EP0164580B1 - Bad und Lösung zum stromlosen Verkupfern - Google Patents

Bad und Lösung zum stromlosen Verkupfern Download PDF

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Publication number
EP0164580B1
EP0164580B1 EP19850105723 EP85105723A EP0164580B1 EP 0164580 B1 EP0164580 B1 EP 0164580B1 EP 19850105723 EP19850105723 EP 19850105723 EP 85105723 A EP85105723 A EP 85105723A EP 0164580 B1 EP0164580 B1 EP 0164580B1
Authority
EP
European Patent Office
Prior art keywords
plating bath
per liter
bath
grams per
bath according
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
Application number
EP19850105723
Other languages
English (en)
French (fr)
Other versions
EP0164580A3 (en
EP0164580A2 (de
Inventor
William Joseph Amelio
Peter Gerard Bartolotta
Voya Markovich
Ralph Elliott Parsons
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
International Business Machines Corp
Original Assignee
International Business Machines Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by International Business Machines Corp filed Critical International Business Machines Corp
Publication of EP0164580A2 publication Critical patent/EP0164580A2/de
Publication of EP0164580A3 publication Critical patent/EP0164580A3/en
Application granted granted Critical
Publication of EP0164580B1 publication Critical patent/EP0164580B1/de
Expired legal-status Critical Current

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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

