JPS60200969A - Chemical copper plating solution - Google Patents
Chemical copper plating solutionInfo
- Publication number
- JPS60200969A JPS60200969A JP5633284A JP5633284A JPS60200969A JP S60200969 A JPS60200969 A JP S60200969A JP 5633284 A JP5633284 A JP 5633284A JP 5633284 A JP5633284 A JP 5633284A JP S60200969 A JPS60200969 A JP S60200969A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- plating solution
- copper plating
- chemical copper
- 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
- 238000007747 plating Methods 0.000 title claims abstract description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 38
- 239000010949 copper Substances 0.000 title claims abstract description 38
- 239000000126 substance Substances 0.000 title claims abstract description 24
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001879 copper Chemical class 0.000 claims abstract description 8
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 abstract description 9
- 239000003381 stabilizer Substances 0.000 abstract description 9
- 239000003002 pH adjusting agent Substances 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000008021 deposition Effects 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- FCNQQKLIOWCSMP-UHFFFAOYSA-N 2,3-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=1C=CC=CC=1C1=C(C)C(C)=NC(C2=NC=C3)=C1C=CC2=C3C1=CC=CC=C1 FCNQQKLIOWCSMP-UHFFFAOYSA-N 0.000 description 1
- WPTCSQBWLUUYDV-UHFFFAOYSA-N 2-quinolin-2-ylquinoline Chemical compound C1=CC=CC2=NC(C3=NC4=CC=CC=C4C=C3)=CC=C21 WPTCSQBWLUUYDV-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 1
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- IYRGXJIJGHOCFS-UHFFFAOYSA-N neocuproine Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 description 1
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 1
- 150000005041 phenanthrolines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は化学銅めっき液に関し、更に詳しくはめっき液
の安定性が優れ、かつ銅の高速析出が可能な化学鋼めっ
き液に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a chemical copper plating solution, and more particularly to a chemical steel plating solution that has excellent plating solution stability and is capable of high-speed copper deposition.
通常、化学銅めっき液は、硫酸銅、塩化第２銅などの銅
塩；エチレンジアミン四酢酸（ＥＤＴＡ）、Ｎ 、 Ｎ
、 Ｎ’、 Ｎ’−テトラキス−（２−ヒドロキシプ
ロピル）エチレンジアミン、ロッシェル塩などの錯化剤
：ホルムアルデヒド、ジメチルアミノボラン、ナトリウ
ムボロハイドライドなどの還元剤；水酸化ナトリウム、
水酸化カリウムなどのＰＨ調整剤を成分としている。Usually, chemical copper plating solutions include copper salts such as copper sulfate and cupric chloride; ethylenediaminetetraacetic acid (EDTA), N, N
, N', N'-tetrakis-(2-hydroxypropyl)ethylenediamine, a complexing agent such as Rochelle's salt; a reducing agent such as formaldehyde, dimethylaminoborane, sodium borohydride; sodium hydroxide,
Contains pH adjusters such as potassium hydroxide.
しかしながら、これらの成分のみから成る化学銅めっき
液は、不安定であるため、自己分解し易いという欠点が
あった。However, chemical copper plating solutions consisting only of these components have the disadvantage of being unstable and prone to self-decomposition.
そこで、このような欠点を改良するために、安定剤を添
加して、化学銅めっき液の安定性の向上を図ることが試
みられている（特公昭４３−１１５２１号、特開昭５２
−１７３３３号公報参照）。Therefore, in order to improve these drawbacks, attempts have been made to improve the stability of chemical copper plating solutions by adding stabilizers (Japanese Patent Publication No. 43-11521, JP-A-52
(Refer to Publication No.-17333).
しかしながら、上記した安定剤の添加によシめっき液の
安定性は向上するが、その反面、安定剤の添加濃度の増
大に伴い、銅の析出速度が減少して作業時間が長くなる
などの欠点があった。However, although the stability of the plating solution is improved by adding the above-mentioned stabilizer, on the other hand, as the concentration of the stabilizer added increases, the copper precipitation rate decreases and the working time becomes longer. was there.
