US3453123A - Electroless copper plating solutions - Google Patents
Electroless copper plating solutions Download PDFInfo
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- US3453123A US3453123A US598962A US3453123DA US3453123A US 3453123 A US3453123 A US 3453123A US 598962 A US598962 A US 598962A US 3453123D A US3453123D A US 3453123DA US 3453123 A US3453123 A US 3453123A
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- US
- United States
- Prior art keywords
- solution
- electroless copper
- fehlings
- copper plating
- additive
- 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
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 21
- 229910052802 copper Inorganic materials 0.000 title description 19
- 239000010949 copper Substances 0.000 title description 19
- 238000007747 plating Methods 0.000 title description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 239000000654 additive Substances 0.000 description 14
- 230000000996 additive effect Effects 0.000 description 14
- 239000003638 chemical reducing agent Substances 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 238000000151 deposition Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000012990 dithiocarbamate Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 2
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- OBBCYCYCTJQCCK-UHFFFAOYSA-L copper;n,n-diethylcarbamodithioate Chemical compound [Cu+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S OBBCYCYCTJQCCK-UHFFFAOYSA-L 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229950004394 ditiocarb Drugs 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CTAGWAHHVKDYTF-UHFFFAOYSA-M potassium;n,n-dibutylcarbamodithioate Chemical compound [K+].CCCCN(C([S-])=S)CCCC CTAGWAHHVKDYTF-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 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
- the present invention is related to electroless plating solutions and, more particularly, it concerns electroless copper solutions which are particularly resistant to rapid decomposition.
- electroless copper solutions are either Fehlings solutions or modifications thereof. They, however, contain incorporated therein a reducing agent such as formaldehyde. It is known that the above-mentioned solutions begin to decompose Within about twenty minutes after make-up and, ordinarily, cannot be utilized for deposition purposes after about three hours.
- the main object of the present invention to provide a highly stable electroless copper solution, superior to those mentioned hereabove.
- the amount of the above compound added to sufiiciently stabilize the solution ranges from about 0.05 to milligrams of compound per liter of Fehlings solution, to which formaldehyde is to be added.
- the resultant solution has been found to allow highly satisfactory depositions at rates faster than any other tested known copper solutions and yet with a stability remarkably increased.
- a Fehlings solution was prepared as specified, which consisted of 34.64 g./l. of CuSO -5H O, 173 g./l. of Rochelle salt 4H O, 50 g./l. of NaOH, and the balance distilled water. Certain aliquots of solutions were mixed with 36% formaldehyde (containing 12.5% of methanol as a preservative) in quantity such as to give various solution concentrations. To other aliquots of Fehlings solution were added varying concentrations of selected compounds of the invention and, subsequently, varying quantities of the above-mentioned 36% formaldehyde. Comparative tests between a solution containing an additive of the invention and a solution free from such additive were conducted, with the following tabulated results:
- EXAMPLE 1 (1) Solution concentration without additive (percen 100 (2) Additive, mg./l. (sodium dlhexyl-dithio carbamate 0 20 (3) Solution temperature C.) 25 25 (4) Deposit weight (mg/0.25 hr.) 49 39 (5) Bath stability Poor Fair (8) Deposit appearance Poor Good (7) Deposition after 3 hours (mg/0.25 hr.) 29
- EXAMPLE 2 (1) Solution concentration without additive (percent) 100 100 (2) Additive, mg./l. (potassium dibutyl-dithio carbarnate) 0 0. 05 (3) Solution temperature C.) 25 25 (4) Deposit weight (mg/0.25 hr.) 49 35 (5) Bath stability Poor Poor (6) Deposit appearance Poor Fair (7) Deposition after 3 hours (mg/0.25 hr.) 0 24 EXAMPLE 3 (1) Solution concentration without additive (percen 50 50 (2) Additive, mg./1. (copper diethyl-dithio carbainate 0 1 (3) Solution temperature C.) 25 25 (4) Deposit weight (mg/0.25 hr.). 36 31 (5) Bath stability Poor Good (6) Deposit appearance Poor Good (7) Deposition after 3 hours (mg/0.25 hr.) 26
- EXAMPLE 4 (1) Solution concentration without additive (percent) 50 50 (2) Additive, mg./l. (lithium dimethyldithio carbamate) 0 5 (3) Solution temperature 0.). 25 25 (4) Deposit weight (mg/0.25 hr. 36 3G (5) Bath stability Poor Poor (6) Deposit appearance Poor Fair (7) Deposition after 3 hours (mg/0.25 hr.) 28
- EXAMPLE 5 (1) Solution concentration without additive (percen 25 25 (2) Additive, mg./l. (sodium dunethyl-dithio carbamate 0 0. 25 (3) Solution temperature C.) 25 25 (4) Deposit weight (mg/0.25 hr. 23 5 (5) Bath stability Fair Good (6) Deposit appearance Good Good (7) Deposition after 24 hours (mg./ 0.25 hr.) 3
- EXAMPLE 6 (1) Solution concentration without additive (percent) 25 25 (2) Additive, mgJl. (sodium (liethyl-dithio carbamate) 0 4 (3) Solution temperature 0.). 25 25 (4) Deposit weight (mg/0.25 hr. 23 20 (5) Bath stability Fair Good (6) Deposit appearance Good Good (7) Deposition after 24 hours (mg/0.25 hr.) 0 15 With reference to the above examples, it should be understood that poor bath stability is one in which the bath is substantially decomposed within about 3 hours, a fair bath stability is one which is relatively undecomposed within 3 hours but almost completely decomposed in 24 hours; and a good bath stability shows little or no decomposition after 24 hours.
