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EP0179212B1 - Stromlose Kupferplattierlösung - Google Patents

Stromlose Kupferplattierlösung Download PDF

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Publication number
EP0179212B1
EP0179212B1 EP85109921A EP85109921A EP0179212B1 EP 0179212 B1 EP0179212 B1 EP 0179212B1 EP 85109921 A EP85109921 A EP 85109921A EP 85109921 A EP85109921 A EP 85109921A EP 0179212 B1 EP0179212 B1 EP 0179212B1
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EP
European Patent Office
Prior art keywords
plating solution
copper plating
chemical copper
compound
group
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.)
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Application number
EP85109921A
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English (en)
French (fr)
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EP0179212A2 (de
EP0179212A3 (en
Inventor
Akira Endo
Kazuhiro Takeda
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Toshiba Corp
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Toshiba Corp
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Filing date
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Priority claimed from JP20044584A external-priority patent/JPS6179775A/ja
Priority claimed from JP27330384A external-priority patent/JPS61153281A/ja
Application filed by Toshiba Corp filed Critical Toshiba Corp
Publication of EP0179212A2 publication Critical patent/EP0179212A2/de
Publication of EP0179212A3 publication Critical patent/EP0179212A3/en
Application granted granted Critical
Publication of EP0179212B1 publication Critical patent/EP0179212B1/de
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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