従って、安定化剤を添加しても、析出速度が減少するこ
とがない化学銅めっき液の開発が望まれていた。Therefore, it has been desired to develop a chemical copper plating solution in which the deposition rate does not decrease even when a stabilizer is added.
本発明は、前記した欠点を解消することによって、安定
性が優れ、かつ速やかな銅の析出が可能な化学銅めっき
液を提供することを目的とする０〔発明の概要〕
本発明の化学銅めっき液は、銅塩と還元剤とＰＨｇ整剤
と、錯化剤としてエチレンジアミンテトラ酢塊と、Ｎ、
Ｎ、Ｎ’、Ｎ’−テトラキス−（２−ヒドロキシプロピ
ル）エチレンジアミンの混合物ヲ用い、且つ硫黄含有化
合物と非イオン系界面活絶剤及びα、α′−ジピリジル
又はフェナントロリン誘導体の少なくとも１種を含有す
ることを特徴とする。An object of the present invention is to provide a chemical copper plating solution that has excellent stability and is capable of rapidly depositing copper by eliminating the above-described drawbacks. [Summary of the Invention] The chemical copper plating solution of the present invention The plating solution contains a copper salt, a reducing agent, a PHg stabilizer, an ethylenediaminetetraacetic acid lump as a complexing agent, N,
Using a mixture of N,N',N'-tetrakis-(2-hydroxypropyl)ethylenediamine, and containing a sulfur-containing compound, a nonionic surfactant, and at least one α,α'-dipyridyl or phenanthroline derivative It is characterized by
本発明にかかる錯化剤、Ｎ、Ｎ’、Ｎ’、Ｎ’−テトラ
キス（２−ヒドロキシプロピル）エチレンジアミンとエ
チレンジアミンテトラ酢酸の混合物の添加量は、通常銅
塩の１〜１０倍モル、好ましくは１．１〜５倍モルの範
囲に設定される。等倍モル未溝の場合には、銅塩がアル
カリ性の銅めつき液中で水酸化銅となって沈殿するとい
う不都合が生じ、また１０倍モルを超えると、錯化剤の
添加効果が飽和するため、経済的に好ましくない。又、
混合比は通常１：４〜４：１、好ましくは１：３〜３：
１の範囲に限定される。Ｎ 、 Ｎ 、 Ｎ’、 Ｎ’
−テトラキス（２−ヒドロキシプロビル）エチレンジア
ミン単独で用いた場合には、析出速度は早いが、液の安
定性、析出銅皮膜の機械的特性の低下を招き、又、エチ
レンジアミンテトラ酢酸単独で用いた場合には析出速度
が低下する。The amount of the complexing agent according to the present invention, a mixture of N,N',N',N'-tetrakis(2-hydroxypropyl)ethylenediamine and ethylenediaminetetraacetic acid, is usually 1 to 10 times the mole of the copper salt, preferably It is set in the range of 1.1 to 5 times the mole. If the same molar ratio is not used, there will be an inconvenience that the copper salt will precipitate as copper hydroxide in the alkaline copper plating solution, and if it exceeds 10 times the molar ratio, the effect of adding the complexing agent will be saturated. Therefore, it is economically unfavorable. or,
The mixing ratio is usually 1:4 to 4:1, preferably 1:3 to 3:
1. N, N, N', N'
- When using tetrakis(2-hydroxypropyl)ethylenediamine alone, the precipitation rate is fast, but it causes a decrease in the stability of the solution and the mechanical properties of the deposited copper film. In some cases, the precipitation rate decreases.
