JPH0222152B2 - - Google Patents
Info
- Publication number
- JPH0222152B2 JPH0222152B2 JP59123657A JP12365784A JPH0222152B2 JP H0222152 B2 JPH0222152 B2 JP H0222152B2 JP 59123657 A JP59123657 A JP 59123657A JP 12365784 A JP12365784 A JP 12365784A JP H0222152 B2 JPH0222152 B2 JP H0222152B2
- Authority
- JP
- Japan
- Prior art keywords
- plating solution
- germanium
- electroless copper
- copper plating
- 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
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
-
- 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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/187—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating means therefor, e.g. baths, apparatus
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
〔発明の利用分野〕
本発明は無電解銅めつき液に係り、特に、機械
的性質の優れた銅めつき膜を生成する、無電解銅
めつき液に関する。
〔発明の背景〕
従来より、銅イオンとその錯化剤を含む溶液
に、ホルムアルデヒド等の銅イオンの還元剤を加
えることにより、金属銅を析出させる、無電解銅
めつき法が知られていた。しかし、このような基
本成分のみからなる無電解銅めつき液において
は、めつき液が不安定で、自己分解反応を起しや
すく、長時間のめつきを行うことは困難であつ
た。
このため、特公昭43−12966号においては、め
つき液の安定性を改善する目的で、チオ尿素、２
−メルカプトベンゾチアゾール等の硫黄化合物の
添加が開示されている。しかしながら、これらの
添加剤を用いても、プリント配線板の導体回路
や、めつきスルーホールを無電解銅めつき液によ
つて形成する、いわゆるアデイテイブ法プリント
配線板の製造プロセスに適用する場合には、めつ
き膜の機械的性質が、十分ではなく、より高い機
械的性質を示すめつき膜を生成する無電解銅めつ
き液の添加剤が望まれていた。
〔発明の目的〕
本発明の目的は、機械的性質の優れためつき膜
を生成する無電解銅めつき液を提供することにあ
り、特に、プリント配線板における回路形成に好
適な無電解銅めつき液を提供することにある。
〔発明の概要〕
本発明の特徴とする所は、銅イオンとその錯化
剤及び還元剤を含む無電解銅めつき液において、
ゲルマニウムを含有するが、アミン系エトキシ界
面活性剤、α，α′−ジピリジル、ｏ−フエナント
ロリン、及びそれらの誘導体のいずれをも含有し
ていない点にある。本発明のめつき液によれば、
プリント配線板のスルーホールめつき、導体回路
の形成に好適な、機械的性質の優れためつき膜を
得ることができる。
本発明において、基本となる無電解銅めつき液
は、銅イオンとその錯化剤及び銅イオンの還元
剤、更に必要に応じてPH調整剤を含む無電解銅め
つき液である。
銅イオンの供給源としては、硫酸銅、硝酸銅、
塩化銅等、通常の可溶性銅塩であればよく、場合
によつては、水酸化銅等を用いることもできる。
また、金属銅を化学的に、或いは電気化学的に溶
解させて銅イオンを供給することも可能である。
銅イオンの錯化剤としては、エチレンジアミン
四酢酸、Ｎ−ヒドロキシエチルエチレンジアミン
三酢酸、Ｎ，N′−ビス（2′−ヒドロキシエチル）
エチレンジアミン二酢酸、シクロヘキサンジアミ
ン四酢酸、ジエチレントリアミン五酢酸、ジアミ
ノプロパン四酢酸、テトラキス（２−ヒドロキシ
プロピル）エチレンジアミン、ペンタキス（２−
ヒドロキシプロピル）ジエチレントリアミン等の
Ｎ−Ｃ−Ｃ−Ｎ骨格を持つ錯化剤が好適であ
る。酸型の錯化剤の場合、そのアルカリ金属塩を
用いても同様な効果を得ることができる。
銅イオンの還元剤としては、通常用いられてい
るホルムアルデヒドを用いることができ、パラホ
ルムアルデヒド、グリオキサール、トリオキサン
とそのホルムアルデヒド縮合物等を用いても良
い。また、ホウ水酸化物のアルカリ金属塩、アル
キルアミンポランとその誘導体を還元剤として使
用することも可能である。
本発明のめつき液においては、通常の無電解銅
めつき液におけるように、PH調整剤を使用しても
よく、その例としては、水酸化ナトリウム等の水
酸化アルカリを用いることができ、また、イオン
交換等により、PHを維持してもよい。PHは、25℃
で測定した値として、11.0〜14.0の間に保つこと
が望ましい。
本発明に使用するゲルマニウムとしては、水溶
性無機塩、或いは酸化物を用いることができる。
例えば、ゲルマニウム酸のナトリウム塩、カリウ
ム塩等を用いることができる。また、ゲルマニウ
ムは、酸化物の形で加えても良く、例えば、二酸
化ゲルマニウムを直接めつき液に溶解させても、
本発明の目的を達成することができる。この他、
塩化ゲルマニウム、硫酸ゲルマニウム、硝酸ゲル
マニウム等の塩として添加しても、同様の効果を
得ることができる。めつき膜の物性を改善する上
で望ましい添加量は、ゲルマニウムとして10mg／
以上であり、これ未満の量では十分な効果は望
めない。めつき温度については、本発明の目的か
らは、特に制限はないが、めつき速度の観点から
は、高い方が望ましい。
なお、本発明の無電解銅めつき液において、必
要に応じて、更に他の添加剤を併用することもで
きる。例えば、ポリアルキレンオキシド系非イオ
ン界面活性剤、シアン化ナトリウムやヘキサシア
ノ鉄酸塩等のシアン化合物等を添加することによ
り、更に液安定性を向上させたり、めつき膜の機
械的性質を改善したりすることができる。
〔発明の実施例〕
以下、本発明を実施例により更に具体的に説明
するが、本発明はこれら実施例に限定されない。
実施例１〜６、比較例１〜２
表面を平滑に研磨したステンレス・スチール板
を、無電解めつき用触媒液で処理した後、下記第
１表の組成の無電解銅めつき液を用いて、無電解
めつきを行い、厚さ30〜35μｍのめつき膜を得
た。めつき温度は70℃とし、めつき液のPHは、25
℃で12.9となるように調整した。このめつき膜を
ステンレス・スチール板からはく離して、幅10mm
の試験片に切断し、引張試験機によりめつき膜の
機械的物性を評価した。このようにして測定し
た、破断までの伸び率、引張強度の値を第２表に
記した。
実施例１〜６により得ためつき膜は比較例１〜
