JPH01125891A - Gold plating of printed board - Google Patents
Gold plating of printed boardInfo
- Publication number
- JPH01125891A JPH01125891A JP28222787A JP28222787A JPH01125891A JP H01125891 A JPH01125891 A JP H01125891A JP 28222787 A JP28222787 A JP 28222787A JP 28222787 A JP28222787 A JP 28222787A JP H01125891 A JPH01125891 A JP H01125891A
- Authority
- JP
- Japan
- Prior art keywords
- gold
- plating solution
- electroless
- plating
- gold 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.)
- Pending
Links
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 67
- 239000010931 gold Substances 0.000 title claims abstract description 67
- 238000007747 plating Methods 0.000 title claims abstract description 64
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 238000007772 electroless plating Methods 0.000 claims abstract description 5
- 239000002738 chelating agent Substances 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 150000001638 boron Chemical class 0.000 abstract 2
- 239000013522 chelant Substances 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 13
- 238000006073 displacement reaction Methods 0.000 description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- FCKYPQBAHLOOJQ-UWVGGRQHSA-N 2-[[(1s,2s)-2-[bis(carboxymethyl)amino]cyclohexyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)[C@H]1CCCC[C@@H]1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UWVGGRQHSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
プリント基板上に形成された銅配線の表面に金をメツキ
する方法に係り、特に無電解法により金をメツキする場
合のメツキ浴の組成に関する。[Detailed Description of the Invention] [Industrial Application Field] This invention relates to a method for plating gold on the surface of copper wiring formed on a printed circuit board, and in particular to the composition of a plating bath when plating gold by an electroless method. .
プリント基板上の銅配線の表面には耐食性、および電気
的接続の信頼性に優れた金が一般にメツキされ、金メツ
キ法としては電解法あるいは無電解法が用いられている
。The surface of copper wiring on a printed circuit board is generally plated with gold, which has excellent corrosion resistance and reliability of electrical connection, and an electrolytic method or an electroless method is used as the gold plating method.
電解法により金メツキを行５場合には、まず、プリント
基板上に多数の銅配線とこれらを連結する共通電極とを
形成したのち、中間層としてニッケルあるいはコバルト
を、さらにその上に上層として金をいずれも共通電極を
介して電解メツキしている。メツキ後に共通電極部分は
切断により除去される。電解法で金メツキする場合には
、共通電極の形成、切り離しを行５ため工程が複雑であ
り、また、切り離される共通電極部分にメツキされる金
が無駄になり、さらに切り離し部分では銅配線が断面に
露出し耐食性に問題があった。When gold plating is performed using the electrolytic method5, first a large number of copper wiring lines and a common electrode connecting them are formed on the printed circuit board, then nickel or cobalt is applied as an intermediate layer, and then gold is applied as an upper layer on top of that. Both are electrolytically plated via a common electrode. After plating, the common electrode portion is removed by cutting. When gold plating is performed using the electrolytic method, the process is complicated because the common electrode is formed and separated5, and the gold plated on the common electrode part that is separated is wasted, and furthermore, copper wiring is lost in the separated part. It was exposed in the cross section and had a problem with corrosion resistance.
これらの問題点を解決するため、無電解法による金メツ
キ方法が提案された。無電解法により金メツキする場合
には一般に置換金メツキと自己触媒型無電解金メツキと
の二段階のメツキ工程を必要とするが、共通電極を形成
する必要がないため電解法に比べて工程が簡単である。In order to solve these problems, an electroless gold plating method was proposed. Gold plating using the electroless method generally requires a two-step plating process of displacement gold plating and autocatalytic electroless gold plating, but since there is no need to form a common electrode, the process is shorter than the electrolytic method. is easy.
無電解法による金メツキ方法は、まずプリント基板に銅
配線を形成し、次に中間層としてニッケルあるいはコバ
ルトをメツキした後に、置換金メツキを行い、次に自己
触媒型無電解金メツキを行うものである。The electroless gold plating method involves first forming copper wiring on a printed circuit board, then plating nickel or cobalt as an intermediate layer, followed by displacement gold plating, and then autocatalytic electroless gold plating. It is.
