US3222195A - Stabilized electroless copper solution - Google Patents
Stabilized electroless copper solution Download PDFInfo
- Publication number
- US3222195A US3222195A US175372A US17537262A US3222195A US 3222195 A US3222195 A US 3222195A US 175372 A US175372 A US 175372A US 17537262 A US17537262 A US 17537262A US 3222195 A US3222195 A US 3222195A
- Authority
- US
- United States
- Prior art keywords
- solution
- electroless copper
- fehlings
- mercaptobenzothiazole
- formaldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 23
- 229910052802 copper Inorganic materials 0.000 title claims description 23
- 239000010949 copper Substances 0.000 title claims description 23
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 24
- 238000007747 plating Methods 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 230000000087 stabilizing effect Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 62
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 27
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 10
- 230000008021 deposition Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical class [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
Definitions
- This invention relates to electroless copper solutions and more particularly 'concerns such solutions having improved resistance to general and rapid decomposition.
- Electroless copper solutions in the main, are Fehlings solutions or variations thereof, having incorporated therein a reducing agent such as formaldehyde. Such solutions generally start decomposing within about 20 minutes after make-up and cannot ordinarily be used for deposition afterabout 3 hours.
- Electroless copper solutions reported in the literature comprise Fehlings solutionand formaldehyde with substantial quantities of complexing agents added thereto, such as sodium carbonate, Versene, andthe like.
- complexing agents such as sodium carbonate, Versene, andthe like.
- the stability of these solutions, and the rate at which deposits form therefrom leaves much to be desired.
- Another object of the invention is to provide such a solution as aforementioned which requires a very minor amount of an abundantly available compound.
- the electroless copper solution without 2-mercaptobenzo'thiazole coinprisesFehlings'solution and ml. of'36% formaldehyde for each liter of Fehlings solution.
- the Fehlings solution is diluted 1 to l with distilled water and 100 ml. of 36% formaldehyde added per liter of undiluted Fehlings solution.
- the 2-mercaptobenzothiazole may be added directly to the Fehlings solution or the Fehlings solution may be diluted and the Z-mercaptobenzothiazole added thereto. In any case, the Z-mercaptobenzothiazole will be added prior to the formaldehyde.
- Poor bath stability is defined as one in which the bath is substantially decomposed within about 3 hours; a fair bath stability being one which is relatively undecomposed within about 3 hours but almost completely decomposed within 24 hours; and a good bath stability showing little or no decomposition after about 24 hours.
- a poor deposit appearance is discontinuous or powdery whereas a good deposit appearance is coppery metallic. The appearance of the fair deposit lies therebetween.
- An electroless copper plating solution according to claim 3, said solution comprising an additional volume of water ranging from 1 to 3 times the volume of undiluted Fehlings solution.
- a process for improving stability of an electroless copper plating solution consisting essentially of Fehlings solution and a reducing agent, comprising adding a stablizing amount of Z-mercaptobenzothiazole to said electroless copper solution.
- a process for improving stability of an electroless copper plating solution consisting essentially of Fehlings solution and aqueous formaldehyde solution in the volume ratio of 10 to 1, respectively, comprising adding to said electroless copper solution 5 to 80 milligrams of 2-mercaptobenzothiazole per liter of undiluted Fehlings solution.
- a process according to claim 7 including the step of adding to said electroless copper solution an additional volume of water ranging from 1 to 3 times the volume of undiluted Fehlings 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)
Description
United States Patent Oflice 3,222,195 Patented Dec. 7, 1965 3,222,195 STABILIZED ELECTROLESS COPPER SOLUTION Fred Pearlstein, Philadelphia, Pa., assignor to the United States of America as represented by the Secretary of the Army 'No Drawing. Filed Feb. 23, 1962, Ser. No. 175,372 8 Claims. (Cl. 106-1) "(Granted under Title 35, US. Code (1952), sec. 266) The invention described herein may be manufactured and used by or for the Government for governmental purposes without the payment to me of any royalty thereon.
This invention relates to electroless copper solutions and more particularly 'concerns such solutions having improved resistance to general and rapid decomposition.
Electroless copper solutions, in the main, are Fehlings solutions or variations thereof, having incorporated therein a reducing agent such as formaldehyde. Such solutions generally start decomposing within about 20 minutes after make-up and cannot ordinarily be used for deposition afterabout 3 hours.
Electroless copper solutions reported in the literature, comprise Fehlings solutionand formaldehyde with substantial quantities of complexing agents added thereto, such as sodium carbonate, Versene, andthe like. The stability of these solutions, and the rate at which deposits form therefrom leaves much to be desired.
Accordingly, it is an object of this invention to provide a highly stable electroless copper solution.
Another object of the invention is to provide such a solution as aforementioned which requires a very minor amount of an abundantly available compound.
Other and further objects of the invention will be apparent to those skilled in the art upon study of this disclosure.