２から得られるめつき膜に比べて、いずれも、極
めて延性に富む、高品質のめつき膜であり、プリ
ント配線板の導体回路の形成に適用した場合、十
分高い信頼性を得ることができる。
[Field of Application of the Invention] The present invention relates to an electroless copper plating solution, and particularly to an electroless copper plating solution that produces a copper plating film with excellent mechanical properties. [Background of the Invention] Conventionally, an electroless copper plating method has been known in which metal copper is deposited by adding a reducing agent for copper ions such as formaldehyde to a solution containing copper ions and their complexing agent. . However, in an electroless copper plating solution consisting only of such basic components, the plating solution is unstable and prone to self-decomposition reactions, making it difficult to conduct plating for a long time. For this reason, in Japanese Patent Publication No. 43-12966, for the purpose of improving the stability of plating solution, thiourea,
- Addition of sulfur compounds such as mercaptobenzothiazole is disclosed. However, even when these additives are used, they cannot be applied to the manufacturing process of printed wiring boards using the so-called additive method, in which conductor circuits and plated through holes of printed wiring boards are formed using an electroless copper plating solution. The mechanical properties of the plated film were not sufficient, and an additive for electroless copper plating solution was desired that would produce a plated film with higher mechanical properties. [Object of the Invention] An object of the present invention is to provide an electroless copper plating solution that produces a plating film with excellent mechanical properties, and in particular, to provide an electroless copper plating solution suitable for forming circuits on printed wiring boards. The purpose is to provide a dipping liquid. [Summary of the Invention] The present invention is characterized in that an electroless copper plating solution containing copper ions, a complexing agent thereof, and a reducing agent,
Although it contains germanium, it does not contain any of the amine-based ethoxy surfactants, α,α'-dipyridyl, o-phenanthroline, and their derivatives. According to the plating liquid of the present invention,
It is possible to obtain a plating film with excellent mechanical properties, which is suitable for through-hole plating of printed wiring boards and for forming conductor circuits. In the present invention, the basic electroless copper plating solution is an electroless copper plating solution containing copper ions, a complexing agent thereof, a reducing agent for the copper ions, and, if necessary, a PH adjuster. Sources of copper ions include copper sulfate, copper nitrate,
Any ordinary soluble copper salt such as copper chloride may be used, and in some cases, copper hydroxide or the like may also be used.
It is also possible to supply copper ions by dissolving metallic copper chemically or electrochemically. Examples of complexing agents for copper ions include ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, and N,N'-bis(2'-hydroxyethyl).
