US4167601A — Method of depositing a stress-free electroless co…

Claim 1

Independent Claim 112 words

A method of depositing a stress-free copper deposit on a surface which comprises contacting a catalyzed surface with a solution comprising: (a) a source of cupric ions; (b) a reducing agent for said cupric ions; (c) a complexing agent for the solution selected from the group consisting of (1) an ethyleneamine acetic acid compound, (2) a salt of (1), and (3) a mixture of at least two of the foregoing complexing agents; (d) a stabilizer for the solution comprising a mercury compound; and (e) an accelerator for the solution comprising a water-soluble compound containing a cyanide radical complexed with a metal selected from Group VIII of the Periodic Table of the Elements.

Claim 2

Independent Claim 112 words

A method of depositing a stress-free copper deposit on a surface which comprises contacting a catalyzed surface with a solution comprising: (a) a source of cupric ions; (b) a reducing agent for said cupric ions; (c) a complexing agent for the solution selected from the group consisting of (1) an ethyleneamine acetic acid compound, (2) a salt of (1), and (3) a mixture of at least two of the foregoing complexing agents; (d) a stabilizer for the solution comprising a mercury compound; and (e) an accelerator for the solution comprising a water-soluble compound containing a cyanide radical complexed with a metal selected from Group VIII of the Periodic Table of the Elements.

Claim 3

Dependent Claim 38 words

The method as defined in claim 1 wherein said ethyleneamine acetic acid compound is selected from the group consisting of (a) ethylenediaminetetraacetic acid, (b) 2-hydroxyethyl ethylenediaminetriaacetic acid, (c) diethylenetriaminepentaacetic acid and (d) a salt of any of (a)-(c).

Claim 4

Dependent Claim 27 words

The method as defined in claim 1 wherein said accelerator compound contains a radical selected from the group consisting of hexacyanoferrate (II), hexacyannoferrate (III), and mixtures thereof.

Claim 5

Dependent Claim 41 words

The method as defined in claim 1 wherein said accelerator is present in an amount ranging from about 1.5×10 -5 to about 1.2×10 -1 moles per liter of the solution, calculated as the metal with which the cyanide radical is complexed.

Claim 6

Dependent Claim 23 words

The method as defined in claim 1 wherein said accelerator comprises a metal selected from the group consisting of iron, iridium and rhenium.

Claim 7

Dependent Claim 13 words

The method as defined in claim 1 wherein said reducing agent comprises formaldehyde.

Claim 8

Dependent Claim 34 words

The method as defined in claim 2 wherein said accelerator compound is in the form of a salt of a member selected from the group consisting of alkali metal, alkaline earth metal and ammonium.

Claim 9

Dependent Claim 130 words

The method as defined in claim 1 wherein said mercury compound is one selected from the group consisting of (a 1 ) a mercury compound capable of providing a source of mercury ions in the solution; (b 1 ) a covalent mercury compound corresponding to the formula R--Hg--R', where R is a covalenting bonded organic radical selected from the group of alkyl, cycloalkyl, aryl, alkaryl, aralalkyl, alkoxy, aryloxy, and heterocyclic radicals and R' is the same as R or a polar group selected from the groups of --NO 2 , --SO 2 OH and alkali metal salts thereof, --COOH and alkali metal salts thereof, --NH 2 , --CN 1 and halide; (c 1 ) phenyl mercuric acetate; and (d 1 ) a mixture comprising at least two of the foregoing.

Claim 10

Dependent Claim 18 words

The method as defined in claim 8 wherein in (a 1 ) said R' is a polar group.

Claim 11

Dependent Claim 35 words

The method as defined in claim 8 wherein said compound in (b 1 ) or (c 1 ) is present in an amount ranging from 1 to 100 parts per million parts of the solution.

Claim 12

Dependent Claim 36 words

The method as defined in claim 8 wherein said compound in (a 1 ) is present in an amount ranging from at least one part per million parts of the solution to saturation of the solution.

Claim 13

Dependent Claim 23 words

The method as defined in claim 1 wherein said stabilizer is selected from the group consisting of mercuric chloride and phenyl mercuric acetate.