  • an electroless or autocatalytic copper plating bath usually contains a cupric ion source, a reducing agent for the cupric ion, a chelating or complexing agent, and a pH adjustor.
  • a suitable catalyst is deposited on the surface prior to contact with the plating bath.
  • stannous chloride sensitizing solutuion and a palladium chloride activator to form a layer of metallic palladium particles.
  • a major reason for yield loss in electroless copper plating is the formation of what is known as extraneous copper or nodules.
  • the formation of nodules in unwanted areas on a substrate can result in short-circuiting by forming contact between circuit lines on the substrate.
  • such processes as providing protective coatings, providing solder, and pin insertion are adversely affected by the presence of nodules on the surface.
  • the plating bath of the present invention provides high-quality deposited copper of improved ductility. Moreover, the longevity of the baths of the present invention is relatively long (e.g., a bath can be used for about one week).
  • electroless copper plating bath of improved stability and capable of providing of increased plating rates can be achieved by providing 1 part per 10 9 to 1,000 parts per 10 9 and preferably 1 part per 10 9 to about 500 parts per 10 9 of a cationic polymer from acrylamide and/or from methacrylamide.
  • the cationic polymer in the concentrations employed, helps in the oxidation of Cu + , thereby preventing bulk precipitation of C U2 0 which, in turn, enhances the stability of the bath and helps in reducing nodule formation.
  • the cationic polymer acts as a complexing or chelating agent for the cupric ion.
  • the presence of the cationic polymer in the plating bath acts as a bridging ligand between the metal ions and the surface to be coated, thereby enhancing the rate of the electrochemical reaction providing increased plating rate.
  • the preferred cationic polymers employed are available under the trade designation "Reten".
  • the polymer from acrylamide and/or methacrylamide is a multifunctional cationic material in that it must contain at least two active or available cationic moieties.
  • the polymers are at least water-miscible and are preferably water-soluble or at least soluble in the water compositions employed in the present invention.
  • the preferred cationic moieties are quaternary phosphonium and quaternary ammonium groups. Polymers containing at least two cationic moieties are commercially available and need not be described herein in any great detail.
  • Reten 210 examples of commercially available multifunctional cationic polymers are Reten 210, Reten 220, and Reten 300, marketed by Hercules, description of which can be found in "Water-Soluble Polymers", Bulletin VC-482A, Hercules Incorporated, Wilmington, Delaware 19899, disclosure of which is incorporated herein by reference.
  • Reten 210 is in powder form and is a copolymer of acrylamide and betamethacryloxyethyltrimethylammonium methyl sulfate having a Brookfield viscosity of a 1% solution of 600-1000 cps.
  • Reten 220 is in powder form and is a copolymer of acrylamide and betamethacryloxyethyltrimethylammonium methyl sulfate having a Brookfield viscosity of a 1 % solution of 800-1200 cps.
  • Reten 300 is a liquid and is a homopolymer of betamethacryloxyethyltrimethylammonium methyl sulfate having a Brookfield viscosity of a 1% solution of 300-700 cps.
  • the molecular weight of the Reten polymers is usually relatively high and varies from about 50,000 to about 1,000,000 or more. These high molecular weight polymers are solid products and their main chemical backbone structure is polyacrylamide.
  • the cationic Reten (positive charge) is obtained by attaching to the polyacrylamide various tetraalkyl ammonium compounds.
  • Such copper electroless plating baths generally are aqueous compositions which include a source of cupric ion, a reducing agent, a complexing agent for the cupric ion, and a pH adjustor.
  • the plating baths also preferably include a cyanide ion source and an anionic surface-active agent.
  • the cupric ion source generally used is a cupric sulfate or a cupric salt of the complexing agent to be employed.
  • the cupric ion source is generally employed in amounts from about 3 to about 15 grams per liter and preferably about 8 to about 12 grams per liter calculated as cupric sulfate.
  • the most common reducing agent employed is formaldehyde which in the preferred aspects of the present invention are used in amounts from about 0.7 to about 7 grams per liter and most preferably from about 0.7 to about 2.2 grams per liter.
  • Examples of other reducing agents include formaldehyde derivatives or precursors such as paraformaldehyde, trioxane, dimethylhydantoin, and glyoxal; borohydrides such as alkali metal alkali borohydrides (sodium and potassium borohydride) and substituted borohydrides such as sodium trimethoxy borohydride; boranes such as amine borane (isoproply amine borane and morpholine borane).
  • formaldehyde derivatives or precursors such as paraformaldehyde, trioxane, dimethylhydantoin, and glyoxal
  • borohydrides such as alkali metal alkali borohydrides (sodium and potassium borohydride) and substituted borohydrides such as sodium trimethoxy borohydride
  • boranes such as amine borane (isoproply amine borane and morpholine borane).
  • Suitable complexing agents includes Rochelle Salts, ethylene diamine tetraacetic acid, the sodium (mono-, di-, tri-, and tetra-sodium) salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid and its alkali salts, gluconic acid, gluconates, triethanol amine, glucono(gamma)-lactone, modified ethylene diamine acetates such as N-hydroxy ethyl, ethylene diamine triacetate.
  • suitable cupric complexing agents are suggested in U.S Patents 2,996,408; 3,075,856; 3,075,855; and 2,938,805 disclosures of which are incorporated herein by reference.
  • the amount of complexing agent is dependent upon the amount of cupric ions present in the solution as generally from about 20 to about 50 grams per liter or in a 3 ⁇ 4 fold molar excess.
  • the plating bath also preferably contains an anionic surface active agent which assists in wetting the surface to be coated.
  • an anionic surface active agent is, for instance, an organic phosphate ester available under the trade designation "Gafac RE-610".
  • the anionic surface active agent is present in amounts from about 0.02 to about 0.3 grams per liter.
  • the pH of the bath is usually generally controlled, for instance, by the addition of a basic compound such as sodium hydroxide or potassium hydroxide in the necessary amount to achieve the desired pH.
  • a basic compound such as sodium hydroxide or potassium hydroxide in the necessary amount to achieve the desired pH.
  • the preferred pH of the electroless plating bath employed in accordance with the present invention is between 11.8 and 12.5.
  • the plating bath contains a cyanide ion and most preferably contains about 10 to about 25 milligrams per liter to provide a cyanide ion concentration in the bath within the range of 0.0002 to 0.0004 molar.
  • cyanide ion examples include the alkali metal, alkaline earth metal, and ammonium cyanides.
  • the plating bath can include other minor additives as known in the art.
  • the preferred plating baths employed have a specific gravity within the range of 1.060 to 1.080. Moreover, the temperature of the bath is preferably maintained between 70°C and 80°C and most preferably between 70°C and 75°C. For a discussion of the preferred plating temperature coupled with the preferred cyanide ion concentrations, see U.S. Patent 3,844,799.
  • the 0 2 content can be controlled by injecting oxygen and an inert gas into the bath.
  • the overall flow rate of the gases into the bath is generally from about 28.32 to about 566.4 I per minute per 3785 I (about 1 to about 20 standard cubicfeet per minute per thousand gallons) of bath and preferably from about 141.6 to about 283.2 I per minute per 3785 (about 5 to about 10 standard cubic feet per minute per thousand gallons) of bath.
  • the preferred plating rates employed in accordance with the present invention are about 5.08 to about 7.62 !-1m (about 0.2 to about 0.3 mils) of plated copper thickness per hour.
  • a plating bath containing about 9 grams per liter of cupric sulfate, about 2.0 grams per liter of formaldehyde, about 36 grams per liter of ethylene diamine tetraacetic acid, about 28 milligrams per liter of sodium cyanide, about 1.2 parts per 10 9 of Reten 210, and about 0.05 grams per liter of Gafac is preferred.
  • the bath has a pH of about 12.
  • the bath is fed through a plating tank at at temperature of about 73°C.
  • the plating tank contains substrates having a thin layer of copper on the surface thereof.
  • the oxygen content of the bath during plating is about 3 ppm.
  • the rate of plating is about 5.08 um per hour.
  • the nodule rating of the substrate is 1 (nodule rating refers to nodules per 6.4516 cm 2 (1 square inch) with 1 being the best and 5 being the worst). Similar results are obtained with dielectric substrates catalyzed for plating copper electroless plating.

