US3743584A - Acid bright copper plating bath - Google Patents
Acid bright copper plating bath Download PDFInfo
- Publication number
- US3743584A US3743584A US00149335A US3743584DA US3743584A US 3743584 A US3743584 A US 3743584A US 00149335 A US00149335 A US 00149335A US 3743584D A US3743584D A US 3743584DA US 3743584 A US3743584 A US 3743584A
- Authority
- US
- United States
- Prior art keywords
- acid
- liter
- copper
- compounds
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000010949 copper Substances 0.000 title claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- 239000002253 acid Substances 0.000 title abstract description 24
- 238000007747 plating Methods 0.000 title description 3
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 230000008021 deposition Effects 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- -1 alkyl radicals Chemical class 0.000 description 10
- 239000000975 dye Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 9
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000007792 addition Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 229960000443 hydrochloric acid Drugs 0.000 description 5
- 235000011167 hydrochloric acid Nutrition 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 235000010288 sodium nitrite Nutrition 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 150000001989 diazonium salts Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 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 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001522 polyglycol ester Polymers 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 125000003107 substituted aryl group Chemical group 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000002585 base Substances 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 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 1
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical compound O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 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
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000001049 brown dye Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000034303 cell budding Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- ZNNYSTVISUQHIF-UHFFFAOYSA-N formaldehyde;thiourea Chemical compound O=C.NC(N)=S ZNNYSTVISUQHIF-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000003381 solubilizing effect Effects 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
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940032330 sulfuric acid Drugs 0.000 description 1
- 150000003580 thiophosphoric acid esters Chemical class 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
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/46—Phenazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0694—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring, e.g. polyquinoxalines
Definitions
- the invention relates to new polymeric phenazonium compounds, methods for their production, as well as their use in acid electrolytes for the deposition of bright, leveling copper coatings.
- an acid copper electrolyte which is characterized by a content of at least one compound of the general formula wherein R R,, R R R R R R and R, are identical or different and represent hydrogen, a low alkyl or possibly substituted aryl, and R and R represent moreover monomeric or polymeric phenazonium radicals, A is an acid radical, and n an integer from 2 to 100, preferably from 4 to 20.
- An aryl radical may be, for example, phenyl, which may be substituted by methyl, ethyl, methoxy or ethoxy, etc.
- acid radicals there enter into consideration, for example, those of hydro-chloric acid (Cl'), sulfuric acid (HSOf), nitric acid (NO and acetic acid (Cl-[,coo), etc. a
- the radicals R and R may signify moreover, for example phenazonium radicals of the parent substance.
- the quantities in which the identified compounds must be added to the copper baths in order to obtain a clear improvement of the copper deposition are surprisingly very small and amount to about 0.0005 to 0.1 g/liter, preferably 0.0005 to 0.03 g/liter.
- Table l contains examples for substances according to the invention and data on the preferred concentrations in the electrolyte.
- the linkage points of the radicals are not fully clarified.
- the linkage may take place, besides through the 3-position of the phenazonium radical, also through the disadvantages of the known acid copper baths and S-and the 7-position.
- the invention therefore, further relates to a method for the production of the compounds identified above.
- A is an acid radical, from which then the desired reaction products are formed by diazotizing in acid solution and subsequent boiling down of the resulting diazonium salts.
- the diazotizing of the amino compounds is effected in sulfuric acid, hydrochloric acid, or acetic acid solution. These acids then form the above-mentioned acid radical A.
- diazotizing agents that are suitable are sodium nitrite or nitrosylsulfuric acid, etc.
- the so-called boiling down of the formed diazonium salts may take place at temperatures of about 5 to C, preferably about 10 to 25 C.
- reaction products precipitate from the acid reaction solution or can be precipitated therefrom by neutralization with bases, e.g., ammonia, soda or potash lye. Isolation is then effected by common methods.
- bases e.g., ammonia, soda or potash lye.
- Copper sulfate CuSo 5 H,O -260 g/liter Sulfuric'acid l-l SO 20-85 g/liter instead of copper sulfate, at least in part, other copper salts may be used.