Definitions

  • This invention relates to a chemical copper plating solution. More particularly, it is concerned with a chemical copper plating solution having a novel composition which makes it possible to deposit copper at a high speed and is stable over a prolonged period of application and can form a plated film having favourable mechanical properties.
  • a chemical copper plating solution may usually contain as essential components a water-soluble copper salt such as copper sulfate, cupric chloride, etc.; a complexing agent such as ethylenediaminetetraacetic acid (EDTA), N,N,N',N'-tetrakis-(2-hydroxypropyl)ethylenediamine, Rochelle salt, etc.; a reducing agent such as formaldehyde, dimethylaminoborane, sodium borohydride, etc.; a pH adjustor such as sodium hydroxide, potassium hydroxide, etc.; and, where necessary, a surface active agent such as a polyethylene oxide, a polyether, a polyester, etc.
  • a water-soluble copper salt such as copper sulfate, cupric chloride, etc.
  • a complexing agent such as ethylenediaminetetraacetic acid (EDTA), N,N,N',N'-tetrakis-(2-hydroxypropyl)ethylenediamine, Rochelle
  • a chemical copper plating solution having the composition of such components generally tends to lack stability and readily undergo self-decomposition; moreover, a plated film or deposited film made from said chemical plating solution is brittle and insufficient in mechanical strength, particularly bending strength for practical utility.
  • EP-A-0 039 757 discloses a chemical copper-plating solution capable of providing a plated film, excellent especially in ductility.
  • the solution comprises a copper salt, a complex-forming agent, a reducing agent and a pH-controller and a nonionic surfactant having the formula wherein m and n are integers of 1 or more, and wherein m + n ⁇ 12.
  • This solution may further contain at least one compound selected from the group consisting of 1,10-phenanthroline, 1,10-phenanthroline derivatives, 2,2'-dipyridyl, 2,2'-biquinoline and water-soluble cyanides.
  • the primary object of this invention is to provide a chemical copper plating solution having a novel composition which can dissolve the aforesaid problems, show a good stability, without reducing high speed deposit in plating, and provide good mechanical properties, especially a favourable spreadability of the resultant plated film.
  • the chemical copper plating solution of this invention is a chemical copper plating solution containing a copper salt, a complexing agent, a reducing agent and a pH adjustor, which further comprises the under-mentioned Group:
  • the chemical copper plating solution may furthermore contain the following group (B):
  • the chemical copper plating solution according to this invention is composed of, in addition to the four components of a copper salt, a complexing agent, a reducing agent and a pH adjustor, compounds of the group (A) comprising (i) at least one compound selected from the group consisting of nonionic surface active agents mentioned below and (ii) at least one Compound selected from the group consisting of 1,10-phenanthroline, a 1,10-phenanthroline derivative, 2,2'-dipyridyl, 2,2'-biquinoline and a water-soluble cyan compound; favourably the composition furthermore comprises as group (B) an organic sulfur compound and/or an ethyleneamine compound.
  • group (A) comprising (i) at least one compound selected from the group consisting of nonionic surface active agents mentioned below and (ii) at least one Compound selected from the group consisting of 1,10-phenanthroline, a 1,10-phenanthroline derivative, 2,2'-dipyridyl, 2,2'-biquinoline and a water-soluble
  • a copper salt may supply a copper ion, while a reducing agent may reduce said copper ion to a metallic state.
  • a complexing agent may form a stable complex with copper ions to prevent, in a plating bath (alkaline), a formation of cupric hydroxide, while a pH adjustor may adjust the optimum plating deposit potential in a plating bath.
  • the nonionic surface active agent may contribute to mechanical properties and deposit rate of a plating solution and is represented by the formula (I) or (II).
  • each of m1, m2, n1 and n2 is an integer of 1 or more. If any of them is 0 (zero), a nonionic surface active agent shows a low solubility so that a sufficient amount thereof to contribute to improvement in stability or mechanical properties of a plating solution could not be dissolved in a plating solution.
  • a nonionic surface active agent shows a low solubility so that a sufficient amount thereof to contribute to improvement in stability or mechanical properties of a plating solution could not be dissolved in a plating solution.
  • m1 + n1 or m2 + n2 is increased, stability and mechanical properties of a plating solution may be correspondingly improved. In any case, its effect may approximately reach the upper limit at the neighborhood of 20 to a saturated state.
  • here is particularly no upper limit with regard to m1 + n1 or m2 + n2, but not more than 500 is preferred in view of workability.
  • a concentration of the compound (I) or (II) in a plating solution is preferably in the range of 10 mg/l to 30 g/l.
  • a concentration of the compound (I) or (II) in a plating solution is preferably in the range of 10 mg/l to 30 g/l.
  • m1 + n1 and m2 + n2 is less than 20, a range of 30 mg/l to 20 g/l is preferred.
  • m1 + n1 and m2 + n2 is not less than 20, a range of 10 mg/l to 5 g/l is preferred.
  • 1,10-phenanthroline a 1,10-phenanthroline derivative, 2,2'-dipyridyl, 2,2'-biquinoline or a water-soluble cyan compound, in order that the aforesaid effects by nonionic surface active ageant, especially stability of a plating solution or mechanical properties of a plated film may be far more enhanced.
  • the 1,10-phenanthroline derivative may preferably have a substituent such as a lower alkyl group, e.g., a methyl group, an ethyl group, etc. or a phenyl group and there may illustratively be mentioned 2,9-dimethyl-1,10-phenanthroline, 4,7-diphenyl-2,9-dimethyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline and so on.
  • a substituent such as a lower alkyl group, e.g., a methyl group, an ethyl group, etc. or a phenyl group and there may illustratively be mentioned 2,9-dimethyl-1,10-phenanthroline, 4,7-diphenyl-2,9-dimethyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline and so on.
