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US4554182A Expired / Lapsed US ⏱️ 0.0 years remaining

Method for conditioning a surface of a dielectric substrate for electroless plating

Assignee: International Business Machines Corp
•
Filing: 1985-01-31
•
Granted: 1985-11-19
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Expires: 2005-01-31
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Abstract

Abstract Method for electroless plating metals, such as copper, onto non-conductive substrate surfaces. The method comprises bringing the surfaces into contact with an aqueous composition containing H 2 SO 4 and a multifunctional cationic copolymer containing at least two available cationic moieties and then activating the surfaces by treating them with a colloidal solution containing palladium chloride, stannous chloride and HCl. The inventive method is particularly useful in processes for producing metal circuits on substrates of glass, thermoplastics and thermosetting resins, such as epoxy cards and boards. The method is also applied in reworking substrates having already undergone copper plating and having been rejected due to failures.

Inventors

  • 👤 James R. Bupp
  • 👤 Gary K. Lemon
  • 👤 Voya Markovich
  • 👤 Carlos J. Sambucetti
  • 👤 Stephen L. Tisdale
  • 👤 Donna J. Trevitt

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-23 16:38
CPC Classifications
H; H05; H05K; H05K3/00; H05K3/38; H05K3/381; C; C23; C23C; C23C18/00; C23C18/16; C23C18/18; C23C18/20; C23C18/28