（参考文献＝「表面処理技術Ｊ 、 ｖ ｄ−２５，Ｎ
ｈ２＋ ｐ、５６゜１９７４）無電解法による金メツキ
は上述のように工程が簡単であるが、自己触媒型無電解
金メツキの工程で、■プリント基板に中間層としてメツ
キしたニッケルあるいはコバルトが自己触媒型無電解金
メツキ液に溶出し、自己触媒型無電解金メツキ液を短時
間で分解する。■自己触媒型無電解金メツキ液中のニッ
ケルあるいはコバルト濃度の増加に伴い、金の析出量が
低下する等の問題があった。(Reference: “Surface Treatment Technology J, v d-25, N
h2+ p, 56°1974) Electroless gold plating is a simple process as mentioned above, but in the autocatalytic electroless gold plating process, ■Nickel or cobalt plated as an intermediate layer on a printed circuit board is self-plated. Elutes into catalytic electroless gold plating solution and decomposes autocatalytic electroless gold plating solution in a short time. ■There were problems such as a decrease in the amount of gold deposited as the nickel or cobalt concentration in the autocatalytic electroless gold plating solution increased.
本発明の目的は、プリント基板上の銅配線の表面に中間
層としてニッケルあるいはコバルトをメツキし、さらに
その表面に金を無電解メツキする場合の金の析出量を増
加させること、同時に自己触媒型無電解メツキ液寿命を
延長し、メツキ液の利用効率を高めることである。The purpose of the present invention is to increase the amount of gold deposited when nickel or cobalt is plated as an intermediate layer on the surface of copper wiring on a printed circuit board, and then gold is electrolessly plated on the surface. The objective is to extend the life of the electroless plating solution and increase the efficiency of use of the plating solution.
上記目的のため本発明においては、自己触媒型無電解金
メツキ液として少なくとも金塩およびボロン系還元剤を
含有するアルカリ性無電解金メツキ液に適量のアルカリ
可溶性キレート剤を添加したものを用いるようにした。For the above purpose, in the present invention, an alkaline electroless gold plating solution containing at least a gold salt and a boron-based reducing agent is used as an autocatalytic electroless gold plating solution, with an appropriate amount of an alkali-soluble chelating agent added. did.
以下、本発明を実施例に基づき説明する。 The present invention will be explained below based on examples.
（実施例１）
銅配線を形成したガラエポプリント基板に、メツキ液シ
ューマ８７５３（日本カニゼン社製）で、温度８５℃、
ｐＨ５，５の条件下で無電解ニッケルメッキを行った。(Example 1) A glass epoxy printed circuit board on which copper wiring was formed was coated with a plating liquid Schumer 8753 (manufactured by Nippon Kanizen Co., Ltd.) at a temperature of 85°C.
Electroless nickel plating was performed under conditions of pH 5.5.
次に温度８０〜９０℃、ｐＨ７〜７．５の条件下、第１
表に示す組成のメツキ液で置換金メツキを行った。この
とき金のメッキ厚は０．１μｍであった。Next, under the conditions of temperature 80-90°C and pH 7-7.5,
Displacement gold plating was performed using a plating solution with the composition shown in the table. At this time, the gold plating thickness was 0.1 μm.
第 １ 表
次に、イオン交換水に第２表の物質を溶解させた無電解
金メツキ液に、アルカリ可溶性キレート剤としてエチレ
ンジアミンテトラ酢酸−２Ｎａ（以下ＥＤＴＡ・２Ｎａ
と記す）を添加し、ＥＤＴＡ−２Ｎａの添加量を変化さ
せ、プリント基板に自己触媒型無電解金メツキを行った
。ＥＤＴＡ・２ Ｎａを添加した場合のメツキ膜は均一
な外現の明るいワインカラーを呈し、ＥＤＴＡ・２ Ｎ
ａを添加しなかった場合には、表面の粗いかっ色を呈し
た。Table 1 Next, ethylenediaminetetraacetic acid-2Na (hereinafter referred to as EDTA・2Na
) was added, and the amount of EDTA-2Na added was varied, and autocatalytic electroless gold plating was performed on the printed circuit board. When EDTA・2Na is added, the plating film exhibits a bright wine color with a uniform appearance;
When a was not added, the surface exhibited a rough brown color.
第 ２ 表
第１図は、ＥＴ）ＴＡ・２ Ｎａ の添加量と金の析
出量の関係を示すグラフである。ＥＤＴＡ・２Ｎａを添
加しなかった場合、金の析出量は０．８μｍ／）（ｒＫ
対し、ＥＤＴＡ・２ Ｎａ を添加した場合、金の析出
量はほぼ１μｍ ／ Ｈｒ以上であり、ＥＤＴＡ・２
Ｎａ を添加することにより金の析出量を向上させる
ことができた。Table 2 FIG. 1 is a graph showing the relationship between the amount of ET)TA.2Na added and the amount of gold precipitated. When EDTA・2Na was not added, the amount of gold precipitation was 0.8 μm/) (rK
On the other hand, when EDTA・2Na is added, the amount of gold precipitated is approximately 1 μm/Hr or more;
By adding Na, the amount of gold deposited could be improved.
