Catalyst for electroless deposition of metals

• US 3,937,857 A
• Filed: 07/22/1974
• Issued: 02/10/1976
• Est. Priority Date: 07/22/1974
• Status: Expired due to Term

• Current Assignee: AMP Incorporated (Johnson Controls International plc)
• Original Assignee: AMP Incorporated (Johnson Controls International plc)
• Inventors: Andrews, Daniel Marshall, Shaak, Ray Ned, Brummett, Charles Roscoe
• Primary Examiner(s): Weiffenbach, Cameron K.
• Application Number:
  US05/490,817
• Time in Patent Office: 568 Days
• Field of Search: 117/217, 117/201, 117/212, 117/71 R, 117/47 A, 117/45, 427/306, 427/229, 427/259, 427/261, 427/282, 427/307, 427/98, 427/226, 156/3
• US Class Current: 216/13
• CPC Class Codes: C23C 18/30 Activating or accelerating or sensitising with palladium or other noble metal
• CPC Class Codes: Y10T 428/12396 Discontinuous surface component
• CPC Class Codes: Y10T 428/12569 Synthetic resin

Abstract

A solvent method for the metallization of a non-conductive surface with gold, nickel or copper is shown whereby on a substrate a thermosensitive coordination complex of palladium is deposited; the complex has the formula LmPdXn wherein L is a ligand or unsaturated organic radical, X is a halide, alkyl group or a bidentate ligand and m is an integer from 1 to 4 and n is from 0 to 3; trimethyl phosphite palladium dichloride complex is an appropriate illustration of the complex; the palladium complex is applied on the substrate in a suitable non-aqueous solution such as tetrahydrofuran solution; the complex is then baked in air at elevated temperature; the exposure to high temperature decomposes the complex leaving a residue which is catalytic to the deposition of gold, nickel, cobalt or copper from an electroless bath thereof; the non-conductive material is then immersed in an electroless bath to metallize the areas which have been rendered catalytic; the preferred thermosensitive coordination complex of palladium is trimethyl phosphite palladium dichloride; a requirement for a proper thermal exposure of the complex is that the substrate is capable of withstanding the elevated temperatures such as above 210°C; illustrative organic substrates are polyimides, polysulfones, silicones, vulcanizates, fluoroplastics, polyphenylene sulfides, polyparabanic acids, and polyhydantoin, etc.

Claims

1. A method for the decomposition of a metal into an inert substrate from a bath containing said metal, said metal comprising the steps of:

applying to said substrate a thin film of a thermally decomposable complex of palladium or platimum having the formulae

LmPdXn or

LmPtXn wherein

L is a ligand or an unsaturated organic group;

Pd or Pt is palladium or platinum metal;

X is a halide, an alkyl group or a bidentate ligand; and

m is from 1 to 4 and n is from 0 to 3;

exposing said substrate to which said complex has been applied to heat at a temperature of about 300°

C and less to effect decomposition of said complex and to create a residue catalytic to a metal in an electroless bath solution; and

depositing a metal from said electroless bath on said substrate in an area rendered catalytic by decomposition of said complex.

2. The process as defined in claim 1 and wherein the complex is bis-trimethylphosphite palladium dichloride.

3. The method as defined in claim 1 and wherein said ligand L is a phosphine moiety, a phosphite moiety;

a nitrile moiety;

a diene moiety;

a diamine, a tetramine;

diethanol alkyl amine;

or a triethanol alkyl amine;

X is a halide, i.e., chloride, bromide, or iodide, an alkyl group of 1 to 6 carbon atoms, or a bidentate ligand of oxalate, succinate, citrate or borohydride.

4. As an article of manufacture, a polyimide film having a circuit pattern thereon defined by an electroless metal deposit and as catalyst for said electroless deposit a thermal decomposition product of a complex defined in claim 1.

5. A method for the metallization of a non-conductive substrate with nickel, cobalt, gold or copper comprising the steps of:

a. applying to said substrate a thermally sensitive, coordination complex of palladium or platinum having the formula

LmPdXn or

LmPtXm

b. forming residue catalytic to electroless nickel, cobalt, gold or copper on said substrate by decomposing the said complex at a temperature from 210°

C to 300°

C; and

immersing said substrate in an electroless solution of nickel, cobalt, gold or copper and depositing nickel, cobalt, gold or copper therefrom on the catalytic film formed by decomposition of said palladium or platinum complex.

