JPS61217581A - Chemical copper plating solution and chemical copper plating method - Google Patents
Chemical copper plating solution and chemical copper plating methodInfo
- Publication number
- JPS61217581A JPS61217581A JP5468285A JP5468285A JPS61217581A JP S61217581 A JPS61217581 A JP S61217581A JP 5468285 A JP5468285 A JP 5468285A JP 5468285 A JP5468285 A JP 5468285A JP S61217581 A JPS61217581 A JP S61217581A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- chemical
- copper plating
- plating solution
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は化学銅めっきに係シ、特にプリント配線基板用
として好適な化学銅めっき液に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to chemical copper plating, and particularly to a chemical copper plating solution suitable for use in printed wiring boards.
従来化学銅めっき液は、一般に銅膜として硫酸鋼、錯化
剤として酒石酸ナトリウムカリウム、エチレンジアミン
四酢酸又はそのナトリウム塩、還元剤としてホルマリン
、バラホルムアルデヒド、アルカリとしては水酸化ナト
リウム等が使用されている。Conventional chemical copper plating solutions generally use steel sulfate as the copper film, sodium potassium tartrate, ethylenediaminetetraacetic acid or its sodium salt as the complexing agent, formalin or paraformaldehyde as the reducing agent, and sodium hydroxide as the alkali. .
しかし、主要成分として上記の組み合せから成る化学銅
めっき液で得られた銅膜は、一般に脆弱であり延性に欠
ける。プリント配線基板の導体部をめっきした膜が脆い
と、加工や熱的歪によって回路の断線を生ずる事がある
。However, copper films obtained with chemical copper plating solutions consisting of the above-mentioned combinations as main components are generally brittle and lack ductility. If the film plated on the conductor portion of a printed wiring board is brittle, circuit breakage may occur due to processing or thermal strain.
この点を考慮して該めっき液に、さらにシアン化合物や
ジピリジル、およびポリエチレングリコール等を添加し
て銅めっき膜の延性を向上する方法が実用されている。In consideration of this point, a method of improving the ductility of the copper plating film by further adding a cyanide compound, dipyridyl, polyethylene glycol, etc. to the plating solution has been put into practice.
このようなめつき液を使用して得られるめっき膜は、３
〜７％の延性と３０〜５０ｋｇＷ、／１ｔ１１Ｌ２の引
張り強さがあシブリント配線基板の導体膜として実用に
供し得るものである。The plating film obtained using such a plating solution is 3
It has a ductility of ~7% and a tensile strength of 30 to 50 kgW, /1t11L2, which can be used practically as a conductive film for a syblind wiring board.
しかしながら、近年高密度又は多層線板用の需要が多く
なるに従って、さらに延性に優れた銅めっき膜が望まれ
ている現状にある。However, as the demand for high-density or multilayer wire boards increases in recent years, there is a current demand for copper plating films with even better ductility.
又このプリント配線基板上に、３０〜４０μｍと厚い銅
膜を形成する場合には、めっき反応を維持するだめに、
銅、還元剤、アルカリ等を順次補給しなければならない
が、そうすると析出する銅膜の延性は低下する傾向を示
し、該めっき液の安定性も損われる。In addition, when forming a thick copper film of 30 to 40 μm on this printed wiring board, in order to maintain the plating reaction,
Copper, reducing agent, alkali, etc. must be replenished in sequence, but if this is done, the ductility of the deposited copper film tends to decrease, and the stability of the plating solution is also impaired.