Claim 14

Dependent Claim 29 words

The method as defined in claim 12, wherein: said reducing agent comprises formaldehyde, said complexing agent comprises the tetrasodium salt of ethylenediaminetetraacetic acid, and said accelerator comprises potassium ferrocyanide.

Claim 15

Independent Claim 101 words

A method of rendering an electroless copper deposition solution capable of having deposited therefrom a stress-free copper deposit which comprises combining in the solution: (a) a complexing agent for the solution selected from the group consisting of (1) an ethyleneamine acetic acid, (2) a salt of (1), and (3) a mixture of at least two of the foregoing complexing agents; (b) a stabilizer for the solution comprising a mercury compound; and (c) an accelerator for the solution comprising a water-soluble compound containing a cyanide radical complexed with a metal selected from the Group VIII of the Periodic Table of the Elements.

Claim 16

Independent Claim 101 words

A method of rendering an electroless copper deposition solution capable of having deposited therefrom a stress-free copper deposit which comprises combining in the solution: (a) a complexing agent for the solution selected from the group consisting of (1) an ethyleneamine acetic acid, (2) a salt of (1), and (3) a mixture of at least two of the foregoing complexing agents; (b) a stabilizer for the solution comprising a mercury compound; and (c) an accelerator for the solution comprising a water-soluble compound containing a cyanide radical complexed with a metal selected from the Group VIII of the Periodic Table of the Elements.

Claim 17

Dependent Claim 38 words

The method as defined in claim 14 wherein said ethyleneamine acetic acid is a member of the group consisting of (a) ethylenediaminetetraacetic acid, (b) 2-hydroxyethyl ethylenediaminetriaacetic acid, (c) diethylenetriaminepentaacetic acid and (d) a salt of any of (a)-(c).

Claim 18

Dependent Claim 150 words

The method as defined in claim 14 wherein: said mercury compound is one selected from the group consisting of (a 1 ) a first mercury compound capable of providing a source of mercry ions in the solution; (b 1 ) a covalent mercury compound corresponding to the formula R--Hg--R', where R is a covalently bonded organic radical selected from the group of alkyl, cycloalkyl, aryl, alkaryl, aralalkyl, alkoxy, aryloxy, and heterocyclic radicals and R' is the same as R or a polar group selected from the groups of --NO 2 , --SO 2 OH and alkali metal salts thereof, --COOH and alkali metal salts thereof, --NH 2 , --CN and halide; (c 1 ) phenyl mercuric acetate; and (d 1 ) a mixture comprising at least two of the foregoing; and said accelerator compound contains a radical selected from the group consisting of hexacyanoferrate (II), hexacyannoferrate (III), and mixtures thereof.

Claim 19

Dependent Claim 39 words

The method as defined in claim 14 wherein: said complexing agent comprises a salt of ethylenediaminetetraacetic acid, said stabilizer is selected from the group consisting of mercuric chloride and phenyl mercuric acetate, and said accelerator compound comprises potassium ferrocyanide.

Claim 20

Dependent Claim 104 words

An aqueous electroless plating solution capable of depositing therefrom an essentially stress free copper deposit comprising: (a) a source of cupric ions; (b) a reducing agent for said cupric ions; (c) a complexing agent for the solution selected from the group consisting of (1) an ethyleneamine acetic acid, (2) a salt of (1), and (3) a mixture of at least two of the foregoing complexing agents; (d) stabilizer for the solution comprising a mercury compound; and (e) an accelerator for the solution comprising a water-soluble compound containing a cyanide radical complexed with a metal selected from Group VIII of the Periodic Table of Elements.

Claim 21

Dependent Claim 104 words

An aqueous electroless plating solution capable of depositing therefrom an essentially stress free copper deposit comprising: (a) a source of cupric ions; (b) a reducing agent for said cupric ions; (c) a complexing agent for the solution selected from the group consisting of (1) an ethyleneamine acetic acid, (2) a salt of (1), and (3) a mixture of at least two of the foregoing complexing agents; (d) stabilizer for the solution comprising a mercury compound; and (e) an accelerator for the solution comprising a water-soluble compound containing a cyanide radical complexed with a metal selected from Group VIII of the Periodic Table of Elements.