また、ＥＤＴＡ・２Ｎａの添加量５ ｇ／ｌのとき、金
の析出量が１．４μｍ／Ｈｒで最大となりＥＤＴＡ・２
Ｎａの添加量には最適値があることがわかった。Furthermore, when the amount of EDTA・2Na added was 5 g/l, the amount of gold precipitation reached the maximum at 1.4 μm/Hr, and
It was found that there is an optimum value for the amount of Na added.
（実施例２）
銅配線の形成されたガラエボプリント基板に、実施例１
と同一の条件で無電解ニッケルメッキおよび置換金メツ
キを行った。次に、イオン交換水に第２表の物質を溶解
させた無電解金メツキ液に、ＥＤＴＡ−２Ｎａを５ ｇ
／ｌ 添加し、温度６０’Ｃ１ｐＨ１３，７で、前記
プリント基板に自己触媒型無電解金メツキを行った。こ
のとき自己触媒型無電解金メツキに不純物としてＮ Ｈ
１＋を添加し、不純物濃度と金の析出量の関係を第２図
に示した。(Example 2) Example 1 was applied to the Gala Evo printed circuit board on which copper wiring was formed.
Electroless nickel plating and displacement gold plating were performed under the same conditions as above. Next, 5 g of EDTA-2Na was added to an electroless gold plating solution in which the substances listed in Table 2 were dissolved in ion-exchanged water.
/l was added, and the printed circuit board was subjected to autocatalytic electroless gold plating at a temperature of 60'C and a pH of 13.7. At this time, N H was added as an impurity to the autocatalytic electroless gold plating.
1+ was added, and the relationship between the impurity concentration and the amount of gold deposited is shown in FIG.
また、比較のため、ＥＤＴＡ・２ Ｎａ を添加しな
い自己触媒型無電解メツキ液で金メツキを行い、結果を
第２図に点線で示した。得られたメツキ膜は、ＥＤＴＡ
・２Ｎａを添加した場合、均一な外観で明るいワインカ
ラーを呈し、ＥＤＴＡ・２Ｎａを添加しなかった場合に
は表面が粗くかっ色を呈した。For comparison, gold plating was carried out using an autocatalytic electroless plating solution to which EDTA.2Na was not added, and the results are shown by dotted lines in FIG. The obtained plating film was coated with EDTA
- When 2Na was added, it had a uniform appearance and a bright wine color, whereas when EDTA/2Na was not added, the surface was rough and brownish.
第２図に示したように、ＥＤＴＡ・２Ｎａを添加した自
己触媒型無電解金メツキ液でメツキした方が、添加しな
かったものに比べ金の析出量が速＜、ＥＤＴＡ・２Ｎａ
を添加することにより金の析出量を向上させることがで
きる。As shown in Figure 2, the amount of gold deposited is faster when plating with an autocatalytic electroless gold plating solution containing EDTA/2Na than when no EDTA/2Na is added.
By adding , the amount of gold deposited can be improved.
また、ＥＤＴＡ・２Ｎａを添加しない自己触媒型無電解
金メツキ液では、Ｎｉ 濃度がＨ−’Ｍになるとメツ
キ浴中に金が析出し３０分以内に自己触媒型無電解金メ
ツキ液の分解が起きに０一方、ＥＤＴＡ・２Ｎａを添加
したメツキ液はＮ Ｉ ２＋の濃度１０−’Ｍで十分メ
ツキを行うことができ、分解はＮ１＋濃度１０”−”Ｍ
で起きた。Furthermore, in an autocatalytic electroless gold plating solution that does not contain EDTA/2Na, when the Ni concentration reaches H-'M, gold precipitates in the plating bath and the autocatalytic electroless gold plating solution decomposes within 30 minutes. On the other hand, a plating solution containing EDTA/2Na can be sufficiently plated at an N I 2+ concentration of 10"-"M, and decomposition can be performed at an N1+ concentration of 10"-"M.
I woke up.
従って、ＥＤＴＡＳ２Ｎａを添加することにより中間層
であるニッケルメッキ層から不純物として溶出するＮｉ
２＋イオンによるメツキ液の劣化が有効に防止できるこ
とが実証された。Therefore, by adding EDTAS2Na, Ni is eluted as an impurity from the nickel plating layer, which is the intermediate layer.
It has been demonstrated that deterioration of the plating solution due to 2+ ions can be effectively prevented.
また、中間層としてコバルトメツキを用いた場合のコバ
ルトイオンによる不純物の影響についても同様の効果が
認められた。Furthermore, a similar effect was observed regarding the influence of impurities due to cobalt ions when cobalt plating was used as the intermediate layer.
