US3051634A - Baths for the production of copper electroplates - Google Patents
Baths for the production of copper electroplates Download PDFInfo
- Publication number
- US3051634A US3051634A US775354A US77535458A US3051634A US 3051634 A US3051634 A US 3051634A US 775354 A US775354 A US 775354A US 77535458 A US77535458 A US 77535458A US 3051634 A US3051634 A US 3051634A
- Authority
- US
- United States
- Prior art keywords
- acid
- copper
- group
- bath
- liter
- 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 38
- 229910052802 copper Inorganic materials 0.000 title claims description 37
- 239000010949 copper Substances 0.000 title claims description 37
- 239000002253 acid Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 238000005282 brightening Methods 0.000 claims description 16
- 238000009713 electroplating Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 150000003566 thiocarboxylic acids Chemical class 0.000 claims description 5
- 239000011260 aqueous acid Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- CNJLMVZFWLNOEP-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[4.1.0]heptan-5-one Chemical group O=C1C(C)CCC2C(C)(C)C12 CNJLMVZFWLNOEP-UHFFFAOYSA-N 0.000 claims 1
- 150000001721 carbon Chemical class 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- -1 cyclic thioamides Chemical class 0.000 description 31
- 239000002659 electrodeposit Substances 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 9
- 125000005842 heteroatom Chemical group 0.000 description 8
- 159000000000 sodium salts Chemical class 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 125000000542 sulfonic acid group Chemical group 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 150000003556 thioamides Chemical class 0.000 description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229960004635 mesna Drugs 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 3
- CJXBHFANXQMZBF-UHFFFAOYSA-N 2-phenylethanethioamide Chemical compound NC(=S)CC1=CC=CC=C1 CJXBHFANXQMZBF-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 229940117927 ethylene oxide Drugs 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- HXDOQOJZRQVNEP-UHFFFAOYSA-N n-cyclohexylethanethioamide Chemical compound CC(=S)NC1CCCCC1 HXDOQOJZRQVNEP-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- OAXSBIJZTFSWRG-UHFFFAOYSA-N 2-(2-sulfanylidenepyrrolidin-1-yl)acetamide Chemical compound NC(=O)CN1CCCC1=S OAXSBIJZTFSWRG-UHFFFAOYSA-N 0.000 description 1
- JFYIBFCXQUDFQE-UHFFFAOYSA-N 2-hydroxybenzenecarbothioamide Chemical compound NC(=S)C1=CC=CC=C1O JFYIBFCXQUDFQE-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001674048 Phthiraptera Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 241000272534 Struthio camelus Species 0.000 description 1
- QIOZLISABUUKJY-UHFFFAOYSA-N Thiobenzamide Chemical compound NC(=S)C1=CC=CC=C1 QIOZLISABUUKJY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KYBYXUFWFJNTGI-UHFFFAOYSA-N n-cyclohexylbutanethioamide Chemical compound CCCC(=S)NC1CCCCC1 KYBYXUFWFJNTGI-UHFFFAOYSA-N 0.000 description 1
- BOQKCADLPNLYCZ-UHFFFAOYSA-N n-phenylbenzenecarbothioamide Chemical compound C=1C=CC=CC=1C(=S)NC1=CC=CC=C1 BOQKCADLPNLYCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- GCVHYGRJLCAOGI-UHFFFAOYSA-N piperidine-2-thione Chemical compound S=C1CCCCN1 GCVHYGRJLCAOGI-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001391 thioamide group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- This invention relates to a process for producing bright copper electrodeposits from acid copper plating baths using organic compounds as brightening additives. It more specifically relates to supplementary additives for such copper plating baths to permit operation of the bath over wider ranges of temperature and current density without reducing the effectiveness of the bath and the quality of the electrodeposits.
- organic brighteners may be added to copper electroplating baths to achieve bright copper electrodeposits. These brighteners produce a substantial improvement in the brighteners, depending upon their nature, but in many cases their effectiveness is strongly dependent upon temperature, i.e., they can be used effectively only within relatively narrow temperature limits.
- Another object is to provide a method and bath for producing bright copper electrodeposits at lower current density.
- a further object of this invention is to provide additives for an acid bright copper electroplating bath which will permit operation of the bath over wider temperature and current density ranges without loss of brightness in the metal deposits.
- this temperature range can be widened by adding acyclic or cyclic thioamides or isothioamides to the baths in addition to the brightening agents.
- the efiect achieved thereby is that the undesirable dull zones which form at higher temperatures in the range of low current densities of about -4 amp./dm. no longer occur.
- Suitable brighteners are the known, previously customary agents such as thiourea, thiourea derivatives, safranins or also, with particular advantage, modern highquality bn'ghteners.
- the latter are characterized by a carbon atom linked only to heteroatoms, the carbon atom being also linked through a sulfur or nitrogen atom to an aliphatic radical which in turn has a water-solubilizing group, such as a sulfonic acid group, attached thereto.
- thioamides or isothioamides which are the subject matter of this invention, have a general structural formula as follows:
- R, R and R" are aliphatic, cycloaliphatic, alkylaromatic or aromatic hydrocarbon radicals, and R or R" may also be hydrogen.
- R and R (or R") as well as R and R" may also form a polymethylene chain which may, in the latter case, be interrupted by heteroatoms.
- the radicals R, R and R may carry substituents, such as halogen, cyano, thiocyano and/ or hydroxyl groups, or may be interrupted by heteroatoms or heteroatom groups; particularly, they may contain additional thioamide groups. Products of this type are soluble in the acid copper baths in the customary concentrations. They may be improved with respect to solubility properties, if necessary, by introducing non-ionic, Water-solubilizing groups, such as polyethylene-oxide groups.
- thioamides or isothioamides which may be used in accordance with the present invention are:
- Thioacetamide Thiopropionamide Thiobutyramide Adipic acid dithioamide Thiobenzamide Z-hydroxy-thiobenzamide Phenyl-thioacetamide Thionaphthamide N,N-diethyl-thioacetamide N,N-diethanol-thioacetamide N-ethyl-thioacetamide Thioacetanilide 'I'hioacet-m-chloroanilide N-cyclohexyl-thioacetamide N- (fifl e-trichloro-a-hydroXy-ethyl) -thioacetarnide Thioacet-morpholide Thioacet-piperidide 1,2-ethylene-bis-(thioacetiminoester-S,S) Thioacetimino-allylester N-methyl-N-B-chloroethyl-thiopropionamide N-methyl-N-q -chloropropyl-thiopropionamide N
- suitable brighteners are the known previously customary agents such as thiourea derivatives, safranins and the full brightening agents which may be used are primarily those organic compounds which are characterized by one or more carbon atoms linked only to heteroatoms, and which contain a short aliphatic radical linked to the carbon atom through a sulfur or nitrogen atom, the aliphatic radical having attached thereto a water-solubilizing group, especially a sulfonic acid group.
- full brightening agents are water-soluble salts of N,N-diethyl-dithiocarbamic acid-n-propylester-wsulfonic acid; N,N-pentamethylene-dithiocarbamic acid-npropylester-w-SO H; 1,3,S-triazine-2,4,6-tris-(mercapto-2'- hydroXy-propane-sulfonic acid); and other full brightening agents of similar structure, such as those which are described in French Patent No. 1,097,123 and Belgian Patents Nos. 543,413 and 540,564 or which are the subject matter of copending application Serial No. 618,183, filed October 25, 1956, now Patent No. 2,849,352.
- the baths may be modified with agents which render bath impurities harmless and which improve the ductility of the electrodeposits.
- the baths may contain additional brightening and/ or Wetting agents.
- agents which render bath impurities 3 harmless has the effect that inorganic impurities, such as the hardness components of water or impurities in technical grade metal salts, do not exert a detrimental eflect upon the properties of metal electrodeposits which are produced with the aid of the above full brighteners. Furthermore, these compounds have the property of increasing the ductility of the electrodeposits.
- the additives according to the present invention may also be used conjointly with the above-described hardnessbinding and ductility-improving amino compounds free from car-boxyl groups, as well as with the full brighteners in the process for directly copper plating non-precious metals in accordance with copending application Serial No. 458,983, now US. Patent No. 2,903,403. According to that process it is possible to deposit firmly adhering copper electroplates on non-precious metals, such as iron, without a cyanide pre-dip by pre-treating the metal objects to be copper plated in an acid pickling bath in the presence of inhibitors having a high inhibiting effect, and subsequently directly electroplating them in a copper bath without intermediate rinsing.
- non-precious metals such as iron
- the additives according to the present invention are employed in amounts of about 0.001 to 6 gm./1iter, preferably in amounts of 0.01 to 1 gm./ liter of bath.
- Example 1 Metal objects were electroplated at room temperature in an acid copper bath which contained 200 gm./liter CuSo .5H O, 60 gm./Iiter concentrated H SO 0.2 gm./ liter N,N-diethyl-dithiocarbamic acid-n-propylester-w-sulfonic acid (sodium salt) and 0.4 gm./liter 1,3,5-triazine- 2,4,6-tris-(mercapto-ethane sulfonic acid) (sodium salt) as a brightening agent, 0.25 gn1./liter N,N,N,N'-tetraethyl-ethylenediarnine as a ductility-improving agent, and 3 gm./1iter of a condensation product formed from dodccylalcohol and 10 mols ethyleneoxide, which had been 25% converted into the sulfuric acid ester, as a wetting agent.
- an acid copper bath which contained 200 gm
- thioamides may be used with comparable results: N-fi-chloroethylcaprothiolactam, methyl-valerothiolactam, N,N-bis-(thioacet)-ethylenediamine, thioacetmorpholide, N,N-diethanol-thioacetamide thioacetimino-allylester, N-cyclohexylthioacetamide.
- Example II The copper electroplating bath described in Example I was modified in additon with 0.008 gm./liter thioacet-mchloroanilide. Full bright copper electrodeposits were obtained even at 55 C. In this case the eifective current density range was 0.5-8.5 amp./dm.
- Example 111 In an acid copper electroplating bath, containing 200 gm./liter CuSO .5H O, 60 gm./ liter concentrated H 30 0.025 gm./ liter of the sodium salt of N,N-dimethyl-dithiocarbamic acid-ethyl ester-w-sulfonic acid, 0.5 gm./liter dimethyl-,B-chloroethyl-amine hydrochloride, 4 gm./liter of a condensation product of dodecyl alcohol and 10 mols ethyleneoxide, which had been completely transformed into the sulfuric acid ester, full bright electrodeposits were obtained at a temperature of 35 C. within a current density range of 0-8 amp./dm. when 0.003 gm./liter phenylthioacetamide was added to the bath.
- Example IV To an acid copper bath, containing 200 gm./liter CUSO4-5H2O 60 grn./liter concentrated H 50 and 4 gm./liter of the wetting agent of Example III, 0.1 gm./liter N,N-diethyldithiocarbamic acid-n-propylester-w-sodium sulfonate were added as brightening agents, 2.5 gm./liter of the of 0-7 amp./drn.
- Example V In place of the brightener, ductility-improving agent acid additive for increasing the temperature range indicated in Example IV, 0.25 gm.,/liter N,Ndiethyl-dithiocarbarnic acid-n-2-hydroxy propyl ester-w-sodium sulfonate, 0.15 gm./1it er 1,3-diamino-propanol-2-sulfuric acid ester and 0.02 gin/liter N-(p,fi, 3-trich1oro-arhydroxyethyl)-thioacetamide were added to the acid copper bath. Full bright copper electrodeposits were obtained in this bath at a temperature of 38 C.
- Example VI In an acid copper bath, containing 200 gm./ liter CuSO .5H O
- An acid copper electroplating bath for producing bright copper deposits comprising an aqueous acid solution of a copper salt, an organic sulfonic acid full brightening agent having at least one carbon atom linked only to heteroatoms and a short aliphatic radical linked to the said carbon atom through a member of the group consisting of a nitrogen atom and a sulfur atom, the aliphatic radical having attached thereto a sulfonic acid group, and a compound in sufiicient amount to broaden the effective operating ranges of current density and temperature, said compound being selected from the group consisting of thiocarboxylic acid amides and isothiocarboxylic acid amides.
