US3502551A - Acid electrolyte for the deposition of bright,levelling copper coatings - Google Patents
Acid electrolyte for the deposition of bright,levelling copper coatings Download PDFInfo
- Publication number
- US3502551A US3502551A US659608A US65960867A US3502551A US 3502551 A US3502551 A US 3502551A US 659608 A US659608 A US 659608A US 65960867 A US65960867 A US 65960867A US 3502551 A US3502551 A US 3502551A
- Authority
- US
- United States
- Prior art keywords
- acid
- copper
- polyvinyl
- electrolyte
- 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
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 29
- 239000003792 electrolyte Substances 0.000 title description 27
- 229910052802 copper Inorganic materials 0.000 title description 25
- 239000010949 copper Substances 0.000 title description 25
- 239000002253 acid Substances 0.000 title description 18
- 230000008021 deposition Effects 0.000 title description 8
- 238000000576 coating method Methods 0.000 title description 5
- 229920002554 vinyl polymer Polymers 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000000151 deposition Methods 0.000 description 8
- 239000002932 luster Substances 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 229920000151 polyglycol Polymers 0.000 description 5
- 239000010695 polyglycol Substances 0.000 description 5
- -1 thioethylurethane Chemical compound 0.000 description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920001522 polyglycol ester Polymers 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- 150000003580 thiophosphoric acid esters Chemical class 0.000 description 2
- 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
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical compound C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 1
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical compound O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- IOEJYZSZYUROLN-UHFFFAOYSA-M Sodium diethyldithiocarbamate Chemical compound [Na+].CCN(CC)C([S-])=S IOEJYZSZYUROLN-UHFFFAOYSA-M 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- FFBZKUHRIXKOSY-UHFFFAOYSA-N aziridine-1-carboxamide Chemical compound NC(=O)N1CC1 FFBZKUHRIXKOSY-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 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
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229940042396 direct acting antivirals thiosemicarbazones Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical class C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000003560 thiocarbamic acids Chemical class 0.000 description 1
- 150000003584 thiosemicarbazones Chemical class 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 230000037303 wrinkles Effects 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 an acid electrolyte for the deposition of bright leveling copper coatings.
- An object in particular is to improve electrolytic deposition from aqueous acid solutions of copper salts.
- R is the amino group or its functional derivatives or a heterocyclic radical combined through a nitrogen atom and possibly containing additional hetero atoms, and n is an integer between about 5 and 1000. More specifically, R is bound to said (CH CH) by a carbon-nitrogen bond and is the radical of a base selected from the group consisting of ammonia, dimethylamine, acetamide, thioethylurethane, carbamic acid, thiourea, succinimide, imidazole, N,N'-ethyleneurea, pyrollidone- (2), morpholine, morpholinone-(3), benzibidazol, 5- alkyloxazolidone-(Z), and caprolactam.
- a base selected from the group consisting of ammonia, dimethylamine, acetamide, thioethylurethane, carbamic acid, thiourea, succinimide, imidazole, N,N'-ethyleneurea, pyrollidone- (2),
- polyvinyl amine and its functional derivatives as Well as N heterocyclic polyvinyl compounds. These are known per se and can be produced in a manner known in the art.
- Polyvinyl amine for example, is formed by acid or alkaline saponification of cyclic N-vinyl imides, such as N-polyvinylphthalimide, as disclosed in US. Patent 2,484,423, or by saponification of poly-ethyl-N-vinyl carbamate, as disclosed in German Patent 865,901.
- N-polyvinylacetamide is obtained, for example, by acylation of polyvinyl amine with acid chloride or acid anhydride by generally practiced methods disclosed in US. Patent 2,507,181.
- N-polyvinyl carbamates (-N-polyvinyl carbamide esters) are formed, for example, by polymerization of vinyl isocyanates with alcohols in the presence of azoisobutyric acid dinitrile, as disclosed in Belgian Patent 540,975.
