US1969553A - Electrolyte for the deposition of - Google Patents
Electrolyte for the deposition of Download PDFInfo
- Publication number
- US1969553A US1969553A US1969553DA US1969553A US 1969553 A US1969553 A US 1969553A US 1969553D A US1969553D A US 1969553DA US 1969553 A US1969553 A US 1969553A
- Authority
- US
- United States
- Prior art keywords
- copper
- deposition
- bath
- baths
- electrolyte
- 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
- 239000003792 electrolyte Substances 0.000 title description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 30
- 229910052802 copper Inorganic materials 0.000 description 30
- 239000010949 copper Substances 0.000 description 30
- OXBLHERUFWYNTN-UHFFFAOYSA-M Copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 20
- 229940045803 cuprous chloride Drugs 0.000 description 20
- XFXPMWWXUTWYJX-UHFFFAOYSA-N cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 18
- 229910045601 alloy Inorganic materials 0.000 description 16
- 239000000956 alloy Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- AKHNMLFCWUSKQB-UHFFFAOYSA-L Sodium thiosulphate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 10
- 239000004133 Sodium thiosulphate Substances 0.000 description 10
- 235000019345 sodium thiosulphate Nutrition 0.000 description 10
- 229910000881 Cu alloy Inorganic materials 0.000 description 8
- -1 Thiosulphate ion Chemical class 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910001297 Zn alloy Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L Copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L Nickel(II) chloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L Zinc chloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L Zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 230000001464 adherent Effects 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 2
- 230000003334 potential Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000004763 sulfides Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- 235000009529 zinc sulphate Nutrition 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Definitions
- My invention relates to an electrolyte for the deposition of copper and copper alloys.
- Copper can be deposited very successfully from the acid copper sulphate bath, but its use is limited, be cause many of the common metals and alloys, which it would be desirable to plate will cause deposition by immersion when placed in the bath, or are attacked by the acid in the bath. Consequently, the cyanide baths have been used extensively for the deposition of copper and copper alloys, especially on iron and steel.. Although dense and adherent deposits can be obtained from the cyanide baths, they .are far from de- 4. Specific resistivity of cyanide solutions is high; r
- the function of the cyanide. ion in the cyanide baths for alloy deposition is to form complex ions with the ions of the metals to be deposited, in order to reduce the efiective metal ion concentrations, so that the single electrode potentials of the various metals will be brought sufliciently close to one another to permit an alloy to be deposited.
- the effective copper ion concentration is reduced far enough so that deposition by immersion will not occur.
- An object of my invention is, therefore, to provide a method involving the use of some other complex copper ion.
- Thiosulphate ion appears to form a complex ion with cuprous ion as shown by the following facts:
- Cuprous chloride has a much greater solubility in a 40% solution of NazSzOa.5Hz0 than in pure water.
- Iron or steel does not replace the copper from thiosulphate solutions in which cuprous chloride has been dissolved.
- a solution containing only sodium thiosulphate and cuprous chloride is satisfactory.
- the maximum current density is limited by the concentration of the cuprous chloride and the sodium thiosulphate, and by the temperature of the bath. Above a certain value of current density, a deposit of cuprous sulphide forms onthe cathode. The value of the maximum current density is increased by increasing the temperature or the concentration of cuprous chloride.
- the concentration of the sodium thiosulphate (hypo) should be at least 200 g. per liter of solution, or the solubility of the complex copper salt will be too small to permit a desirable current density.
- a desirable composition for a copper bath would be:
- either zinc chloride or sulphate may be used.
- ammonium salts or other salts which will maintain the solution slightly acid is very desirable, especially if a, high concentration of zinc salt is used.
- H2 is liberated innearly all of the baths, but current efliciencies of at least 80% are obtainable even at high current densities.
- the composition of the deposit may be varied over a wide range by changing the current density or temperature in some of the baths, while in others, the composition remains nearly constant for a large change in current density. An increase in temperature always causes an increase in the copper content of the deposit.
- the current densities allowable with the baths for the deposition of copper-zinc alloys are higher than with the cyanide baths.
- a cyanide bath for the deposition of brass will give good deposits at a current density of about 0.3 amp. per sq. dm.
- a thiosulphate bath for a similar alloy permits current densities as high as 2 amp. per
- cuprous chloride free as possible from cupric compounds, to form the complex copper thiosulphate ion appears to give the best results.
- a process for the preparation of the cuprous chloride which I employ is disclosed and claimed in my co-pending application, Serial Number 623,295, filed July 18, 1932. Baths prepared with impure cuprous chloride frequently decompose continually with the formation of a brown or black precipitate. -The specific resistivity of these baths ranges from 3 to 6 ohm-cm. The voltage drop across the baths,
- An electrolyte for depositing a copper coating comprising a solution of a soluble thiosulphate and pure cuprous chloride.
- An electrolyte for depositing a copper coating comprising a solution of sodium thiosulphate substantially in the proportion of 400 grams per
Description
Patented Aug. 7, 1934- UNITED STATES PATENTZ- OFFICE ELECTROLYTE FOR THE DEPOSITION OF No Drawing. Application July 30, 1932,
Serial No. 627,126
4 Claims.
My invention relates to an electrolyte for the deposition of copper and copper alloys. Copper can be deposited very successfully from the acid copper sulphate bath, but its use is limited, be cause many of the common metals and alloys, which it would be desirable to plate will cause deposition by immersion when placed in the bath, or are attacked by the acid in the bath. Consequently, the cyanide baths have been used extensively for the deposition of copper and copper alloys, especially on iron and steel.. Although dense and adherent deposits can be obtained from the cyanide baths, they .are far from de- 4. Specific resistivity of cyanide solutions is high; r
5. Cyanide baths decompose slowly with formation of carbonates, necessitating additions of cyanide from time to time.
The function of the cyanide. ion in the cyanide baths for alloy deposition is to form complex ions with the ions of the metals to be deposited, in order to reduce the efiective metal ion concentrations, so that the single electrode potentials of the various metals will be brought sufliciently close to one another to permit an alloy to be deposited. When pure copper is to be deposited, the effective copper ion concentration is reduced far enough so that deposition by immersion will not occur. An object of my invention is, therefore, to provide a method involving the use of some other complex copper ion.
The full objects and advantages of my invention will appear in connection with the detailed description thereof, and the novel features of my inventive idea will be particularly. pointed out in the claims.
Thiosulphate ion appears to form a complex ion with cuprous ion as shown by the following facts:
1. Cuprous chloride has a much greater solubility in a 40% solution of NazSzOa.5Hz0 than in pure water.
2. Iron or steel does not replace the copper from thiosulphate solutions in which cuprous chloride has been dissolved.
3. Measurements of the potential of the copper electrode in solutions containing varying concentrations of sodium thiosulphate and cuprous chloride, indicate a far more negative value than would be obtained if no complex ions were formed in the solutions.
For pure copper deposition, a solution containing only sodium thiosulphate and cuprous chloride is satisfactory. The maximum current density is limited by the concentration of the cuprous chloride and the sodium thiosulphate, and by the temperature of the bath. Above a certain value of current density, a deposit of cuprous sulphide forms onthe cathode. The value of the maximum current density is increased by increasing the temperature or the concentration of cuprous chloride. The concentration of the sodium thiosulphate (hypo) should be at least 200 g. per liter of solution, or the solubility of the complex copper salt will be too small to permit a desirable current density. A desirable composition for a copper bath would be:
' NazSzOsfiHzO, (400 g. per liter of solution), C112C12(60 g. per liter of solution). Current densities from 14.5 amp. per sq. dm. could be used at 30 degrees C. The voltage drop across the bath'is less than a volt.
No H2 is set free in this bath, and current efficiencies very close to are obtained.
For alloy deposition, other metal chlorides or sulphates are added to the copper bath. In the deposition of copper-nickelalloys, nickel chloride is used instead of the sulphate in order to insure good anode corrosion, for sulphates have a tendency to cause anode passivity. No H2 is liberated at the current densities which give satisfactory deposits. Consequently, very good current efiicienciesare realized. The addition of considerable quantities of ammonium chloride to the baths is beneficial for deposition at the higher current densities, but quitedetrimental ior deposition at low current densities. Current density does not affect the composition of the deposits to any great extent. The best deposits appear to be obtained at room temperature. The composition of the deposit is best altered by using a different composition of the bath.
In the deposition of copper-zinc alloys, either zinc chloride or sulphate may be used. The presence of ammonium salts or other salts which will maintain the solution slightly acid is very desirable, especially if a, high concentration of zinc salt is used. H2 is liberated innearly all of the baths, but current efliciencies of at least 80% are obtainable even at high current densities. The composition of the deposit may be varied over a wide range by changing the current density or temperature in some of the baths, while in others, the composition remains nearly constant for a large change in current density. An increase in temperature always causes an increase in the copper content of the deposit. The current densities allowable with the baths for the deposition of copper-zinc alloys are higher than with the cyanide baths. For example, a cyanide bath for the deposition of brass will give good deposits at a current density of about 0.3 amp. per sq. dm., while a thiosulphate bath for a similar alloy permits current densities as high as 2 amp. per
sq. dm. With alloys richer in zinc, still higher current densities can be used.
In the deposition of copper and copper alloys, air agitation can be used. It allows a higher current density to be used, and increases the copper content of the deposit if an alloy is being deposited. The use of cuprous chloride, free as possible from cupric compounds, to form the complex copper thiosulphate ion appears to give the best results. A process for the preparation of the cuprous chloride which I employ is disclosed and claimed in my co-pending application, Serial Number 623,295, filed July 18, 1932. Baths prepared with impure cuprous chloride frequently decompose continually with the formation of a brown or black precipitate. -The specific resistivity of these baths ranges from 3 to 6 ohm-cm. The voltage drop across the baths,
even at the highest current densities is only slightly over 1 volt.
It is to be understood that this method of depositingcopper and copper alloys is not to be restricted by any of the following factors:
1. Concentration of the constituents of the bath;
2. Current density;
3. Temperature;
4. Composition of the alloy deposited, excep that it must contain copper.
I claim:
1. An electrolyte for depositing a copper coating,comprising a solution of a soluble thiosulphate and pure cuprous chloride.
2. An electrolyte for depositing a copper coating, comprising a solution of sodium thiosulphate substantially in the proportion of 400 grams per
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1969553A true US1969553A (en) | 1934-08-07 |
Family
ID=3426499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US1969553D Expired - Lifetime US1969553A (en) | Electrolyte for the deposition of |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1969553A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2472393A (en) * | 1944-09-25 | 1949-06-07 | American Steel & Wire Co | Process and bath for copper coating ferrous metal |
| US3833481A (en) * | 1972-12-18 | 1974-09-03 | Buckbel Mears Co | Electroforming nickel copper alloys |
| US5302278A (en) * | 1993-02-19 | 1994-04-12 | Learonal, Inc. | Cyanide-free plating solutions for monovalent metals |
| US5800930A (en) * | 1994-01-21 | 1998-09-01 | Olin Corporation | Nodular copper/nickel alloy treatment for copper foil |
| US7799684B1 (en) * | 2007-03-05 | 2010-09-21 | Novellus Systems, Inc. | Two step process for uniform across wafer deposition and void free filling on ruthenium coated wafers |
| US7964506B1 (en) | 2008-03-06 | 2011-06-21 | Novellus Systems, Inc. | Two step copper electroplating process with anneal for uniform across wafer deposition and void free filling on ruthenium coated wafers |
| US8513124B1 (en) | 2008-03-06 | 2013-08-20 | Novellus Systems, Inc. | Copper electroplating process for uniform across wafer deposition and void free filling on semi-noble metal coated wafers |
| US8575028B2 (en) | 2011-04-15 | 2013-11-05 | Novellus Systems, Inc. | Method and apparatus for filling interconnect structures |
| US8703615B1 (en) | 2008-03-06 | 2014-04-22 | Novellus Systems, Inc. | Copper electroplating process for uniform across wafer deposition and void free filling on ruthenium coated wafers |
| US11598015B2 (en) * | 2018-04-26 | 2023-03-07 | Arizona Board Of Regents On Behalf Of Arizona State University | Fabrication of dendritic structures and tags |
| US11875501B2 (en) | 2014-11-07 | 2024-01-16 | Arizona Board Of Regents On Behalf Of Arizona State University | Information coding in dendritic structures and tags |
-
0
- US US1969553D patent/US1969553A/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2472393A (en) * | 1944-09-25 | 1949-06-07 | American Steel & Wire Co | Process and bath for copper coating ferrous metal |
| US3833481A (en) * | 1972-12-18 | 1974-09-03 | Buckbel Mears Co | Electroforming nickel copper alloys |
| US5302278A (en) * | 1993-02-19 | 1994-04-12 | Learonal, Inc. | Cyanide-free plating solutions for monovalent metals |
| USRE35513E (en) * | 1993-02-19 | 1997-05-20 | Learonal, Inc. | Cyanide-free plating solutions for monovalent metals |
| US5800930A (en) * | 1994-01-21 | 1998-09-01 | Olin Corporation | Nodular copper/nickel alloy treatment for copper foil |
| US7799684B1 (en) * | 2007-03-05 | 2010-09-21 | Novellus Systems, Inc. | Two step process for uniform across wafer deposition and void free filling on ruthenium coated wafers |
| US7964506B1 (en) | 2008-03-06 | 2011-06-21 | Novellus Systems, Inc. | Two step copper electroplating process with anneal for uniform across wafer deposition and void free filling on ruthenium coated wafers |
| US8513124B1 (en) | 2008-03-06 | 2013-08-20 | Novellus Systems, Inc. | Copper electroplating process for uniform across wafer deposition and void free filling on semi-noble metal coated wafers |
| US8703615B1 (en) | 2008-03-06 | 2014-04-22 | Novellus Systems, Inc. | Copper electroplating process for uniform across wafer deposition and void free filling on ruthenium coated wafers |
| US8575028B2 (en) | 2011-04-15 | 2013-11-05 | Novellus Systems, Inc. | Method and apparatus for filling interconnect structures |
| US10006144B2 (en) | 2011-04-15 | 2018-06-26 | Novellus Systems, Inc. | Method and apparatus for filling interconnect structures |
| US11875501B2 (en) | 2014-11-07 | 2024-01-16 | Arizona Board Of Regents On Behalf Of Arizona State University | Information coding in dendritic structures and tags |
| US11598015B2 (en) * | 2018-04-26 | 2023-03-07 | Arizona Board Of Regents On Behalf Of Arizona State University | Fabrication of dendritic structures and tags |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US1969553A (en) | Electrolyte for the deposition of | |
| US2693444A (en) | Electrodeposition of chromium and alloys thereof | |
| KR910004972B1 (en) | Manufacturing method of tin-cobalt, tin-nickel, tin-lead binary alloy electroplating bath and electroplating bath manufactured by this method | |
| GB503008A (en) | Improvements in the electrodeposition of metals on alloys containing chromium | |
| US2250556A (en) | Electrodeposition of copper and bath therefor | |
| US4249999A (en) | Electrolytic zinc-nickel alloy plating | |
| US2075623A (en) | Zinc plating | |
| US4141803A (en) | Method and composition for electroplating chromium and its alloys and the method of manufacture of the composition | |
| Liebreich | The effects of film formation on the structure of electro-deposited metallic coatings | |
| US2504272A (en) | Electrodeposition of silver | |
| US2577365A (en) | Rhodium plating | |
| US1960029A (en) | Electrodeposition of alloys | |
| US2398614A (en) | Electrodeposition of manganese | |
| US3206382A (en) | Electrodeposition of platinum or palladium | |
| US1837355A (en) | Electrodeposition of alloys | |
| US1590170A (en) | Process of plating with chromium | |
| Jacobs et al. | Improving cathode morphology at a copper electrowinning plant by optimizing Magnafloc 333 and chloride concentrations | |
| US2866740A (en) | Electrodeposition of rhodium | |
| US2432894A (en) | Electrodeposition of iron-tungsten alloys | |
| US2729602A (en) | Electrodeposition of bright zinc plate | |
| US2973308A (en) | Complexed plating electrolyte and method of plating therewith | |
| US2305133A (en) | Anode | |
| JPS5928598A (en) | Insoluble anode made of pb alloy for electroplating | |
| US2177392A (en) | Chromium plating | |
| US2831803A (en) | Electro-deposition of alloys |