US3767539A - Acid galvanic copper bath - Google Patents
Acid galvanic copper bath Download PDFInfo
- Publication number
- US3767539A US3767539A US00186548A US3767539DA US3767539A US 3767539 A US3767539 A US 3767539A US 00186548 A US00186548 A US 00186548A US 3767539D A US3767539D A US 3767539DA US 3767539 A US3767539 A US 3767539A
- Authority
- US
- United States
- Prior art keywords
- liter
- sulfophenyl
- electrolyte
- copper
- sulfonaphthyl
- 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 abstract description 19
- 239000010949 copper Substances 0.000 title abstract description 19
- 229910052802 copper Inorganic materials 0.000 title abstract description 18
- 239000002253 acid Substances 0.000 title abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- -1 fluoborate Chemical compound 0.000 claims description 63
- 150000001875 compounds Chemical class 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000004964 sulfoalkyl group Chemical group 0.000 claims description 9
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 5
- 125000005036 alkoxyphenyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 3
- 125000002541 furyl group Chemical group 0.000 claims description 3
- 125000006501 nitrophenyl group Chemical group 0.000 claims description 3
- 125000005359 phenoxyalkyl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 9
- 230000008021 deposition Effects 0.000 abstract description 8
- 150000003957 organoselenium compounds Chemical class 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 34
- 239000011591 potassium Substances 0.000 description 19
- 229910052700 potassium Inorganic materials 0.000 description 19
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 17
- 229910000365 copper sulfate Inorganic materials 0.000 description 17
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- 229910052708 sodium Inorganic materials 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 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 16
- 229940108928 copper Drugs 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 15
- 238000000151 deposition Methods 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 229920000151 polyglycol Polymers 0.000 description 8
- 239000010695 polyglycol Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 125000001931 aliphatic group Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003118 aryl group Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 3
- 229920001522 polyglycol ester Polymers 0.000 description 3
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 3
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- JJFXAWUZVLKMSC-UHFFFAOYSA-N 2-nonylphenol;potassium Chemical compound [K].CCCCCCCCCC1=CC=CC=C1O JJFXAWUZVLKMSC-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- KNXXNPDFGLQEBM-UHFFFAOYSA-N 3-benzylselanylpropane-1-sulfonic acid Chemical compound C1=CC=C(C=C1)C[Se]CCCS(=O)(=O)O KNXXNPDFGLQEBM-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000054822 Lycaena cupreus Species 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 235000014987 copper Nutrition 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- BQJTUDIVKSVBDU-UHFFFAOYSA-L copper;sulfuric acid;sulfate Chemical compound [Cu+2].OS(O)(=O)=O.[O-]S([O-])(=O)=O BQJTUDIVKSVBDU-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 150000003959 diselenides Chemical class 0.000 description 1
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QKWLEZCBHBKUDK-UHFFFAOYSA-N methaneselone Chemical compound [Se]=C QKWLEZCBHBKUDK-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 125000001824 selenocyanato group Chemical group *[Se]C#N 0.000 description 1
- CRDYSYOERSZTHZ-UHFFFAOYSA-N selenocyanic acid Chemical class [SeH]C#N CRDYSYOERSZTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 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
- ABSTRACT Acid aqueous electrolytes for the deposition of bright, low-tension, ductile copper coatings containing organo selenium compounds are used.
- the invention relates to an acid aqueous electrolyte for the deposition of bright, low-tension, ductile copper coatings.
- the problem underlying the invention herein is to prevent the formation of black, streaky depositions and to make possible the precipitation of lustrous, low tension and ductile copper depositions of high anti-corrosion value over a wide current density range.
- an acid aqueous copper electrolyte which is characterized by a content of at least one compound of the general formula in which R and R are identical or different and represent possibly a monoor'multi-substituted aromatic, aliphatic, cycloaliphatic, araliphatic, or heterocyclic hydrocarbon radical, at least one of the two radicals containing a sulfonic acid group, or in whichR has the above-stated meaning and R represents the cyanide or the sulfonic acid group and n is equal to l or 2, or the salts thereof.