- N-polyvinyl pyrrolidone as disclosed in German Patent 922,378
- N-polyvinyl morpholinone-(3) as disclosed in British Patent 849,038
- N-polyvinyl-S-alkyl-oxazolidone-(2) as disclosed in US. Patent 2,946,773
- these compounds are present in the copper bath as salts, for example as sulfates in the usual sulfuric acid electrolytes, but they may alternately be added in salt form, such as hydrochloride, methyl iodide, ethyl bromide, etc.
- the quantities needed for a marked improvement of the copper deposition, in particular of the leveling effect are extremely small, ranging from between 0.0005 and 0.1 g./liter, generally 0.0005 to 0.03 g./liter, depending on which basic luster former the copper bath contains.
- the electrolyte there is used as the electrolyte a sulfuric acid copper sulfate solution of the following composition g./liter Copper sulfate CuSO -5H O 125-260 Sulfuric acid H 80 2085
- copper sulfates other copper salts may be used at least in part.
- the sulfuric acid may be replaced in part or wholly by fiuoroboric acid, phosphoric acid, or other acids.
- the electrolyte may be chloride free or, and this is advantageous for improvement of the luster, contain chlorides, e.g. alkali chlorides in quantities of 0.001 to 0.2 g./liter.
- other common lusters formers and/or wetting agents may be used.
- Oxygen-containing high-molecular compounds 0.01-1O g./liter, preferably 0.02-5 g./liter Organic thio compounds with water-solubilizing groups 0.0020.2 g./liter, preferably 0.005-0.1 g./liter TABLE 2 Preferred concen- Substance: tration, g./liter 1) Polyvinyl alcohol 0.05-.4 -(2) Carboxymethyl cellulose 0.05-0.1 (3) Polyethylene glycol 0.05-0.5 (4) Polypropylene glycol 0.01-0.2 Stearic acid polyglycol ester 0.5 5.0 (6) Oleic acid polyglycol ester 0.5-5.0 (7) Steryl alcohol polyglycol ether 05-50 (8) Nonylphenol polyglycol ether 0.52.0
- the compounds of Tables 2 and 3 are used together with one or more substances of Table 1 in acid copper electrolytes, there is obtained a distinct and drastic improvement of the leveling effect.
- the mixture ratios of the individual components may vary within wide limits. It has proved to be favorable, if there is a ratio by weight of the substances listed by Way of example in Tables 1, 2 .and 3 of approximately 1:102 to approximately 1:200:20.
- the electrolyte may contain other known luster formers, such as thiourea or its derivatives, dithiocarbarnic acid esters, thiosemicarbazones, phenazine dyes, or alkaloids.
- the electrolyte with a current density of an average of 4.0 a./sq. dm. and with cathode movement, bright copper precipitates are indeed obtained, but the leveling of the wrinkles of the base material is only 46% at a film thickness of 24 millimicrons. If additionally, 0.005 g./liter of N-polyvinyl pyrrolidone-(Z) is charged in the bath, the leveling increases to under the same operating conditions, an apparent increase of 63%.
- the leveling effect at a film thickness of 24 millimicrons copper is about 50%.
- the leveling increases to 83%, so that the increment is 66%.
- An equally great improvement of the deposition is obtained if one adds to the copper bath, instead of the polyvinyl amine, 0.02 g./liter N-polyvinyl imidazole or 0.004 g./ liter of an N-polyvinyl- 5-alkyl-oxazolidone-( 2)
- excellent effects can be attained with the joint use of the other substances listed in Table 1 with the compounds of Tables 2 and 3.
- said additional brightener being present in said electrolyte in an amount sufficient to produce a leveling effect on the deposited copper.
- the amount of said additional brightener being between 0.0005 and 0.1 gram per liter of said electrolyte.
- the amount of said additional brightener being not greater than 0.03 gram per liter.
- said mem ber of said first group being present in said electrolyte in an amount of 0.02 to 5 grams per liter, and said member of said second group being present in said electrolyte in an amount of 0.005 to 0.1 gram per liter.