  • water-soluble cyan compound there may be mentioned, for instance, potassium cyanide, sodium cyanide, sodium nitroprusside, potassium ferrocyanide, potassium ferricyanide, potassium tetracyanoniccolate and so on.
  • a total amount of 1,10-phenanthroline, a 1,10-phenanthroline derivative, 2,2'-dipyridyl and 2,2'-biquinoline to be added is preferably 1 - 200 mg/l, a range of 2 - 50 mg/l being particularly preferred. If the added amount is less than 1 mg/l, one could not obtain effects at all; if said amount is more than 200 mg/l, there would undesirably produce a reduced stability of a plating solution or a reduced mechanical property of a plated film.
  • An amount of the water-soluble cyan compound to be added is preferably 1 mg/l to 3 g/l, a range of 5 mg/l to 1 g/l being particularly preferred. If the added amount is less than 1 mg/l, it does not at all contribute to improvement in stability and mechanical properties, while, if more than 3 g/l, there would undesirably produce a lowered deposit rate or a reduced mechanical property of a plated film.
  • the organic sulfur compound added as the Group (B) may contribute to improved stability of a plating solution, while the ethyleneamine compound may contribute to speed-up of a deposit rate.
  • organic sulfur compound which may be employed as the Group (B)
  • organic sulfur compound which may be employed as the Group (B)
  • 2-mercaptobenzothiazole thiourea, ethylene thiourea, 1-phenyl-2-thiourea, 1-allyl-2-thiourea, thiodiglycol, thiomalic acid, thiodiethanol, 2-mercaptobenzimidazole, dodecylmercaptan, thioglycolic acid, thiodiglycolic acid, etc.
  • An amount of the organic sulfur compound to be added is preferably 0.01 mg/l to 10 mg/l, a range of 0.1 mg/l to 5 mg/l being particularly preferred. If the added amount is less than 0.01 mg/l, stability of a plating solution is not so much improved; if more than 10 mg/l, a deposit rate is extremely lowered, which leads to a reduced working efficiency.
  • ethyleneamine compound there may be mentioned, for instance, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and so on.
  • An amount of the compound to be added is preferably 1 mg/l to 500 mg/l, a range of 5 mg/l to 100 mg/l being particularly preferred. If the added amount is less than 1 mg/1, a deposit rate of the plating solution or mechanical properties of the plated film is not so much improved; if more than 500 mg/l, a plating solution becomes unstable.
  • the chemical copper plating solution of the present invention can become a chemical copper plating solution having respective merits of the compounds, that is to say, the plating solution having an excellent stability and producing a highly spreadable plated film with a high speed deposit, when the above compounds having the above-mentioned functions are used in combination therewith at the predetermined proportion.
  • Preferable plating conditions under which the present chemical copper plating solution may be applied, are the range of a temperature of 40 - 80 o C, more preferably 50 - 70 o C and a pH value of 10.8 - 13.0, more preferably 12.0 - 13.0. According to such plating condition, characteristic of the present plating solution can be fully put to use and there can be formed a plated film which can be deposited at a high speed and has a high spreadability.
  • a stainless steel plate with a thickness of 0.3 mm was polished with a cleanser, dipped in a 10 % sodium hydroxide solution at 80 o C for one minute, taken out and washed with water. Then, it was dipped in a 10 % sulfuric acid at ordinary temperature for 30 seconds and washed with water to clean the surface thereof. The resultant stainless steel plate was then dipped in a solution having the composition of; for 2 minutes and washed in a running water for one minute. Thereafter, the plate was dipped in a solution having the composition of; for one minutes and washed in a running water for one minute.
  • the chemical copper plating solutions thus prepared were measured for deposit rate of copper. Such a measurement was accomplished by dipping a copper foil with a thickness of 10 ⁇ m, the surface of which was previously cleaned, in the plating solution under conditions of a plating temperature of 60 o C and a pH value of the plating solution of 12.5 for one hour and calculating a deposit rate from the difference in weight before and after plating.
  • the catalyzed stainless steel plate with a thickness of 0.3 mm as described above was treated with the chemical cooper plating solution to deposit plated films with a thickness of 30 - 35 ⁇ m over both sides thereof, respectively, using plating conditions of a plating temperature of 60 o C and a pH value of the plating solution of 12.5.
  • the copper plated film thus deposited was peeled off from the stainless steel plate and applied to a spreadability test.
  • Spreadability was measured according to the following folding test at 180 o C; a plated film was first folded to one direction at 180 o to make a fold and then restored to an original position and pressed to flat the fold. Such a procedure was counted as one folding and repeated until the plated film was broken at the folding portion. According to this test, spreadability of the plated film is represented in terms of the numbers of foldings which the plated film could resist.
  • nonionic surface active agents of the formulae (I) and (II) are represented with A-x and B-x, respectively, said "x"s in A-x and B-x indicating m1 + n1 and m2 + n2, respectively.
  • Comparative Example 1 a plating solution was prepared in the same manner as in the above Examples except for using a compound other than the present invention in place of the component other than the nonionic surface active agents in the Group(A).
  • the chemical copper plating solution of the present invention can show an excellent stability usable over prolonged period, together with a high speed deposit, and produce a plated film having superior mechanical properties, inter alia , a good spreadability as illustrated with folding strength.
  • application of the chemical copper plating solution of the present invention can greatly improve working efficiency for plating and further enhance reliability in forming a plated film.
  • the chemical copper plating solution of the present invention may be most suitable for production of, e.g., a continuity circuit in a print distributing plate and is highly valuable in an industrial field.