Claims Analysis

Total Claims: 49
Claim 1
Independent Claim 91 words
Method for conditioning at least one surface of a dielectric substrate for eliminating resist blistering from subsequently applied photoresist and for electrolessly plating of a conductive metal thereon comprising: bringing said at least one surface into contact with a composition containing H 2 SO 4 and a multifunctional cationic polymer containing at least two available cationic moieites and wherein said composition has a pH value of between about 0 and about 3, and then activating the surface by treating it with a colloidal solution containing palladium chloride, stannous chloride and HCl.
Claim 2
Dependent Claim 91 words
Method for conditioning at least one surface of a dielectric substrate for eliminating resist blistering from subsequently applied photoresist and for electrolessly plating of a conductive metal thereon comprising: bringing said at least one surface into contact with a composition containing H 2 SO 4 and a multifunctional cationic polymer containing at least two available cationic moieites and wherein said composition has a pH value of between about 0 and about 3, and then activating the surface by treating it with a colloidal solution containing palladium chloride, stannous chloride and HCl.
Claim 3
Dependent Claim 37 words
Method according to claim 1 wherein a polymer of polyacrylamide forming the inert backbone and functionally active tetra alkyl ammonium compounds in a H 2 SO 4 solution is used for contacting said at least one surface.
Claim 4
Dependent Claim 32 words
Method according to claim 2 wherein an about 0.05 to about 0.5 weight percent solution of the polymer in H 2 SO 4 is used for contacting said at least one surface.
Claim 5
Dependent Claim 30 words
Method according to claim 2 wherein a polymer of polyacrylamide and betamethacryloxyethyltrimethylammonium methyl sulphate in an H 2 SO 4 solution is used for contacting said at least one surface.
Claim 6
Dependent Claim 131 words
Method according to claim 1 wherein the surface brought into contact with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.25 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 7
Dependent Claim 131 words
Method according to claim 2 wherein the surface brought into contacted with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.25 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 8
Dependent Claim 131 words
Method according to claim 3 wherein the surface brought into contact with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.25 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 9
Dependent Claim 131 words
Method according to claim 4 wherein the surface brought into contact with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.6 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 10
Dependent Claim 88 words
Method for conditioning at least one surface of a dielectric substrate for eliminating resist blistering from subsequently applied photoresist and for electroless plating with copper thereon comprising: bringing into contact said at least one surface with a composition containing H 2 SO 4 and a multifunctional cationic polymer containing at least two available cationic moieties wherein said composition has a pH value of between about 0 and about 3, and then activating the surface by treating it with a colloidal solution containing palladium chloride, stannous chloride and HCl.
Claim 11
Dependent Claim 88 words
Method for conditioning at least one surface of a dielectric substrate for eliminating resist blistering from subsequently applied photoresist and for electroless plating with copper thereon comprising: bringing into contact said at least one surface with a composition containing H 2 SO 4 and a multifunctional cationic polymer containing at least two available cationic moieties wherein said composition has a pH value of between about 0 and about 3, and then activating the surface by treating it with a colloidal solution containing palladium chloride, stannous chloride and HCl.
Claim 12
Dependent Claim 37 words
Method according to claim 9 wherein a polymer of polyacrylamide forming the inert backbone and functionally active tetra alkyl ammonium compounds in a H 2 SO 4 solution is used for contacting said at least one surface.
Claim 13
Dependent Claim 32 words
Method according to claim 10 wherein an about 0.05 to about 0.5 weight percent solution of the polymer in H 2 SO 4 is used for contacting said at least one surface.
Claim 14
Dependent Claim 30 words
Method according to claim 10 wherein a polymer of polyacrylamide and betamethacryloxyethyltrimethylammonium methyl sulphate in an H 2 SO 4 solution is used for contacting said at least one surface.
Claim 15
Dependent Claim 131 words
Method according to claim 9 wherein the surface brought into contact with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.6 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 100-140 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 16
Dependent Claim 131 words
Method according to claim 10 wherein the surface brought into contact with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.25 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 17
Dependent Claim 131 words
Method according to claim 11 wherein the surface brought into contact with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.25 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 18
Dependent Claim 131 words
Method according to claim 12 wherein the surface brought into contact with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.6 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 19
Dependent Claim 183 words
Method according to claim 9 wherein prior to conditioning said at least one surface, a copper plate is laminated to said at least one surface and subsequently removed by etching and wherein after the activation of said at least one surface said at least one activated surface is rinsed with deionized water, brought into contact with an aqueous solution of HCl, rinsed again and dried at elevated temperatures, a photoresist layer is applied to said at least one dried surface exposed to selective radiation and developed and plating said at least one selectively masked surface by contacting it for a period of from about 15 minutes to about 30 minutes with a first plating bath containing CuSO 4 , a complexing agent, HCHO and a surfactant with the oxygen content being less than 2 ppm and then for a period of from about 10 hours to about 20 hours with a second plating bath differing from the first plating bath by an increased oxygen content of about 3 ppm to about 4 ppm and an NaCN content of 10 ppm to 20 ppm.
Claim 20
Dependent Claim 183 words
Method according to claim 14 wherein prior to conditioning said at least one surface a copper plate is laminated to said at least one surface and subsequently removed by etching and wherein after the activation of said at least one surface said at least one activated surface is rinsed with deionized water, brought into contact with an aqueous solution of HCl, rinsed again and dried at elevated temperatures, a photoresist layer is applied to said at least one dried surface exposed to selective radiation and developed and plating said at least one selectively masked surface by contacting it for a period of from about 15 minutes to about 30 minutes with a first plating bath containing CuSO 4 , a complexing agent, HCHO and a surfactant with the oxygen content being less than 2 ppm and then for a period of from about 10 hours to about 20 hours with a second plating bath differing from the first plating bath by an increased oxygen content of about 3 ppm to about 4 ppm and an NaCN content of 10 ppm to 20 ppm.