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)
- Paints Or Removers (AREA)
- Electrolytic Production Of Metals (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DESC039431 | 1966-08-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3502551A true US3502551A (en) | 1970-03-24 |
Family
ID=7435168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US659608A Expired - Lifetime US3502551A (en) | 1966-08-20 | 1967-08-10 | Acid electrolyte for the deposition of bright,levelling copper coatings |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US3502551A (enrdf_load_stackoverflow) |
| GB (1) | GB1199494A (enrdf_load_stackoverflow) |
| SE (1) | SE322956B (enrdf_load_stackoverflow) |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3725220A (en) * | 1972-04-27 | 1973-04-03 | Lea Ronal Inc | Electrodeposition of copper from acidic baths |
| US3743584A (en) * | 1970-06-06 | 1973-07-03 | Schering Ag | Acid bright copper plating bath |
| US3767539A (en) * | 1970-10-29 | 1973-10-23 | Schering Ag | Acid galvanic copper bath |
| US3770598A (en) * | 1972-01-21 | 1973-11-06 | Oxy Metal Finishing Corp | Electrodeposition of copper from acid baths |
| US3770599A (en) * | 1971-05-24 | 1973-11-06 | Oxy Metal Finishing Corp | Acid zinc plating baths |
| US3865744A (en) * | 1971-04-02 | 1975-02-11 | Alan James Parker | Method of producing copper and composition therefor |
| US3961028A (en) * | 1971-04-02 | 1976-06-01 | Anumin Pty. Limited | Method of producing cuprous sulfate and bisulfate solutions |
| US3966890A (en) * | 1971-04-02 | 1976-06-29 | Anumin Pty. Limited | Method of producing solutions containing cuprous ions |
| US4113848A (en) * | 1971-04-02 | 1978-09-12 | Anumin Pty. Limited | Method of producing solutions containing cuprous ions |
| DE2746938A1 (de) * | 1977-10-17 | 1979-04-19 | Schering Ag | Saures galvanisches kupferbad |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| US4604175A (en) * | 1982-12-07 | 1986-08-05 | Naumov Jury I | Process for regeneration of iron-copper chloride etching solution |
| DE3836521A1 (de) * | 1988-10-24 | 1990-04-26 | Schering Ag | Waessriges saures bad zur galvanischen abscheidung von glaenzenden und rissfreien kupferueberzuegen und verwendung dieses bades |
| US5151170A (en) * | 1991-12-19 | 1992-09-29 | Mcgean-Rohco, Inc. | Acid copper electroplating bath containing brightening additive |
| US5232575A (en) * | 1990-07-26 | 1993-08-03 | Mcgean-Rohco, Inc. | Polymeric leveling additive for acid electroplating baths |
| EP0785297A2 (de) | 1990-03-19 | 1997-07-23 | ATOTECH Deutschland GmbH | Wässriges saures Bad zur galvanischen Abscheidung von glänzenden und rissfreien Kupferüberzügen und Verwendung dieses Bades |
| US5730854A (en) * | 1996-05-30 | 1998-03-24 | Enthone-Omi, Inc. | Alkoxylated dimercaptans as copper additives and de-polarizing additives |
| DE19758121A1 (de) * | 1997-12-17 | 1999-07-01 | Atotech Deutschland Gmbh | Wäßriges Bad und Verfahren zum elektrolytischen Abscheiden von Kupferschichten |
| US20050148480A1 (en) * | 2003-12-03 | 2005-07-07 | For Your Ease Only, Inc. | Anti-tarnish aqueous treatment |