Ethylenediaminediacetic acid, cyclohexanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, diaminopropanetetraacetic acid, tetrakis(2-hydroxypropyl)ethylenediamine, pentakis(2-
Complexing agents having an N-C-C-N skeleton such as (hydroxypropyl) diethylenetriamine are preferred. In the case of an acid-type complexing agent, a similar effect can be obtained by using its alkali metal salt. As a reducing agent for copper ions, commonly used formaldehyde can be used, and paraformaldehyde, glyoxal, trioxane and its formaldehyde condensate, etc. may also be used. It is also possible to use alkali metal salts of boron hydroxide, alkylamine poranes and their derivatives as reducing agents. In the plating solution of the present invention, a PH adjuster may be used as in a normal electroless copper plating solution, such as an alkali hydroxide such as sodium hydroxide, Further, the pH may be maintained by ion exchange or the like. PH is 25℃
It is desirable to keep the value between 11.0 and 14.0 as measured by . As germanium used in the present invention, a water-soluble inorganic salt or an oxide can be used.
For example, sodium salt, potassium salt, etc. of germanic acid can be used. Further, germanium may be added in the form of an oxide, for example, germanium dioxide may be directly dissolved in the plating solution.
The purpose of the present invention can be achieved. In addition,
Similar effects can be obtained by adding it as a salt such as germanium chloride, germanium sulfate, or germanium nitrate. The desirable addition amount for improving the physical properties of the plated film is 10mg/germanium.
This is the above amount, and if the amount is less than this amount, a sufficient effect cannot be expected. Regarding the plating temperature, there is no particular restriction from the purpose of the present invention, but from the viewpoint of the plating speed, the higher the temperature is, the more desirable it is. In addition, in the electroless copper plating solution of the present invention, other additives can also be used in combination, if necessary. For example, by adding polyalkylene oxide type nonionic surfactants, cyanide compounds such as sodium cyanide and hexacyanoferrate, etc., the liquid stability can be further improved and the mechanical properties of the plated film can be improved. You can [Examples of the Invention] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Examples 1 to 6, Comparative Examples 1 to 2 A stainless steel plate with a smooth polished surface was treated with a catalyst solution for electroless plating, and then treated with an electroless copper plating solution having the composition shown in Table 1 below. Then, electroless plating was performed to obtain a plated film with a thickness of 30 to 35 μm. The plating temperature was 70℃, and the pH of the plating solution was 25.
The temperature was adjusted to 12.9°C. Peel off this plating film from the stainless steel plate to a width of 10 mm.
The plated film was cut into test pieces, and the mechanical properties of the plated film were evaluated using a tensile tester. The values of elongation to break and tensile strength measured in this manner are shown in Table 2. The impregnated films obtained in Examples 1 to 6 were those of Comparative Examples 1 to 6.
Compared to the plating film obtained from No. 2, both are extremely ductile and high-quality plating films, and when applied to the formation of conductor circuits on printed wiring boards, sufficiently high reliability can be obtained. .
【表】【table】
【表】
実施例７〜20、比較例３〜15
前例と同様にして、後記各表に記載の条件下、
各種のめつき膜を作製し、それらの機械的物性を
評価した。作製条件、評価結果を、下記の各表に
示す。[Table] Examples 7 to 20, Comparative Examples 3 to 15 In the same manner as in the previous example, under the conditions described in each table below,
Various plated films were prepared and their mechanical properties were evaluated. The production conditions and evaluation results are shown in the tables below.
【表】【table】
【表】【table】
【表】【table】
以上の実施例からも明らかなように、本発明に
よれば極めて延性に富んだ、機械的性質の優れた
めつき膜を得ることが可能である。すなわち、本
発明によれば、同量のゲルマニウム化合物を使用
した場合、アミン系エトキシ界面活性剤、α，
α′−ジピリジル、ｏ−フエナントロリン、及びそ
れらの誘導体のいずれも使用しないことによつ
て、めつき膜の破断伸び率を向上させることがで
きる。更に、他の添加剤を使用することによつ
て、液安定性を向上させ、めつき膜の機械的性質
を高めることができる。
As is clear from the above examples, according to the present invention, it is possible to obtain a laminated membrane that is extremely ductile and has excellent mechanical properties. That is, according to the present invention, when the same amount of germanium compound is used, the amine-based ethoxy surfactant, α,
By not using α'-dipyridyl, o-phenanthroline, or any of their derivatives, the elongation at break of the plated film can be improved. Furthermore, by using other additives, the liquid stability can be improved and the mechanical properties of the plated film can be enhanced.