- An acid copper electroplating bath for producing bright copper deposits comprising an aqueous acid solution of a copper salt, an organic sulfonic acid full brightening agent having at least one carbon atom linked only to herteoatoms and a short aliphatic radical linked to the said carbon atom through a member of the group consisting of a nitrogen atom and a sulfur atom, the aliphatic radical having attached thereto a sulfonic acid group, and a compound in suflicient amount to broaden the elfective operating ranges of current density and temperature, said compound being selected from the group consisting of thiocarboxylic acid amides and isothiocarboxylic acid amides having the respective formulas wherein R, R and R are radicals selected from the group consisting of hydrogen, aliphatic, cycloaliphatic, alkyl-aromatic and aromatic hydrocarbon radicals and derivatives of the said hydrocarbon radicals.
- R radical is a derivative of said hydrocarbon radicals substituted with radicals selected from the group consisting of halogen, cyano, thiocyano and hydroxyl radicals.
- An acid copper electroplating bath for producing bright copper deposits comprising an aqueous acid solution of a copper salt, an organic brightening agent, comprising a mixture of N,N-diethyl-dithiocarbamic acid-N- propylester-w-sulfonic acid (sodium salt) and 1,3,5-triazine-2,4,6-tris-(mercapto-ethane sulfonic acid) (sodium salt), and as a compound for broadening the effective operating ranges of current density and temperature, thioacet-m-chloroanilide.
- a method for broadening the efiective operating ranges of temperature and current density in an acid copper electroplating bath containing organic sulfonic acid full brightening agent having at least one carbon atom linked only to heteroatoms and a short aliphatic radical linked to the said carbon atom through a member of the group consisting of a nitrogen atom and a sulfur atom, the aliphatic radical having attached thereto a sulfonic acid group comprising the step of adding to said bath a compound selected from the group consisting of thiocarboxylic acid amides and isothiocarboxylic acid amides.
- a method for broadening the effective operating ranges of temperature and current density in an acid copper electroplating bath containing organic sulfonic acid full brightening agent having at least one carbon atom linked only to heteroatoms and a short aliphatic radical linked to the said carbon atom through a member of the group consisting of a nitrogen atom and a sulfur atom, the aliphatic radical having attached thereto a sulfonic acid group comprising the step of adding to said bath a compound selected from the group consisting of thiocarboxylic acid amides and isothiocarboxylic acid amides having the respective formulas wherein R, R and R" are radicals selected from the group consisting of hydrogen, aliphatic, cycloaliphatic, alkylaromatic and aromatic hydrocarbon radicals and derivatives of said hydrocarbon radicals.
- R radical is a derivative of said hydrocarbon radicals substituted with radicals selected from the group consisting of halogen, cyano, thiocyano and hydroxyl radicals.
- a method for broadening the effective operating ranges of temperature and current density in an acid copper electroplating bath containing organic brightening agents comprising a mixture of N,N-diethyldithiocarbamic acid-N-propylester-w-sulfonic acid (sodium salt) and 1,3,5-triazine-2,4,6-tris-(mercapto-ethane sulfonic acid) (sodium salt), comprising the step of adding to said bath thioacet-m-chloroanilide.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Hydrogenated Pyridines (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED26934A DE1084098B (de) | 1957-11-30 | 1957-11-30 | Saure Baeder fuer die Herstellung galvanischer Kupferueberzuege |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3051634A true US3051634A (en) | 1962-08-28 |
Family