| WO2006094755A1 (en) | 2005-03-11 | 2006-09-14 | Atotech Deutschland Gmbh | Polyvinylammonium compound, method of manufacturing same, acidic solution containing said compound and method of electrolytically depositing a copper deposit |
| US20060207886A1 (en) * | 2004-07-23 | 2006-09-21 | C. Uyemura & Co., Ltd. | Electrolytic copper plating bath and plating process therewith |
| US20070084732A1 (en) * | 2005-09-30 | 2007-04-19 | Rohm And Haas Electronic Materials Llc | Leveler compounds |
| US20080121527A1 (en) * | 2002-03-05 | 2008-05-29 | Enthone Inc. | Defect reduction in electrodeposited copper for semiconductor applications |
| US20100219081A1 (en) * | 2007-05-21 | 2010-09-02 | C. Uyemura & Co., Ltd. | Copper electroplating bath |
| CN101935854A (zh) * | 2010-09-20 | 2011-01-05 | 东莞华威铜箔科技有限公司 | 电解铜箔用添加剂的制备方法、制品及其应用 |
| CN102021616A (zh) * | 2009-09-16 | 2011-04-20 | 上村工业株式会社 | 铜电镀浴及使用该铜电镀浴的电镀方法 |
| US9493884B2 (en) | 2002-03-05 | 2016-11-15 | Enthone Inc. | Copper electrodeposition in microelectronics |
| US10106512B2 (en) | 2015-04-28 | 2018-10-23 | Dow Global Technologies Llc | Metal plating compositions |
| US10196751B2 (en) | 2013-11-06 | 2019-02-05 | Rohm And Haas Electronic Materials Llc | Nitrogen containing polymers as levelers |
| US10665865B2 (en) * | 2018-10-01 | 2020-05-26 | Chang Chun Petrochemical Co., Ltd. | Copper foil for current collector of lithium secondary battery and negative electrode including the same |
| CN113881984A (zh) * | 2021-10-21 | 2022-01-04 | 深圳市励高表面处理材料有限公司 | 一种脉冲电镀整平剂及制备方法和应用该整平液的电镀液 |
| CN114875409A (zh) * | 2022-06-07 | 2022-08-09 | 深圳市板明科技股份有限公司 | 一种线路板微蚀粗化液循环再生添加剂及其应用 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117684222A (zh) * | 2022-09-02 | 2024-03-12 | 宁波安集微电子科技有限公司 | 一种用于电解铜涂层的金属电镀组合物及其应用方法 |
| CN117684223A (zh) * | 2022-09-02 | 2024-03-12 | 宁波安集微电子科技有限公司 | 一种金属电镀组合物及其使用方法 |
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| US2849351A (en) * | 1953-09-19 | 1958-08-26 | Dehydag Gmbh | Electroplating process |
| US2853444A (en) * | 1955-10-18 | 1958-09-23 | Dow Chemical Co | Electrowinning of metals |
| US2872346A (en) * | 1956-05-21 | 1959-02-03 | Miller Adolph | Metal plating bath |
| US2931760A (en) * | 1957-09-25 | 1960-04-05 | Leon R Westbrook | Acid copper plating |
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Cited By (54)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3743584A (en) * | 1970-06-06 | 1973-07-03 | Schering Ag | Acid bright copper plating bath |
| US3767539A (en) * | 1970-10-29 | 1973-10-23 | Schering Ag | Acid galvanic copper bath |
| US3966890A (en) * | 1971-04-02 | 1976-06-29 | Anumin Pty. Limited | Method of producing solutions containing cuprous ions |
| US4113848A (en) * | 1971-04-02 | 1978-09-12 | Anumin Pty. Limited | Method of producing solutions containing cuprous ions |
| US3865744A (en) * | 1971-04-02 | 1975-02-11 | Alan James Parker | Method of producing copper and composition therefor |
| US3961028A (en) * | 1971-04-02 | 1976-06-01 | Anumin Pty. Limited | Method of producing cuprous sulfate and bisulfate solutions |
| US3770599A (en) * | 1971-05-24 | 1973-11-06 | Oxy Metal Finishing Corp | Acid zinc plating baths |