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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)

Claims (11)

1. Bad zum stromlosen Verkupfern, folgendes enthaltend:
A. eine Kupfer (II)-Ionenquelle in einer Menge von ca. 3 bis ca. 15 g/1 kalkuliert als Kupfer (II)-sulfat;
B. ein Reduzierungsmittel für die Kupfer (II)-lonenquelle in einer Menge von ca. 0,7 bis ca. 7 g/I kalkuliert als Formaldehyd;
C. einen Komplexbildnerfür das Kupfer(II)-lon in einer Menge von ca. 20 bis 50 g/I; und
D. 1 Teil pro 109 bis 1,000 Teile pro 109 eines kationischen Polymers aus Akrylamid oder Methakrylamid, oder aus beiden.
2. Plattierungsbad nach Anspruch 1, welches 1 Teil pro 109 bis ca. 500 Teile pro 109 des kationischen Polymers enthält.
3. Plattierungsbad nach Anspruch 1 oder 2, welches ein anionisches oberflächenaktives Mittel enthält, bevorzugt in einer Menge von ca. 0,02 bis ca. 0,3 g/l.
4. Plattierungsbad nach einem der Ansprüche 1 bis 3, mit einem pH von ca. 11,8 bis ca. 12,5.
5. Plattierungsbad nach einem der Ansprüche 1 bis 4, welches außerdem ca. 10 bis ca. 25 mg eines Zyanidions/1 enthält.
6. Plattierungsbad nach einem der Ansprüche 1 bis 5, bei dem das kationische Polymer ein polyfunktionelles kationisches Polymer ist.
7. Plattierungsbad nach einem der Ansprüche 1 bis 6, bei dem das kationische Polymer ein Kopolymer aus Akrylamid und einer quaternären Ammoniumverbindung ist.
8. Plattierungsbad nach einem der Ansprüche 1 bis 7, das außerdem zwischen ca. 2 und ca. 4 ppm 02 enthält.
9. Plattierungsbad nach einem der Ansprüche 1 bis 8, welches die Kupfer(II)-lonenquelle in einer Menge von ca. 8 bis ca. 12 g/I kalkuliert als Kupfer(II)-Sulfat, das Reduzierungsmittel in einer Menge von ca. 0,7 und ca. 2,2 g/I kalkuliert als Formaldehyd, und als Komplexbildner Äthylendiamin-Tetraessigsäure oder ein Salz derselben für das Kupfer(II)-lon in einer Menge von ca. 20 bis 50 g/I enthält.
10. Verfahren zum Plattieren eines Substrats, bei dem das Substrat mit einem Bad zum stromlosen Verkupfern nach Anspruch 1 kontaktiert wird.
11. Verfahren nach Anspruch 10, bei dem das Bad beim stromlosen Verkupfern auf einer Temperaturzwischen ca. 70°C und ca. 80°C gehalten wird.
EP19850105723 1984-05-17 1985-05-10 Bad und Lösung zum stromlosen Verkupfern Expired EP0164580B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US61127884A 1984-05-17 1984-05-17
US611278 1996-03-19

Publications (3)

Publication Number Publication Date
EP0164580A2 EP0164580A2 (de) 1985-12-18
EP0164580A3 EP0164580A3 (en) 1986-12-30
EP0164580B1 true EP0164580B1 (de) 1989-09-20

Family

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Family Applications (1)

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EP19850105723 Expired EP0164580B1 (de) 1984-05-17 1985-05-10 Bad und Lösung zum stromlosen Verkupfern

Country Status (3)

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EP (1) EP0164580B1 (de)
JP (1) JPS60245783A (de)
DE (1) DE3573139D1 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4654126A (en) * 1985-10-07 1987-03-31 International Business Machines Corporation Process for determining the plating activity of an electroless plating bath
JPH0723539B2 (ja) * 1986-11-06 1995-03-15 日本電装株式会社 化学銅めっき液及びそれを用いた銅めっき皮膜の形成方法
AU579776B2 (en) * 1986-11-06 1988-12-08 Nippondenso Co. Ltd. Electroless copper plating solution and process for electrolessly plating copper
US4814009A (en) * 1986-11-14 1989-03-21 Nippondenso Co., Ltd. Electroless copper plating solution
JP2595319B2 (ja) * 1988-07-20 1997-04-02 日本電装株式会社 化学銅めっき液及びそれを用いた銅めっき皮膜の形成方法
JPH02161130A (ja) * 1988-12-15 1990-06-21 Hino Motors Ltd ターボチャージャーの制御装置
US5965211A (en) * 1989-12-29 1999-10-12 Nippondenso Co., Ltd. Electroless copper plating solution and process for formation of copper film
WO2005038086A1 (ja) * 2003-10-17 2005-04-28 Nikko Materials Co., Ltd. 無電解銅めっき液

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1530167A (fr) * 1967-07-03 1968-06-21 Shipley Co Composition et procédé pour le dépôt chimique non électrolytique de cuivre sur des objets à surface catalytique
JPS5230131B2 (de) * 1973-07-11 1977-08-05
JPS5220339A (en) * 1975-08-08 1977-02-16 Hitachi Ltd Chemical copper plating solution

Also Published As

Publication number Publication date
EP0164580A3 (en) 1986-12-30
JPS60245783A (ja) 1985-12-05
JPH0214430B2 (de) 1990-04-09
EP0164580A2 (de) 1985-12-18
DE3573139D1 (en) 1989-10-26

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