6. A process as recited in claim 5 wherein the palladium complex is trimethyl phosphite palladium dichloride.

7. A process as recited in claim 5 wherein the said substrate after application of said complex and electroless metal in a nickel, cobalt, or copper electroless bath solution is masked and exposed to further additive electroless deposition.

8. A process as recited in claim 7 wherein said substrate after said further additive deposition is stripped of said mask and back etched in areas wherein said electroless metal has been deposited.

9. A method for the preparation of an inert substrate to electroless deposition of a metal upon said substrate comprising the steps of:

a. applying to said substrate a thin film of a thermally decomposable coordination complex of palladium having the formula

space="preserve" listing-type="equation">LmPdXn

wherein L = a ligand or unsaturated organic group, Pd is metal palladium and

X = a halide, alkyl group or bidentate ligand,

m is an integer from 1 to 4 and n is from 0 to 3, and

b. exposing said substrate to which said complex has been applied, to heat, at a temperature of about 300°

C and less, to effect decomposition of said complex and create residue catalytic to a metal in an electroless bath.

10. The process as defined in claim 9 and wherein the complex is bis-trimethylphosphite palladium dichloride.

11. A process as recited in claim 9 wherein said complex is bis-triphenylphosphine palladium dimethyl.

12. A process as recited in claim 9 wherein said complex is bis-tri-n-butylphosphine palladium dichloride.

13. A process as recited in claim 9 wherein said complex is palladium acetylacetonate.

14. The process as defined in claim 9 and wherein the substrate is etched before applying said complex to same.

15. The process as defined in claim 9 and wherein a complex or a mixture of complexes is applied to said substrate and said complex is bis-triphenylphosphine palladium dichloride;

bis-triphenylphosphine dimethyl palladium;

bis(triphenylphosphine) di(secondarybutyl) palladium;

bis-triphenylphosphine palladium oxalate;

bis-triphenylphosphine palladium borohydride;

bis-triphenylphosphine palladium diamine;

tris-triphenylphosphine palladium chloride;

tetrakis-triphenylphosphine palladium (0);

bis-triethyl phosphine or bis-tri-n-butyl phosphine palladium chloride or the dialkyl, oxalate, and borohydride bidentate substituents of said complex;

bis-trimethylphosphite palladium dichloride or the dialkyl oxalate, succinate, citrate, and borohydride bidentate substituent of said complex;

bis-benzonitrile, palladium dichloride;

bis-acetonitrile palladium dichloride, 1,3-butadiene palladium dichloride;

bis-triethylene tetramine palladium dichloride or bis-triethylene tetramine palladium oxalate, or mixtures thereof;

said alkyl moieties, defined above, being from 1 to 6 carbon atoms.

16. The method as defined in claim 9 and wherein the ligand is a phosphite or phosphine substituted with (a) aromatic mono or polynuclear groups, (b) an alkyl group or mixed alkyl group of 1 to 10 carbon atoms in said alkyl group;

an aromatic nitrile, an aliphatic nitrile, said aromatic or aliphatic group having from 1 up to 8 carbon atoms in said nitrile moiety;

an aliphatic diene of 4 to 8 carbon atoms;

an alicyclic diene, an alkylene diamine or a tetramine of 2 to 4 carbon atoms in the alkylene portion thereof;

or triethanol or diethanol alkylamine of 1 to 4 carbon atoms in the alkyl group.

17. As an article of manufacture a nonconductive substrate having a circuit pattern thereon defined by an electroless metal deposit and as catalyst for said electroless deposit a thermal decomposition product of the complex defined in claim 9.

18. The article of manufacture as defined in claim 17 with an electrolytic overplate on said catalyst and electroless deposit.

19. The article of manufacture as defined in claim 17 and wherein the complex is trimethyl phosphite palladium dichloride.

20. As an article of manufacture, a polyimide film having a circuit pattern thereon defined by an electroless metal deposit and as catalyst for said electroless deposit a thermal decomposition product of a complex defined in claim 9.