- the sulfuric acid may be replaced partly or wholly by fluoroboric acid, phosphoric acid and/or other suitable acids.
- the electrolyte may be chloride-free, or this being usually advantageous for improving the luster and the leveling, it may contain chlorides, such as, alkali chlorides or hydrochloric acid, in quantities of 0.001 to 0.2 g/liter.
- the normally crystallinedull precipitate turns out bright in a wide current density range.
- the cathodic current density may be increased by about 50 percent without the formation of flaws, in particular budding, in the range of high current densities. To attain a certain layer thickness, therefore, the time of exposure may be reduced accordingly and in a unit of given size more merchandise can be put through.
- the substances according to the invention are also particularly suited for depositing haze-free and highbrighteners coatings in conjunction with other common luster-formers and/or wetting agents. Electrolytes containing the substances of Table I show also excellent ageing. Even after a current passage of 200-400 Ah/ltr and more, the copper coatings turn out just as highly lustrous, leveling and ductile as in a fresh batch of electrolyte. No harmful decomposition products of these substances are formed that would require purification, for example, with active carbon.
- Organic thio compounds with water solubilizing groups 0.0005-0.2 g/liter, preferably0.0l-0.l g/liter.
- Table II below contains examples of oxygencontaining, high-molecular compounds and their preferred concentrations.
- Table III contains examples of organic thio compounds with water-colubilizing groups and their preferred concentrations.
- the applicable cathodic current density is increased up to 50 percent
- the leveling effect i.e., the reduction of roughness of the ground material, is increased (measured at a layer thickness of 24 microns) from 40-50 percent to about 70-80 percent.
- the concentration ratios of the individual compounds in the copper electrolyte may vary within wide limits. It has proved favorable to have a weight ratio of the substances, listed by way of example in Tables I, II and Ill, of about I l 2 to about I 200 20.
- EXAMPLE 2 To a copper bath of the composition 200 g/liter copper sulfate (CuSO, 5 H 0) 60 g/liter sulfuric acid, concentrated 0.05 g/liter sodium chloride there are added as brighteners 0.6 g/liter polypropylene glycol and 0.02 g/liter sodium 3-mercaptopropane-l sulfonate.
- CuSO copper sulfate
- 5 H 0 sulfuric acid
- concentrated 0.05 g/liter sodium chloride there are added as brighteners 0.6 g/liter polypropylene glycol and 0.02 g/liter sodium 3-mercaptopropane-l sulfonate.
- an acid electrolyte for the deposition of bright copper coatings comprising (a) an oxygen containing high molecular weight compound selected from the group consisting of polyvinyl alcohol, carboxymethyl cellulose, polyethylene glycol, stearic acid polyglycol ester, oleic acid polycol ester, and nonylphenol polyglycol ester; (b) an organic thio compound selected from the group consisting of sodium salt of N N-diethyl-dithiocarbamic acid (sulfopropyl ester), sodium mercaptobenzothiazol-S-propanesulfonate, sodium S-mercapto-propane-l-sulfonate, bis-(S-sodium sulfopropyl)-disulfide, disodium salt of thiophosphoric acidacid-O-ethyl-bis-(sulfopropyl) ester, trisodium salt of thiophosphoric acid-tri-(sulfo
- An electrolyte according to claim 2 characterized in that it additionally contains oxygen-containing, highmolecular compounds and organic thio compounds with water-solubilizing groups.
- Electrolyte according to claim 3 characterized in that it contains the oxygen-containing, high-molecular compounds in quantities of 0.01 to 20.0 g/liter, preferably 0.02 to 8.0 g/liter and the organic thio compounds with water-solubilizlng groups in quantities of 0.0005 to 0.2 g/liter, preferably 0.01 to 0.1 g/liter.