この問題点に対して１）イオン交換膜を用いて反応副成
物を分離する。２）隔膜電解によジエチレンジアミン４
酢酸（以下Ｅ、Ｄ、’ｊＡ と略す）水溶液に銅を溶
解させてＥ、Ｄ、Ｔ、Ａ−Ｃｕ錯体を調整する方法など
が提案されているが、１）の方法は抽出効率が低いので
実用性に乏しい。２）の方法は、銅濃度を２０〜２５
Ｆｌ／ｌ とするまでに長時間を要し効率的ではない
。To solve this problem, 1) Separate reaction byproducts using an ion exchange membrane. 2) Diethylenediamine 4 by diaphragm electrolysis
Methods have been proposed to prepare E, D, T, and A-Cu complexes by dissolving copper in aqueous acetic acid (hereinafter abbreviated as E, D, and 'jA), but method 1) has low extraction efficiency. Therefore, it is impractical. Method 2) sets the copper concentration to 20 to 25
It takes a long time to reach Fl/l, which is not efficient.
又１）、２）の双方とも電解を伴なうため、化学めっき
工程と対応させて装置を稼動させる必要があシ煩雑でコ
スト高などの欠点がある。In addition, since both 1) and 2) involve electrolysis, it is necessary to operate the apparatus in conjunction with the chemical plating process, which is complicated and has drawbacks such as high cost.
本発明の目的は、上記の欠点がなく優れた延性と物性と
を備えた銅膜が得られる化学銅めっき液及び化学銅めっ
き方法を提供することにある。An object of the present invention is to provide a chemical copper plating solution and a chemical copper plating method that do not have the above-mentioned drawbacks and can provide a copper film with excellent ductility and physical properties.
この目的を達成するため、本発明者等は鋭意研究の結果
、従来の錯化剤、還元剤、ｐＨ調整剤、２．２′ジピリ
ジルおよびポリエチレングリコール等の主要組成物に銅
膜として酸化銅粉末の所定量を添加してなる化学鋼めっ
き液を見出した。In order to achieve this objective, the present inventors conducted intensive research and found that copper oxide powder was added to the main compositions such as conventional complexing agents, reducing agents, pH adjusters, 2.2' dipyridyl and polyethylene glycol as a copper film. We have discovered a chemical steel plating solution in which a predetermined amount of is added.
即ち本発明の銅膜としては、酸化銅粉末好ましくは鉱酸
および有機酸に易溶性の酸化第二銅粉末、よシ好ましく
は、電気銅及び阻極を隔膜袋中に収納し、０．３〜１．
１モル／ｌの硫酸ナトリウム水溶液を電解液として、ｐ
Ｈ５〜１３、液温５５〜７５Ｃ１陰極電流密度１５０〜
３ｏｏＡ／ｍ２の条件で製造された酸化第二銅粉末の所
定量を使用し、他は公知の組成の水溶液が使用できる。That is, as the copper film of the present invention, copper oxide powder, preferably cupric oxide powder easily soluble in mineral acids and organic acids, preferably electrolytic copper and blocking electrode are stored in a diaphragm bag, and 0.3 ~1.
Using 1 mol/l sodium sulfate aqueous solution as the electrolyte, p
H5~13, liquid temperature 55~75C1 cathode current density 150~
A predetermined amount of cupric oxide powder produced under the condition of 3ooA/m2 is used, and an aqueous solution having a known composition can be used for the rest.
その１例を示せば第１表の如くである。An example of this is shown in Table 1.