- R is phenyl, nitrophenyl, alkylphenyl, alkoxyphenyl, carboxyphenyl, carbmethoxyphenyl, dimethylaminophenyl, alkylmercaptophenyl, aminophenyl, alkyl containing preferably 2 to 8 carbon atoms, benzyl, phenoxyalkyl, sulfonlanyl, furyl, cyclohexylalkyl, pyridylalkyl, carboxyalkyl, dihydroxpropyl, sulfoalkyl containing preferably 2 to 6 carbon atoms, sulfophenyl, alkoxy-sulfophenyl, alkylmercapto-sulfophenyl, halogen-sulfophenyl, sulfonaphthyl, disulfonaphthyl or sulf
- sulfophenyl alkoxysulfophenyl, alkylmercaptosulfophenyl, halogen-sulfophenyl, sulfonaphthyl, disulfonaphthyl, sulfophenylalkyl, R represents the cyanide or the sulfonic acid group, and n is the number 1
- the compounds to be used according to the invention are known in themselves or can be produced by methods known in themselves, as described for example in HOUBEN-WEYL Methoden der organischen Chemie, volume 9 (1955), pages 972 1002 and pages 1,086 1,099.
- alkylor aryl-selenoalkylsulfonic acids can be prepared by reaction of the respective alkali selenolates with sulfoalkyl halides.
- the symmetrical sulfoalkylor sulfoaryl-diselenides are formed, for example, by hydrolysis of the respective selenoxyanates of the alkali-alkyl-selenosulfates.
- Alkylselenocyanates and, or, respectively, alkylselenosulfates are formed by reaction of alkyl halides with alkali-selenocyanates or selenosulfates.
- Aromatic selenocyanates are formed by reaction of corresponding diazonium slats with alakliselenocyanates.
- the characterized compounds are used as such or better in the form of their salts, e.g. the alkali, ammonium or amino salts.
- the alkali, ammonium or amino salts e.g. the sodium, potassium, ammonium and triethylammonium salt.
- the following table lists compounds to be used according to the invention:
- the sulfuric acid may be replaced in part or entirely by fluoroboric acid, phosphoric acid and/or other acids.
- the electrolyte may be chloride-free or, and this is usually advantageous for improving the luster and the leveling, it may contain chlorides,such as alkali chlorides, or hydrochloric acid in quantities of from 0.001 to 0.2 g/liter.
- the quantities in which the substances according to the invention must be added to the copper baths in order to achieve an improvement of the copper deposition are, surprisingly, very low and amount to about 0.0005 to 0.5 g/liter, preferably 0.0005 to 0.1 g/liter. With these additions one obtains a definite fining of the grain, in certain current density ranges even lustrous copper coatings.
- the substances according to the invention are also especially suitable, in conjunction with other common luster-formers and/or wetting agents, for depositing high-luster coatings which show a great leveling of rugosities of the base material and yet are very ductile and possess a high extensibility.
- oxygen-containing high-molecular compounds As known additives which can be used together with the substances according to the invention there are suitable primarily oxygen-containing high-molecular compounds.
- the quantities of these substances that one adds to the copper electrolyte are about 0.01 to 20.0 g/liter, preferably 0.02 to 8.0 g/liter.
- Table III contains examples of oxygen-containing high-molecular compounds.
- EXAMPLE 1 Copper sulfate (CuS0 .5H O) 220 g/liter Sulfuric acid, cone. 50 g/liter Di-(ILpotassiumsulfopropyl)-diselenide 0.05 g/liter Temperature: 25C Current density: 4.0 A/dm Stock is mixed by agitation
- EXAMPLE 2 Copper fluoroborate (Cu(BF 300 g/liter Fluoroboric acid 20 g/liter 2-(phenylseleno)-ethylsulfonate of sodium 03 g/liter Temperature: 25C Current density: 8.0 A/dm The electrolyte is agitated by injection of air
- EXAMPLE 3 Copper sulfate (CuSO .5H O) Sulfuric acid, conc.