本発明にかかる硫黄含有化合物としては、例えば、硫化
ナトリウム、硫化カリウム、硫化銀などの無機硫黄化合
物；２−メルカプトベンゾチアゾール、２−メルカプト
ベンゾイミダゾール、１−アリル−２−チオ尿素、１−
フェニル−２−チオ尿素、エチレンチオ尿素、１，３−
ジメチルチオ尿素、１，３−ジエチルチオ尿素、１，３
−ジブチルチオ尿素、ドデシルメルカプタン、ｎ−オク
タデシルメルカプタンなどの有機硫黄化合物があげられ
る。これらの添加量は、通常０，０１〜ＩＱｍｇ／Ａ！
、好ましくは０．１〜５ ｍｇ／ｌの範囲に設定され
るｏ Ｏ，０１ｍｇ／ｌ未滴の場合には、安定性がさほ
ど向上せず、また１０ｍσノを超えると、析出速度が極
端に低下するため作業能率の低下を招く。Examples of the sulfur-containing compound according to the present invention include inorganic sulfur compounds such as sodium sulfide, potassium sulfide, and silver sulfide; 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 1-allyl-2-thiourea, 1-
Phenyl-2-thiourea, ethylenethiourea, 1,3-
Dimethylthiourea, 1,3-diethylthiourea, 1,3
-Organic sulfur compounds such as dibutylthiourea, dodecylmercaptan, and n-octadecylmercaptan. The amount of these additions is usually 0.01 to IQmg/A!
, preferably set in the range of 0.1 to 5 mg/l. If the amount is 0.01 mg/l, the stability will not improve much, and if it exceeds 10 mσ, the precipitation rate will be extremely low. This results in a decrease in work efficiency.
本発明にかかる非イオン系界面活性剤のめっき液に対す
る添加量は、 ３０ｍｇ／１３〜２０ ｇＡ！の範囲に
あることが好ましい。添加量がこの範囲を外れると得ら
れる銅めっき膜の機械的特性、浴安定性析出速度の低下
等の原因となる。The amount of the nonionic surfactant according to the present invention added to the plating solution is 30 mg/13 to 20 gA! It is preferable that it is in the range of . If the amount added is out of this range, it will cause a decrease in the mechanical properties, bath stability, and deposition rate of the resulting copper plating film.
本発明において使用されるツェナトロリン誘導体として
は、例えば１，１０−フェナントロリン、２．９−ジメ
チルフェナントロリン、２，３−ジメチル−４，７−ジ
フェニルフェナントロリン、２．９−ジメチル−４，７
−シヒドロキシフエナントロリン、２，３，８．９−ジ
ベンゾ−４，７−シメチルー５，６−シヒドロキシフエ
ナントロリン等が挙げられる０又、α、α′−ジピリジ
ル又はフェナントロリン誘導体のめっき浴に対する添加
量は、２〜１００ｒｎｖ’ｌｊの範囲にあることが好ま
しい。Zenatroline derivatives used in the present invention include, for example, 1,10-phenanthroline, 2,9-dimethylphenanthroline, 2,3-dimethyl-4,7-diphenylphenanthroline, 2,9-dimethyl-4,7
-Plating bath of α,α'-dipyridyl or phenanthroline derivatives, including 2,3,8.9-dibenzo-4,7-dimethyl-5,6-dihydroxyphenanthroline, etc. The amount added is preferably in the range of 2 to 100rnv'lj.
一般に、２ｍｇ／１未満の添加量では延展性改良の効果
は期待できず、２００ｍｇ／ノを越える添加量を添加し
ても延展性改良の効果は飽和状態に達していて意味がな
いばかシか、時には、めっき析出速度が急激に増加して
めっき液を自然分解させることかあるため好ましくない
。In general, the effect of improving spreadability cannot be expected with an addition amount of less than 2 mg/1, and even if the addition amount exceeds 200 mg/1, the effect of improving spreadability has reached a saturated state and is meaningless. However, this is not preferable because the plating deposition rate may increase rapidly and the plating solution may spontaneously decompose.