- a poor deposit appearance is a non-uniform or powdery deposit, while a good deposit appearance is very coppery metallic.
- An intermediate appearance is rated, obviously, as fair.
- the deposition tests were conducted on 2 square inch, cleaned and sensitized Mylar sheet of 3 mil thickness.
- the main advantage of the present invention is an electroless copper solution which is usable for at least several days, thus obviating the necessity for time-consuming make-ups.
- An electroless copper plating solution consisting essentially of Fehlings solution, a reducing agent, and a stabilizing amount of a compound having the empirical formula II R: S
- A is a sodium, potassium, lithium or copper atom
- X is nitrogen
- R and R are hydrogen or straight or branched chain radicals having from 1 to 6 carbon atoms.
- the electroless copper plating solution of claim 1 consisting essentially of Fehlings solution, a reducing agent, an additional volume of water from 1 to 3 times the volume of undiluted Fehlings solution, and from 0.05 to 20 mg./liter of undiluted Bathings solution of sodium dihexyl-dithio carbamate.
- the electroless copper plating solution of claim 1 consisting essentially of Fehlings solution, a reducing agent, an additional volume of water from 1 to 3 times the volume of undiluted Fehlings solution, and from 0.05 to 20 mg./liter of undiluted Bathings solution of potassium dibutyl-dithio carbamate.
- the electroless copper plating solution of claim 1 consisting essentially of Fehlings solution, a reducing agent, an additonial volume of water from 1 to 3 times the volume of undiluted Fehlings solution, and from 0.05 to 20 mg./liter of undiluted Bathings solution of copper diethyl-dithio carbamate.
- the electroless copper plating solution of claim 1 consisting essentially of Fehlings solution, a reducing agent, an additional volume of water from 1 to 3 times the volume of undiluted Fehlings solution and from 0.05 to 20 mg./liter of undiluted Bathings solution of lithium dimethyl-dithio carbamate.
- the electroless copper plating solution of claim 1 consisting essentially-of Fehlings solution, a reducing agent, anadditional volume of wat r from 1 to 3 times the volume of undiluted Fehlings so ution, and from 0.05 to 20 mg./liter of undiluted Bathings solution of sodium dimethyl-dithio carbamate.
- the electroless copper plating solution of claim 1 consisting essentially of Fehlings solution, a reducing agent, an additional volume of water from 1 to 3 times the volume of undiluted Fehlings solution, and from 0.05 to 20 mg./liter of undiluted'Fehlings solution of sodium diethyl-dithio carbamate.
- a process for improving the stability of an electroless copper plating solution consisting essentially of Fehlings solution and a reducing agent which comprises adding a stabilizing amount of a compound having the empirical formula References Cited UNITED STATES PATENTS 1/1968 Schneble et al. 1061 4/1968 Torigai et al. 106-1 JULIUS FROME, Primary Examiner. L. HAYES, Assistant Examiner.
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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 US. Cl. 106-1 Claims ABSTRACT OF THE DISCLOSURE Highly stable electroless copper solutions are obtained by incorporating thereto small quantities of a complexing agent having the empirical formula wherein A is a sodium, potassium, lithium or copper atom, R and R are hydrogen or straight or branched chain radicals having from 1 to 6 carbon atoms, and X is nitrogen.
The present invention is related to electroless plating solutions and, more particularly, it concerns electroless copper solutions which are particularly resistant to rapid decomposition.
Generally, electroless copper solutions are either Fehlings solutions or modifications thereof. They, however, contain incorporated therein a reducing agent such as formaldehyde. It is known that the above-mentioned solutions begin to decompose Within about twenty minutes after make-up and, ordinarily, cannot be utilized for deposition purposes after about three hours.