ID=7039058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US775354A Expired - Lifetime US3051634A (en) | 1957-11-30 | 1958-11-21 | Baths for the production of copper electroplates |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3051634A (de) |
| BE (1) | BE572016A (de) |
| CH (1) | CH375581A (de) |
| DE (1) | DE1084098B (de) |
| FR (1) | FR1227239A (de) |
| GB (1) | GB902082A (de) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3414493A (en) * | 1965-10-19 | 1968-12-03 | Lea Ronal Inc | Electrodeposition of copper |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| CN102995077A (zh) * | 2012-12-28 | 2013-03-27 | 武汉吉和昌化工科技有限公司 | 一种无氰碱性光亮镀铜溶液、其制备方法及其电镀工艺 |
| US20130240368A1 (en) * | 2011-09-09 | 2013-09-19 | Rohm And Haas Electronic Material Llc | Low internal stress copper electroplating method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1184172B (de) * | 1961-08-31 | 1964-12-23 | Dehydag Gmbh | Verfahren zum galvanischen Abscheiden festhaftender und hochglaenzender Kupferueberzuege |
| DE1184584B (de) * | 1963-02-07 | 1964-12-31 | Langbein Pfanhauser Werke Ag | Saures galvanisches Bad, insbesondere saures Kupferbad |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2489538A (en) * | 1941-05-24 | 1949-11-29 | Gen Motors Corp | Electrodeposition of copper |
| US2663684A (en) * | 1952-06-02 | 1953-12-22 | Houdaille Hershey Corp | Method of and composition for plating copper |
| US2773022A (en) * | 1953-08-17 | 1956-12-04 | Westinghouse Electric Corp | Electrodeposition from copper electrolytes containing dithiocarbamate addition agents |
| US2837472A (en) * | 1953-09-19 | 1958-06-03 | Dehydag Gmbh | Brighteners for electroplating baths |
| US2849352A (en) * | 1956-06-15 | 1958-08-26 | Dehydag Gmbh | Electroplating process |
| US2910413A (en) * | 1955-01-19 | 1959-10-27 | Dehydag Gmbh | Brighteners for electroplating baths |
| US2937978A (en) * | 1953-08-13 | 1960-05-24 | Dehydag Gmbh | Electroplating of nickel |
-
0
- BE BE572016D patent/BE572016A/xx unknown
-
1957
- 1957-11-30 DE DED26934A patent/DE1084098B/de active Pending
-
1958
- 1958-09-18 CH CH6407758A patent/CH375581A/de unknown
- 1958-10-21 GB GB33513/58A patent/GB902082A/en not_active Expired
- 1958-11-21 US US775354A patent/US3051634A/en not_active Expired - Lifetime
- 1958-11-28 FR FR780323A patent/FR1227239A/fr not_active Expired
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2489538A (en) * | 1941-05-24 | 1949-11-29 | Gen Motors Corp | Electrodeposition of copper |
| US2663684A (en) * | 1952-06-02 | 1953-12-22 | Houdaille Hershey Corp | Method of and composition for plating copper |
| US2937978A (en) * | 1953-08-13 | 1960-05-24 | Dehydag Gmbh | Electroplating of nickel |
| US2773022A (en) * | 1953-08-17 | 1956-12-04 | Westinghouse Electric Corp | Electrodeposition from copper electrolytes containing dithiocarbamate addition agents |
| US2837472A (en) * | 1953-09-19 | 1958-06-03 | Dehydag Gmbh | Brighteners for electroplating baths |
| US2849351A (en) * | 1953-09-19 | 1958-08-26 | Dehydag Gmbh | Electroplating process |
| US2910413A (en) * | 1955-01-19 | 1959-10-27 | Dehydag Gmbh | Brighteners for electroplating baths |
| US2849352A (en) * | 1956-06-15 | 1958-08-26 | Dehydag Gmbh | Electroplating process |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3414493A (en) * | 1965-10-19 | 1968-12-03 | Lea Ronal Inc | Electrodeposition of copper |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| US20130240368A1 (en) * | 2011-09-09 | 2013-09-19 | Rohm And Haas Electronic Material Llc | Low internal stress copper electroplating method |
| US9493886B2 (en) * | 2011-09-09 | 2016-11-15 | Rohm And Haas Electronic Materials Llc | Low internal stress copper electroplating method |
| CN102995077A (zh) * | 2012-12-28 | 2013-03-27 | 武汉吉和昌化工科技有限公司 | 一种无氰碱性光亮镀铜溶液、其制备方法及其电镀工艺 |
| CN102995077B (zh) * | 2012-12-28 | 2014-12-31 | 武汉吉和昌化工科技有限公司 | 一种无氰碱性光亮镀铜溶液、其制备方法及其电镀工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1227239A (fr) | 1960-08-19 |
| BE572016A (de) | |
| GB902082A (en) | 1962-07-25 |
| DE1084098B (de) | 1960-06-23 |
| CH375581A (de) | 1964-02-29 |
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