前記した銅化剤の作用としては、第１に、銅塩が水酸化
銅として沈殿することを防止する作用があげられる。ま
た、本発明においては硫黄含有化合物を添加している。The first effect of the above-mentioned copperizing agent is to prevent the copper salt from precipitating as copper hydroxide. Further, in the present invention, a sulfur-containing compound is added.
しかし、該化合物は、一般に化学銅めっき液の安定性を
向上させるという利点を有しているが、反面、銅の析出
゛速度及びめっき皮膜の延展性を低下させる欠点のある
ことが知られている。ここに、上記した錯化剤の第２の
作用として、硫黄含有化合物の欠点を解消し、加えて銅
の析出速度及びめっき液の安定性を更に向上させるとい
う作用があげられる。この第２の作用は、本発明者らに
よシ初めて見出されたものである。However, although these compounds generally have the advantage of improving the stability of chemical copper plating solutions, they are known to have the disadvantage of reducing the copper precipitation rate and the spreadability of the plating film. There is. Here, the second function of the above-mentioned complexing agent is to eliminate the drawbacks of sulfur-containing compounds and further improve the copper precipitation rate and the stability of the plating solution. This second effect was discovered for the first time by the present inventors.
１．１０−７エナントロリン及びその誘導体、α、α′
−ジピリジル、２．２’−ビキノリンは、化学めっき液
の安定化作用に加えて、めっき皮膜の延展性を向上せし
める作用を有する。1.10-7 enanthroline and its derivatives, α, α'
- Dipyridyl and 2,2'-biquinoline not only have the effect of stabilizing the chemical plating solution, but also have the effect of improving the spreadability of the plating film.
本発明の化学銅めっき液を用いるに好ましいめっき条件
は、温度が５０〜８０°Ｃ１更に好ましくは５０〜７０
℃の範囲であり、ＰＨが１０．８〜１３．０、更に好ま
しくは１２．０〜１３．０の範囲である０かかるめっき
条件によれば、本発明のめつき液の特性をｌ充分に生か
しながら、安定性を維持しつつ、銅を高速析出させるこ
とが可能である０
〔発明の効果〕
本発明の化学銅めっき液においては、一般に析出速度が
速くなると不安定になシ、析出銅皮膜の物性が悪くなる
という欠点を、錯化剤として、エチレンジアミンテトラ
酢酸と、Ｎ、Ｎ、Ｎ’、Ｎ’−テトラキス−（２−ヒド
ロキシプロピル）エチレンジアミンの混合物を用い、更
に安定剤として硫黄含有化合物等を用′いることにより
解消されているＯその結果、本発明の化学めっき液は、
めっき液の安定性に極めて優れておシ、かつ安定剤が添
加されているにもかかわらず、良好な延展性を有するめ
っき皮膜が得られる、という利点を有する。Preferred plating conditions for using the chemical copper plating solution of the present invention include a temperature of 50 to 80°C, more preferably 50 to 70°C.
According to such plating conditions, the characteristics of the plating solution of the present invention can be sufficiently improved. [Effects of the Invention] In the chemical copper plating solution of the present invention, generally, as the deposition rate increases, copper becomes unstable and the deposited copper becomes unstable. To solve the problem of poor physical properties of the film, a mixture of ethylenediaminetetraacetic acid and N,N,N',N'-tetrakis-(2-hydroxypropyl)ethylenediamine was used as a complexing agent, and a sulfur-containing stabilizer was used. As a result, the chemical plating solution of the present invention has
It has the advantage that the stability of the plating solution is extremely excellent, and a plating film with good spreadability can be obtained despite the addition of a stabilizer.
しかも、銅の析出速度は、従来のめつき液と比べて、格
段に速くなっているため、本発明の化学銅めっき液を用
いれば、作業能率を大きく改善することができる。Furthermore, since the copper deposition rate is much faster than that of conventional plating solutions, the use of the chemical copper plating solution of the present invention can greatly improve work efficiency.