第１表
水酸化すｌ−ＩＪウム （ｐＨ調整に必要な量）
ＣｕＯ粉末 ＣＵとして２０７１／ＩＥ、
Ｄ、Ｔ、Ａ、 ４Ｈ１１０ｊ！／１２．２′ジピリジ＃
０．００５〜０．０２１／／１ポＩＪ エチレ
７り’） ：＋ −３０，０５〜０．２０１／／１残部
水
ｐＨ１１，５〜１３
（初期ｐＨ５，０）
〔作用〕
本発明に於ける銅以外の主要組成物は、前にも述べたよ
うに公知のものが所定範囲内で使用できるが、銅分とし
ては極力高純度の酸化銅粉末の所定量を用いるのが好ま
しい。一般に市販されている酸化第二銅粉末や水酸化銅
等は、Ｅ、Ｄ、Ｔ、Ａなどの錯化剤に溶解する際に不溶
解物が残留し且つ溶解に長時間を要する。このような銅
膜は特にめっきの建浴や補給用としては不都合である。Table 1 Sourium hydroxide (amount required for pH adjustment)
CuO powder 2071/IE as CU,
D, T, A, 4H110j! /12.2'dipyridi#
0.005 to 0.021 // 1 point IJ Echire 7ri'): + -30,05 to 0.201 // 1 remainder Water pH 11.5 to 13 (Initial pH 5.0) [Operation] In the present invention As mentioned above, the main components other than copper can be used within a predetermined range, but as the copper content, it is preferable to use a predetermined amount of copper oxide powder of as high purity as possible. Generally available commercially available cupric oxide powder, copper hydroxide, etc., when dissolved in complexing agents such as E, D, T, and A, leave undissolved substances and require a long time for dissolution. Such a copper film is particularly inconvenient for preparing or replenishing a plating bath.
本発明で推奨する塩酸、硝酸等の鉱酸、ＥＤＴＡ等の有
機酸に易溶性の酸化第二銅を用いて、高濃度のＥ、Ｄｊ
、Ａ−Ｃｕ溶液（Ｃｕとして２０１／／１程度）を造る
例としては、まずＥ；、Ｄ、Ｔ、Ａ、４Ｈ１１０！ｉに
極力高濃度の水酸化ナトリウム水溶液を添加攪拌して、
ｐＨ５，０に調整して１．Ｄ、Ｔ、Ａ２Ｂを完全に溶解
する。Using cupric oxide, which is easily soluble in mineral acids such as hydrochloric acid and nitric acid, and organic acids such as EDTA, which are recommended in the present invention, high concentrations of E and Dj can be obtained.
, A-As an example of making a Cu solution (approximately 201//1 as Cu), first, E;, D, T, A, 4H110! Add and stir an aqueous solution of sodium hydroxide as highly concentrated as possible to i.
Adjust the pH to 5.0 and add 1. Completely dissolve D, T, and A2B.
次に該浴液に上記の酸化第二銅粉末２５．ｉ？（Ｃｕと
して２０Ｉ）を添加して例えばエアレーションを行なう
と約２０分間でＢＥ、Ｄ、Ｔ、Ａ−Ｃｕ 錯体が得ら
れる。Next, add 25% of the above cupric oxide powder to the bath solution. i? (20I as Cu) is added and, for example, aeration is performed to obtain a BE, D, T, A-Cu complex in about 20 minutes.
この反応は下式に従うものと思われる。This reaction seems to follow the formula below.
Ｅ、Ｄ、Ｔ、Ａ・２Ｈ・２Ｎａ＋Ｃｕ○＋Ｈ２０→（Ｅ
ＤＴＡ−Ｃｕ）２Ｈ＋２ＮａＯＨ
反応式から解るように、この錯化反応によシ初期ｐＨ５
，０は通常１０，５〜１１．０まで上昇する。E, D, T, A・2H・2Na+Cu○+H20→(E
DTA-Cu)2H+2NaOH As can be seen from the reaction formula, this complexation reaction results in an initial pH of 5.
,0 usually rises to 10.5-11.0.
このように同じＣｕのＥ、Ｄ、ｊＡ錯塩を得るのに、従
来技術の２）として説明した電解法と本発明法との比較
では約１／１０と所要時間が短縮され、不溶解残渣も極
めて少なく且つ被めっき物に析出した膜の物性が大巾に
向上する。In this way, in order to obtain the same E, D, jA complex salts of Cu, when comparing the electrolytic method described in 2) of the prior art and the method of the present invention, the time required is shortened to about 1/10, and there is no insoluble residue. The amount is extremely small and the physical properties of the film deposited on the object to be plated are greatly improved.
