.
【００１５】本発明の置換金めっき液は無電解金めっき
工程において、亜硫酸金塩及び亜硫酸塩を主成分とする
厚付け無電解金めっき液と組合わせることにより、置換
金めっき処理後、水洗することなく直接厚付け無電解金
めっき処理を行うことができる。厚付け無電解金めっき
液は、置換金めっき液の持込みにより液が不安定になる
ことはなく、パターンめっき性についてもパターン外の
絶縁物上への金の異常析出は見られず、ニッケル皮膜上
に優れた金皮膜が得られる。In the electroless gold plating step, the displacement gold plating solution of the present invention is combined with a thick electroless gold plating solution containing a sulfite gold salt and a sulfite salt as a main component, and then washed with water after the displacement gold plating treatment. It is possible to directly perform the thick electroless gold plating treatment without the need. The thick electroless gold plating solution does not become unstable when the replacement gold plating solution is brought in, and the pattern plating property does not show any abnormal deposition of gold on the insulator outside the pattern. An excellent gold film is obtained on the top.
【００１６】[0016]
【実施例】レジストを使用して、ライン／スペース４０
／４０（μｍ）から２００／２００（μｍ）の銅パター
ンを有する５cm×５cm基板を形成し被めっき材とした。
この被めっき材を、脱脂、水洗、ソフトエッチング、水
洗、酸洗、水洗し、置換パラジウム触媒液ＳＡ−１００
（日立化成工業株式会社製、商品名）に２５℃、２分浸
漬し、水洗し、無電解ニッケルめっき液ＮＩＰＳ−１０
０（日立化成工業株式会社製、商品名）に７０℃、２５
分浸漬し、厚さ３μｍのニッケル皮膜を形成した。次
に、水洗し、表１に示すNo１からNo１２の置換金めっき
液に浸漬し、金の置換量、めっき外観、液分解の有無に
ついて測定を行った。次に、水洗を行わず厚付け無電解
金めっき液ＨＧＳ−２０００（日立化成工業株式会社
製、商品名）に６５℃、４０分浸漬し、厚さ０．５μｍ
の金皮膜を形成させ、パターン外への金析出の有無を調
べた。最後に、硝酸１００ml入った硝酸雰囲気のデシケ
ータ中に３時間入れた後、ピンホール数の測定を行っ
た。Example: Using resist, line / space 40
A 5 cm × 5 cm substrate having a copper pattern of / 40 (μm) to 200/200 (μm) was formed as a material to be plated.
This material to be plated is degreased, washed with water, soft-etched, washed with water, pickled, washed with water, and then substituted palladium catalyst solution SA-100 is prepared.
(Hitachi Chemical Co., Ltd., trade name), immersed at 25 ° C. for 2 minutes, washed with water, and electroless nickel plating solution NIPS-10
0 (Hitachi Chemical Co., Ltd., trade name) at 70 ° C, 25
It was dipped for a minute to form a nickel film having a thickness of 3 μm. Next, it was washed with water and immersed in the No. 1 to No. 12 displacement gold plating solutions shown in Table 1 to measure the displacement amount of gold, the appearance of plating, and the presence or absence of solution decomposition. Next, it is immersed in a thick electroless gold plating solution HGS-2000 (manufactured by Hitachi Chemical Co., Ltd., trade name) without washing with water at 65 ° C. for 40 minutes to give a thickness of 0.5 μm.
Then, the presence of gold deposition outside the pattern was examined. Finally, after placing in a desiccator in a nitric acid atmosphere containing 100 ml of nitric acid for 3 hours, the number of pinholes was measured.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【比較例】実施例と同様に、表２に示すNo１３からNo２
４の置換金めっき液について、金置換量、めっき外観、
液分解の有無、パターン外への金析出の有無、ピンホー
ル数について測定を行った。[Comparative Example] Similar to the example, No. 13 to No. 2 shown in Table 2
For the replacement gold plating solution of 4, the gold replacement amount, plating appearance,
The presence or absence of liquid decomposition, the presence or absence of gold deposition outside the pattern, and the number of pinholes were measured.