Claim 21
Dependent Claim 101 words
Method for conditioning at least one surface of a dielectric substrate of a thermosetting or thermoplastic resin or of a glass for eliminating resist blistering from subsequently applied photoresist and for the electroless plating of conductive metal thereon comprising: bringing into contact said at least one surface with a composition containing H 2 SO 4 and a multifunctional cationic polymer containing at least two available cationic moieties and wherein said composition has a pH value of between about 0 and about 3, and then activating the surface by treating it with a colloidal solution containing palladium chloride, stannous chloride and HCl.
Claim 22
Dependent Claim 101 words
Method for conditioning at least one surface of a dielectric substrate of a thermosetting or thermoplastic resin or of a glass for eliminating resist blistering from subsequently applied photoresist and for the electroless plating of conductive metal thereon comprising: bringing into contact said at least one surface with a composition containing H 2 SO 4 and a multifunctional cationic polymer containing at least two available cationic moieties and wherein said composition has a pH value of between about 0 and about 3, and then activating the surface by treating it with a colloidal solution containing palladium chloride, stannous chloride and HCl.
Claim 23
Dependent Claim 37 words
Method according to claim 19 wherein a polymer of polyacrylamide forming the inert backbone and functionally active tetra alkyl ammonium compounds in a H 2 SO 4 solution is used for contacting said at least one surface.
Claim 24
Dependent Claim 32 words
Method according to claim 20 wherein an about 0.05 to about 0.5 weight percent solution of the polymer in H 2 SO 4 is used for contacting said at least one surface.
Claim 25
Dependent Claim 30 words
Method according to claim 20 wherein a polymer of polyacrylamide and betamethacryloxyethyltrimethylammonium methyl sulphate in an H 2 SO 4 solution is used for contacting said at least one surface.
Claim 26
Dependent Claim 131 words
Method according to claim 19 wherein the surface brought into contact with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.25 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 27
Dependent Claim 131 words
Method according to claim 20 wherein the surface brought into contact with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.25 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 28
Dependent Claim 131 words
Method according to claim 21 wherein the surface brought into contact with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.25 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 29
Dependent Claim 131 words
Method according to claim 22 wherein the surface brought into contact with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.25 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 30
Dependent Claim 21 words
Method according to claim 19 wherein the at least one surface of a dielectric is conditioned for electroless plating of copper.
Claim 31
Dependent Claim 37 words
Method according to claim 27, wherein a polymer of polyacrylamide forming the inert backbone and functionally active tetra alkyl ammonium compounds in a H 2 SO 4 solution is used for contacting said at least one surface.
Claim 32
Dependent Claim 32 words
Method according to claim 28 wherein an about 0.05 to about 0.5 weight percent solution of the polymer in H 2 SO 4 is used for contacting said at least one surface.
Claim 33
Dependent Claim 30 words
Method according to claim 28 wherein a polymer of polyacrylamide and betamethacryloxyethyltrimethylammonium methyl sulphate in an H 2 SO 4 solution is used for contacting said at least one surface.
Claim 34
Dependent Claim 131 words
Method according to claim 27 wherein the surface brought into contact with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.25 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 35
Dependent Claim 131 words
Method according to claim 28 wherein the surface brought into contact with the cationic copolymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.25 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 36
Dependent Claim 131 words
Method according to claim 29 wherein the surface brought into contact with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.25 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 37
Dependent Claim 131 words
Method according to claim 30 wherein the surface brought into contact with the cationic polymer is activated with a colloidal solution prepared from a mixture formed by mixing a solution of SnCl 2 .2H 2 O in 37% HCl and a solution of PdCl 2 in diluted HCl, boiling for two hours and adding a surfactant and containing per liter of solution about 600 grs of SnCl 2 .2H 2 O, about 10 grs of PdCl 2 , about 650 ml of 37% HCl and 0.7 gr of a surfactant, by diluting fixed amounts of said mixture with deionized water, the colloidal solution containing per liter 1.2-2.5 grs of PdCl 2 , 80-150 grs of SnCl 2 .2H 2 O, 85-160 ml of 37% HCl and 0.09-0.16 gr of the surfactant.
Claim 38
Dependent Claim 48 words
The method of claim 1 wherein an aqueous solution of about 0.01% to about 1% by weight of the copolymer in H 2 SO 4 with the solution have a pH value of between about 0 and about 2 is used for contacting said at least one surface.
Claim 39
Dependent Claim 14 words
The method of claim 1 wherein the pH of said composition is about 1.
Claim 40
Dependent Claim 26 words
The method of claim 35 wherein the H 2 SO 4 is present in said composition in amounts of about 2% to about 4% by weight.
Claim 41
Dependent Claim 26 words
The method of claim 1 wherein the H 2 SO 4 is present in said composition in amounts of about 2% to about 4% by weight.
Claim 42
Dependent Claim 48 words
The method of claim 11 wherein an aqueous solution of about 0.01% to about 1% by weight of the copolymer in H 2 SO 4 with the solution have a pH value of between about 0 and about 2 is used for contacting said at least one surface.
Claim 43
Dependent Claim 14 words
The method of claim 11 wherein the pH of said composition is about 1.
Claim 44
Dependent Claim 26 words
The method of claim 39 wherein the H 2 SO 4 is present in said composition in amounts of about 2% to about 4% by weight.
Claim 45
Dependent Claim 26 words
The method of claim 11 wherein the H 2 SO 4 is present in said composition in amounts of about 2% to about 4% by weight.
Claim 46
Dependent Claim 48 words
The method of claim 19 wherein an aqueous solution of about 0.01% to about 1% by weight of the copolymer in H 2 SO 4 with the solution have a pH value of between about 0 and about 2 is used for contacting said at least one surface.
Claim 47
Dependent Claim 14 words
The method of claim 19 wherein the pH of said composition is about 1.
Claim 48
Dependent Claim 26 words
The method of claim 43 wherein the H 2 SO 4 is present in said composition in amounts of about 2% to about 4% by weight.
Claim 49
Dependent Claim 26 words
The method of claim 19 wherein the H 2 SO 4 is present in said composition in amounts of about 2% to about 4% by weight.

References Cited (Backward Citations)

DE3137587A1 Cited
US4478883A Cited
US4448804A Cited

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