次にめっきの操作は６０Ｃ以上好ましくは８０Ｃ以下で
行なうが、その理由はこれ以下の温度ではめつきに要す
る時間が長く、より高温では還元反応が強くなりすぎ浴
が分解する等好ましくないためである。Next, the plating operation is carried out at a temperature of 60C or higher, preferably 80C or lower, because at lower temperatures, the time required for plating is longer, and at higher temperatures, the reduction reaction becomes too strong and the bath decomposes, which is undesirable. be.
尚めつき前の板の活性化は、通常の方法が適用できるが
１例として説明すると、紙フェノール基板あるいはエポ
キシ樹脂をガラスクロスに含浸し積層させて造られた基
板を、常法による脱脂を行ったのち、軽くエツチングし
、被エツチ部に少量の錫を付着させ更にパラジウム水溶
液中に浸漬してパラジウムと買換する事によって行われ
る。The activation of the board before plating can be done using the usual methods, but as an example, a paper phenol board or a board made by impregnating glass cloth with epoxy resin and laminating them is degreased by the usual method. After etching, the etched area is lightly etched, a small amount of tin is attached to the etched area, and the etched area is immersed in an aqueous palladium solution to be replaced with palladium.
尚めつき時のｐＨ範囲は１１．５〜１３．０とする。The pH range during plating is 11.5 to 13.0.
この範囲外では好適なめつき膜は得られず、めっき膜の
コーナークラック発生の原因ともなるからである。This is because, outside this range, a suitable plated film cannot be obtained and may cause corner cracks to occur in the plated film.
以下実施例について説明する。 Examples will be described below.
第２表に示した組み合せにより、まず酸に易溶性の酸化
第二銅粉末（クレーム３項により製造したもの）又は各
種銅膜とに、Ｄ、Ｔ、Ａ、４Ｈ及び水酸化ナトリウム水
溶液を添加して初期ｐＨ５，０としてエアレーションを
行ってＪＤ、Ｔ、Ａ−Ｃｕ 錯体を得、これに各添加剤
及び水を加え、第２表の化学鋼めっき液を夫々調製した
。According to the combinations shown in Table 2, D, T, A, 4H and an aqueous sodium hydroxide solution are first added to the easily acid-soluble cupric oxide powder (manufactured according to claim 3) or various copper films. The initial pH was set to 5.0 and aeration was performed to obtain JD, T, and A-Cu complexes, and each additive and water were added thereto to prepare chemical steel plating solutions shown in Table 2.
第２表 尚試薬は特級品を用いた。Table 2 Note that special grade reagents were used.
第２表のめつき液に、エポキシ樹脂をガラスクロスに含
浸し積層させたプリント配線基板を、常法によシ脱脂、
パラジウムによる活性化したのち゛夫々浸漬し、１５時
間後に引揚げ２０〜４０μｍ厚さの銅膜を形成させ、析
出皮膜の機械的特性を東洋測器社製の引張り試験により
測定しその結果を、第３表に、２６０Ｃはんだ上げ試験
を行った結果を第４表に、従来のめつき液を使用した場
合と対比して夫々示す。該めっき液の組成をマイクロコ
ンピュータ−によシ管理しながら容量５０１の槽でロン
グラン試験を行った結果を第５表に参考値として示した
。A printed wiring board made by impregnating glass cloth with epoxy resin and laminating it in the plating solution shown in Table 2 is degreased by the usual method.
After activation with palladium, they were immersed, and after 15 hours, a copper film with a thickness of 20 to 40 μm was formed.The mechanical properties of the deposited film were measured using a tensile test manufactured by Toyo Sokki Co., Ltd., and the results were as follows: Table 3 shows the results of the 260C soldering test, and Table 4 shows the results of the 260C soldering test in comparison with the case where a conventional plating solution was used. A long run test was conducted in a tank with a capacity of 501 cm while the composition of the plating solution was controlled by a microcomputer, and the results are shown in Table 5 as reference values.