【００１９】[0019]
【表２】 [Table 2]
【００２０】[0020]
【発明の効果】以上に説明したように、本発明の置換金
めっき液及びこの液を用いた金めっき方法は、シアン化
合物を含まないため、毒性が低く、中性かつ低温のめっ
き条件で使用できるため、めっきの耐レジストに優れ、
低金濃度でもニッケル皮膜上に優れた金皮膜が形成可能
である。As described above, the displacement gold plating solution of the present invention and the gold plating method using this solution do not contain a cyanide compound, and therefore have low toxicity and are used under neutral and low temperature plating conditions. Therefore, it has excellent resistance to plating,
An excellent gold film can be formed on a nickel film even at a low gold concentration.
Claims (2)
くは塩化金酸塩、金の錯化剤としてアンモニウム塩及び
エチレンジアミンテトラ酢酸塩を含む置換金めっき液に
おいて、テトラアルキルアンモニウム塩を含み、ｐＨ調
整剤でｐＨを６から７に調整することを特徴とする置換
金めっき液。1. A substituted gold plating solution containing a gold sulfite or a chloroauric acid salt as a supply source of gold ions, an ammonium salt and an ethylenediaminetetraacetic acid salt as a gold complexing agent, and a tetraalkylammonium salt, and a pH value. A displacement gold plating solution, wherein the pH is adjusted to 6 to 7 with a regulator.
くは塩化金酸塩、金の錯化剤としてアンモニウム塩及び
エチレンジアミンテトラ酢酸塩を含む置換金めっき液に
おいて、テトラアルキルアンモニウム塩を含み、ｐＨ調
整剤でｐＨを６から７に調整し、処理温度を３０℃から
８０℃の範囲、金濃度を０．１g/lから５g/lの範囲で使
用することを特徴とする金めっき方法。2. A substituted gold plating solution containing a gold sulfite or chloroauric acid salt as a gold ion source, an ammonium salt and an ethylenediaminetetraacetic acid salt as a gold complexing agent, and a tetraalkylammonium salt, and a pH value. A gold plating method characterized in that the pH is adjusted to 6 to 7 with an adjusting agent, the treatment temperature is in the range of 30 ° C. to 80 ° C., and the gold concentration is in the range of 0.1 g / l to 5 g / l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9251795A JPH08291389A (en) | 1995-04-18 | 1995-04-18 | Gold plating liquid not substituted with cyanide and gold plating method using this liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9251795A JPH08291389A (en) | 1995-04-18 | 1995-04-18 | Gold plating liquid not substituted with cyanide and gold plating method using this liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08291389A true JPH08291389A (en) | 1996-11-05 |
Family
ID=14056526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9251795A Pending JPH08291389A (en) | 1995-04-18 | 1995-04-18 | Gold plating liquid not substituted with cyanide and gold plating method using this liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08291389A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136702A (en) * | 1999-11-29 | 2000-10-24 | Lucent Technologies Inc. | Thin film transistors |
| US7390354B2 (en) | 2004-07-09 | 2008-06-24 | Nikko Materials Co., Ltd. | Electroless gold plating solution |
| US7396394B2 (en) | 2004-11-15 | 2008-07-08 | Nippon Mining & Metals Co., Ltd. | Electroless gold plating solution |
| US7419536B2 (en) | 2003-06-05 | 2008-09-02 | Nikko Materials Co., Ltd. | Electroless gold plating liquid |
| JP2009155671A (en) * | 2007-12-25 | 2009-07-16 | Ne Chemcat Corp | Immersion gold plating solution for copper base and gold plating method using the same |
-
1995
- 1995-04-18 JP JP9251795A patent/JPH08291389A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136702A (en) * | 1999-11-29 | 2000-10-24 | Lucent Technologies Inc. | Thin film transistors |
| US7419536B2 (en) | 2003-06-05 | 2008-09-02 | Nikko Materials Co., Ltd. | Electroless gold plating liquid |
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| US7396394B2 (en) | 2004-11-15 | 2008-07-08 | Nippon Mining & Metals Co., Ltd. | Electroless gold plating solution |
| JP2009155671A (en) * | 2007-12-25 | 2009-07-16 | Ne Chemcat Corp | Immersion gold plating solution for copper base and gold plating method using the same |
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