| US3770598A (en) * | 1972-01-21 | 1973-11-06 | Oxy Metal Finishing Corp | Electrodeposition of copper from acid baths |
| US3725220A (en) * | 1972-04-27 | 1973-04-03 | Lea Ronal Inc | Electrodeposition of copper from acidic baths |
| DE2746938A1 (de) * | 1977-10-17 | 1979-04-19 | Schering Ag | Saures galvanisches kupferbad |
| JPS5464025A (en) * | 1977-10-17 | 1979-05-23 | Schering Ag | Acidic copper plating bath |
| DE2746938C2 (de) | 1977-10-17 | 1987-04-09 | Schering AG, 1000 Berlin und 4709 Bergkamen | Wäßriges saures Bad zur galvanischen Abscheidung von glänzenden und rißfreien Kupferüberzügen und Verwendung dieses Bades |
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| US4604175A (en) * | 1982-12-07 | 1986-08-05 | Naumov Jury I | Process for regeneration of iron-copper chloride etching solution |
| DE3836521A1 (de) * | 1988-10-24 | 1990-04-26 | Schering Ag | Waessriges saures bad zur galvanischen abscheidung von glaenzenden und rissfreien kupferueberzuegen und verwendung dieses bades |
| EP0785297A2 (de) | 1990-03-19 | 1997-07-23 | ATOTECH Deutschland GmbH | Wässriges saures Bad zur galvanischen Abscheidung von glänzenden und rissfreien Kupferüberzügen und Verwendung dieses Bades |
| EP0785297A3 (enrdf_load_stackoverflow) * | 1990-03-19 | 1997-08-20 | Atotech Deutschland Gmbh | |
| US5232575A (en) * | 1990-07-26 | 1993-08-03 | Mcgean-Rohco, Inc. | Polymeric leveling additive for acid electroplating baths |
| US5151170A (en) * | 1991-12-19 | 1992-09-29 | Mcgean-Rohco, Inc. | Acid copper electroplating bath containing brightening additive |
| US5730854A (en) * | 1996-05-30 | 1998-03-24 | Enthone-Omi, Inc. | Alkoxylated dimercaptans as copper additives and de-polarizing additives |
| DE19758121A1 (de) * | 1997-12-17 | 1999-07-01 | Atotech Deutschland Gmbh | Wäßriges Bad und Verfahren zum elektrolytischen Abscheiden von Kupferschichten |
| DE19758121C2 (de) * | 1997-12-17 | 2000-04-06 | Atotech Deutschland Gmbh | Wäßriges Bad und Verfahren zum elektrolytischen Abscheiden von Kupferschichten |
| US6425996B1 (en) * | 1997-12-17 | 2002-07-30 | Atotech Deutschland Gmbh | Water bath and method for electrolytic deposition of copper coatings |
| US9493884B2 (en) | 2002-03-05 | 2016-11-15 | Enthone Inc. | Copper electrodeposition in microelectronics |
| US9222188B2 (en) * | 2002-03-05 | 2015-12-29 | Enthone Inc. | Defect reduction in electrodeposited copper for semiconductor applications |
| US20080121527A1 (en) * | 2002-03-05 | 2008-05-29 | Enthone Inc. | Defect reduction in electrodeposited copper for semiconductor applications |
| US7037379B2 (en) * | 2003-12-03 | 2006-05-02 | For Your Ease Only, Inc. | Anti-tarnish aqueous treatment |
| US20050148480A1 (en) * | 2003-12-03 | 2005-07-07 | For Your Ease Only, Inc. | Anti-tarnish aqueous treatment |
| CN100595343C (zh) * | 2004-07-23 | 2010-03-24 | 上村工业株式会社 | 电镀铜浴和电镀铜的方法 |
| US20060207886A1 (en) * | 2004-07-23 | 2006-09-21 | C. Uyemura & Co., Ltd. | Electrolytic copper plating bath and plating process therewith |
| US7220347B2 (en) * | 2004-07-23 | 2007-05-22 | C. Uyemura & Co., Ltd. | Electrolytic copper plating bath and plating process therewith |