めっきの際の温度は７０Ｃ一定で行った。The temperature during plating was kept constant at 70C.
第３表より明らかなように、本発明のめつき液を使用し
ためつき膜の延性は飛躍的に向上し、その他の物性もは
ソ同等を示した。特に第５表に示した延性は長期間経過
するほど差が大きくなった。As is clear from Table 3, the ductility of the plating film using the plating solution of the present invention was dramatically improved, and other physical properties were also the same. In particular, the difference in ductility shown in Table 5 increased over time.
第４．５表は夫々めっき膜の穴のコーナ一部にクラック
の発生が見られるかどうかを比較したものであるが、こ
＼でも本発明めっき膜が優れて諭ることか示された。Table 4.5 compares the occurrence of cracks in some corners of the holes in each plating film, and this also shows that the plating film of the present invention is superior.
（効果）
化学銅めっき液の銅膜として、酸に易溶性又は高純度の
酸化第二銅粉末を用いるというだけで、めっき液の調製
も容易で優れためつき膜が得られるだけでなく、Ｅ、Ｄ
、Ｔ、Ａ−Ｃｕの錯塩を調製する際の副生成物も少いの
でめっき液の寿命も長い等の利点が得られる。(Effects) By using easily acid-soluble or high-purity cupric oxide powder as the copper film in the chemical copper plating solution, the plating solution is easy to prepare and an excellent plating film can be obtained. ,D
, T, and A-Cu complex salts are produced in small quantities, which provides advantages such as a long life of the plating solution.
Claims (1)
リジル、およびポリエチレングリコールを含有する化学
めつき液において、銅膜として酸化銅粉末を用いる事を
特徴とする化学銅めつき液。 ２）銅膜は酸に易溶性の酸化第二銅粉末である、特許請
求の範囲第１項記載の化学銅めつき液。 ３）酸化第二銅粉末は、電気銅を陽極とし陰陽両極とも
隔膜袋中に収納した状態で０．３〜１．１モル／ｌの硫
酸ナトリウム水溶液を電解液として、電解液のｐＨ、温
度、陰極電流密度を規制して電解して得られたものであ
る特許請求の範囲第１項又は第２項に記載の化学銅めつ
き液。 ４）板表面を脱脂し、活性化し、次いで化学銅めつき液
によるめつきを行なう化学銅めつき方法において、前記
化学銅めつき液の組成が、錯化剤、還元剤、ｐＨ調整剤
、２，２′−ジピリジル、ポリエチレングリコール及び
酸化銅粉末より成るものであり該めつき浴を６０℃以上
、ｐＨ１１．５〜１３として化学銅めつきを行なうこと
を特徴とする特許請求の範囲第１項から第３項に記載の
化学銅めつき液を使用する化学鋼めつき方法。[Claims] 1) Use of copper oxide powder as a copper film in a chemical plating solution containing a copper salt, a complexing agent, a reducing agent, a pH adjuster, 2,2' dipyridyl, and polyethylene glycol. Characteristic chemical copper plating liquid. 2) The chemical copper plating solution according to claim 1, wherein the copper film is a cupric oxide powder that is easily soluble in acids. 3) Cupric oxide powder is prepared by using electrolytic copper as an anode and both negative and anode electrodes stored in a diaphragm bag, using a 0.3 to 1.1 mol/l sodium sulfate aqueous solution as an electrolyte, and adjusting the pH and temperature of the electrolyte. The chemical copper plating solution according to claim 1 or 2, which is obtained by electrolyzing while regulating the cathode current density. 4) In a chemical copper plating method in which the plate surface is degreased and activated, and then plated with a chemical copper plating solution, the composition of the chemical copper plating solution includes a complexing agent, a reducing agent, a pH adjuster, 2,2'-dipyridyl, polyethylene glycol, and copper oxide powder, and chemical copper plating is carried out at a temperature of 60° C. or higher and a pH of 11.5 to 13. A chemical steel plating method using the chemical copper plating solution described in Items 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5468285A JPS61217581A (en) | 1985-03-20 | 1985-03-20 | Chemical copper plating solution and chemical copper plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5468285A JPS61217581A (en) | 1985-03-20 | 1985-03-20 | Chemical copper plating solution and chemical copper plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61217581A true JPS61217581A (en) | 1986-09-27 |
| JPH0425348B2 JPH0425348B2 (en) | 1992-04-30 |