Claim 22

Dependent Claim 38 words

The method as defined in claim 18 wherein said ethyleneamine acetic acid is a member of the group consisting of (a) ethylenediaminetetraacetic acid, (b) 2-hydroxyethyl ethylenediaminetriaacetic acid, (c) diethylenetriaminepentaacetic acid and (d) a salt of any of (a)-(c).

Claim 23

Dependent Claim 27 words

The solution as defined in claim 18 wherein the accelerator compound contains a radical selected from the group consisting of hexacyanoferrate (II), hexacyannoferrate (III), and mixtures thereof.

Claim 24

Dependent Claim 41 words

The solution as defined in claim 18 wherein said accelerator is present in an amount ranging from about 1.5×10 -5 to about 1.2×10 -1 moles per liter of the solution, calculated as the metal with which the cyanide radical is complexed.

Claim 25

Dependent Claim 21 words

The solution as defined in claim 18 wherein the metal is selected from the group consisting of iron, iridium and rhenium.

Claim 26

Dependent Claim 13 words

The solution as defined in claim 18 wherein said reducing agent comprises formaldehyde.

Claim 27

Dependent Claim 34 words

The solution as defined in claim 20 wherein said accelerator compound is in the form of a salt of a member selected from the group consisting of alkali metal, alkaline earth metal and ammonium.

Claim 28

Dependent Claim 128 words

The solution as defined in claim 18 wherein said mercury compound is one selected from the group consisting of (a 1 ) a covalent mercury compound corresponding to the formula R--Hg--R', where R is a covalently bonded organic radical selected from the group of alkyl, cycloalkyl, aryl, alkaryl, aralalkyl, alkoxy, aryloxy, and heterocyclic radicals and R' is the same as R or a polar group selected from the groups of --NO 2 , --SO 2 OH and alkali metal salts thereof, --COOH and alkali metal salts thereof, --NH 2 , --CN and halide; (b 1 ) phenyl mercuric acetate; (c 1 ) a mercury compound capable of providing mercury ions in the solution; and (d 1 ) a mixture of at least two of the foregoing mercury compounds.

Claim 29

Dependent Claim 18 words

The solution as defined in claim 25 wherein in (a 1 ) said R' is a polar group.

Claim 30

Dependent Claim 35 words

The solution as defined in claim 25 wherein said compound in (a 1 ) or (b 1 ) is present in an amount ranging from 1 to 100 parts per million parts of the solution.

Claim 31

Dependent Claim 36 words

The solution as defined in claim 25 wherein said compound in (c 1 ) is present in an amount ranging from at least one part per million parts of the solution to saturation of the solution.

Claim 32

Dependent Claim 46 words

The solution as defined in claim 19, wherein: said reducing agent comprises formaldehyde; said complexing agent comprises a salt of ethylenediaminetetraacetic acid; said stabilizer is selected from the group consisting of mercuric chloride, phenyl mercuric acetate and a mixture thereof; and said accelerator comprises potassium ferrocyanide.

Claim 33

Dependent Claim 20 words

An article of manufacture comprising a substrate having an essentially stress-free copper coat deposited from the solution of claim 19.

Claim 34

Dependent Claim 20 words

An article of manufacture comprising a substrate having an essentially stress-free copper coat deposited from the solution of claim 29.

Claim 35

Dependent Claim 115 words

An article of manufacture comprising a substrate and a stress-free copper deposit on at least one surface thereof, deposited from an electroless copper plating solution comprising: (a) a source of cupric ions; (b) a reducing agent for said cupric ions; (c) a complexing agent for the solution selected from the group consisting of (1) an ethyleneamine acetic acid, (2) a salt of (1), and (3) a mixture of at least two of the foregoing complexing agents; (d) a stabilizer for the solution comprising a mercury compound; and (e) an accelerator for the solution comprising a water-soluble compound containing a cyanide radical complexed with a metal selected from Group VIII of the Periodic Table of Elements.