Claims (1)
含する無電解銅めつき液において、該めつき液が
ゲルマニウムを含有するが、アミン系エトキシ界
面活性剤、α，α′−ジピリジル、ｏ−フエナント
ロリン、及びそれらの誘導体のいずれも含有しな
いものであることを特徴とする無電解銅めつき
液。 ２ 該ゲルマニウムが、ゲルマニウム酸化物又は
ゲルマニウム酸塩である特許請求の範囲第１項記
載の無電解銅めつき液。 ３ 該ゲルマニウムの含量が、ゲルマニウム量と
して10mg／以上である特許請求の範囲第１項記
載の無電解銅めつき液。 ４ 該めつき液が、ポリアルキレンオキシド系非
イオン界面活性剤を含有している特許請求の範囲
第１項〜第３項のいずれか１項に記載の無電解銅
めつき液。[Scope of Claims] 1. An electroless copper plating solution containing copper ions, a copper ion complexing agent, and a reducing agent, wherein the plating solution contains germanium, but contains an amine-based ethoxy surfactant, α, An electroless copper plating solution characterized in that it does not contain α'-dipyridyl, o-phenanthroline, or any of their derivatives. 2. The electroless copper plating solution according to claim 1, wherein the germanium is germanium oxide or germanate. 3. The electroless copper plating solution according to claim 1, wherein the germanium content is 10 mg/or more as germanium amount. 4. The electroless copper plating solution according to any one of claims 1 to 3, wherein the plating solution contains a polyalkylene oxide nonionic surfactant.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59123657A JPS613884A (en) | 1984-06-18 | 1984-06-18 | Electroless copper plating liquid |
| KR1019850004219A KR920002710B1 (en) | 1984-06-18 | 1985-06-14 | Chemical copper plating method |
| US06/746,099 US4632852A (en) | 1984-06-18 | 1985-06-18 | Process for electroless copper plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59123657A JPS613884A (en) | 1984-06-18 | 1984-06-18 | Electroless copper plating liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS613884A JPS613884A (en) | 1986-01-09 |
| JPH0222152B2 true JPH0222152B2 (en) | 1990-05-17 |
Family
ID=14866041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59123657A Granted JPS613884A (en) | 1984-06-18 | 1984-06-18 | Electroless copper plating liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS613884A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7682431B1 (en) * | 2008-11-12 | 2010-03-23 | Lam Research Corporation | Plating solutions for electroless deposition of ruthenium |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6337187A (en) * | 1986-08-01 | 1988-02-17 | Matsushita Electric Ind Co Ltd | liquid crystal display device |
-
1984
- 1984-06-18 JP JP59123657A patent/JPS613884A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS613884A (en) | 1986-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4099974A (en) | Electroless copper solution | |
| JPS5818430B2 (en) | Electroless plating bath and plating method | |
| JPH0247551B2 (en) | ||
| US4557762A (en) | Electroless copper plating solution | |
| EP0039757B1 (en) | Chemical copper-plating bath | |
| JPH01149971A (en) | Catalyst for electroless plating treatment | |
| JP2794741B2 (en) | Electroless copper plating solution | |
| JPH0222152B2 (en) | ||
| US4036651A (en) | Electroless copper plating bath | |
| US4520052A (en) | Method for electroless copper-plating and a bath for carrying out the method | |
| JPH08158060A (en) | Electroless nickel plating method for aluminum | |
| CN117966140B (en) | Chemical palladium plating solution and application thereof | |
| JPS59211564A (en) | Chemical copper plating solution | |
| JPH01147073A (en) | Electroless coppering bath | |
| JPS61227176A (en) | Electroless copper plating solution | |
| JPS59133394A (en) | Palladium high speed plating bath and process | |
| JPS6156283A (en) | Electroless copper plating solution | |
| JPS5933666B2 (en) | chemical copper plating liquid | |
| CA1206818A (en) | Method of producing gold-alloy layers and patterns on substrates, products thus produced and the solutions to be used therefore | |
| JP2873751B2 (en) | Electroless tin or tin-lead alloy plating solution and electroless tin or tin-lead alloy plating method | |
| JPH0416550B2 (en) | ||
| JPS6179775A (en) | Chemical copper plating solution | |
| JPH07286281A (en) | Electroless copper plating solution | |
| JPS5856031B2 (en) | Chemical copper plating liquid | |
| JPS61153281A (en) | Chemical copper plating solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |