US2742412A - Electrolytic deposition of copper - Google Patents
Electrolytic deposition of copper Download PDFInfo
- Publication number
- US2742412A US2742412A US348582A US34858253A US2742412A US 2742412 A US2742412 A US 2742412A US 348582 A US348582 A US 348582A US 34858253 A US34858253 A US 34858253A US 2742412 A US2742412 A US 2742412A
- Authority
- US
- United States
- Prior art keywords
- copper
- thiourea
- bath
- group
- water
- 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 group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 25
- 229910052802 copper Inorganic materials 0.000 title description 25
- 239000010949 copper Substances 0.000 title description 25
- 230000008021 deposition Effects 0.000 title description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 26
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 5
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 claims description 5
- 229960001748 allylthiourea Drugs 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 4
- IPCRBOOJBPETMF-UHFFFAOYSA-N N-acetylthiourea Chemical compound CC(=O)NC(N)=S IPCRBOOJBPETMF-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims 1
- 238000007747 plating Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 description 9
- 150000003585 thioureas Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 methyl thiourea Chemical class 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Definitions
- the electrolytic deposition of copper is an operation which is applied very frequently in the metal industry and is carried out either to embellish the surface of the treated objects, or to increase the corrosion resistance thereof, while the electro-deposited copper also serves as a base for a further treatment such as the electrolytic ers mostly do cover the unevennesses in the metal surface but do not fill them up, so that they, although lustrous, yet remain visible.
- the acid copper bath in so far makes a favorable exception that it has some filling action, but the copper baths proposed up till now do not have the combination of an excellently filling activity and the capacity of depositing a lustrous, soft copper layer.
- objects are .electrolytically provided with a copper deposit with the aid of an acid bath by using a bath containing the combination of a substance selected from the group consisting of thiourea and the water-soluble derivatives of thiourea, and a substance selected from the group consisting of the water-soluble di or trivalent a1- cohols. and the water-soluble derivatives thereof.
- the invention extends to the preparation of an acid copper bath containing the combination of a substance selected from the group consisting of thiourea and the water-soluble derivatives of thiourea, and a substance se- 2,742,412 Patented Apr. :17," 1956 di and trivalent alcohols and the water-soluble derivatives thereof, as-well as the objects electrolytically provided with a copper layer with the aid of the bath.
- glycerol is preferred, while ethylene glycol monoethyl ether and diethylene glycol monobutyl ether as derivatives of the bivalent alcohols ethylene glycol and diethylene glycol are preferred, because the former of these two com pounds very much improves the adherence to the base and the latter excells by the combination of lustre and filling up capacity of the bath.
- thiourea derivatives used in combination with the di or trivalent alcohols particularly allylthiourea and acetyl thiourea are preferred, while thiourea itself, if possible, still exceeds in activity these two derivatives.
- the invention is elucidated by the following exam ples':
- Example I An acid copper bath of the following composition was prepared:
- Example II To the acid copper bath of Example I instead of the thiourea as much allylthiourea and instead of the glycerol mg./l. ethylene glycol monoethyl ether were added. A similar tube as in Example I was electrolytically provided with a copper layer in this bath. The
- Example III sulfate, sulfuric acid, a brightener in a proportion of 5- 50 mgQ/liter, said brightener being selected from the group consisting of thiourea, allylthiourea and acetyl thiourea, and a filler selected fromthe group consisting of glycerol, glycol, ethylene glycol mono ethyl ether and diethylene glycol mono butyl ether.
- a bath according to claim 1, wherein said filler is diethylene glycol mono butyl ether.
Description
nited States Patent fi fl 1,742,412 k I "Emmomm DEPOSITION on corral: Rolf Cransberg and Hendricus Andreas Van Dusterhout, Loosdrecht, Netherlands, assignors to N. V.
" Metallic Industry, Loosdrecht, Netherlands, a limited liability company of the Netherlands No Drawing. Application April 13, 1953,
Serial No. 348,582
Claims priority, application Netherlands July 5, 1952 8 Claims. (Cl. 204-52) The electrolytic deposition of copper is an operation which is applied very frequently in the metal industry and is carried out either to embellish the surface of the treated objects, or to increase the corrosion resistance thereof, while the electro-deposited copper also serves as a base for a further treatment such as the electrolytic ers mostly do cover the unevennesses in the metal surface but do not fill them up, so that they, although lustrous, yet remain visible. The acid copper bath in so far makes a favorable exception that it has some filling action, but the copper baths proposed up till now do not have the combination of an excellently filling activity and the capacity of depositing a lustrous, soft copper layer.
From the U. S. P. 1,903,860 it is known to add thiourea or a water-soluble derivative of thiourea, such as methyl thiourea, to metal baths. These baths, however, have the drawback that the copper coating which is precipitated from the copper baths thus prepared is very hard, so that it easily springs off on bending and moreover has a very small lustrous range. Also the action of a copper bath exclusively containing thiourea as an organic compound very rapidly decreases.
From the U. S. P. 2,462,870 it is known to add thiourea and molasses to an acid copper bath from which bath, however, a copper precipitate with an entirely insuflicient lustre is obtained.
It has now been found that a soft copper layer is obtained if the combination of a substance selected from the group consisting of thiourea and a water-soluble derivative of thiourea, and a water-soluble di or trivalent alcohol is added to an acid copper bath. The bath thus prepared displays'moreover an excellent filling capacity and has a very high lustre, while the adherence to the base also is very good. I According to the invention objects, particularly metal objects, are .electrolytically provided with a copper deposit with the aid of an acid bath by using a bath containing the combination of a substance selected from the group consisting of thiourea and the water-soluble derivatives of thiourea, and a substance selected from the group consisting of the water-soluble di or trivalent a1- cohols. and the water-soluble derivatives thereof.
The invention extends to the preparation of an acid copper bath containing the combination of a substance selected from the group consisting of thiourea and the water-soluble derivatives of thiourea, and a substance se- 2,742,412 Patented Apr. :17," 1956 di and trivalent alcohols and the water-soluble derivatives thereof, as-well as the objects electrolytically provided with a copper layer with the aid of the bath. Of the water-soluble di or trivalent alcohols which are used in the acid copper bath in combination with thiourea or a water-soluble derivative of thiourea, glycerol is preferred, while ethylene glycol monoethyl ether and diethylene glycol monobutyl ether as derivatives of the bivalent alcohols ethylene glycol and diethylene glycol are preferred, because the former of these two com pounds very much improves the adherence to the base and the latter excells by the combination of lustre and filling up capacity of the bath. Of the thiourea derivatives used in combination with the di or trivalent alcohols, particularly allylthiourea and acetyl thiourea are preferred, while thiourea itself, if possible, still exceeds in activity these two derivatives.
The invention is elucidated by the following exam ples':
Example I An acid copper bath of the following composition was prepared:
CuSOaS aq g./l 150 H2504 g./l 15 Ammonium sulphate g./l 15 Thiourea mg./l. 10 Glycerol mg./l 95 An iron tube with a length of 2 dm. and a diameter of 1.75 cm. was arranged as the cathode after a pretreatment in a cyanidic copper bath in the above described acid copper bath which had a temperature of 30 C. As the anode a copper bar was used. The cathode current density was adjusted at 8 a./dm. and after 20 minutes 32 of copper had deposited on the surface. The copper layer was soft and adhered excellently to the base and the scratches originally present on the surface had practically disappeared. Moreover the surface obtained was lustrous.
Example II To the acid copper bath of Example I instead of the thiourea as much allylthiourea and instead of the glycerol mg./l. ethylene glycol monoethyl ether were added. A similar tube as in Example I was electrolytically provided with a copper layer in this bath. The
properties of this bath in broad outlines corresponded to those of the bath according to Example'I, but the lustre was still better than that obtained with the bath of Example I. Y
Example III sulfate, sulfuric acid, a brightener in a proportion of 5- 50 mgQ/liter, said brightener being selected from the group consisting of thiourea, allylthiourea and acetyl thiourea, and a filler selected fromthe group consisting of glycerol, glycol, ethylene glycol mono ethyl ether and diethylene glycol mono butyl ether.
2. A bath according to claim 1, wherein said bright- V ener is thiourea.
'3. A bath according to claim 1, wherein said brightener is allylthiourea.
glycerol.
6. A bath according to claim 1-,v wherein said filler is.
ethylene glycol mono ethyl ether.
7. A bath according to claim 1, wherein said filler is diethylene glycol mono butyl ether.
8. A bath according to claim 1, wherein said filler is glycol.
References Cited in the file of this patent UNITED STATES PATENTS Brown Nov. 20, 1945 Beaver Dec. 18, 1945 Keller Mar. 1, 1949 Avallone et al. June 7, 1949
Claims (1)
1. A BRIGHT COPPER PLATING BATH COMPRISING COPPER SULFATE, SULFURIC ACID, A BRIGHTENER IN A PROPORTION OF 550 MG./LITER, SAID BRIGHTENER BEING SELECTED FROM THE GROUP CONSISTING OF THIOUREA, ALLYLTHIOUREA AND ACETYLTHIOUREA, AND A FILLER SELECTED FROM THE GROUP CONSISTING OF GLYCEROL, GLYCOL, ETHYLENE GLYCOL MONO ETHYL ETHER AND DIETHYLENE GLYCOL MONO BUTYL ETHER.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL2742412X | 1952-07-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2742412A true US2742412A (en) | 1956-04-17 |
Family
ID=19875526
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US348582A Expired - Lifetime US2742412A (en) | 1952-07-05 | 1953-04-13 | Electrolytic deposition of copper |
| US348581A Expired - Lifetime US2742413A (en) | 1952-07-05 | 1953-04-13 | Bright copper plating bath |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US348581A Expired - Lifetime US2742413A (en) | 1952-07-05 | 1953-04-13 | Bright copper plating bath |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US2742412A (en) |
| BE (1) | BE518440A (en) |
| DE (2) | DE962129C (en) |
| NL (4) | NL81606C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2853443A (en) * | 1956-04-25 | 1958-09-23 | Westinghouse Electric Corp | Addition agent for acid copper electrolytes |
| US2903403A (en) * | 1954-02-10 | 1959-09-08 | Dehydag Gmbh | Method of copper-plating metal surfaces |
| US2910413A (en) * | 1955-01-19 | 1959-10-27 | Dehydag Gmbh | Brighteners for electroplating baths |
| US2931760A (en) * | 1957-09-25 | 1960-04-05 | Leon R Westbrook | Acid copper plating |
| US3770599A (en) * | 1971-05-24 | 1973-11-06 | Oxy Metal Finishing Corp | Acid zinc plating baths |
| US4474649A (en) * | 1982-06-21 | 1984-10-02 | Asarco Incorporated | Method of thiourea addition of electrolytic solutions useful for copper refining |
| EP0375180A2 (en) * | 1988-12-21 | 1990-06-27 | International Business Machines Corporation | Additive plating bath and process |
| EP1064417A1 (en) * | 1998-03-20 | 2001-01-03 | Semitool, Inc. | Apparatus and method for electrolytically depositing copper on a semiconductor workpiece |
| US20050245083A1 (en) * | 1998-03-20 | 2005-11-03 | Semitool, Inc. | Apparatus and method for electrochemically depositing metal on a semiconductor workpiece |
| US20100140098A1 (en) * | 2008-05-15 | 2010-06-10 | Solopower, Inc. | Selenium containing electrodeposition solution and methods |
| WO2015077772A1 (en) * | 2013-11-25 | 2015-05-28 | Enthone Inc. | Electrodeposition of copper |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE565994A (en) * | 1957-04-16 | |||
| NL238490A (en) * | 1958-04-26 | |||
| US4009087A (en) * | 1974-11-21 | 1977-02-22 | M&T Chemicals Inc. | Electrodeposition of copper |
| US6113771A (en) * | 1998-04-21 | 2000-09-05 | Applied Materials, Inc. | Electro deposition chemistry |
| US6551484B2 (en) | 1999-04-08 | 2003-04-22 | Applied Materials, Inc. | Reverse voltage bias for electro-chemical plating system and method |
| US6571657B1 (en) | 1999-04-08 | 2003-06-03 | Applied Materials Inc. | Multiple blade robot adjustment apparatus and associated method |
| US20030213772A9 (en) * | 1999-07-09 | 2003-11-20 | Mok Yeuk-Fai Edwin | Integrated semiconductor substrate bevel cleaning apparatus and method |
| US6913680B1 (en) | 2000-05-02 | 2005-07-05 | Applied Materials, Inc. | Method of application of electrical biasing to enhance metal deposition |
| WO2001090446A2 (en) | 2000-05-23 | 2001-11-29 | Applied Materials, Inc. | Method and apparatus to overcome anomalies in copper seed layers and to tune for feature size and aspect ratio |
| US6576110B2 (en) | 2000-07-07 | 2003-06-10 | Applied Materials, Inc. | Coated anode apparatus and associated method |
| JP2004536217A (en) * | 2000-10-03 | 2004-12-02 | アプライド マテリアルズ インコーポレイテッド | Method and related apparatus for tilting a semiconductor substrate upon entry for metal deposition |
| US6610189B2 (en) | 2001-01-03 | 2003-08-26 | Applied Materials, Inc. | Method and associated apparatus to mechanically enhance the deposition of a metal film within a feature |
| US20040020780A1 (en) * | 2001-01-18 | 2004-02-05 | Hey H. Peter W. | Immersion bias for use in electro-chemical plating system |
| US6478937B2 (en) | 2001-01-19 | 2002-11-12 | Applied Material, Inc. | Substrate holder system with substrate extension apparatus and associated method |
| US20030146102A1 (en) * | 2002-02-05 | 2003-08-07 | Applied Materials, Inc. | Method for forming copper interconnects |
| US6911136B2 (en) * | 2002-04-29 | 2005-06-28 | Applied Materials, Inc. | Method for regulating the electrical power applied to a substrate during an immersion process |
| US20040200725A1 (en) * | 2003-04-09 | 2004-10-14 | Applied Materials Inc. | Application of antifoaming agent to reduce defects in a semiconductor electrochemical plating process |
| US20040206628A1 (en) * | 2003-04-18 | 2004-10-21 | Applied Materials, Inc. | Electrical bias during wafer exit from electrolyte bath |
| US20050092602A1 (en) * | 2003-10-29 | 2005-05-05 | Harald Herchen | Electrochemical plating cell having a membrane stack |
| US20050092601A1 (en) * | 2003-10-29 | 2005-05-05 | Harald Herchen | Electrochemical plating cell having a diffusion member |
| US20060102467A1 (en) * | 2004-11-15 | 2006-05-18 | Harald Herchen | Current collimation for thin seed and direct plating |
| US20060175201A1 (en) * | 2005-02-07 | 2006-08-10 | Hooman Hafezi | Immersion process for electroplating applications |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2389179A (en) * | 1941-02-21 | 1945-11-20 | Udylite Corp | Electrodeposition of metals |
| US2391289A (en) * | 1941-09-15 | 1945-12-18 | Jr John F Beaver | Bright copper plating |
| US2462870A (en) * | 1942-07-09 | 1949-03-01 | Gen Motors Corp | Electrodeposition of copper |
| US2472393A (en) * | 1944-09-25 | 1949-06-07 | American Steel & Wire Co | Process and bath for copper coating ferrous metal |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA461186A (en) * | 1949-11-22 | John Franklin Beaver, Jr. | Bright copper plating | |
| CA477508A (en) * | 1951-10-02 | Brown Henry | Electrodeposition of nickel from acid baths | |
| DE104111C (en) * | ||||
| US2196588A (en) * | 1937-05-26 | 1940-04-09 | Du Pont | Electroplating |
| US2315802A (en) * | 1940-04-20 | 1943-04-06 | Harshaw Chem Corp | Nickel plating |
| US2489538A (en) * | 1941-05-24 | 1949-11-29 | Gen Motors Corp | Electrodeposition of copper |
| US2355505A (en) * | 1941-10-03 | 1944-08-08 | Purdue Research Foundation | Electrodeposition of bright zinc |
| BE504701A (en) * | 1950-07-17 | |||
| US2700020A (en) * | 1952-06-02 | 1955-01-18 | Houdaille Hershey Corp | Plating copper |
-
0
- NL NLAANVRAGE7106028,A patent/NL170870B/en unknown
- NL NLAANVRAGE7413473,A patent/NL170871B/en unknown
- NL NL84048D patent/NL84048C/xx active
- NL NL81606D patent/NL81606C/xx active
- BE BE518440D patent/BE518440A/xx unknown
-
1952
- 1952-07-30 DE DEN5865A patent/DE962129C/en not_active Expired
- 1952-07-30 DE DEN5864A patent/DE940860C/en not_active Expired
-
1953
- 1953-04-13 US US348582A patent/US2742412A/en not_active Expired - Lifetime
- 1953-04-13 US US348581A patent/US2742413A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2389179A (en) * | 1941-02-21 | 1945-11-20 | Udylite Corp | Electrodeposition of metals |
| US2391289A (en) * | 1941-09-15 | 1945-12-18 | Jr John F Beaver | Bright copper plating |
| US2462870A (en) * | 1942-07-09 | 1949-03-01 | Gen Motors Corp | Electrodeposition of copper |
| US2472393A (en) * | 1944-09-25 | 1949-06-07 | American Steel & Wire Co | Process and bath for copper coating ferrous metal |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2903403A (en) * | 1954-02-10 | 1959-09-08 | Dehydag Gmbh | Method of copper-plating metal surfaces |
| US2910413A (en) * | 1955-01-19 | 1959-10-27 | Dehydag Gmbh | Brighteners for electroplating baths |
| US2853443A (en) * | 1956-04-25 | 1958-09-23 | Westinghouse Electric Corp | Addition agent for acid copper electrolytes |
| US2931760A (en) * | 1957-09-25 | 1960-04-05 | Leon R Westbrook | Acid copper plating |
| US3770599A (en) * | 1971-05-24 | 1973-11-06 | Oxy Metal Finishing Corp | Acid zinc plating baths |
| US4474649A (en) * | 1982-06-21 | 1984-10-02 | Asarco Incorporated | Method of thiourea addition of electrolytic solutions useful for copper refining |
| EP0375180A2 (en) * | 1988-12-21 | 1990-06-27 | International Business Machines Corporation | Additive plating bath and process |
| EP0375180A3 (en) * | 1988-12-21 | 1991-01-30 | International Business Machines Corporation | Additive plating bath and process |
| EP1064417A1 (en) * | 1998-03-20 | 2001-01-03 | Semitool, Inc. | Apparatus and method for electrolytically depositing copper on a semiconductor workpiece |
| US20050139478A1 (en) * | 1998-03-20 | 2005-06-30 | Semitool, Inc. | Apparatus and method for electrolytically depositing copper on a semiconductor workpiece |
| US20050150770A1 (en) * | 1998-03-20 | 2005-07-14 | Semitool, Inc. | Apparatus and method for electrolytically depositing copper on a semiconductor workpiece |
| US20050173252A1 (en) * | 1998-03-20 | 2005-08-11 | Semitool, Inc. | Apparatus and method for electrolytically depositing copper on a semiconductor workpiece |
| US20050245083A1 (en) * | 1998-03-20 | 2005-11-03 | Semitool, Inc. | Apparatus and method for electrochemically depositing metal on a semiconductor workpiece |
| EP1064417A4 (en) * | 1998-03-20 | 2006-07-05 | Semitool Inc | Apparatus and method for electrolytically depositing copper on a semiconductor workpiece |
| US7332066B2 (en) | 1998-03-20 | 2008-02-19 | Semitool, Inc. | Apparatus and method for electrochemically depositing metal on a semiconductor workpiece |
| US20100140098A1 (en) * | 2008-05-15 | 2010-06-10 | Solopower, Inc. | Selenium containing electrodeposition solution and methods |
| WO2015077772A1 (en) * | 2013-11-25 | 2015-05-28 | Enthone Inc. | Electrodeposition of copper |
| CN105917032A (en) * | 2013-11-25 | 2016-08-31 | 乐思股份有限公司 | Electrodeposition of copper |
Also Published As
| Publication number | Publication date |
|---|---|
| DE940860C (en) | 1956-03-29 |
| DE962129C (en) | 1957-04-18 |
| BE518440A (en) | |
| US2742413A (en) | 1956-04-17 |
| NL84048C (en) | |
| NL170871B (en) | |
| NL81606C (en) | |
| NL170870B (en) |
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