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  • 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)
  • Manufacturing Of Printed Wiring (AREA)

Claims (11)

  1. Chemische Kupferplattierlösung, umfassend ein Kupfersalz, ein Komplexierungsmittel, ein Reduktionsmittel und ein pH-Einstellmittel, welche weiterhin die folgende Gruppe (A) enthält

    Gruppe (A):

    zumindest ein nicht-ionisches oberflächenaktives Mittel, ausgewählt aus der Gruppe, bestehend aus einem nicht-ionischen, oberflächenaktiven Mittel der Formel
    Figure imgb0013
     (worin m₁ und n₁ jeweils eine ganze Zahl von 1 oder mehr bedeuten) und einen nicht-ionischen oberflächenaktiven Mittel der Formel
    Figure imgb0014
     (worin m₂ und n₂ jeweils eine ganze Zahl von 1 oder mehr darstellen);

    und zumindest eine Verbindung, ausgewählt aus der Gruppe, die aus 1,10-Phenanthrolin, einem 1,10-Phenanthrolinderivt, 2,2'-Dipyridyl, 2,2'-Dichinolin und einer wasserlöslichen Cyanverbindung besteht.
  2. Chemische Kupferplattierlösuung nach Anspruch 1, dadurch gekennzeichnet, dass sie weiterhin die folgende Gruppe (B) umfasst:

    Gruppe (B):

    eine organische Schwefelverbindung und/oder eine Ethylenaminverbindung.
  3. Chemische Kupferplattierlösung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Komplexierungsmittel ein
    Kupferionen-Komplexierungsmittel ist.
  4. Chemische Kupferplattierlösung nach Anspruch 2, dadurch gekennzeichnet, dass die Ethylenaminverbindung eine Ethylenpolyaminverbindung ist.
  5. Chemische Kupferplattierlösung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass eine Konzentration des nicht-ionischen oberflächenaktiven Mittels der Formel (I) und (II) 10 mg/l bis 30 g/l ausmacht.
  6. Chemische Kupferplattierlösung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass m₁ + n₁ und m₂ + n₂ jeweils nicht mehr als 500 ausmachen.
  7. Chemische Kupferplattierlösung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass eine Gesamtkonzentration von 1,10-Phenanthrolin, einem 1,10-Phenanthrolinderivat, 2,2'-Dipyridyl und 2,2-Dichinolin 1 bis 200 mg/l ausmacht.
  8. Chemische Kupferplattierlösung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass eine Konzentration der wasserlöslichen Cyanverbindung 1 mg/l bis 3 g/l ausmacht.
  9. Chemische Kupferplattierlösung nach Anspruch 2, dadurch gekennzeichnet, dass die Konzentration der organischen Schwefelverbindung 0,01 bis 10 mg/l ist.
  10. Chemische Kupferplattierlösung nach Anspruch 2, dadurch gekennzeichnet, dass die Konzentration der Ethylenaminverbindung 1 bis 500 mg/l ist.
  11. Verfahren zur Anwendung einer chemischen Kupferplattierlösung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Anwendungsbedingung 40 bis 80°C und der pH-Wert 10,8 bis 13,0 sind.
EP85109921A 1984-09-27 1985-08-07 Stromlose Kupferplattierlösung Expired - Lifetime EP0179212B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP20044584A JPS6179775A (ja) 1984-09-27 1984-09-27 化学銅めつき液
JP200445/84 1984-09-27
JP27330384A JPS61153281A (ja) 1984-12-26 1984-12-26 化学銅めつき液
JP273303/84 1984-12-26

Publications (3)

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EP0179212A2 EP0179212A2 (de) 1986-04-30
EP0179212A3 EP0179212A3 (en) 1988-01-27
EP0179212B1 true EP0179212B1 (de) 1991-12-27

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DE (1) DE3585017D1 (de)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3902907A (en) * 1973-08-17 1975-09-02 Kazutaka Kishita System for electroless plating of copper and composition
FR2436192A1 (fr) * 1978-09-13 1980-04-11 Kollmorgen Tech Corp Perfectionnement apporte au depot non-galvanique du cuivre

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3377174A (en) * 1963-10-24 1968-04-09 Torigai Eiichi Method and bath for chemically plating copper
US3959531A (en) * 1971-04-23 1976-05-25 Photocircuits Corporation Improvements in electroless metal plating
US3661597A (en) * 1971-05-20 1972-05-09 Shipley Co Electroless copper plating
JPS56156749A (en) * 1980-05-08 1981-12-03 Toshiba Corp Chemical copper plating solution
US4548644A (en) * 1982-09-28 1985-10-22 Hitachi Chemical Company, Ltd. Electroless copper deposition solution

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3902907A (en) * 1973-08-17 1975-09-02 Kazutaka Kishita System for electroless plating of copper and composition
FR2436192A1 (fr) * 1978-09-13 1980-04-11 Kollmorgen Tech Corp Perfectionnement apporte au depot non-galvanique du cuivre

Also Published As

Publication number Publication date
DE3585017D1 (de) 1992-02-06
EP0179212A2 (de) 1986-04-30
EP0179212A3 (en) 1988-01-27

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