- An electrolyte for the deposition of bright copper coatings comprising at least one compound of the wherein R through R, are individually selected from the group-consisting of hydrogen, lower alkyl, aryl, and substituted aryl, R and R being additionally a monomeric or polymeric phenazonium radical; A is an acid radical; and n is an integer from 2 to 100.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Detergent Compositions (AREA)
- Paints Or Removers (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2039831A DE2039831C3 (de) | 1970-06-06 | 1970-06-06 | Saures Bad zur galvanischen Abscheidung glänzender Kupferüberzüge |
| DE2028803A DE2028803C3 (de) | 1970-06-06 | 1970-06-06 | Polymere Phenazoniumverbindungen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3743584A true US3743584A (en) | 1973-07-03 |
Family
ID=25759264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00149335A Expired - Lifetime US3743584A (en) | 1970-06-06 | 1971-06-02 | Acid bright copper plating bath |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3743584A (enrdf_load_stackoverflow) |
| AT (1) | AT302764B (enrdf_load_stackoverflow) |
| CA (1) | CA961494A (enrdf_load_stackoverflow) |
| CH (1) | CH556347A (enrdf_load_stackoverflow) |
| DE (2) | DE2028803C3 (enrdf_load_stackoverflow) |
| FR (1) | FR2095876A5 (enrdf_load_stackoverflow) |
| GB (1) | GB1357442A (enrdf_load_stackoverflow) |
| NL (1) | NL173277C (enrdf_load_stackoverflow) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50104143A (enrdf_load_stackoverflow) * | 1974-01-23 | 1975-08-16 | ||
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| US4786746A (en) * | 1987-09-18 | 1988-11-22 | Pennsylvania Research Corporation | Copper electroplating solutions and methods of making and using them |
| US4948474A (en) * | 1987-09-18 | 1990-08-14 | Pennsylvania Research Corporation | Copper electroplating solutions and methods |
| US5433840A (en) * | 1991-08-07 | 1995-07-18 | Atotech Deutschland Gmbh | Acid bath for the galvanic deposition of copper, and the use of such a bath |
| US5730854A (en) * | 1996-05-30 | 1998-03-24 | Enthone-Omi, Inc. | Alkoxylated dimercaptans as copper additives and de-polarizing additives |
| US5849171A (en) * | 1990-10-13 | 1998-12-15 | Atotech Deutschland Gmbh | Acid bath for copper plating and process with the use of this combination |
| EP1054080A3 (en) * | 1999-05-17 | 2004-03-03 | Shipley Company LLC | Electrolytic copper plating solutions |
| US20040231995A1 (en) * | 2003-05-23 | 2004-11-25 | Kenji Murao | Printed circuit boards and the methods of their production |
| WO2005049584A1 (en) * | 2003-11-19 | 2005-06-02 | Atotech Deutschland Gmbh | Acidic bath for electrolytically depositing a copper deposit containing halogenated or pseudohalogenated monomeric phenazinium compounds |
| US20080142370A1 (en) * | 2003-08-08 | 2008-06-19 | Wolfgang Dahms | Aqueous, Acidic Solution and Method for Electrolytically Depositing Copper Coatings as Well as Use of Said Solution |
| CN101899687A (zh) * | 2010-08-03 | 2010-12-01 | 济南德锡科技有限公司 | 单剂染料型光亮酸性镀铜添加剂及其制备方法和应用 |
| WO2012040417A1 (en) | 2010-09-24 | 2012-03-29 | Macdermid Acumen, Inc. | Improved method of producing polymeric phenazonium compounds |
| US8735580B2 (en) | 2010-09-24 | 2014-05-27 | Andrew M. Krol | Method of producing polymeric phenazonium compounds |