以上、実施例においてアルカリ可溶性キレート剤として
ＥＤＴＡ・２Ｎａを使用したが、本発明はこれに限定さ
れるものではない。キレート剤としてトリエチレンテト
ラミンヘキサ酢酸（ＴＴＨＡ）、トランス−１，２−シ
クロヘキサンジアミンテトラ酢酸（（４ＴＡ）等、種々
のキレート剤をアルカリ可溶性にしたものを使用するこ
とが可能である。Although EDTA.2Na was used as the alkali-soluble chelating agent in the examples above, the present invention is not limited thereto. As the chelating agent, it is possible to use various alkali-soluble chelating agents such as triethylenetetraminehexaacetic acid (TTHA) and trans-1,2-cyclohexanediaminetetraacetic acid ((4TA)).
銅配線を形成し、中間層として無電解法でニッケルある
いはコバルトをメツキし、次に置換金メツキを行ったプ
リント基板に、アルカリ可溶性キレート剤が添加され、
かつ、少なくとも金塩およびボロン系還元剤を含有する
アルカリ性自己触媒型無電解金メツキ液で金メツキを行
った結果、中間層から溶出する不純物イオンにより規定
される自己触媒型無電解金メツキ液の寿命を約１０倍に
延長でき、また、金の析出量を向上させることができる
。An alkali-soluble chelating agent is added to a printed circuit board on which copper wiring is formed, nickel or cobalt is electrolessly plated as an intermediate layer, and substitution gold plating is then performed.
Moreover, as a result of performing gold plating with an alkaline autocatalytic electroless gold plating solution containing at least a gold salt and a boron-based reducing agent, the autocatalytic electroless gold plating solution defined by impurity ions eluted from the intermediate layer. The service life can be extended about 10 times, and the amount of gold deposited can be improved.
第１図は本発明の一実施例におけるＥＤＴＡΦ２Ｎａ添
加量と金の析出量の関係を示すグラフ尋。
第２図は本発明の他の実施例において不純物として添加
したＮ！２＋濃度と金の析出量の関係を示すグラフであ
る。
ＥＤＴＡ−２Ｎａ＞ｆ＋加量（９Ａ）FIG. 1 is a graph showing the relationship between the amount of EDTAΦ2Na added and the amount of gold deposited in an example of the present invention. FIG. 2 shows N! added as an impurity in another embodiment of the present invention! It is a graph showing the relationship between the 2+ concentration and the amount of gold precipitation. EDTA-2Na>f+addition (9A)
Claims (2)
層としてニッケルあるいはコバルトをメッキし、さらに
その表面に無電解法により金をメッキするプリント基板
に金をメツキする方法において、無電解金メッキ液とし
て少なくとも金塩およびボロン系還元剤を含有するアル
カリ性無電解メッキ液にアルカリ可溶性キレート剤を添
加した自己触媒型無電解金メッキ液を用いることを特徴
とするプリント基板に金をメッキする方法。(1) Electroless gold plating is a method of plating gold on a printed circuit board in which the surface of the copper wiring formed on the printed circuit board is plated with nickel or cobalt as an intermediate layer, and then gold is plated on the surface by an electroless method. A method for plating gold on a printed circuit board, characterized by using an autocatalytic electroless gold plating solution prepared by adding an alkali-soluble chelating agent to an alkaline electroless plating solution containing at least a gold salt and a boron-based reducing agent.
ｇ／ｌである自己触媒型無電解金メッキ液を用いること
を特徴とするプリント基板に金をメッキする方法。(2) Addition amount of alkali-soluble chelating agent is 2 to 100
1. A method for plating gold on a printed circuit board, characterized by using an autocatalytic electroless gold plating solution having a g/l ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28222787A JPH01125891A (en) | 1987-11-10 | 1987-11-10 | Gold plating of printed board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28222787A JPH01125891A (en) | 1987-11-10 | 1987-11-10 | Gold plating of printed board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01125891A true JPH01125891A (en) | 1989-05-18 |
Family
ID=17649712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28222787A Pending JPH01125891A (en) | 1987-11-10 | 1987-11-10 | Gold plating of printed board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01125891A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0575246A (en) * | 1990-09-12 | 1993-03-26 | Macdermid Inc | Printed-circuit forming method |
| CN102560451A (en) * | 2012-02-22 | 2012-07-11 | 江苏大学 | Chemical nano-silver plating solution and preparation method thereof, and silver plating method for copper part |
-
1987
- 1987-11-10 JP JP28222787A patent/JPH01125891A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0575246A (en) * | 1990-09-12 | 1993-03-26 | Macdermid Inc | Printed-circuit forming method |
| CN102560451A (en) * | 2012-02-22 | 2012-07-11 | 江苏大学 | Chemical nano-silver plating solution and preparation method thereof, and silver plating method for copper part |
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