| WO2006094755A1 (en) | 2005-03-11 | 2006-09-14 | Atotech Deutschland Gmbh | Polyvinylammonium compound, method of manufacturing same, acidic solution containing said compound and method of electrolytically depositing a copper deposit |
| JP2008533224A (ja) * | 2005-03-11 | 2008-08-21 | アトーテヒ ドイッチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング | ポリビニルアンモニウム化合物、ポリビニルアンモニウム化合物の製造方法、ポリビニルアンモニウム化合物を含有する酸性溶液及び銅めっきを電気分解的に析出する方法 |
| US20080210569A1 (en) * | 2005-03-11 | 2008-09-04 | Wolfgang Dahms | Polyvinylammonium Compound, Method of Manufacturing Same, Acidic Solution Containing Said Compound and Method of Electrolytically Depositing a Copper Deposit |
| US8114263B2 (en) | 2005-03-11 | 2012-02-14 | Atotech Deutschland Gmbh | Polyvinylammonium compound, method of manufacturing same, acidic solution containing said compound and method of electrolytically depositing a copper deposit |
| CN1940146B (zh) * | 2005-09-30 | 2010-05-12 | 罗门哈斯电子材料有限公司 | 匀平剂化合物 |
| US20070084732A1 (en) * | 2005-09-30 | 2007-04-19 | Rohm And Haas Electronic Materials Llc | Leveler compounds |
| EP1798314A1 (en) * | 2005-09-30 | 2007-06-20 | Rohm and Haas Electronic Materials, L.L.C. | Leveler compounds |
| US8262891B2 (en) * | 2005-09-30 | 2012-09-11 | Rohm And Haas Electronic Materials Llc | Leveler compounds |
| US8506788B2 (en) | 2005-09-30 | 2013-08-13 | Rohm And Haas Electronic Materials Llc | Leveler compounds |
| US8679317B2 (en) | 2007-05-21 | 2014-03-25 | C. Uyemura & Co., Ltd. | Copper electroplating bath |
| US20100219081A1 (en) * | 2007-05-21 | 2010-09-02 | C. Uyemura & Co., Ltd. | Copper electroplating bath |
| EP2161355A4 (en) * | 2007-05-21 | 2012-01-25 | Uyemura C & Co Ltd | KUPFERGALVANISIERUNGSBAD |
| CN102021616A (zh) * | 2009-09-16 | 2011-04-20 | 上村工业株式会社 | 铜电镀浴及使用该铜电镀浴的电镀方法 |
| CN102021616B (zh) * | 2009-09-16 | 2016-04-27 | 上村工业株式会社 | 铜电镀浴及使用该铜电镀浴的电镀方法 |
| CN101935854B (zh) * | 2010-09-20 | 2011-11-30 | 东莞华威铜箔科技有限公司 | 电解铜箔用添加剂的制备方法、制品及其应用 |
| CN101935854A (zh) * | 2010-09-20 | 2011-01-05 | 东莞华威铜箔科技有限公司 | 电解铜箔用添加剂的制备方法、制品及其应用 |
| US10196751B2 (en) | 2013-11-06 | 2019-02-05 | Rohm And Haas Electronic Materials Llc | Nitrogen containing polymers as levelers |
| US10106512B2 (en) | 2015-04-28 | 2018-10-23 | Dow Global Technologies Llc | Metal plating compositions |
| US10435380B2 (en) | 2015-04-28 | 2019-10-08 | Rohm And Haas Electronic Materials Llc | Metal plating compositions |
| US10665865B2 (en) * | 2018-10-01 | 2020-05-26 | Chang Chun Petrochemical Co., Ltd. | Copper foil for current collector of lithium secondary battery and negative electrode including the same |
| CN113881984A (zh) * | 2021-10-21 | 2022-01-04 | 深圳市励高表面处理材料有限公司 | 一种脉冲电镀整平剂及制备方法和应用该整平液的电镀液 |
| CN114875409A (zh) * | 2022-06-07 | 2022-08-09 | 深圳市板明科技股份有限公司 | 一种线路板微蚀粗化液循环再生添加剂及其应用 |
| CN114875409B (zh) * | 2022-06-07 | 2023-09-01 | 深圳市板明科技股份有限公司 | 一种线路板微蚀粗化液循环再生添加剂及其应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1521031A1 (de) | 1969-09-04 |
| GB1199494A (en) | 1970-07-22 |
| DE1521031B2 (de) | 1975-09-25 |
| SE322956B (enrdf_load_stackoverflow) | 1970-04-20 |
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