JPH0222153B2 - - Google Patents
Info
- Publication number
- JPH0222153B2 JPH0222153B2 JP12747584A JP12747584A JPH0222153B2 JP H0222153 B2 JPH0222153 B2 JP H0222153B2 JP 12747584 A JP12747584 A JP 12747584A JP 12747584 A JP12747584 A JP 12747584A JP H0222153 B2 JPH0222153 B2 JP H0222153B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- plating solution
- chemical copper
- copper plating
- mechanical properties
- 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
Links
- 238000007747 plating Methods 0.000 claims description 78
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 34
- 229910052802 copper Inorganic materials 0.000 claims description 34
- 239000010949 copper Substances 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 150000001879 copper Chemical class 0.000 claims description 12
- 229910021331 inorganic silicon compound Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 239000008139 complexing agent Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 33
- 238000007664 blowing Methods 0.000 description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 235000019795 sodium metasilicate Nutrition 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 1
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 description 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 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor 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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000004762 orthosilicates Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
Description
〔産業上の利用分野〕
本発明は機械的性質に優れた銅めつき膜を析出
させる化学銅めつき方法に係り、特にプリント回
路板製造の厚付けめつきに好適な化学銅めつき方
法に関する。
〔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、金属鋼を析出させる、無電解め
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。例えば、添加剤とし
てシアン化合物、２−2′−ビピリジル、ポリエチ
レングリコールなどがある。
しかしながらこれらの添加剤は毒性が強いなど
取扱いが難しかつたり、めつき中に消費するので
分析補給の必要があるなど、必ずしも取扱いやす
いものではなかつた。
〔発明の目的〕
本発明の目的はめつき液管理が容易でかつ機械
的に優れためつき膜の得られる化学銅めつき方法
を提供するにある。
〔発明の概要〕
本発明の特徴とするところは銅塩、銅塩の錯化
剤、銅塩の還元剤、PH調整剤を含む化学銅めつき
液を用いて化学銅めつきを行う方法において、該
化学銅めつき液に添加剤として可溶性無機ケイ素
化合物を加え、且つ該化学銅めつき液に酸素含有
ガスを吹込むこともしくは過酸化水素、過硫酸塩
などの酸化剤を添加することの少なくともいずれ
か一方を適用して化学銅めつきを行うところにあ
る。
本発明は可溶性無機ケイ素化合物の添加と、酸
素含有ガスもしくは酸化剤の少なくともいずれか
一方を併用することによつて目的が達成できる。
従来より、水ガラス、メタケイ酸ナトリウム、
オルトケイ酸ナトリウムの無機ケイ素化合物を化
学銅めつき液に添加することは知られているが、
これだけでは化学銅めつき液の安定性が不十分で
本発明のように厚付け化学銅めつきを行うときは
めつき半ばにしてめつき液が不安定になつて十分
な厚さのめつきを行うことが実質的に不可能にな
る。この点は、金属表面技術誌、第16巻、11月号
（1965年）にめつき液の自己分解を防止するのに
効果はあるがめつき槽の底部に銅が析出すること
が記載されていることから明らかである。また、
上記引例記載の化学銅めつき液から得られためつ
き膜についてめつき膜の物性を測定したが膜は脆
く十分な機械特性を示さなかつた。
比較例３に見られるように、単に、めつき液に
無機ケイ素化合物を加えても、めつき槽に銅析出
が起こることが確認された。また、錯化剤の種類
によつては、めつき中に自己分解と起こす場合も
あつた。また、このような液から得られるめつき
膜の機械的性質は、一般にあまり良好なものでは
なかつた。
一方、化学銅めつき液に酸素含有ガス例えば空
気を吹込むことは特公昭36−9063号公報に記載さ
れており、化学銅めつき液の安定化に効果がある
ことが知られている。しかし、酸素含有ガスを吹
込むだけではめつき膜の機械的性質の大幅向上は
不可能である。
第１表及び第２表に見られるように、めつき液
中に空気を吹き込むことにより、めつき液の自己
分解を抑制し、ある程度めつき液の安定性を向上
させることが可能であつた。しかしながら、比較
例４に示すようにめつき液中に空気を吹き込むこ
とのみによつて得られためつき膜の機械的性質も
また、あまり良好なものではなく、酸素含有ガス
を吹き込むことだけでは十分優れた機械的性質を
得ることはできないのである。これらの点につい
て、発明者らが種々検討を行つた結果、化学銅め
つき液中に、無機ケイ素化合物を添加し、更に、
空気を吹き込みながらめつきを行うことにより、
第１表及び第２表に示されるように、めつき膜の
機械的性質を飛躍的に向上させ得ることを見出し
た。この効果は、比較的少ない量の空気の吹き込
みによつても認めることができたが、吹き込み量
の増加と共に機械的性質が改善され、空気吹き込
み量として0.01／minを超える領域では、安定
してほぼ一定の機械的性質を持つめつき膜が得ら
れた。また、めつき液の安定性についても、無機
ケイ素化合物の添加と、酸素含有ガスの吹き込み
を併用することにより、大幅に向上させうること
が明らかになつた。安定性については、機械的性
質の場合とは、やや異なり、吹き込み量が多い程
安定性も向上した。但し、過大な量の吹き込みを
行うと、めつき液が飛散したり、被めつき体があ
おられたりする問題や、水分の蒸発によるめつき
液の濃縮、減量、あるいは温度低下等の問題が起
こるので、あまり多量の空気を吹き込むことは困
難である。めつき液の組成にもよるが、第１表及
び第２表に見られるように、１〜５／minの空
気を吹き込むことにより、十分な安定性を確保す
ることができ、この時得られるめつき膜の機械的
性質は、きわめてすぐれた水準を有している。ま
た、空気を吹き込むことによつて得られた、機械
的性質の改善効果は、空気中に含まれる酸素に依
存していることが明らかになつた。従つて、酸素
を含有するガスを吹き込むことによつても同等の
効果を得ることが可能である。例えば、アルゴン
や窒素等の不活性ガスと酸素とを適当な比で混合
して用いることができ、このときの必要な吹き込
み量は、酸素ガスの混合比に依存する。また、酸
素含有ガスを吹き込むことにかえて、めつき液に
酸化剤を加えることによつても、同様に機械的性
質のすぐれためつき膜を安定に析出させることが
できた。
本発明は可溶性無機ケイ素化合物を添加し、且
つ、酸素含有ガスもしくは酸化剤の少なくとも一
方を併用することによつて、めつき膜の機械的性
質が大幅に改善できるという相乗効果を見出した
ことに基づくものである。
本発明において適用可能な可溶性無機ケイ素化
合物としては水ガラス、メタケイ酸ナトリウムな
どのメタケイ酸塩、オルトケイ酸ナトリウムなど
のオルトケイ酸塩、ケイ酸ナトリウムやケイ酸カ
リウムなどのケイ酸塩、ポリケイ酸ナトリウムな
どのポリケイ酸塩、二酸化ケイ素、ケイ素含有ガ
スなどがあげられる。めつき膜の機械的性質向上
に効果のある添加量としてはケイ素量として10
mg／以上必要であり、それ以下では顕著な効果
は期待できない。
単に、めつき液の安定性のみを目的とするなら
ば、これ以下の添加量でも、空気吹き込み量を大
幅に増加させることにより、或程度安定性を向上
させることは可能であつた。しかし、めつき膜の
機械的性質については、ケイ素量として10mg／
未満の量しか添加しない場合には、空気吹き込み
量を増加させても、これを改善することはできな
かつた。
添加量の上限については、本発明の目的から
は、特に制限はない。但し、水ガラスとして知ら
れているような、高濃度のケイ酸ナトリウム水溶
液（メタケイ酸ナトリウム300ｇ／以上）のよ
うに液の粘度が高くなると、取扱いが困難にな
り、実質的に、めつき液として使用することはむ
ずかしい。
本発明の目的とする機械的性質の改善のために
は、めつき液の他の成分の構成にもよるが、ケイ
素量として１ｇ／以下の添加で実用上十分な効
果が得られる。発明者らの検討した限りでは、添
加量をこれ以上増しても特に大きい効果は得られ
ない。例えば、添加量を大幅に増加させても、酸
素含有ガスの吹き込みや、酸化剤の添加を行わな
い場合には、めつき膜の機械的性質を大幅に改善
することはできない。
また、発明者らの検討した結果によれば、無機
ケイ素化合物の添加量を増加させてゆくと、めつ
き速度が次第に低下する傾向がある。めつき速度
の低下は、工業的に適用する場合には、経済的に
好ましくないので、使用する目的によつて、得ら
れる効果とのバランスによつて添加量を決定すべ
きである。このような観点から見ると、通常の目
的、例えば、プリント配線板のめつきに使用する
場合には、特別の仕様がない限り、１ｇ／以上
添加することの利点はあまりないように思われ
る。
本発明で使用する可溶性無機ケイ素化合物はシ
アン化合物のような強い毒性はない。またBOD
やCODの問題も無く、めつき中にほとんど消費
しない。更に安価であるという点も工業的には大
きなメリツトがあり、取扱いがきわめて容易であ
る。
本発明において、酸素含有ガスは一般的には空
気が用いられ、空気吹込みによつて化学銅めつき
液の安定性が保たれる。また酸素含有ガスとして
は純酸素も当然ながら適用できる。また、酸化剤
は過酸化水素、過硫酸カリウムなどの過硫酸塩が
適用できる。それらの添加量は酸化剤の種類によ
つても異なるが約0.5ｇ／以上必要である。そ
れ以下では化学銅めつき液の安定性は十分保つこ
とができず、実質的に厚付けめつきを行うことは
不可能である。過酸化水素、過硫酸塩も取扱いは
比較的容易であり、BODやCOD上もあまり問題
とならない。
本発明において、めつき温度は50℃以上が好ま
しく、50℃未満では十分に良好な機械的性質のめ
つき膜が得られない。
更に、本発明で使用する化学銅めつき液は銅
塩、銅塩の錯化剤、銅塩の還元剤、PH調整剤を基
本成分とするが、銅塩は硫酸銅、塩化第二銅、酢
酸銅など公知のものが使用できる。銅塩の錯化剤
は、
[Industrial Application Field] The present invention relates to a chemical copper plating method for depositing a copper plating film with excellent mechanical properties, and particularly to a chemical copper plating method suitable for thick plating in the manufacture of printed circuit boards. . [Background of the Invention] Conventionally, an electroless plating method has been known in which metallic steel is deposited by adding a reducing agent for copper ions, such as formaldehyde, to a solution containing copper ions and a complexing agent thereof. However, in an electroless copper plating solution consisting only of such basic ingredients,
The plating solution was unstable and prone to self-decomposition reactions, making it difficult to perform 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 so-called additive printed wiring boards, in which conductor circuits and plated through holes of printed wiring boards are formed by electroless copper plating. However, the mechanical properties of the plated film were not sufficient, and there was a desire for an additive for electroless copper plating solution that would produce a plated film with higher mechanical properties. For example, additives include cyanide compounds, 2-2'-bipyridyl, polyethylene glycol, and the like. However, these additives are not necessarily easy to handle because they are highly toxic and difficult to handle, and because they are consumed during plating, it is necessary to replenish them for analysis. [Object of the Invention] An object of the present invention is to provide a chemical copper plating method that allows easy management of the plating solution and provides a mechanically excellent matted film. [Summary of the Invention] The present invention is characterized by a method for chemical copper plating using a chemical copper plating solution containing a copper salt, a complexing agent for the copper salt, a reducing agent for the copper salt, and a PH adjuster. , adding a soluble inorganic silicon compound as an additive to the chemical copper plating solution, and blowing an oxygen-containing gas into the chemical copper plating solution or adding an oxidizing agent such as hydrogen peroxide or persulfate. Chemical copper plating is performed by applying at least one of these methods. The objects of the present invention can be achieved by adding a soluble inorganic silicon compound and using at least one of an oxygen-containing gas and an oxidizing agent. Traditionally, water glass, sodium metasilicate,
It is known that an inorganic silicon compound of sodium orthosilicate is added to chemical copper plating solutions;
This alone does not provide sufficient stability for the chemical copper plating solution, and when performing thick chemical copper plating as in the present invention, the plating solution becomes unstable midway through plating and does not allow for sufficient thickness of plating. becomes virtually impossible to do. Regarding this point, the Metal Surface Technology Magazine, Volume 16, November issue (1965) states that although the plating solution is effective in preventing self-decomposition, copper is deposited at the bottom of the plating bath. It is clear from the fact that Also,
The physical properties of the plating film obtained from the chemical copper plating solution described in the above reference were measured, but the film was brittle and did not exhibit sufficient mechanical properties. As seen in Comparative Example 3, it was confirmed that simply adding an inorganic silicon compound to the plating solution caused copper precipitation in the plating tank. Furthermore, depending on the type of complexing agent, self-decomposition may occur during plating. Furthermore, the mechanical properties of plated films obtained from such liquids were generally not very good. On the other hand, blowing an oxygen-containing gas such as air into a chemical copper plating solution is described in Japanese Patent Publication No. 36-9063, and is known to be effective in stabilizing the chemical copper plating solution. However, it is not possible to significantly improve the mechanical properties of the plated film simply by blowing in oxygen-containing gas. As shown in Tables 1 and 2, by blowing air into the plating solution, it was possible to suppress the self-decomposition of the plating solution and improve the stability of the plating solution to some extent. . However, as shown in Comparative Example 4, the mechanical properties of the plating film obtained only by blowing air into the plating solution are not very good, and blowing oxygen-containing gas alone is insufficient. Excellent mechanical properties cannot be obtained. As a result of various studies conducted by the inventors regarding these points, an inorganic silicon compound was added to the chemical copper plating solution, and furthermore,
By performing plating while blowing air,
As shown in Tables 1 and 2, it has been found that the mechanical properties of the plated film can be dramatically improved. This effect could be observed even when a relatively small amount of air was blown, but the mechanical properties improved as the air blown amount increased, and it remained stable in the region where the air blown amount exceeded 0.01/min. A plated film with almost constant mechanical properties was obtained. It has also become clear that the stability of the plating solution can be significantly improved by adding an inorganic silicon compound and blowing in an oxygen-containing gas. Regarding stability, it was slightly different from the case of mechanical properties, and the stability improved as the amount of injection increased. However, if an excessive amount is blown, problems may occur such as the plating liquid scattering, the body to be plated being agitated, or the plating liquid becoming concentrated due to evaporation of water, reducing its weight, or lowering the temperature. It is difficult to blow in too much air as this may occur. Although it depends on the composition of the plating solution, as shown in Tables 1 and 2, sufficient stability can be ensured by blowing air at a rate of 1 to 5 min. The mechanical properties of the plated film are of an extremely excellent level. It has also been revealed that the improvement in mechanical properties obtained by blowing air depends on the oxygen contained in the air. Therefore, the same effect can be obtained by blowing in a gas containing oxygen. For example, an inert gas such as argon or nitrogen may be mixed with oxygen at an appropriate ratio, and the amount of blowing required at this time depends on the mixing ratio of the oxygen gas. Furthermore, by adding an oxidizing agent to the plating solution instead of blowing in oxygen-containing gas, a plating film with excellent mechanical properties could be deposited stably. The present invention is based on the discovery of a synergistic effect in which the mechanical properties of a plated film can be significantly improved by adding a soluble inorganic silicon compound and using at least one of an oxygen-containing gas or an oxidizing agent. It is based on Examples of soluble inorganic silicon compounds that can be used in the present invention include water glass, metasilicates such as sodium metasilicate, orthosilicates such as sodium orthosilicate, silicates such as sodium silicate and potassium silicate, and sodium polysilicate. Examples include polysilicates, silicon dioxide, and silicon-containing gases. The amount of silicon added that is effective in improving the mechanical properties of the plated film is 10
mg/or more is required, and no significant effect can be expected with less. If the sole purpose was to improve the stability of the plating solution, it was possible to improve the stability to some extent even if the amount added was less than this by significantly increasing the amount of air blown. However, regarding the mechanical properties of the plating film, the amount of silicon is 10mg/
When less than the amount added, even if the amount of air blowing was increased, this could not be improved. Regarding the upper limit of the amount added, there is no particular restriction from the purpose of the present invention. However, when the viscosity of the liquid becomes high, such as a highly concentrated sodium silicate aqueous solution (more than 300 g of sodium metasilicate), which is known as water glass, it becomes difficult to handle, and the plating liquid becomes difficult to handle. It is difficult to use it as In order to improve the mechanical properties, which is the objective of the present invention, a practically sufficient effect can be obtained by adding silicon in an amount of 1 g or less, although it depends on the composition of other components of the plating solution. As far as the inventors have investigated, no particularly large effect can be obtained even if the amount added is increased further. For example, even if the amount added is significantly increased, the mechanical properties of the plated film cannot be significantly improved unless blowing in oxygen-containing gas or adding an oxidizing agent. Further, according to the results of studies conducted by the inventors, as the amount of the inorganic silicon compound added increases, the plating speed tends to gradually decrease. Since a decrease in plating rate is economically undesirable when applied industrially, the amount added should be determined depending on the purpose of use and the balance with the effect to be obtained. From this point of view, when used for normal purposes, such as plating printed wiring boards, it seems that there is not much advantage in adding 1 g/or more unless there are special specifications. The soluble inorganic silicon compound used in the present invention does not have strong toxicity like cyanide compounds. Also BOD
There are no problems with COD or COD, and it consumes almost nothing during plating. Furthermore, it has a great industrial advantage in that it is inexpensive, and it is extremely easy to handle. In the present invention, air is generally used as the oxygen-containing gas, and the stability of the chemical copper plating solution is maintained by air blowing. Naturally, pure oxygen can also be used as the oxygen-containing gas. Furthermore, persulfates such as hydrogen peroxide and potassium persulfate can be used as the oxidizing agent. Although the amount added varies depending on the type of oxidizing agent, it is necessary to add about 0.5 g/or more. If it is less than that, the stability of the chemical copper plating solution cannot be maintained sufficiently, and it is virtually impossible to perform thick plating. Hydrogen peroxide and persulfate are also relatively easy to handle and do not pose much of a problem in terms of BOD and COD. In the present invention, the plating temperature is preferably 50°C or higher; if it is lower than 50°C, a plated film with sufficiently good mechanical properties cannot be obtained. Furthermore, the chemical copper plating solution used in the present invention has a copper salt, a complexing agent for the copper salt, a reducing agent for the copper salt, and a PH adjuster as basic components, and the copper salts include copper sulfate, cupric chloride, Known materials such as copper acetate can be used. The copper salt complexing agent is
【式】を骨格とするものが好適
であり、エチレンジアミン四酢酸、Ｎ−ヒドロキ
シエチレンジアミン三酢酸、１，２−ジアミノプ
ロパン四酢酸、ジエチレントリアミン五酢酸、シ
クロヘキサンジアミン四酢酸などが適用できる。
トリエタノールアミン、イミノ二酢酸、イミノ三
酢酸などのモノアミン、あるいはロツセル塩など
を使用した場合は十分な機械的性質のめつき膜を
得ることができなかつたり、またはめつき液の安
定性が不十分で実質的な厚付けめつきができなか
つたりする問題が生じる。銅塩の還元剤は一般的
に使用されるホルマリンが好適であり、更にPH調
整剤には水酸化ナトリウムが適用できる。
〔発明の実施例〕
次に本発明を実施例により具体的に説明する。
実施例 １〜13
表面を滑らかに研磨したステンレススチール板
を脱脂し、めつき反応の開始剤であるパラジウム
を該表面に付着させた。次に、第１表に示した化
学銅めつき液組成、ならびにめつき条件下で化学
銅めつきを行い、約30μｍの厚さのめつき膜を得
た。このめつき膜をステンレススチール板より剥
離して幅10mmに切断し、初期の引張間隔を50mmと
して東洋測器社製の引張試験機により破断までの
伸び率と引張強度とを測定した。その結果を第２
表に示した。
比較例 １〜６
第１表の比較例欄に記載した条件下で、実施例
１〜13と同様にめつきし、評価した。その結果を
第２表に合わせて示した。Those having the skeleton [Formula] are preferred, and ethylenediaminetetraacetic acid, N-hydroxyethylenediaminetriacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, and the like can be used.
If monoamines such as triethanolamine, iminodiacetic acid, iminotriacetic acid, or Rotussel salt are used, it may not be possible to obtain a plated film with sufficient mechanical properties, or the stability of the plating solution may be unstable. A problem arises in that sufficient and substantially thick plating cannot be achieved. Formalin, which is commonly used, is suitable as a reducing agent for copper salts, and sodium hydroxide can be used as a pH adjusting agent. [Examples of the Invention] Next, the present invention will be specifically explained with reference to Examples. Examples 1 to 13 A stainless steel plate whose surface was polished smoothly was degreased, and palladium, which is an initiator for a plating reaction, was attached to the surface. Next, chemical copper plating was performed using the chemical copper plating solution composition and plating conditions shown in Table 1 to obtain a plated film with a thickness of about 30 μm. This plated film was peeled off from the stainless steel plate and cut to a width of 10 mm, and the elongation rate and tensile strength until break were measured using a tensile tester manufactured by Toyo Sokki Co., Ltd. with an initial tension interval of 50 mm. The second result is
Shown in the table. Comparative Examples 1 to 6 Plating was performed and evaluated in the same manner as Examples 1 to 13 under the conditions described in the Comparative Examples column of Table 1. The results are also shown in Table 2.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
本発明の化学銅めつき法により、機械的性質の
優れためつき膜を得ることができる。また、化学
銅めつき液の安定性も良好に保たれ、実質的な厚
付けめつきが可能である。
By the chemical copper plating method of the present invention, a plating film with excellent mechanical properties can be obtained. In addition, the stability of the chemical copper plating solution is maintained well, and substantial thick plating is possible.
Claims (1)
調整剤を含む化学銅めつき液を用いて化学銅めつ
きを行う方法において、前記化学銅めつき液に添
加剤として可溶性無機ケイ素化合物を加え、かつ
このめつき液に酸素含有ガスを吹込み、及び／ま
たは酸化剤を添加することを特徴とする化学銅め
つき方法。 ２ 特許請求の範囲第１項記載において、添加剤
の含有量がケイ素量として10mg／以上であるこ
とを特徴とする化学銅めつき方法。 ３ 特許請求の範囲第１項記載において、めつき
温度は50℃以上であることを特徴とする化学銅め
つき方法。[Claims] 1. Copper salt, copper salt complexing agent, copper salt reducing agent, and PH
In a method of performing chemical copper plating using a chemical copper plating solution containing a regulating agent, a soluble inorganic silicon compound is added as an additive to the chemical copper plating solution, and an oxygen-containing gas is blown into the plating solution. A chemical copper plating method characterized by adding , and/or an oxidizing agent. 2. The chemical copper plating method as set forth in claim 1, characterized in that the content of the additive is 10 mg/or more as silicon content. 3. The chemical copper plating method as set forth in claim 1, characterized in that the plating temperature is 50°C or higher.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59127475A JPS619578A (en) | 1984-06-22 | 1984-06-22 | Method for chemically plating copper |
| 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 |
|---|---|---|---|
| JP59127475A JPS619578A (en) | 1984-06-22 | 1984-06-22 | Method for chemically plating copper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS619578A JPS619578A (en) | 1986-01-17 |
| JPH0222153B2 true JPH0222153B2 (en) | 1990-05-17 |
Family
ID=14960847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59127475A Granted JPS619578A (en) | 1984-06-18 | 1984-06-22 | Method for chemically plating copper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS619578A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014098064A1 (en) | 2012-12-21 | 2014-06-26 | 奥野製薬工業株式会社 | Conductive coating film forming bath |
| CN105765104A (en) | 2014-01-27 | 2016-07-13 | 奥野制药工业株式会社 | Conductive film-forming bath |
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
- 1984-06-22 JP JP59127475A patent/JPS619578A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS619578A (en) | 1986-01-17 |
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