Briefly, I have found that minor additions of 2-mercaptobenzothiazole (MBT) to diluted Fehlings solution and formaldehyde produces a marked increase in the stability of the resultant electroless copper solution. More specifically, when 2-mercaptobenzothiazole is added in amounts ranging between about 0.0005 to 0.008% Weight/ volume of the original Fehlings solution (the expression percent weight/volume being defined as grams of solute/ 100 milliliters of solvent and hence 0.0005 to 0.008% weight/volume equals 5 to 80 milligrams/liter) and to which is added formaldehyde, the resultant solution permits good deposition therefrom at rates faster than any of the known proprietary electroless copper solutions and yet its stability is vastly improved.
In accordance with my invention, Fehlings solution, as specified by the Association of Official Agricultural Chemists, consists of 34.64 g./l. CuSO .5H O, 173 g./l. rochelle salts.4H O, 50 g./l. sodium hydroxide and the balance water. The 2-mercaptobenzothiazole is readily added to the Fehlings solution from a stock solution consisting of '10 g./l. Z-MBT dissolved in .2 N sodium hydroxide solution. 100 ml. of 36% formaldehyde (containing 12 /2% methanol as a preservative) will then be added to the 2- mercaptobenzothiazole-Fehlings solution for each liter of original Fehlings solution present. The results of deposition tests conducted at a solution temperature of 25 C. and with varying solutions are shown below in Table I. Each solution was allowed to stand for at least 1 hour before running the tests.
Table I [Electroless copper deposition] The weight per volume percentage of 2-mercaptobenzothiazole given in Table I above and Table II to follow is'bas ed on the undiluted Fehlings solution.
Distilled water and reagent grade chemicals werc used in preparing the solutions describedherein. ,The electroless copper solution without 2-mercaptobenzo'thiazole coinprisesFehlings'solution and ml. of'36% formaldehyde for each liter of Fehlings solution. At the 50% concentration without 2-mercaptobenzothiazole, the Fehlings solution is diluted 1 to l with distilled water and 100 ml. of 36% formaldehyde added per liter of undiluted Fehlings solution. The 2-mercaptobenzothiazole may be added directly to the Fehlings solution or the Fehlings solution may be diluted and the Z-mercaptobenzothiazole added thereto. In any case, the Z-mercaptobenzothiazole will be added prior to the formaldehyde.
Poor bath stability is defined as one in which the bath is substantially decomposed within about 3 hours; a fair bath stability being one which is relatively undecomposed within about 3 hours but almost completely decomposed within 24 hours; and a good bath stability showing little or no decomposition after about 24 hours.
A poor deposit appearance is discontinuous or powdery whereas a good deposit appearance is coppery metallic. The appearance of the fair deposit lies therebetween.
Deposition tests were performed on a 2-in. x 2-in. cleaned and sensitized Mylar sheet of 0.003 inch thickness.
It is apparent from the data presented in Table I that dilution, within the limits shown, improves bath stability but decreases deposition rates. To achieve a good workable compromise between deposition rates and stability, I prefer an electroless copper soltuion consisting of 40% Fehlings solution with 0.0032% weight/volume of 2- mercaptobenzothiazole which is based on the undiluted Fehlings solution. To this is added 100 ml. of the aforedescribed formaldehyde solution for each liter of the undiluted Fehlings solution present, the resultant solution being used between the range of about 20 to 30 C. In Table 11 below, comparison data are presented on my stabilized electroless copper solution and three widely used proprietary solutions. The tests were carried outwith a bath temperature of about 27 C. using the 40% solution aforedescribed.
1 Solution completely decomposed.
2 Poor, discontinuous deposit.
Brand X, Y and Z are modified Felilings solution-formaldehyde solutions.
It is apparent from the foregoing tables and description that I have provided an eleetroless copper solution which is more stable than each of the three well-known and widely used commercial solutions. The appearance of my deposit after my solution had been made up for 192 hours was still good and copper was deposited at the rate of about 14 milligrams in 15 minutes. Further, the 2-mercaptobenzothiazole is incorporated in the Fehlings solution in very minor amounts only and is abundantly available. The principal advantage of my inventive electroless copper solution however resides in its ability to be workable for at least several days thus obviating the necessity for many time consuming solution make-ups.
I claim:
1. In an electroless copper plating solution consisting essentially of Fehlings solution and a reducing agent, the combination therewith of a stabilizing amount of 2-mercaptobenzothiazole.
2. In an electroless copper plating solution consisting essentially of Fehlings solution and formaldehyde, the combination therewith of a stabilizing amount of Z-mercaptobenzothiazole.
3. In an electroless copper plating solution consisting essentially of Fehlings solution and aqueous formaldehyde solution in the volume ratio of 10 to 1, respectively, the combination therewith of a stabilizing compound consisting of about 5 to 80 milligrams of Z-mercaptobenzothiazole per liter of undiluted Fehlings solution.
4. An electroless copper plating solution according to claim 3, said solution comprising an additional volume of water ranging from 1 to 3 times the volume of undiluted Fehlings solution.