- an acidic electrolyte for the electrodeposition of copper essentially consisting of water, sources of copper ions and of hydrogen ions, and a brightening composition in an amount sufficient to increase the luster of copper electrodeposited from said electrolyte, the improvement in said brightening composition which comprises at least one compound of the formula R (Se), R or a salt thereof, the amount of said compound or salt being between 0.0005 g and 0.5 g per liter of said electrolyte, in said formula R, and R being identical or different, R being a radical of monoor multi-substituted aromatic, aliphatic, cycloaliphatic, araliphatic, or heterocyclic hydrocarbon, R being a radical of a monoor multi-substituted aromatic, aliphatic, cycloaliphatic, araliphatic, or heterocyclic hydrocarbon, cyano or the sulfonic acid group, at least one of said R and R containing a sulfonic acid group, and n being 1 or
- the amount of said at least one compound being not more than 0.1 g per liter of said electrolyte.
- said sources having respective anionic moieties selected from the group consisting of sulfate, fluoborate, and phosphate.
- R is phenyl, nitrophenyl, alkylphenyl, alkoxyphenyl, carboxyphenyl, carbmethoxyphenyl, dimethylaminophenyl), alkylmercaptophenyl, aminophenyl, alkyl containing from 2 to 8 carbon atoms, benzyl, phenoxyalkyl, sulfolanyl, furyl, cyclohexylalkyl, pyridylalkyl, carboxyalkyl, dihydroxypropyl, sulfoalkyl containing 2 to 6 carbon atoms, sulfophenyl, alkoxysulfophenyl, alkylmercapto-sulfophenyl, halogen-sulfophenyl, sulfonaphthyl, di-sulfonaphthyl or sulfophenyl-alkyl, R is s
- R is sulfoalkyl containing 2 to 6 carbons atoms, sulfophenyl, alkoxysulfophenyl, alkylmercapto-sulfophenyl, halogen-sulfophenyl, sulfonaphthyl, disulfonaphthyl, sulfonphenylalkyl, R is the cyanide or the sulfonic acid group, and n is the number 1.
Landscapes
- 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)
- Conductive Materials (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2053860A DE2053860C3 (de) | 1970-10-29 | 1970-10-29 | Saures wäßriges Bad zur galvanischen Abscheidung glänzender Kupferüberzüge |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3767539A true US3767539A (en) | 1973-10-23 |
Family
ID=5786940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00186548A Expired - Lifetime US3767539A (en) | 1970-10-29 | 1971-10-04 | Acid galvanic copper bath |
Country Status (18)
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4417956A (en) * | 1980-07-17 | 1983-11-29 | Electrochemical Products, Inc. | Alkaline plating baths and electroplating process |
| US4540473A (en) * | 1983-11-22 | 1985-09-10 | International Business Machines Corporation | Copper plating bath having increased plating rate, and method |
| US6024857A (en) * | 1997-10-08 | 2000-02-15 | Novellus Systems, Inc. | Electroplating additive for filling sub-micron features |
| US6518182B1 (en) * | 1999-11-12 | 2003-02-11 | Ebara-Udylite Co., Ltd. | Via-filling process |
| EP1485522A4 (en) * | 2002-03-18 | 2007-12-19 | Taskem Inc | FAST ACID COPPER |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3492135A (en) * | 1967-02-01 | 1970-01-27 | Schering Ag | Stabilized bath for deposition of copper by chemical reduction |
| US3502551A (en) * | 1966-08-20 | 1970-03-24 | Schering Ag | Acid electrolyte for the deposition of bright,levelling copper coatings |
| US3664852A (en) * | 1969-12-30 | 1972-05-23 | Hooker Chemical Corp | Electroless copper plating solution and process |
-
1970
