US3615735A
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Electroless copper plating
Assignee: Shipley Co Inc
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Filing: 1968-08-13
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Granted: 1971-10-26
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Expires: 1988-08-13
Abstract
Abstract An electroless copper-plating solution comprising a source of cupric ions, hydroxyl radicals, formaldehyde or a formaldehyde precursor preferably paraformaldehyde and a complexing agent for copper; said solution characterized by the addition of a member selected from the group consisting of a formaldehyde addition agent, a solution soluble salt of a Group VIII metal of the Periodic Chart of the elements, preferably a combination thereof and most preferably, the two in combination with an organic silicon compound. The copper plate deposited from the preferred solution is alloyed with the Group VIII metal cation and is distinguishable from prior art electroless copper deposits by substantially improved bending or tensile properties and a smoother, more highly reflecting surface appearance. The electroless copper-plating solution is capable of providing a rapid rate of copper deposition dependent upon the selection of the complexing agent and the stability of its chelate with copper without sacrifice in tensile or bending properties of the copper deposit.
Inventors
- 👤 Charles R Shipley Jr
- 👤 Lucia Shipley
- 👤 Michael Gulla
- 👤 Oleh B Dutkewych
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-28 16:32
CPC Classifications
C; C23; C23C; C23C18/00; C23C18/16; C23C18/31; C23C18/38; C23C18/40; C23C18/405
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
146 words
In an electroless copper-plating solution comprising a source of cupric ions, hydroxyl radicals, formaldehyde and sufficient complexing agent to render said cupric ions soluble in alkaline solution, the improvement comprising an additive in the solution of a combination of (a) an organic silicon compound selected from the group of silanes and polysiloxanes in an amount of from 5 to 250 parts of silicon in solution per million parts of solution, (b) a formaldehyde addition agent selected from the group of alkali metal sulfites, bisulfites and phosphites in an amount of from 0.1 to 1 times the moles of formaldehyde in solution and (c) a solution-soluble salt of a member selected from the group of iron, nickel and platinum salts in an amount of from 5 to 2,500 parts per million parts of solution, said solution soluble salt having an anionic portion noninterfering with the plating solution.
Claim 2
Dependent Claim
18 words
The copper-plating solution of claim 2, having as additives an organic silicon compound and a formaldehyde addition agent.
Claim 3
Dependent Claim
30 words
The copper-plating solution of claim 2, having as additives an organic silicon compound and a solUtion soluble salt of a Group VIII metal of the Periodic Chart of the elements.
Claim 4
Dependent Claim
34 words
The copper-plating solution of claim 2, having as additives an organic silicon compound, a formaldehyde addition agent and a solution soluble salt of a Group VIII metal of the Periodic Chart of the elements.
Claim 5
Dependent Claim
68 words
The copper-plating solution of claim 5 having the following formation: copper salt 0.02 to 0.12 moles formaldehyde 0.1 to 1 moles complexing agent 1 to 3 times the moles of cupric ion free hydroxide 0.1 to 0.8 moles silicon compound 5 to 250 p.p.m. formaldehyde addition agent 0.1 to 1 times the moles formaldehyde Group VIII metal salt 30 to 1,000 p.p.m. water to 1 liter of solution
Claim 6
Dependent Claim
21 words
The copper solution of claim 5 where the organic silicon compound is selected from the group consisting of silanes and polysiloxanes.
Claim 7
Dependent Claim
14 words
The copper solution of claim 7, where the organic silicon compound is a polysiloxane.
Claim 8
Dependent Claim
30 words
The copper solution of claim 7, where the silicon compound is added to the copper solution by dissolution in a solvent and addition of the solution to the copper solution.
Claim 9
Dependent Claim
32 words
The copper solution of claim 5, where at least a portion of the complexing agent is mixture of complexing agents with one member of the mixture comprising a hydroxyalkyl substituted teritary amine.
Claim 10
Dependent Claim
34 words
The copper solution of claim 10 where the complexing agent is in combination with a member selected from the group of cellulose ethers, hydroxyalkyl starch, polyvinyl alcohol, polyvinyl pyrrolidone, peptones, gelatin, polyamides and polyacrylamides.
Claim 11
Dependent Claim
150 words
In an aqueous electroless copper-plating solution comprising a source of cupric ions, hydroxyl radicals formaldehyde and sufficient complexing agent to render said cupric ions soluble in alkaline solution, the improvement comprising an additive in the solution of a small but effective amount of an organic silicon compound in an amount of from 1 part silicon in solution per million parts of solution to that amount that restricts deposition of copper from solution and at least one member selected from the group consisting of a formaldehyde addition agent selected from the group consisting of alkali metal sulfites, bisulfites and phosphites in an amount of from 0.1 moles times the moles of formaldehyde to that amount that restricts copper deposition and a solution soluble salt of a Group VIII metal selected from the group of iron, nickel and platinum in an amount from 5 to 2,500 parts per million parts of solution.
Claim 12
Dependent Claim
27 words
The copper-plating solution of claim 12, having as additive the organic silicon compound and a combination of the formaldehyde addition agent and the Group VIII metal salt.
Claim 13
Dependent Claim
69 words
The copper solution of claim 13 having the following formulation: copper salt 0.02 to 0.12 moles formaldehyde 0.1 to 1 moles complexing agent 1 to 3 times the moles of cupric ion free hydroxide 0.1 to 0.8 moles silicon compound 5 to 250 p.p.m. formaldehyde addition agent 0.1 to 1 times the moles of formaldehyde Group VIII metal salt 30 to 1,000 p.p.m. water to 1 liter of solution
Claim 14
Dependent Claim
23 words
The copper solution of claim 14, where the Group VIII metal salt is selected from the group consisting of NiSO4, Fe2(SO4)3 and H2PtCl6.
Claim 15
Dependent Claim
23 words
The copper solution of claim 14, where the formaldehyde addition agent is selected from the group consisting of Na2SO3, NaHSO3 and Na2 HPO3.5H20.
Claim 16
Dependent Claim
16 words
The copper solution of claim 14 where the organic silicon compound is a dimethylpolysiloxane-polyalkylene oxide copolymer.
Claim 17
Dependent Claim
119 words
In an electroless copper-plating solution comprising a source of cupric ions, hydroxyl radicals, formaldehyde and sufficient complexing agent to render said cupric ions soluble in alkaline solution, the improvement comprising an additive in the solution of a combination of at least two members of the group consisting of an organic silicon compound, a formaldehyde addition agent and a Group VIII metal salt of the Periodic Chart of the elements, said organic silicon compound and said Group VIII metal salt being present in the solution in minor amount sufficient to improve ductility of a copper deposit and said formaldehyde addition agent being present in an amount of from 0.1 moles per mole of formaldehyde to that amount that restricts deposition.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1974-10-25 | 1975-04-26 | 1975-10-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1978-10-25 | 1979-04-26 | 1979-10-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1982-10-25 | 1983-04-26 | 1983-10-26 | $7700.00 | Window Closed / Lapsed |