JPS6311677A - Chemical copper plating bath - Google Patents
Chemical copper plating bathInfo
- Publication number
- JPS6311677A JPS6311677A JP15262186A JP15262186A JPS6311677A JP S6311677 A JPS6311677 A JP S6311677A JP 15262186 A JP15262186 A JP 15262186A JP 15262186 A JP15262186 A JP 15262186A JP S6311677 A JPS6311677 A JP S6311677A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- plating
- acid
- plating bath
- salt
- 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 32
- 239000010949 copper Substances 0.000 title claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000000126 substance Substances 0.000 title claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 5
- 150000001879 copper Chemical class 0.000 claims description 23
- 239000012190 activator Substances 0.000 abstract description 10
- 230000008021 deposition Effects 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 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 description 8
- 238000010306 acid treatment Methods 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 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 5
- 238000000034 method Methods 0.000 description 5
- 101100476210 Caenorhabditis elegans rnt-1 gene Proteins 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- -1 copper salt Chemical class 0.000 description 3
- 230000000694 effects Effects 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
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000010979 pH adjustment Methods 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
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 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
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】
〔産業上の利用分野〕
本発明は、例えばプリント配線板の導体回路の形成など
に用いられる、化学銅メッキ浴に関するものである。さ
らに詳しく述べるならば本発明は高速化学銅めっきに通
しためっき浴ｅに関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a chemical copper plating bath used, for example, in forming conductor circuits on printed wiring boards. More specifically, the present invention relates to a plating bath e for high speed chemical copper plating.
従来、金属銅を化学的に析出させる化学銅めっき液とし
て、エチレンジアミン四酢酸（ＥＤＴＡ）、あるいは、
ロッシェル塩を銅イオンの錯化剤として用い、銅塩とし
て硫酸銅、還元剤としてホルムアルデヒドロＨ１ｉ整剤
として苛性ソーダを用いた浴は最も一般的に用いられて
いる。Conventionally, as a chemical copper plating solution for chemically depositing metallic copper, ethylenediaminetetraacetic acid (EDTA) or
Baths using Rochelle's salt as a complexing agent for copper ions, copper sulfate as the copper salt, formaldehydro H1 as the reducing agent, and caustic soda as the conditioner are most commonly used.
これらの化学銅めっき液をたとえばプリント配線板の回
路形成に適用する場合、析出速度が遅い等の欠点を有し
ている。When these chemical copper plating solutions are applied, for example, to circuit formation on printed wiring boards, they have drawbacks such as slow deposition rate.
近年、プリント基板を例に取ると、コストダウン化の為
に、高速化学銅めっきの要請が強く、それに応じる為、
加速剤を用いた浴（特開昭６０−１５９１７３号公報）
や、還元剤に活性剤を添加した浴（特開昭５５−７６０
５４号公報）等が提出されている。In recent years, taking printed circuit boards as an example, there has been a strong demand for high-speed chemical copper plating to reduce costs.
Bath using accelerator (JP-A-60-159173)
or a bath in which an activator is added to a reducing agent (JP-A-55-760)
Publication No. 54) etc. have been submitted.
活性剤および加速剤の例は電子技術１９８５年６月臨時
増刊号第１２５頁に示されている。かかる活性剤、加速
剤の添加によって最高で１０μｍ ／ ’ｒｒ ｒ程度
の析出速度が達成されている。Examples of activators and accelerators are given in Electronic Technology, June 1985 Special Issue, page 125. By adding such activators and accelerators, a maximum precipitation rate of about 10 μm/'rr is achieved.
加速剤、活性剤の浴中での濃度は■／１オーダーであり
、補充の際も加速剤、活性剤は■オーダーで加える。こ
のような微量加速剤、活性剤の浴中濃度の測定は事実上
不可能であるのでめっきプロセスの自動管理が困難とな
る。よって現状ではめっきのぐあいを目で見て、経験的
に加速剤等を補充しているのが現実である。その為、異
常析出や、液の分解、あるいは、めっき反応停止といっ
た現象が起こる。このことは、化学銅めっき、たとえば
プリント板回路形成のすべてを無電解銅めっきで行う、
フルアディティブ法が普及しない主因ともなっている。The concentration of the accelerator and activator in the bath is on the order of ■/1, and when replenishing the bath, the accelerator and activator are added on the order of ■. Since it is virtually impossible to measure the concentration of such trace amounts of accelerators and activators in the bath, automatic control of the plating process becomes difficult. Therefore, the current reality is that the plating condition is visually checked and accelerators, etc. are added based on experience. Therefore, phenomena such as abnormal precipitation, liquid decomposition, or termination of the plating reaction occur. This means that chemical copper plating, such as electroless copper plating, is used to form all printed circuit board circuits.
This is also the main reason why fully additive methods have not become popular.
〔問題点を解決するための手段および作用〕本発明は、
銅塩、銅塩の錯化剤、銅塩の還元剤、ｐＨＪ整剤を含む
化学銅めっき液において、第２銅塩を、酸処理すること
によって、めっき析出速度を、飛躍的に向上させること
を特色とする。[Means and effects for solving the problems] The present invention has the following features:
To dramatically improve the plating deposition rate by acid-treating a cupric salt in 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 pHJ adjuster. Features:
銅塩は、溶媒に可溶性、不溶性を問わない。The copper salt may be soluble or insoluble in the solvent.
以下、本発明者等の実験により、酸処理によるめっき析
出速度向上効果を説明する。Hereinafter, the effect of improving the plating precipitation rate by acid treatment will be explained based on experiments conducted by the present inventors.
Ｒｕｎ１ （比較例）
銅塩（ＣｕＣｊ！ ｚ） ０．０６ｓ
ｏ ｊ！ ／ １錯化剤（Ｑｕａｄｒｏｌ）
０．１１ｓｏ ｌ ／ １還元剤（ホルムアルデヒ
ド） ０．２５ｓｏ １ ／ １ｐＨ１２，５
浴温 ４５℃Ｒｕｎ２（本
発明）
銅塩としてＣｕ （ＯＨ）ｚを用い、ＨＣｊ２０．１２
ｔ＊ｏｌ／１による酸処理した他はＲｕｎ１と同じ条件
Ｒｕｎ３ （比較例）
錯化剤としてＥＤＴＡを使用した他はＲｕｎ １と同じ
条件
Ｒｕｎ４ （本発明）
銅塩としてＣｕ （ＯＨ）！、錯化剤としてＥＤＴＡを
用い、０．１２ｓｏ ｌ ／ １のＨＣｌによる酸処理
をした他はＲｕｎ１と同じ条件
なお、Ｒｕｎ２．４の０．１２ｓｏ ｌ ／ ｌのＨＣ
ＩはＣｕ （ＯＨｈに対して当モルに相当する。Run1 (comparative example) Copper salt (CuCj!z) 0.06s
oj! /1 Complexing agent (Quadrol)
0.11 so 1 / 1 reducing agent (formaldehyde) 0.25 so 1 / 1 pH 12,5 Bath temperature 45 ° C Run 2 (invention) Using Cu (OH) z as the copper salt, HCj 20.12
Run 3 under the same conditions as Run 1 except for acid treatment with t*ol/1 (comparative example) Run 4 under the same conditions as Run 1 except for using EDTA as a complexing agent (invention) Cu (OH) as the copper salt! , Same conditions as Run 1 except that EDTA was used as a complexing agent and acid treatment was performed with 0.12 sol/l HC1, except for Run 2.4 with 0.12 sol/l HC
I corresponds to equimolar Cu (OHh).
上記Ｒｕｎは不溶性銅塩を用いたものである。The above Run uses an insoluble copper salt.
さらに、可溶性銅塩を用いた次の実験を行なった。Furthermore, the following experiment using a soluble copper salt was conducted.
Ｒｕｎ５ （比較例）
銅塩（ＣｕＳＯｎ） ０．０６ｓｏ
４！ ／ ｊ！錯化剤（Ｑｕａｄｒｏｌ）
０．１１ｓｏ １２ ／ １還元剤（ホルムアルデ
ヒド） ０．２５＋ｗｏ ｉｔ ／ ＩｔｐＨ１２
，５
浴温 ４５℃Ｒｕｎ５ （
本発明）
ＣｕＳ０４を３０ｍＪ／ｊ！のＨＢＦ、で酸処理した他
はＲｕｎ５と同じ条件
各Ｒｕｎのめっき析出速度を第１図に示す。第１図より
酸処理によりめっき析出速度が飛躍的に向上することが
明らかである。Run5 (comparative example) Copper salt (CuSOn) 0.06so
4! / j! Complexing agent (Quadrol)
0.11so 12/1 Reducing agent (formaldehyde) 0.25+wo it/ItpH12
,5 Bath temperature 45℃Run5 (
present invention) CuS04 at 30 mJ/j! Figure 1 shows the plating deposition rate for each Run under the same conditions as Run 5 except that the acid treatment was carried out with HBF. It is clear from FIG. 1 that the acid treatment dramatically improves the plating deposition rate.
上述のように本発明に係る酸処理法は、基本浴成分以外
に活性化剤、加速剤（アミノ酸、２−メルカプトベンゾ
チアゾール）などを加える方法とは基本的に異なってい
る。As described above, the acid treatment method according to the present invention is fundamentally different from a method in which an activator, accelerator (amino acid, 2-mercaptobenzothiazole), etc. are added in addition to the basic bath components.
以下、本発明に係る化学銅めっき浴の組成を詳しく説明
する。Hereinafter, the composition of the chemical copper plating bath according to the present invention will be explained in detail.
銅塩としては、硫酸銅、塩化銅、スルファミン銅等特に
限定されず、従来公知の浴成分である水に可溶性な銅塩
を使用することができる。さらに、水に不溶な化合物と
して、水酸化第二銅（Ｃｕ （ＯＨ） ｚ）、酸化第二
銅（Ｃｕｂ）等を用いることができる。The copper salt is not particularly limited, such as copper sulfate, copper chloride, copper sulfamine, etc., and copper salts soluble in water, which are conventionally known bath components, can be used. Furthermore, cupric hydroxide (Cu (OH) z), cupric oxide (Cub), and the like can be used as water-insoluble compounds.
酸としては鉱酸もしくは有機酸のすべてを使用すること
ができる。鉱酸としては、例えばＨＢＦ、 。As acids it is possible to use all mineral acids or organic acids. Examples of mineral acids include HBF.
肝、 ＩＣ１，ＨｚＳＯｎ、ＨＮＯｚ等が、有機酸とし
ては酢酸、ギ酸等が、−Ｓに使用される。銅塩が可溶性
の場合は、使用する酸の種類は特に限定されないが、銅
塩が不溶性の場合はそれを溶解できる酸を使用しなけれ
ばならない。酸と銅塩のアニオンは同種であっても異種
であってもよい。For -S, liver, IC1, HzSOn, HNOz, etc. are used, and as the organic acid, acetic acid, formic acid, etc. are used. When the copper salt is soluble, the type of acid used is not particularly limited; however, when the copper salt is insoluble, an acid that can dissolve it must be used. The anions of the acid and the copper salt may be the same or different.
錯化剤としては不溶性銅化合物と錯体を形成し可溶性に
するものであれば特に限定されない。例えば、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（Ｑｕａｄｒｏｌ）、ロン
シェル塩等を用いることができる。The complexing agent is not particularly limited as long as it forms a complex with the insoluble copper compound and makes it soluble. For example, EDTA
, N, N, N', N'-tetrakis(2-hydroxypropyl)ethylenediamine (Quadrol), Ronchel's salt, and the like can be used.
還元剤としては、銅イオンを還元させる能力のあるもの
なら何でもよい。例えば、ホルムアルデヒド、次亜リン
酸ソーダ、水素化ホウ素ナトリウム等を用いることがで
きる。Any reducing agent may be used as long as it has the ability to reduce copper ions. For example, formaldehyde, sodium hypophosphite, sodium borohydride, etc. can be used.
ｐＨｍ整剤としては、水酸化アルカリ金属塩などｐＨを
調整することを目的としたものなら何でもよい。例えば
水酸化ナトリウム（ＮａＯＨ） 、水酸化カリウム（Ｋ
ＯＨ）等を用いることができる。Any pH adjuster may be used as long as it is intended to adjust the pH, such as an alkali metal hydroxide salt. For example, sodium hydroxide (NaOH), potassium hydroxide (K
OH) etc. can be used.
ｐＨ調整剤は、水酸化アルカリ金属塩等のｐＨを銅イオ
ン還元範囲に調整するものなら何でもよい。The pH adjuster may be anything that adjusts the pH to a copper ion reduction range, such as an alkali metal hydroxide salt.
例えば水酸化ナトリウム、水酸化カリウム等を用いるこ
とができる。For example, sodium hydroxide, potassium hydroxide, etc. can be used.
酸処理の温度は特に限定されないが、０〜１００℃であ
ることが好ましい。The temperature of the acid treatment is not particularly limited, but is preferably 0 to 100°C.
酸処理後錯化までの時間は特に限定されず、予め酸処理
した銅塩浴液を、めっき浴中の銅塩濃度が低下し、補充
する時まで任意の時間保存してから、めっき浴中に添加
することも可能である。The time from acid treatment to complexation is not particularly limited, and the copper salt bath solution that has been acid-treated in advance is stored for an arbitrary period of time until the copper salt concentration in the plating bath decreases and it is time to replenish it. It is also possible to add it to.
錯化後還元剤の添加およびｐＨ調節を任意の順序で行な
う。After complexation, addition of reducing agent and pH adjustment are carried out in any order.
本発明により調製されためっき浴による化学銅めっき方
法は従来の一般的方法と同様である。また、いかなる添
加剤の併用も可能である。The chemical copper plating method using the plating bath prepared according to the present invention is similar to the conventional general method. Further, any additives may be used in combination.
以下、本発明の詳細な説明する。 The present invention will be explained in detail below.
実施例１
銅塩 Ｃｕ （ＯＨ）ｚ Ｏ，０６ａ＋ｏ
ｌ／ ｊ！錯化剤 Ｑｕａｄｒｏｌ
０．１６ｍｏ ｌ ／ １還元剤 ホルムアルデヒド
０．２５ｍｏ ｌ ／ １２酸 ＨＢ Ｆ ４
３０ ｍ ｌ ／ １ｐＨ１２，
５
浴温 ４５℃析出速度
３３μｍ／Ｈｒ実施例２
銅塩 Ｃｕ Ｓ Ｏ４０，０６ｍｏ １ ／ １錯化
剤 Ｑｕａｄｒｏｌ ０．１１ｍｏ １
／ １還元剤 ホルムアルデヒド ０．３ｍｏｌ
ｌ／１酸 ＨＢ Ｆ ４ ３０
ｍ ｌ ／ １ｐＨ１２，５
浴温 ４５℃析出速度
４４μｍ ／ ）（ｒ実施例３
銅塩 Ｃｕ （ＯＨ）ｚ ０．０６ｍｏ
１ ／ １錯化剤 Ｑｕａｄｒｏｌ Ｏ
，１１ｍｏ ｌ ／ １還元剤 ホルムアルデヒド
０．２５ｔａｏ １ ／ １酸 ＨＦ
１０ ｍ ｌ ／ Ｉｌ浴温
４５℃析出速度
１８μｍ／Ｈｒ実施例４
銅塩 Ｃｕ Ｓ Ｏａ ０．０６ｗｏ
ｌ／ １錯化剤 Ｑｕａｄｒｏｌ ０
．１１ｍｏ １ ／ Ｉｔ還元剤 ホルムアルデヒド
０．２５ｎ＋ｏ ｉｔ ／ １酸 ＨＦ
Ｉｏｍ／／ｊ！ｐＨ１２，５
浴温 ４５℃析出速度
１９μｍ／Ｈｒ各実施例において、記
載された濃度の銅塩と酸の各水溶液を混合後、混合水溶
液に錯化剤を添加し、次にｐＨ調整剤と還元剤を添加し
た。Example 1 Copper salt Cu (OH)z O,06a+o
l/j! Complexing agent Quadrol
0.16mol/1 reducing agent formaldehyde
0.25mol/12 acids HB F4
30ml/1pH12,
5 Bath temperature 45℃ Deposition rate
33μm/Hr Example 2 Copper salt Cu S O40.06mo 1/1 Complexing agent Quadrol 0.11mo 1
/ 1 reducing agent formaldehyde 0.3 mol
l/1 acid HB F 4 30
ml/1 pH 12.5 Bath temperature 45℃ Precipitation rate
44μm / ) (r Example 3 Copper salt Cu (OH)z 0.06mo
1/1 complexing agent Quadrol O
, 11mol/1 reducing agent formaldehyde
0.25tao 1/1 acid HF
10ml/Il bath temperature
45℃ precipitation rate
18μm/Hr Example 4 Copper salt Cu S Oa 0.06wo
l/1 complexing agent Quadrol 0
．． 11mo 1/It reducing agent formaldehyde
0.25n+o it/1 acid HF
Iom//j! pH 12.5 Bath temperature 45℃ Precipitation rate
19 μm/Hr In each example, after mixing the respective aqueous solutions of copper salt and acid at the concentrations described, a complexing agent was added to the mixed aqueous solution, and then a pH adjuster and a reducing agent were added.
各実施例にて従来の高速化学銅めっきを上まわるめっき
速度が得られている。In each example, a plating speed exceeding that of conventional high-speed chemical copper plating was obtained.
本発明によれば、めっき析出速度の向上が、加速剤、活
性剤などの添加剤を用いないで実現できるため、浴管理
が簡単であり、本発明の工業的意義は大きい。According to the present invention, since the plating deposition rate can be improved without using additives such as accelerators and activators, bath management is simple, and the present invention has great industrial significance.
第１図は比較例と本発明のめっき析出速度を示すグラフ
である。FIG. 1 is a graph showing the plating deposition rates of the comparative example and the present invention.
Claims (1)
銅めっき浴において、 酸処理された第２銅塩が錯化されていることを特徴とす
る化学銅めっき浴。[Claims] 1. A chemical copper plating bath containing a copper salt, a complexing agent, a reducing agent, and a pH adjuster, characterized in that an acid-treated cupric salt is complexed. Plating bath.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15262186A JPS6311677A (en) | 1986-07-01 | 1986-07-01 | Chemical copper plating bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15262186A JPS6311677A (en) | 1986-07-01 | 1986-07-01 | Chemical copper plating bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6311677A true JPS6311677A (en) | 1988-01-19 |
Family
ID=15544379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15262186A Pending JPS6311677A (en) | 1986-07-01 | 1986-07-01 | Chemical copper plating bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6311677A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0271421U (en) * | 1988-11-16 | 1990-05-31 | ||
| CN1081404C (en) * | 1996-04-15 | 2002-03-20 | 日立金属株式会社 | Permanent magnet field type rotating machine |
-
1986
- 1986-07-01 JP JP15262186A patent/JPS6311677A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0271421U (en) * | 1988-11-16 | 1990-05-31 | ||
| JPH0525537Y2 (en) * | 1988-11-16 | 1993-06-28 | ||
| CN1081404C (en) * | 1996-04-15 | 2002-03-20 | 日立金属株式会社 | Permanent magnet field type rotating machine |
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