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US3841881A - Method for electroless deposition of metal using improved colloidal catalyzing solution - Google Patents

Method for electroless deposition of metal using improved colloidal catalyzing solution Download PDF

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US3841881A
US3841881A US00288777A US28877772A US3841881A US 3841881 A US3841881 A US 3841881A US 00288777 A US00288777 A US 00288777A US 28877772 A US28877772 A US 28877772A US 3841881 A US3841881 A US 3841881A
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metal
solution
salt
catalytic
colloidal
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US00288777A
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N Feldstein
T Lancsek
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RCA Corp
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RCA Corp
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    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating

Definitions

  • Some metallic surfaces are inherently catalytic for initiating deposition of certain metals from autocatalytic electroless plating baths.
  • non-metallic surfaces must be treated to render them catalytic.
  • One common method-of rendering a non-metallic surface catalytic forthe autocatalytic electroless deposition of a number of metals is to treat it, first, with a sensitizing solution of stannous chloride. Then the sensitized surface is treated with an activating solution of palladium chloride which deposits an adherent filmof palladium nuclei. These nuclei serve as catalyst for initiating the reduction of the metal salt and its deposition on the substrate. After an initial layer of the metal is thus deposited, this initial layer catalyzes further deposition.
  • the excess amount of stannous salt reacts to form a protective colloid which inhibits flocculation that would normally occur when stannous ions and noble metal ions are present in the same solution.
  • the surface is treated with the electroless plating bath in the usual way.
  • the colloidal catalyst solution method has been found generally satisfactory for deposition of metals such as nickel and copper, on surfaces such as glass and hydrophilic dielectrics, especially where the catalyzed surface is given a treatment with an accelerator such as a solution of sodium hydroxide prior to contact with the electroless plating bath.
  • the accelerator dissolves the protective colloid which is present on the catalyzed surface.
  • the present invention is an improvement in the colloidal catalyst solution method which enables it to be used on hydrophobic surfaces and also provides improved reliability on other substrates.
  • the improvement consists in adding to the colloidal catalyst solution, a solution of a stannic compound that has been separately aged. The quantity of stannic ion added is enough to make the solution at least 0.01 molar in this ingredient.
  • Copper Plating Bath Compositions CuSO,.5H O 15 g/l Propylenediamine tetraacetic acid, 60 cc/l sodium salt (40% active solution) NaOH 4.0 g/l H CO (37% solution) 40 cell NaCN 4 mg/l Temperature 40C A plating cycle of 5 minutes was used.
  • nickel, cobalt, gold and alloys of any two or more of these four metals can be deposited from conventional electroless plating baths using the colloidal catalyst solutions described herein.
  • colloidal catalyst solutions for catalyzing the surface to be plated.
  • the surface is either dipped in or sprayed with the solution. Treating time can be about 30 seconds or more.
  • Example 1 Example 2
  • Example 3 H 0 600 cell 600 cell 600 cell HCl (Conc.) 300 cc/l 300 cell 300 cell SnCl g/l 37.5 g/l 375 g/l (Anhydrous) Aged SnCl, 3.2 X 10 1.6 X 10 2.4 X l0 (molar conc.)
  • the aged SnCl may be prepared as an aqueous 0.5 molar solution aged for one week at room temperature.
  • its concentration is preferably 0.01 to 0.5 molar.
  • Aging time varies with conditions. At elevated temperatures it can be as little as a few hours. At ordinary room temperature it is preferably at least 4 days to 1 week.
  • the surface is rinsed with water and then preferably treated with an accelerator as described in US. Pat. No. 3,011,921. This may be a 5 percent solution of sodium hydroxide, for example, and treating time is a few minutes.
  • the surface is again rinsed with water after treatment with the accelerator and it is then treated with the plat ing bath.
  • Platings on Teflon using the above-described materials and procedures have produced about 95 percent plating coverage with all three examples.
  • another three Teflon plates were treated with similar colloidal catalyst solutions except that the aged SnCl was omitted.
  • the plating baths and plating cycles were the same. However, in these comparison examples, plating coverage was only about 5 percent on each plate.
  • An example of a nickel autocatalytic electroless plating bath that can be used in the present process is:
  • the colloidal catalytic metal can be gold or any one of the platinum group of metals.
  • the platinum group of metals consists of platinum, ruthenium, rhodium, palladium, osmium and iridium.
  • a colloidal catalytic solution for catalyzing a substrate prior to electroless metal deposition thereon comprising the solution resulting from the admixture of an acid soluble salt of a catalytic metal selected from the group consisting of gold, and the platinum family of metals, hydrochloric acid, a stannous salt soluble in aqueous solution, said stannous salt being in excess of the amount necessary to reduce said metal lytic metal is palladium.
  • the method of making a colloidal catalyst solution for application to a substrate surface prior to electroless metal deposition thereon comprising admixing an acid soluble salt of a catalytic metal selected from the group consisting of gold, and the platinum family of metals, hydrochloric acid, a stannous salt soluble in aqueous solution, said stannous salt being in excess of the amount necessary to reduce said metal salt to colloidal metal, and a quantity of stannic chloride solution which has been separately aged for a period which is the equivalent of at least 4 days at room temperature and said stannic compound being present in a concentration of about 0.01 to 0.5 molar in said catalyst solution.

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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)

Abstract

A colloidal solution of a catalytic metal is prepared by admixing an acid-soluble salt of the metal, hydrochloric acid, a soluble stannous salt present in excess of the amount necessary to reduce the metal salt to colloidal metal, and a quantity of stannic chloride that has been separately aged. A substrate surface upon which metal is to be deposited is treated with the catalytic colloidal solution. The catalyzed surface is then subjected to an electroless plating bath.

Description

United States Patent 1191 Feldstein et al.
[ METHOD FOR ELECTROLESS DEPOSITION OF METAL USING IMPROVED COLLOIDAL CATALYZING SOLUTION [75] Inventors: Nathan Feldstein, Kendall Park,
N.J.; Thomas Stephen Lancsek, Morrisville, Pa.
[73] Assignee: RCA Corporation, New York, NY. [22] Filed: Sept. 13, 1972 21 Appl. No.: 288,777
[52] U.S. Cl. 106/1, 117/47 A, 117/130 E, 204/30 [51] Int. Cl. C23c 3/02 [58] Field of Search 106/1; 204/30; 117/47 A, ll7/l30 E [56] References Cited UNITED STATES PATENTS 3,011,920 12/1961 Shipley mm A .Oct. 15, 1974 DOttavio 106/1 3,616,296 l0/l971 Bernhardt et al.... 204/30 3,650,777 3/1972 Schneble et al. 106/1 3,672,923 6/l972 Zeblisky ct al. 106/1 3,698,919 10/1972 Kuzmik 106/1 Primary Examiner Lorenzo B, Hayes Attorney, Agent, or Firm-G. H. Bruestle; W. S. Hill [57] ABSTRACT 8 Claims, No Drawings 1. METHOD FOR ELECTROLESS DEPOSITION OF METAL USING IMPROVED COLLOIDAL CATALYZING SOLUTION BACKGROUND OF THE INVENTION Various metals can be deposited on certain substrate surfaces by a process known as autocatalytic electroless plating. Autocatalytic electroless plating baths usually contain a salt of the meta] being deposited, at reducing agent for the metal salt, a complexing or chelating agent and a pH adjustor.
Some metallic surfaces are inherently catalytic for initiating deposition of certain metals from autocatalytic electroless plating baths. However, non-metallic surfaces must be treated to render them catalytic. One common method-of rendering a non-metallic surface catalytic forthe autocatalytic electroless deposition of a number of metals is to treat it, first, with a sensitizing solution of stannous chloride. Then the sensitized surface is treated with an activating solution of palladium chloride which deposits an adherent filmof palladium nuclei. These nuclei serve as catalyst for initiating the reduction of the metal salt and its deposition on the substrate. After an initial layer of the metal is thus deposited, this initial layer catalyzes further deposition.
The above described method of autocatalytic electroless deposition has been widely used. Another method that has been widely used commercially for depositing a catalytic coating on a surface is the so-called colloidal catalyst solution method, as described, for example, in US. Pat. No. 3,011,920. In this method, the initial step of sensitizing the surface with a stannous chloride solution is omitted. Instead the surface is treated with a single solution which comprises an acid soluble salt of a catalytic metal (usually, a noble metal), hydrochloric acid, and a soluble stannous salt which is present in excess of the amount necessary to reduce the catalytic metal salt to colloidal metal. The excess amount of stannous salt reacts to form a protective colloid which inhibits flocculation that would normally occur when stannous ions and noble metal ions are present in the same solution. After treatment of the surface to be plated with the colloidal catalyst solution, the surface is treated with the electroless plating bath in the usual way.
The colloidal catalyst solution method has been found generally satisfactory for deposition of metals such as nickel and copper, on surfaces such as glass and hydrophilic dielectrics, especially where the catalyzed surface is given a treatment with an accelerator such as a solution of sodium hydroxide prior to contact with the electroless plating bath. The accelerator dissolves the protective colloid which is present on the catalyzed surface. j
In the case of hydrophobic surfaces, such as Teflon, for example, neither the colloidal catalyst solution method nor the two-step method first described,'has been satisfactory. On this type of surface, coverage of the deposited metal has usually ranged between zero and very poor.
The present invention is an improvement in the colloidal catalyst solution method which enables it to be used on hydrophobic surfaces and also provides improved reliability on other substrates. The improvement consists in adding to the colloidal catalyst solution, a solution of a stannic compound that has been separately aged. The quantity of stannic ion added is enough to make the solution at least 0.01 molar in this ingredient.
The addition of the aged stannic chloride introduces a hydrolyzed compound containing stannic ions. The improvement appears to be due to this compound.
DESCRIPTION OF PREFERRED EMBODIMENTS Examples l-3 In the examples which follow, the surface being coated was a plate of Teflon plastic. The plating bath was one for autocatalytically electrolessly plating copper and had the composition given below.
Copper Plating Bath Compositions CuSO,.5H O 15 g/l Propylenediamine tetraacetic acid, 60 cc/l sodium salt (40% active solution) NaOH 4.0 g/l H CO (37% solution) 40 cell NaCN 4 mg/l Temperature 40C A plating cycle of 5 minutes was used.
Besides copper (from the above-described bath), nickel, cobalt, gold and alloys of any two or more of these four metals, for example, can be deposited from conventional electroless plating baths using the colloidal catalyst solutions described herein.
The following are colloidal catalyst solutions for catalyzing the surface to be plated. The surface is either dipped in or sprayed with the solution. Treating time can be about 30 seconds or more.
Colloidal Catalyst Solutions Example 1 Example 2 Example 3 H 0 600 cell 600 cell 600 cell HCl (Conc.) 300 cc/l 300 cell 300 cell SnCl g/l 37.5 g/l 375 g/l (Anhydrous) Aged SnCl, 3.2 X 10 1.6 X 10 2.4 X l0 (molar conc.)
Na SnO .3H 0 None None 1.5 g/l PdCl 1 g/l None None HAuCl,.H O None 1 g/l None H PtCl None None 1 g/l The pH of these solutions shouldv be maintained below about I.
The aged SnCl, may be prepared as an aqueous 0.5 molar solution aged for one week at room temperature. In the catalyst solution, its concentration is preferably 0.01 to 0.5 molar. Aging time varies with conditions. At elevated temperatures it can be as little as a few hours. At ordinary room temperature it is preferably at least 4 days to 1 week.
After treating the Teflon surface with the catalyst solution, the surface is rinsed with water and then preferably treated with an accelerator as described in US. Pat. No. 3,011,921. This may be a 5 percent solution of sodium hydroxide, for example, and treating time is a few minutes.
The surface is again rinsed with water after treatment with the accelerator and it is then treated with the plat ing bath.
Platings on Teflon using the above-described materials and procedures have produced about 95 percent plating coverage with all three examples. For comparison purposes, another three Teflon plates were treated with similar colloidal catalyst solutions except that the aged SnCl was omitted. The plating baths and plating cycles were the same. However, in these comparison examples, plating coverage was only about 5 percent on each plate.
An example of a nickel autocatalytic electroless plating bath that can be used in the present process is:
NiSO,.6H O 25 g/l Na P O,.l0H. .0 50 g/l Dimethylamine borane 1.5 g/l NH,OH Leone.) 50 cell Temperature 40C In the present method, the colloidal catalytic metal can be gold or any one of the platinum group of metals. The platinum group of metals consists of platinum, ruthenium, rhodium, palladium, osmium and iridium.
We claim:
1. A colloidal catalytic solution for catalyzing a substrate prior to electroless metal deposition thereon, said catalyst comprising the solution resulting from the admixture of an acid soluble salt of a catalytic metal selected from the group consisting of gold, and the platinum family of metals, hydrochloric acid, a stannous salt soluble in aqueous solution, said stannous salt being in excess of the amount necessary to reduce said metal lytic metal is palladium.
3; A solution according to claim 1 in which said catalytic metal is gold.
4. A solution according to claim 1 in which said catalytic metal is platinum.
5. The method of making a colloidal catalyst solution for application to a substrate surface prior to electroless metal deposition thereon. comprising admixing an acid soluble salt of a catalytic metal selected from the group consisting of gold, and the platinum family of metals, hydrochloric acid, a stannous salt soluble in aqueous solution, said stannous salt being in excess of the amount necessary to reduce said metal salt to colloidal metal, and a quantity of stannic chloride solution which has been separately aged for a period which is the equivalent of at least 4 days at room temperature and said stannic compound being present in a concentration of about 0.01 to 0.5 molar in said catalyst solution.
6. The method of claim 1 in which said catalytic metal is palladium.
7. The method of claim 5 in which said catalytic metal is gold.
8. The method of claim 5 in which said catalytic metal is platinum.

Claims (8)

1. A COLLODIAL CATALYTIC SOLUTION FOR CATALYZING A SUBSTRATE PRIOR TO ELECTROLESS METAL DEPOSITION THEREON, SAID CATALYST COMPRISING THE SOLUTION RESULTING FROM THE ADMIXTURE OF AN ACID SOLUBLE SALT OF A CATALYTIC METAL SELCTED FROM THE GROUP CONSISTING OF GOLD, AND THE PLATINUM FAMILY OF METALS, HYDROCHLORIC ACID, A STANNOUS SALT SOLUBLE IN AQUEOUS SOLUTION, SAID STANNOUS SALT BEING IN EXCESS OF THE AMOUNT NECESSARY TO REDUCE SAID METAL SALT TO COLLOIDAL METAL, AND A QUANTITY OF A SOLUTION OF STANNIC CHLORIDE WHICH HAS BEEN SEPARATELY AGED FOR THE EQUIVALENT OF AT LEAST 4 DAYS AT ROOM TEMPRATURE PRIOR TO ADMIXTURE, SAID STANNOUS SALT SOLUBLE IN AQUEOUS SOLUTION, SAI CENTRATION OF ABOUT 0.01 TO 0.5 MOLAR IN SAID CATALYTIC SOLUTION
2. A solution according to claim 1 in which said catalytic metal is palladium.
3. A solution according to claim 1 in which said catalytic metal is gold.
4. A solution according to claim 1 in which said catalytic metal is platinum.
5. The method of making a colloidal catalyst solution for application to a substrate surface prior to electroless metal deposition thereon, comprising admixing an acid soluble salt of a catalytic metal selected from the group consisting of gold, and the platinum family of metals, hydrochloric acid, a stannous salt soluble in aqueous solution, said stannous salt being in excess of the amount necessary to reduce said metal salt to colloidal metal, and a quantity of stannic chloride solution which has been separately aged for a period which is the equivalent of at least 4 days at room temperature and said stannic compound being present in a concentration of about 0.01 to 0.5 molar in said catalyst solution.
6. The method of claim 1 in which said catalytic metal is palladium.
7. The method of claim 5 in which said catalytic metal is gold.
8. The method of claim 5 in which said catalytic metal is platinum.
US00288777A 1972-09-13 1972-09-13 Method for electroless deposition of metal using improved colloidal catalyzing solution Expired - Lifetime US3841881A (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4100037A (en) * 1976-03-08 1978-07-11 Western Electric Company, Inc. Method of depositing a metal on a surface
US4284666A (en) * 1977-07-20 1981-08-18 Nathan Feldstein Process for metal deposition of a non-conductor substrate
US4959121A (en) * 1990-01-05 1990-09-25 General Electric Company Method for treating a polyimide surface for subsequent plating thereon
US5288519A (en) * 1992-04-27 1994-02-22 General Electric Company Method of producing modified polyimide layer having improved adhesion to metal layer thereon
US5290597A (en) * 1992-04-27 1994-03-01 General Electric Company Method of treating halogenated polyimide substrates for increasing adhesion of metal layer thereon
US5302467A (en) * 1992-04-27 1994-04-12 General Electric Company Halogenated polyimide composition having improved adhesion characteristic and articles obtained therefrom
US5395651A (en) * 1989-05-04 1995-03-07 Ad Tech Holdings Limited Deposition of silver layer on nonconducting substrate
US5403650A (en) * 1982-04-27 1995-04-04 Baudrand; Donald W. Process for selectively depositing a nickel-boron coating over a metallurgy pattern on a dielectric substrate and products produced thereby
US6579539B2 (en) 1999-12-22 2003-06-17 C. R. Bard, Inc. Dual mode antimicrobial compositions
US6596401B1 (en) 1998-11-10 2003-07-22 C. R. Bard Inc. Silane copolymer compositions containing active agents
US20070093377A1 (en) * 2003-12-15 2007-04-26 Kiyoshi Miyashita Metal nanocolloidal liguid, method for producing metal support and metal support

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3011920A (en) * 1959-06-08 1961-12-05 Shipley Co Method of electroless deposition on a substrate and catalyst solution therefor
US3532518A (en) * 1967-06-28 1970-10-06 Macdermid Inc Colloidal metal activating solutions for use in chemically plating nonconductors,and process of preparing such solutions
US3616296A (en) * 1969-02-01 1971-10-26 Dynamit Nobel Ag Method for metallizing plastics
US3650777A (en) * 1971-02-11 1972-03-21 Kollmorgen Corp Electroless copper plating
US3672923A (en) * 1970-06-29 1972-06-27 Kollmorgen Corp Solid precious metal sensitizing compositions
US3698919A (en) * 1969-08-14 1972-10-17 Macdermid Inc Preparation of plastic substrates for electroless plating and solutions therefor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3011920A (en) * 1959-06-08 1961-12-05 Shipley Co Method of electroless deposition on a substrate and catalyst solution therefor
US3532518A (en) * 1967-06-28 1970-10-06 Macdermid Inc Colloidal metal activating solutions for use in chemically plating nonconductors,and process of preparing such solutions
US3616296A (en) * 1969-02-01 1971-10-26 Dynamit Nobel Ag Method for metallizing plastics
US3698919A (en) * 1969-08-14 1972-10-17 Macdermid Inc Preparation of plastic substrates for electroless plating and solutions therefor
US3672923A (en) * 1970-06-29 1972-06-27 Kollmorgen Corp Solid precious metal sensitizing compositions
US3650777A (en) * 1971-02-11 1972-03-21 Kollmorgen Corp Electroless copper plating

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4100037A (en) * 1976-03-08 1978-07-11 Western Electric Company, Inc. Method of depositing a metal on a surface
US4284666A (en) * 1977-07-20 1981-08-18 Nathan Feldstein Process for metal deposition of a non-conductor substrate
US5403650A (en) * 1982-04-27 1995-04-04 Baudrand; Donald W. Process for selectively depositing a nickel-boron coating over a metallurgy pattern on a dielectric substrate and products produced thereby
US5565235A (en) * 1982-04-27 1996-10-15 Baudrand; Donald W. Process for selectively depositing a nickel-boron coating over a metallurgy pattern on a dielectric substrate
US5747178A (en) * 1989-05-04 1998-05-05 Adtech Holding Deposition of silver layer on nonconducting substrate
US6224983B1 (en) 1989-05-04 2001-05-01 Ad Tech Holdings Limited Deposition of silver layer on nonconducting substrate
US5965204A (en) * 1989-05-04 1999-10-12 Ad Tech Holdings Limited Deposition of silver layer on nonconducting substrate
US5395651A (en) * 1989-05-04 1995-03-07 Ad Tech Holdings Limited Deposition of silver layer on nonconducting substrate
US4959121A (en) * 1990-01-05 1990-09-25 General Electric Company Method for treating a polyimide surface for subsequent plating thereon
US5290597A (en) * 1992-04-27 1994-03-01 General Electric Company Method of treating halogenated polyimide substrates for increasing adhesion of metal layer thereon
US5302467A (en) * 1992-04-27 1994-04-12 General Electric Company Halogenated polyimide composition having improved adhesion characteristic and articles obtained therefrom
US5288519A (en) * 1992-04-27 1994-02-22 General Electric Company Method of producing modified polyimide layer having improved adhesion to metal layer thereon
US6596401B1 (en) 1998-11-10 2003-07-22 C. R. Bard Inc. Silane copolymer compositions containing active agents
US6579539B2 (en) 1999-12-22 2003-06-17 C. R. Bard, Inc. Dual mode antimicrobial compositions
US20070093377A1 (en) * 2003-12-15 2007-04-26 Kiyoshi Miyashita Metal nanocolloidal liguid, method for producing metal support and metal support
US7648938B2 (en) * 2003-12-15 2010-01-19 Nippon Sheet Glass Company, Limited Metal nanocolloidal liquid, method for producing metal support and metal support

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