- 1970-10-29 DE DE2053860A patent/DE2053860C3/de not_active Expired
-
1971
- 1971-10-04 US US00186548A patent/US3767539A/en not_active Expired - Lifetime
- 1971-10-04 YU YU2509/71A patent/YU34721B/xx unknown
- 1971-10-05 ES ES71395741A patent/ES395741A1/es not_active Expired
- 1971-10-11 SU SU1704167A patent/SU452107A3/ru active
- 1971-10-14 ZA ZA716879A patent/ZA716879B/xx unknown
- 1971-10-18 CH CH1519671A patent/CH563466A5/xx not_active IP Right Cessation
- 1971-10-19 AU AU34734/71A patent/AU450638B2/en not_active Expired
- 1971-10-21 SE SE13374/71A patent/SE364737B/xx unknown
- 1971-10-21 AT AT912871A patent/AT307844B/de not_active IP Right Cessation
- 1971-10-25 GB GB4938671A patent/GB1372850A/en not_active Expired
- 1971-10-25 BR BR7116/71A patent/BR7107116D0/pt unknown
- 1971-10-26 IE IE1352/71A patent/IE35774B1/xx unknown
- 1971-10-29 JP JP46086144A patent/JPS5126893B1/ja active Pending
- 1971-10-29 BE BE774697A patent/BE774697A/xx unknown
- 1971-10-29 NL NLAANVRAGE7114979,A patent/NL169353C/xx not_active IP Right Cessation
- 1971-10-29 CA CA126,465A patent/CA967110A/en not_active Expired
- 1971-10-29 FR FR7138993A patent/FR2111926B1/fr not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3502551A (en) * | 1966-08-20 | 1970-03-24 | Schering Ag | Acid electrolyte for the deposition of bright,levelling copper coatings |
| US3492135A (en) * | 1967-02-01 | 1970-01-27 | Schering Ag | Stabilized bath for deposition of copper by chemical reduction |
| US3664852A (en) * | 1969-12-30 | 1972-05-23 | Hooker Chemical Corp | Electroless copper plating solution and process |
Non-Patent Citations (1)
| Title |
|---|
| H. Koretzky, IBM Tech. Disclosure Bulletin, Vol. 9, No. 11, Apr. 1967. * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4417956A (en) * | 1980-07-17 | 1983-11-29 | Electrochemical Products, Inc. | Alkaline plating baths and electroplating process |
| US4540473A (en) * | 1983-11-22 | 1985-09-10 | International Business Machines Corporation | Copper plating bath having increased plating rate, and method |
| US6024857A (en) * | 1997-10-08 | 2000-02-15 | Novellus Systems, Inc. | Electroplating additive for filling sub-micron features |
| US6284121B1 (en) | 1997-10-08 | 2001-09-04 | Novellus Systems, Inc. | Electroplating system including additive for filling sub-micron features |
| US6518182B1 (en) * | 1999-11-12 | 2003-02-11 | Ebara-Udylite Co., Ltd. | Via-filling process |
| EP1485522A4 (en) * | 2002-03-18 | 2007-12-19 | Taskem Inc | FAST ACID COPPER |
Also Published As
| Publication number | Publication date |
|---|---|
| ES395741A1 (es) | 1974-09-16 |
| CA967110A (en) | 1975-05-06 |
| JPS5126893B1 (enrdf_load_stackoverflow) | 1976-08-09 |
| NL169353B (nl) | 1982-02-01 |
| NL169353C (nl) | 1982-07-01 |
| DE2053860B2 (de) | 1980-03-13 |
| IE35774L (en) | 1972-04-29 |
| SE364737B (enrdf_load_stackoverflow) | 1974-03-04 |
| GB1372850A (en) | 1974-11-06 |
| FR2111926A1 (enrdf_load_stackoverflow) | 1972-06-09 |
| AU450638B2 (en) | 1974-07-18 |
| AU3473471A (en) | 1973-05-03 |
| DE2053860C3 (de) | 1980-11-06 |
| FR2111926B1 (enrdf_load_stackoverflow) | 1974-10-11 |
| ZA716879B (en) | 1972-06-28 |
| CH563466A5 (enrdf_load_stackoverflow) | 1975-06-30 |
| BR7107116D0 (pt) | 1973-03-29 |
| YU34721B (en) | 1979-12-31 |
| SU452107A3 (ru) | 1974-11-30 |
| DE2053860A1 (de) | 1972-06-08 |
| IE35774B1 (en) | 1976-05-12 |
| BE774697A (fr) | 1972-05-02 |
| YU250971A (en) | 1979-04-30 |
| NL7114979A (enrdf_load_stackoverflow) | 1972-05-03 |
| AT307844B (de) | 1973-06-12 |
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