It is also known to add to these solutions various quantities, usually quite substantial, of complexing agents, such as, for example, Rochelle salts, Versene, and the like. However, the resulting stability of the solutions and the rapid rate at which deposit formation occurs leave much to be desired.
It is, therefore, the main object of the present invention to provide a highly stable electroless copper solution, superior to those mentioned hereabove.
It is a further object of this invention to provide a novel solution which requires only very small quantities of a complexing agent to achieve highly stable solutions.
Other objects and advantages of the invention will become apparent from the following detailed description thereof.
It has been found that minor additions of a compound having the empirical formula wherein X is nitrogen, A is a sodium, potassium, lithium, or copper atom, and R and R are hydrogen or straight and/or branch chained radicals having from 1 to 6 carbon atoms to diluted Fehlings solution and formaldehyde results in a clearly remarkable increase in the stability of the electroless copper solution.
The amount of the above compound added to sufiiciently stabilize the solution ranges from about 0.05 to milligrams of compound per liter of Fehlings solution, to which formaldehyde is to be added. The resultant solution has been found to allow highly satisfactory depositions at rates faster than any other tested known copper solutions and yet with a stability remarkably increased.
This invention will become even more apparent from the following examples.
ice
A Fehlings solution was prepared as specified, which consisted of 34.64 g./l. of CuSO -5H O, 173 g./l. of Rochelle salt 4H O, 50 g./l. of NaOH, and the balance distilled water. Certain aliquots of solutions were mixed with 36% formaldehyde (containing 12.5% of methanol as a preservative) in quantity such as to give various solution concentrations. To other aliquots of Fehlings solution were added varying concentrations of selected compounds of the invention and, subsequently, varying quantities of the above-mentioned 36% formaldehyde. Comparative tests between a solution containing an additive of the invention and a solution free from such additive were conducted, with the following tabulated results:
EXAMPLE 1 (1) Solution concentration without additive (percen 100 (2) Additive, mg./l. (sodium dlhexyl-dithio carbamate 0 20 (3) Solution temperature C.) 25 25 (4) Deposit weight (mg/0.25 hr.) 49 39 (5) Bath stability Poor Fair (8) Deposit appearance Poor Good (7) Deposition after 3 hours (mg/0.25 hr.) 29
EXAMPLE 2 (1) Solution concentration without additive (percent) 100 100 (2) Additive, mg./l. (potassium dibutyl-dithio carbarnate) 0 0. 05 (3) Solution temperature C.) 25 25 (4) Deposit weight (mg/0.25 hr.) 49 35 (5) Bath stability Poor Poor (6) Deposit appearance Poor Fair (7) Deposition after 3 hours (mg/0.25 hr.) 0 24 EXAMPLE 3 (1) Solution concentration without additive (percen 50 50 (2) Additive, mg./1. (copper diethyl-dithio carbainate 0 1 (3) Solution temperature C.) 25 25 (4) Deposit weight (mg/0.25 hr.). 36 31 (5) Bath stability Poor Good (6) Deposit appearance Poor Good (7) Deposition after 3 hours (mg/0.25 hr.) 26
EXAMPLE 4 (1) Solution concentration without additive (percent) 50 50 (2) Additive, mg./l. (lithium dimethyldithio carbamate) 0 5 (3) Solution temperature 0.). 25 25 (4) Deposit weight (mg/0.25 hr. 36 3G (5) Bath stability Poor Poor (6) Deposit appearance Poor Fair (7) Deposition after 3 hours (mg/0.25 hr.) 28
EXAMPLE 5 (1) Solution concentration without additive (percen 25 25 (2) Additive, mg./l. (sodium dunethyl-dithio carbamate 0 0. 25 (3) Solution temperature C.) 25 25 (4) Deposit weight (mg/0.25 hr. 23 5 (5) Bath stability Fair Good (6) Deposit appearance Good Good (7) Deposition after 24 hours (mg./ 0.25 hr.) 3
EXAMPLE 6 (1) Solution concentration without additive (percent) 25 25 (2) Additive, mgJl. (sodium (liethyl-dithio carbamate) 0 4 (3) Solution temperature 0.). 25 25 (4) Deposit weight (mg/0.25 hr. 23 20 (5) Bath stability Fair Good (6) Deposit appearance Good Good (7) Deposition after 24 hours (mg/0.25 hr.) 0 15 With reference to the above examples, it should be understood that poor bath stability is one in which the bath is substantially decomposed within about 3 hours, a fair bath stability is one which is relatively undecomposed within 3 hours but almost completely decomposed in 24 hours; and a good bath stability shows little or no decomposition after 24 hours.