従って、本発明の化学銅めっき液は、例えば、印刷配線
板の導通回路の作成に好適でおって、その工業的価値は
大きい。Therefore, the chemical copper plating solution of the present invention is suitable for, for example, creating conductive circuits for printed wiring boards, and has great industrial value.
実施例１〜１１
厚さ０．３ＩｌｌｌＩのステンレススチール板をクレン
ザ−で研摩し、８０°Ｃの１０％水酸化ナトリウム溶液
に５分間浸漬して取出し、これを水洗後、１０％塩酸に
常温で５分間浸漬し、水洗して表面を清浄にした。Examples 1 to 11 A stainless steel plate with a thickness of 0.3IllI was polished with a cleanser, immersed in a 10% sodium hydroxide solution at 80°C for 5 minutes, taken out, washed with water, and then soaked in 10% hydrochloric acid at room temperature. The surface was cleaned by soaking for 5 minutes and rinsing with water.
ついで、得られたステンレススチール板を、塩化錫（Ｉ
ｆ） ５０ ｇ／１１
塩酸 １０ ｍｌＡ
水 残部
なる組成の溶液に２分間浸漬し、流水中で１分間水洗し
た。つぎに、
塩化パラジウム ０．２５ｇ／７
塩 酸 １０ｍ１／ｌ
水 残部
なる組成の液に１分間浸漬し、流水中で１分間水洗した
。しかるのち表に示すように調整しためっき液に浸漬し
銅の析出速度を測定した。Next, the obtained stainless steel plate was treated with tin chloride (I
f) 50 g/11 hydrochloric acid, 10 mlA water, the remainder was immersed in a solution for 2 minutes, and washed under running water for 1 minute. Next, it was immersed for 1 minute in a solution having the following composition: palladium chloride 0.25 g/7 hydrochloric acid 10 ml/l water the remainder, and washed in running water for 1 minute. Thereafter, it was immersed in a plating solution adjusted as shown in the table, and the copper precipitation rate was measured.
測定は次のようにして行なった。即ち、めっき液に、め
っき温度７０℃、めっき液のＰ Ｈ１２，３の条件下で
、表面が清浄化された厚さ１０μｍの銅箔を１時間浸漬
した。ついで、めっき処理前後の重量差から析出速度を
算出した。The measurements were carried out as follows. That is, a 10 μm thick copper foil whose surface had been cleaned was immersed in the plating solution for 1 hour at a plating temperature of 70° C. and a pH of 12.3. Then, the deposition rate was calculated from the difference in weight before and after plating.
次に、各種の銅めっき液を用いて得られるめっき皮膜の
延展性について、次のようにして試験を行なった。Next, the spreadability of plating films obtained using various copper plating solutions was tested as follows.
即ち、これら化学鋼めっき液を用いて、前記のようにし
て触媒化した０、３ｍｍ１のステンレススチール板の表
裏にそれぞれ加〜あμｍのめつき膜を析出させた。かく
して得られた銅めっき皮膜をステンレススチール板から
剥離し延展性試験に供した。That is, using these chemical steel plating solutions, plating films with a thickness of 1 to 1 μm were deposited on the front and back surfaces of a 0.3 mm 1 stainless steel plate, which had been catalyzed as described above. The copper plating film thus obtained was peeled off from the stainless steel plate and subjected to a ductility test.
延展性は次の様な１８０°折り曲げ試験により測定した
。まず、めっき皮膜を一方向に１８００折り曲げて折シ
目をつけ、次に元の位置に戻した後に圧力を加えて折目
を平坦にする。これらの操作を折シ曲げ１回と数える。Spreadability was measured by the following 180° bending test. First, the plating film is bent 1800 degrees in one direction to create a crease, and then, after returning to its original position, pressure is applied to flatten the crease. These operations are counted as one bending.
折シ目の部分でめっき皮膜が破断するまでこれらの操作
を繰シ返す。この試験法では、めっき皮膜の延展性はめ
っき皮膜が耐えた折シ曲げ回数によって表現される。These operations are repeated until the plating film breaks at the crease. In this test method, the ductility of a plating film is expressed by the number of bends that the plating film withstands.
、ついで、各種の銅めっき液の安定性について調べた。Next, we investigated the stability of various copper plating solutions.
即ち、めっき温度７０℃、めっき液のＰＨ１２，３に調
製しためっき液１００ｍ１に、塩化パラジウム ５ ｇ
／ｌ
塩 酸 ４０ｍＡ！力
水 残部
なる組成の溶液を２滴加え、得られためっき液が上記条
件下において分解するまでの時間を測定した０
以上で得られた結果を、各種組成の銅めっき液と対応さ
せて表に一括して示した。That is, 5 g of palladium chloride was added to 100 ml of a plating solution prepared at a plating temperature of 70°C and a plating solution pH of 12.3.
/l Hydrochloric acid 40mA! Two drops of the solution with the composition of the remainder were added, and the time taken for the resulting plating solution to decompose under the above conditions was measured.The results obtained above are shown in relation to the copper plating solutions of various compositions. are shown collectively.
Claims (3)
レンジアミンテトラ酢酸と、 Ｎ、Ｎ、Ｎ’、Ｎ’ −
テトラキス−（２−ヒドロキシプロピル）エチレンジア
ミンの混合物を用いることを特徴とする化学銅めっき液
。(1) Copper salt, reducing agent, PH adjuster, ethylenediaminetetraacetic acid as a complexing agent, N, N, N', N' -
A chemical copper plating solution characterized by using a mixture of tetrakis-(2-hydroxypropyl)ethylenediamine.
’−テトラキス−（２−ヒドロキシプロピル）エチレン
ジアミンの混合比が１：４〜４：１である特許請求の範
囲第１項記載の化学銅めっき液。(2) Ethylenediaminetetraacetic acid and N, N, N', N
The chemical copper plating solution according to claim 1, wherein the mixing ratio of '-tetrakis-(2-hydroxypropyl)ethylenediamine is 1:4 to 4:1.
の硫黄含有化合物と、非イオン系界面活性剤３０ｍｇ／
ｌ〜２０ ｇ ／ ｌと、αα′αジーリジル又はフェ
ナントロリン誘導体の少なくとも一種を２〜１００ｍｇ
／Ａ含有する特許請求の範囲第１項記載の化学銅めっき
液。(3) Concentration in chemical copper plating solution is 0.01 to 10 mσl
of sulfur-containing compounds and 30 mg of nonionic surfactant/
l to 20 g/l and 2 to 100 mg of at least one αα′α diiridyl or phenanthroline derivative.
/A chemical copper plating solution according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5633284A JPS60200969A (en) | 1984-03-26 | 1984-03-26 | Chemical copper plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5633284A JPS60200969A (en) | 1984-03-26 | 1984-03-26 | Chemical copper plating solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60200969A true JPS60200969A (en) | 1985-10-11 |
Family
ID=13024242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5633284A Pending JPS60200969A (en) | 1984-03-26 | 1984-03-26 | Chemical copper plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60200969A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016516902A (en) * | 2013-03-27 | 2016-06-09 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ | Electroless copper plating solution |
| CN110670050A (en) * | 2019-10-24 | 2020-01-10 | 深圳市松柏实业发展有限公司 | Chemical copper plating activating solution and preparation method thereof |
-
1984
- 1984-03-26 JP JP5633284A patent/JPS60200969A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016516902A (en) * | 2013-03-27 | 2016-06-09 | アトテツク・ドイチユラント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツングＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ ＧｍｂＨ | Electroless copper plating solution |
| CN110670050A (en) * | 2019-10-24 | 2020-01-10 | 深圳市松柏实业发展有限公司 | Chemical copper plating activating solution and preparation method thereof |
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