| US20150030873A1 (en) * | 2013-07-23 | 2015-01-29 | Chang Chun Petrochemical Co., Ltd. | Electrolytic copper foil |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU559896B2 (en) * | 1983-06-10 | 1987-03-26 | Omi International Corp. | Electrolytic copper depositing processes |
| DE4032864A1 (de) * | 1990-10-13 | 1992-04-16 | Schering Ag | Saures bad zur galvanischen abscheidung von kupferueberzuegen und verfahren unter verwendung dieser kombination |
| DE19758121C2 (de) * | 1997-12-17 | 2000-04-06 | Atotech Deutschland Gmbh | Wäßriges Bad und Verfahren zum elektrolytischen Abscheiden von Kupferschichten |
| DE10261852B3 (de) | 2002-12-20 | 2004-06-03 | Atotech Deutschland Gmbh | Gemisch oligomerer Phenaziniumverbindungen und dessen Herstellungsverfahren, saures Bad zur elektrolytischen Abscheidung eines Kupferniederschlages, enthaltend die oligomeren Phenaziniumverbindungen, sowie Verfahren zum elektrolytischen Abscheiden eines Kupferniederschlages mit einem das Gemisch enthaltenden Bad |
| DE102005011708B3 (de) | 2005-03-11 | 2007-03-01 | Atotech Deutschland Gmbh | Polyvinylammoniumverbindung und Verfahren zu deren Herstellung sowie diese Verbindung enthaltende saure Lösung und Verfahren zum elektrolytischen Abscheiden eines Kupferniederschlages |
| EP3483307B1 (en) | 2017-11-09 | 2020-04-01 | ATOTECH Deutschland GmbH | Plating compositions for electrolytic copper deposition, its use and a method for electrolytically depositing a copper or copper alloy layer onto at least one surface of a substrate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2707167A (en) * | 1952-05-26 | 1955-04-26 | Udylite Corp | Electrodeposition of copper from an acid bath |
| US2707166A (en) * | 1952-05-26 | 1955-04-26 | Udylite Corp | Electrodeposition of copper from an acid bath |
| US3267010A (en) * | 1962-04-16 | 1966-08-16 | Udylite Corp | Electrodeposition of copper from acidic baths |
| US3328273A (en) * | 1966-08-15 | 1967-06-27 | Udylite Corp | Electro-deposition of copper from acidic baths |
| US3502551A (en) * | 1966-08-20 | 1970-03-24 | Schering Ag | Acid electrolyte for the deposition of bright,levelling copper coatings |
-
1970
- 1970-06-06 DE DE2028803A patent/DE2028803C3/de not_active Expired
- 1970-06-06 DE DE2039831A patent/DE2039831C3/de not_active Expired
-
1971
- 1971-05-24 CH CH755871A patent/CH556347A/xx not_active IP Right Cessation
- 1971-06-02 US US00149335A patent/US3743584A/en not_active Expired - Lifetime
- 1971-06-02 CA CA114,600A patent/CA961494A/en not_active Expired
- 1971-06-03 AT AT482371A patent/AT302764B/de not_active IP Right Cessation
- 1971-06-03 FR FR7120152A patent/FR2095876A5/fr not_active Expired
- 1971-06-07 NL NLAANVRAGE7107804,A patent/NL173277C/xx not_active IP Right Cessation
- 1971-06-07 GB GB1917271*[A patent/GB1357442A/en not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2707167A (en) * | 1952-05-26 | 1955-04-26 | Udylite Corp | Electrodeposition of copper from an acid bath |
| US2707166A (en) * | 1952-05-26 | 1955-04-26 | Udylite Corp | Electrodeposition of copper from an acid bath |
| US3267010A (en) * | 1962-04-16 | 1966-08-16 | Udylite Corp | Electrodeposition of copper from acidic baths |
| US3328273A (en) * | 1966-08-15 | 1967-06-27 | Udylite Corp | Electro-deposition of copper from acidic baths |
| US3502551A (en) * | 1966-08-20 | 1970-03-24 | Schering Ag | Acid electrolyte for the deposition of bright,levelling copper coatings |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50104143A (enrdf_load_stackoverflow) * | 1974-01-23 | 1975-08-16 | ||