Family
ID=12977557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5468285A Granted JPS61217581A (en) | 1985-03-20 | 1985-03-20 | Chemical copper plating solution and chemical copper plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61217581A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7674401B2 (en) | 2001-12-18 | 2010-03-09 | Asahi Kasei Kabushiki Kaisha | Method of producing a thin conductive metal film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5627594A (en) * | 1979-08-10 | 1981-03-17 | Matsushita Electric Ind Co Ltd | Remote controller |
| JPS5932542A (en) * | 1982-08-17 | 1984-02-22 | Aisin Seiki Co Ltd | Signal transmission device on steering operation board |
-
1985
- 1985-03-20 JP JP5468285A patent/JPS61217581A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5627594A (en) * | 1979-08-10 | 1981-03-17 | Matsushita Electric Ind Co Ltd | Remote controller |
| JPS5932542A (en) * | 1982-08-17 | 1984-02-22 | Aisin Seiki Co Ltd | Signal transmission device on steering operation board |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7674401B2 (en) | 2001-12-18 | 2010-03-09 | Asahi Kasei Kabushiki Kaisha | Method of producing a thin conductive metal film |
| DE10297544B4 (en) * | 2001-12-18 | 2015-10-29 | Asahi Kasei Kabushiki Kaisha | Process for producing a metal thin film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0425348B2 (en) | 1992-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5039576A (en) | Electrodeposited eutectic tin-bismuth alloy on a conductive substrate | |
| EP1892321B1 (en) | A Hard Gold Alloy Plating Bath | |
| KR101502804B1 (en) | Pd and Pd-Ni electrolyte baths | |
| KR101319863B1 (en) | Tin electroplating solution and tin electroplating method | |
| US20060237097A1 (en) | Immersion method | |
| EP0164757A2 (en) | A method of etching copper circuit boards and an etch solution | |
| US4715935A (en) | Palladium and palladium alloy plating | |
| US20030183533A1 (en) | Electrolytic solution for electrochemical deposit of palladium or its alloys | |
| JP3261676B2 (en) | Electric nickel plating bath. | |
| US6743950B2 (en) | Palladium complex salt and use thereof for adjusting palladium concentration of an electrolytic solution for deposit of palladium or one of its alloys | |
| TW201713798A (en) | Electroless platinum plating solution | |
| US6423202B1 (en) | Process for making gold salt for use in electroplating | |
| JP2003147541A (en) | Electroless copper plating solution, replenishing solution for electroless copper plating, and method of producing wiring board | |
| US4297178A (en) | Ruthenium electroplating and baths and compositions therefor | |
| US4468296A (en) | Process for electroplating palladium | |
| JPS61217581A (en) | Chemical copper plating solution and chemical copper plating method | |
| WO1993018211A1 (en) | Cyanide-free copper plating bath and process | |
| US4377450A (en) | Palladium electroplating procedure | |
| US4238300A (en) | Gold electroplating process | |
| JPH0423000B2 (en) | ||
| GB2101633A (en) | Bath for the electrodeposition of ruthenium | |
| KR960015548B1 (en) | Electroplated alloy coating having stable alloy composition | |
| JP3282875B2 (en) | Palladium plating solution and palladium plating method using the plating solution | |
| JP2732972B2 (en) | Reflow tin or reflow tin alloy plating bath | |
| JP2003105581A (en) | Method and apparatus for electrolytic deposition of tin alloy |