A poor deposit appearance is a non-uniform or powdery deposit, while a good deposit appearance is very coppery metallic. An intermediate appearance is rated, obviously, as fair. The deposition tests were conducted on 2 square inch, cleaned and sensitized Mylar sheet of 3 mil thickness.
From the above examplary tests, it is conclusive that, in almost every single instant, a very small addition of one of the compounds of the present invention has contributed definitely to achieve an improvement in the deposition rate and stability of the bath. The main advantage of the present invention is an electroless copper solution which is usable for at least several days, thus obviating the necessity for time-consuming make-ups.
What is claimed is:
1. An electroless copper plating solution consisting essentially of Fehlings solution, a reducing agent, and a stabilizing amount of a compound having the empirical formula II R: S
wherein A is a sodium, potassium, lithium or copper atom; X is nitrogen; and R and R are hydrogen or straight or branched chain radicals having from 1 to 6 carbon atoms.
2. The electroless copper plating solution of claim 1, wherein said reducing agent is formaldehyde.
3. The electroless copper plating solution of claim 2, wherein said stabilizing compound is present in amounts of from about 0.05 to 20 milligrams per liter of undiluted Fehlings solution.
4. The electroless copper plating solution of claim 1, consisting essentially of Fehlings solution, a reducing agent, an additional volume of water from 1 to 3 times the volume of undiluted Fehlings solution, and from 0.05 to 20 mg./liter of undiluted Fehlings solution of sodium dihexyl-dithio carbamate.
5. The electroless copper plating solution of claim 1, consisting essentially of Fehlings solution, a reducing agent, an additional volume of water from 1 to 3 times the volume of undiluted Fehlings solution, and from 0.05 to 20 mg./liter of undiluted Fehlings solution of potassium dibutyl-dithio carbamate.
6. The electroless copper plating solution of claim 1, consisting essentially of Fehlings solution, a reducing agent, an additonial volume of water from 1 to 3 times the volume of undiluted Fehlings solution, and from 0.05 to 20 mg./liter of undiluted Fehlings solution of copper diethyl-dithio carbamate.
7. The electroless copper plating solution of claim 1, consisting essentially of Fehlings solution, a reducing agent, an additional volume of water from 1 to 3 times the volume of undiluted Fehlings solution and from 0.05 to 20 mg./liter of undiluted Fehlings solution of lithium dimethyl-dithio carbamate.
8. The electroless copper plating solution of claim 1, consisting essentially-of Fehlings solution, a reducing agent, anadditional volume of wat r from 1 to 3 times the volume of undiluted Fehlings so ution, and from 0.05 to 20 mg./liter of undiluted Fehlings solution of sodium dimethyl-dithio carbamate.
9. The electroless copper plating solution of claim 1, consisting essentially of Fehlings solution, a reducing agent, an additional volume of water from 1 to 3 times the volume of undiluted Fehlings solution, and from 0.05 to 20 mg./liter of undiluted'Fehlings solution of sodium diethyl-dithio carbamate.
10. A process for improving the stability of an electroless copper plating solution consisting essentially of Fehlings solution and a reducing agent, which comprises adding a stabilizing amount of a compound having the empirical formula References Cited UNITED STATES PATENTS 1/1968 Schneble et al. 1061 4/1968 Torigai et al. 106-1 JULIUS FROME, Primary Examiner. L. HAYES, Assistant Examiner.
US. Cl. X.R. 1l7130
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59896266A | 1966-12-05 | 1966-12-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3453123A true US3453123A (en) | 1969-07-01 |
Family
ID=24397634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US598962A Expired - Lifetime US3453123A (en) | 1966-12-05 | 1966-12-05 | Electroless copper plating solutions |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3453123A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3649350A (en) * | 1970-06-29 | 1972-03-14 | Gen Electric | Electroless copper plating |
| EP3351657A1 (en) | 2017-01-23 | 2018-07-25 | Rohm and Haas Electronic Materials LLC | Electroless copper plating compositions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3361580A (en) * | 1963-06-18 | 1968-01-02 | Day Company | Electroless copper plating |
| US3377174A (en) * | 1963-10-24 | 1968-04-09 | Torigai Eiichi | Method and bath for chemically plating copper |
-
1966
- 1966-12-05 US US598962A patent/US3453123A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3361580A (en) * | 1963-06-18 | 1968-01-02 | Day Company | Electroless copper plating |
| US3377174A (en) * | 1963-10-24 | 1968-04-09 | Torigai Eiichi | Method and bath for chemically plating copper |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3649350A (en) * | 1970-06-29 | 1972-03-14 | Gen Electric | Electroless copper plating |
| 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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