| US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
| US4786746A (en) * | 1987-09-18 | 1988-11-22 | Pennsylvania Research Corporation | Copper electroplating solutions and methods of making and using them |
| US4948474A (en) * | 1987-09-18 | 1990-08-14 | Pennsylvania Research Corporation | Copper electroplating solutions and methods |
| US5849171A (en) * | 1990-10-13 | 1998-12-15 | Atotech Deutschland Gmbh | Acid bath for copper plating and process with the use of this combination |
| US5433840A (en) * | 1991-08-07 | 1995-07-18 | Atotech Deutschland Gmbh | Acid bath for the galvanic deposition of copper, and the use of such a bath |
| US5730854A (en) * | 1996-05-30 | 1998-03-24 | Enthone-Omi, Inc. | Alkoxylated dimercaptans as copper additives and de-polarizing additives |
| EP1054080A3 (en) * | 1999-05-17 | 2004-03-03 | Shipley Company LLC | Electrolytic copper plating solutions |
| US20040231995A1 (en) * | 2003-05-23 | 2004-11-25 | Kenji Murao | Printed circuit boards and the methods of their production |
| US20080142370A1 (en) * | 2003-08-08 | 2008-06-19 | Wolfgang Dahms | Aqueous, Acidic Solution and Method for Electrolytically Depositing Copper Coatings as Well as Use of Said Solution |
| US20070108062A1 (en) * | 2003-11-19 | 2007-05-17 | Atotech Deutschland Gmbh | Acidic bath for electrolytically depositing a copper deposit containing halogenated or pseudohalogenated monomeric phenazinium compounds |
| WO2005049584A1 (en) * | 2003-11-19 | 2005-06-02 | Atotech Deutschland Gmbh | Acidic bath for electrolytically depositing a copper deposit containing halogenated or pseudohalogenated monomeric phenazinium compounds |
| US7786303B2 (en) | 2003-11-19 | 2010-08-31 | Atotech Deutschland Gmbh | Acidic bath for electrolytically depositing a copper deposit containing halogenated or pseudohalogenated monomeric phenazinium compounds |
| CN1882550B (zh) * | 2003-11-19 | 2012-04-18 | 埃托特克德国有限公司 | 用于电解沉积铜沉积物的含有卤化或拟卤化的单体吩嗪鎓化合物的酸浴 |
| CN101899687A (zh) * | 2010-08-03 | 2010-12-01 | 济南德锡科技有限公司 | 单剂染料型光亮酸性镀铜添加剂及其制备方法和应用 |
| WO2012040417A1 (en) | 2010-09-24 | 2012-03-29 | Macdermid Acumen, Inc. | Improved method of producing polymeric phenazonium compounds |
| CN103270081A (zh) * | 2010-09-24 | 2013-08-28 | 麦克德米德尖端有限公司 | 生产聚合的二甲基苯基吡唑酮鎓化合物的改良方法 |
| US8691987B2 (en) | 2010-09-24 | 2014-04-08 | Andrew M. Krol | Method of producing polymeric phenazonium compounds |
| US8735580B2 (en) | 2010-09-24 | 2014-05-27 | Andrew M. Krol | Method of producing polymeric phenazonium compounds |
| CN103270081B (zh) * | 2010-09-24 | 2014-12-03 | 麦克德米德尖端有限公司 | 生产聚合的二甲基苯基吡唑酮鎓化合物的改良方法 |
| US20150030873A1 (en) * | 2013-07-23 | 2015-01-29 | Chang Chun Petrochemical Co., Ltd. | Electrolytic copper foil |
| US9209485B2 (en) * | 2013-07-23 | 2015-12-08 | Chang Chun Petrochemical Co. Ltd. | Electrolytic copper foil |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2028803B2 (de) | 1979-11-29 |
| FR2095876A5 (enrdf_load_stackoverflow) | 1972-02-11 |
| NL7107804A (enrdf_load_stackoverflow) | 1971-12-08 |
| DE2039831B2 (de) | 1979-01-04 |
| AT302764B (de) | 1972-10-25 |
| DE2028803C3 (de) | 1980-08-14 |
| NL173277C (nl) | 1984-01-02 |
| NL173277B (nl) | 1983-08-01 |
| GB1357442A (en) | 1974-06-19 |
| CH556347A (de) | 1974-11-29 |
| DE2028803A1 (de) | 1971-12-16 |
| CA961494A (en) | 1975-01-21 |
| DE2039831A1 (de) | 1972-01-05 |
| DE2039831C3 (de) | 1979-09-06 |
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