Claim 36

Dependent Claim 115 words

An article of manufacture comprising a substrate and a stress-free copper deposit on at least one surface thereof, deposited from an electroless copper plating solution comprising: (a) a source of cupric ions; (b) a reducing agent for said cupric ions; (c) a complexing agent for the solution selected from the group consisting of (1) an ethyleneamine acetic acid, (2) a salt of (1), and (3) a mixture of at least two of the foregoing complexing agents; (d) a stabilizer for the solution comprising a mercury compound; and (e) an accelerator for the solution comprising a water-soluble compound containing a cyanide radical complexed with a metal selected from Group VIII of the Periodic Table of Elements.

Claim 37

Dependent Claim 41 words

The article as defined in claim 32 wherein said ethyleneamine acetic acid is a member of the group consisting of (a) ethylenediaminetetraacetic acid, (b) 2-hydroxyethyl ethylenediaminetriaacetic acid, (c) cyclohexendiaminetetraacetic acid, (d) diethylenetriaminepentaacetic acid and (e) a salt of any of (a)-(d).

Claim 38

Dependent Claim 27 words

The article as defined in claim 32 wherein the accelerator compound contains a radical selected from the group consisting of hexacyanoferrate (II), hexacyannoferrate (III), and mixtures thereof.

Claim 39

Dependent Claim 41 words

The article as defined in claim 32 wherein said accelerator is present in an amount ranging from about 1.5×10 -5 to about 1.2×10 -1 moles per liter of the solution, calculated as the metal with which the cyanide radical is complexed.

Claim 40

Dependent Claim 21 words

The article as defined in claim 32 wherein the metal is selected from the group consisting of iron, iridium and rhenium.

Claim 41

Dependent Claim 13 words

The article as defined in claim 32 wherein said reducing agent comprises formaldehyde.

Claim 42

Dependent Claim 34 words

The article as defined in claim 34 wherein the accelerator compound is in the form of a salt of a member selected from the group consisting of alkali metal, alkaline earth metal and ammonium.

Claim 43

Dependent Claim 124 words

The article as defined in claim 32 wherein said mercury compound is one selected from the group consisting of (a 1 ) a covalent mercury compound corresponding to the formula R--Hg--R', where R is a covalently bonded organic radical selected from the group of alkyl, cycloalkyl, aryl, alkaryl, aralalkyl, alkoxy, aryloxy, and heterocyclic radicals and R' is the same as R or a polar group selected from the groups of --NO 2 , --SO 2 OH and alkali metal salts thereof, --COOH and alkali metal salts thereof, --NH 2 , --CN and halide; (b 1 ) phenyl mercuric acetate; (c 1 ) a mercury compound capable of yielding mercury ions in the solution; and (d 1 ) a mixture of any of the foregoing.

Claim 44

Dependent Claim 18 words

The article as defined in claim 39 wherein in (a 1 ) said R' is a polar group.

Claim 45

Dependent Claim 35 words

The article as defined in claim 39 wherein said compound in (a 1 ) or (b 1 ) is present in an amount ranging from 1 to 100 parts per million parts of the solution.

Claim 46

Dependent Claim 36 words

The article as defined in claim 39 wherein said compound in (c 1 ) is present in an amount ranging from at least one part per million parts of the solution to saturation of the solution.

Claim 47

Dependent Claim 46 words

The article as defined in claim 32, wherein: said reducing agent comprises formaldehyde; said complexing agent comprises a salt of ethylenediaminetetraacetic acid; said stabilizer is selected from the group consisting of mercuric chloride, phenyl mercuric acetate and a mixture thereof; and said accelerator comprises potassium ferrocyanide.

Claim 48

Dependent Claim 19 words

The article as defined in claim 32 in the form of a printed circuit board having ductile copper conductors.

Claim 49

Dependent Claim 11 words

The printed circuit board of claim 44 having copper plated through-holes.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1982-09-10	1983-03-12	1983-09-11	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1986-09-10	1987-03-12	1987-09-11	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1990-09-10	1991-03-12	1991-09-11	$7700.00	Window Closed / Lapsed

Method of depositing a stress-free electroless copper deposit

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