5. A process for improving stability of an electroless copper plating solution consisting essentially of Fehlings solution and a reducing agent, comprising adding a stablizing amount of Z-mercaptobenzothiazole to said electroless copper solution.
6. A process according to claim 5 wherein said reducing agent consists of formaldehyde.
7. A process for improving stability of an electroless copper plating solution consisting essentially of Fehlings solution and aqueous formaldehyde solution in the volume ratio of 10 to 1, respectively, comprising adding to said electroless copper solution 5 to 80 milligrams of 2-mercaptobenzothiazole per liter of undiluted Fehlings solution.
8. A process according to claim 7 including the step of adding to said electroless copper solution an additional volume of water ranging from 1 to 3 times the volume of undiluted Fehlings solution.
References Cited by the Examiner UNITED STATES PATENTS 2,429,970 10/1947 Wernlund 20446 2,663,684 12/1953 Pierce 20452 3,033,703 5/1962 Schneble 1061 ALEXANDER H. BRODMERKEL, Primary Examiner.
JOHN R. SPECK, Examiner.
Claims (1)
1. IN AN ELECTROLESS COPPER PLATING SOLUTION CONSISTING ESSENTIALLY OF FEHLING''S SOLUTION AND A REDUCING AGENT, THE COMBINATION THEREWITH OF A STABILIZING AMOUNT OF 2-MERCAPTOBENZOTHIAZOLE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US175372A US3222195A (en) | 1962-02-23 | 1962-02-23 | Stabilized electroless copper solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US175372A US3222195A (en) | 1962-02-23 | 1962-02-23 | Stabilized electroless copper solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3222195A true US3222195A (en) | 1965-12-07 |
Family
ID=22640001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US175372A Expired - Lifetime US3222195A (en) | 1962-02-23 | 1962-02-23 | Stabilized electroless copper solution |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3222195A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3361580A (en) * | 1963-06-18 | 1968-01-02 | Day Company | Electroless copper plating |
| US3392035A (en) * | 1963-09-02 | 1968-07-09 | Torigai Eiichi | Method and bath for chemically plating copper |
| US3436233A (en) * | 1964-05-27 | 1969-04-01 | Ibm | Method and composition for autocatalytically depositing copper |
| US3649350A (en) * | 1970-06-29 | 1972-03-14 | Gen Electric | Electroless copper plating |
| US3751288A (en) * | 1971-06-23 | 1973-08-07 | Dow Chemical Co | Solidifying a thin layer of metal on plastic film |
| JPS5565355A (en) * | 1978-09-13 | 1980-05-16 | Kollmorgen Tech Corp | Nonelectrolytic copper deposition having rapid plating velocity |
| US4301196A (en) * | 1978-09-13 | 1981-11-17 | Kollmorgen Technologies Corp. | Electroless copper deposition process having faster plating rates |
| EP3351657A1 (en) | 2017-01-23 | 2018-07-25 | Rohm and Haas Electronic Materials LLC | Electroless copper plating compositions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2429970A (en) * | 1944-01-11 | 1947-10-28 | Du Pont | Silver plating |
| US2663684A (en) * | 1952-06-02 | 1953-12-22 | Houdaille Hershey Corp | Method of and composition for plating copper |
| US3033703A (en) * | 1958-12-08 | 1962-05-08 | Photocircuits Corp | Electroless plating of copper |
-
1962
- 1962-02-23 US US175372A patent/US3222195A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2429970A (en) * | 1944-01-11 | 1947-10-28 | Du Pont | Silver plating |
| US2663684A (en) * | 1952-06-02 | 1953-12-22 | Houdaille Hershey Corp | Method of and composition for plating copper |
| US3033703A (en) * | 1958-12-08 | 1962-05-08 | Photocircuits Corp | Electroless plating of copper |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3361580A (en) * | 1963-06-18 | 1968-01-02 | Day Company | Electroless copper plating |
| US3392035A (en) * | 1963-09-02 | 1968-07-09 | Torigai Eiichi | Method and bath for chemically plating copper |
| US3436233A (en) * | 1964-05-27 | 1969-04-01 | Ibm | Method and composition for autocatalytically depositing copper |
| US3649350A (en) * | 1970-06-29 | 1972-03-14 | Gen Electric | Electroless copper plating |
| US3751288A (en) * | 1971-06-23 | 1973-08-07 | Dow Chemical Co | Solidifying a thin layer of metal on plastic film |
| JPS5565355A (en) * | 1978-09-13 | 1980-05-16 | Kollmorgen Tech Corp | Nonelectrolytic copper deposition having rapid plating velocity |
| US4301196A (en) * | 1978-09-13 | 1981-11-17 | Kollmorgen Technologies Corp. | Electroless copper deposition process having faster plating rates |
| EP3351657A1 (en) | 2017-01-23 | 2018-07-25 | Rohm and Haas Electronic Materials LLC | Electroless copper plating compositions |
| US10060034B2 (en) | 2017-01-23 | 2018-08-28 | Rohm And Haas Electronic Materials Llc | Electroless copper plating compositions |
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