EP0598763B1 - Saures bad zur galvanischen abscheidung von kupfer und dessen verwendung - Google Patents
Saures bad zur galvanischen abscheidung von kupfer und dessen verwendung Download PDFInfo
- Publication number
- EP0598763B1 EP0598763B1 EP92916259A EP92916259A EP0598763B1 EP 0598763 B1 EP0598763 B1 EP 0598763B1 EP 92916259 A EP92916259 A EP 92916259A EP 92916259 A EP92916259 A EP 92916259A EP 0598763 B1 EP0598763 B1 EP 0598763B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aqueous
- bath according
- phenazonium
- poly
- acidic bath
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 18
- 239000010949 copper Substances 0.000 title claims abstract description 18
- 230000008021 deposition Effects 0.000 title claims abstract description 4
- 239000002253 acid Substances 0.000 title claims description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims abstract description 8
- 229910017464 nitrogen compound Inorganic materials 0.000 claims abstract description 6
- 150000002830 nitrogen compounds Chemical class 0.000 claims abstract description 6
- 239000004020 conductor Substances 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 18
- 230000002378 acidificating effect Effects 0.000 claims description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- -1 octylene ethers Chemical class 0.000 claims description 12
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 150000001983 dialkylethers Chemical class 0.000 claims description 8
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 5
- OBDVFOBWBHMJDG-UHFFFAOYSA-N 3-mercapto-1-propanesulfonic acid Chemical compound OS(=O)(=O)CCCS OBDVFOBWBHMJDG-UHFFFAOYSA-N 0.000 claims description 3
- LUENVHHLGFLMFJ-UHFFFAOYSA-N 4-[(4-sulfophenyl)disulfanyl]benzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1SSC1=CC=C(S(O)(=O)=O)C=C1 LUENVHHLGFLMFJ-UHFFFAOYSA-N 0.000 claims description 2
- IPCRBOOJBPETMF-UHFFFAOYSA-N N-acetylthiourea Chemical compound CC(=O)NC(N)=S IPCRBOOJBPETMF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229920001281 polyalkylene Polymers 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 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 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 6
- 150000002170 ethers Chemical class 0.000 claims 6
- 229910021653 sulphate ion Inorganic materials 0.000 claims 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 2
- 150000003585 thioureas Chemical class 0.000 claims 2
- BVPHXTUEZOQIBS-UHFFFAOYSA-N 6-methyl-1h-pyrimidine-2-thione Chemical compound CC1=CC=NC(S)=N1 BVPHXTUEZOQIBS-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims 1
- GMEHFXXZSWDEDB-UHFFFAOYSA-N N-ethylthiourea Chemical compound CCNC(N)=S GMEHFXXZSWDEDB-UHFFFAOYSA-N 0.000 claims 1
- 229920002873 Polyethylenimine Polymers 0.000 claims 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- IUOYQVWAOBUMLY-UHFFFAOYSA-N n-carbamothioyl-2,2,2-trifluoroacetamide Chemical compound NC(=S)NC(=O)C(F)(F)F IUOYQVWAOBUMLY-UHFFFAOYSA-N 0.000 claims 1
- NLEQMBHQFHUCST-UHFFFAOYSA-N n-carbamothioyl-2-cyanoacetamide Chemical compound NC(=S)NC(=O)CC#N NLEQMBHQFHUCST-UHFFFAOYSA-N 0.000 claims 1
- ACLZYRNSDLQOIA-UHFFFAOYSA-N o-tolylthiourea Chemical compound CC1=CC=CC=C1NC(N)=S ACLZYRNSDLQOIA-UHFFFAOYSA-N 0.000 claims 1
- 229920000333 poly(propyleneimine) Polymers 0.000 claims 1
- 230000003014 reinforcing effect Effects 0.000 claims 1
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 claims 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 238000007792 addition Methods 0.000 abstract 1
- 239000011260 aqueous acid Substances 0.000 abstract 1
- 229920001521 polyalkylene glycol ether Polymers 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 7
- 229910000365 copper sulfate Inorganic materials 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000009432 framing Methods 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000005282 brightening Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl 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])[H] 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 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
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical class C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 description 1
- MWXMWLZIZRDIBL-UHFFFAOYSA-N 5-phenyl-4a,10-dihydro-4h-phenazin-10-ium-2-amine;chloride Chemical compound [Cl-].C12=CC=CC=C2[NH2+]C2=CC(N)=CCC2N1C1=CC=CC=C1 MWXMWLZIZRDIBL-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JWAZRIHNYRIHIV-UHFFFAOYSA-N beta-hydroxynaphthyl Natural products C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003580 thiophosphoric acid esters Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229920003176 water-insoluble 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
Definitions
- the invention relates to an acid bath for the electrodeposition of shiny, ductile and leveled copper coatings and the use of this combination.
- the bath according to the invention can be used both to reinforce the conductor tracks of printed circuits and in the decorative sector.
- the prior art includes baths which contain a mixture of oxygen-containing high-molecular compounds with organic, in particular aromatic thio compounds (DE-AS 1521062). However, these show unimportant results with regard to metal scattering and / or leveling.
- DE-AS 2039831 describes an acidic copper bath which, in addition to a polymeric oxygen-containing compound and a thio compound with a water-soluble group, also contains at least one dye from the series of polymeric phenazonium compounds in solution. Further work describes the combination of organic thio compounds and polymeric oxygen-containing compounds with other dyes such as crystal violet (EP-PS 071512) or phthalocyanine derivatives with aposafranine (DE-PS 3420999) or a combination with amides (DE-PS 2746938) .
- a disadvantage when using conventional oxygen-containing high molecular weight Connections is the stability in the electrolyte. With normal use, these compounds decompose slowly during the electrolysis to water-insoluble polymers, which accumulate more and more in the electrolyte, frame them as jellies on the walls and finally deposit on the goods themselves, so that the goods become damaged and thus unusable. This decomposition is extremely increased when the bath temperature rises above 28 ° C.
- the object of this invention is to avoid these disadvantages.
- the amount in which the polyalkylene glycol dialkyl ether can be added in order to achieve a significant improvement in the copper deposition is approximately 0.005 to 30 g / liter; preferably 0.02 to 8.0 g / liter.
- the relative molar mass can be between 500 and 35,000 g / mol; preferably 800 to 4000 g / mol.
- polyalkylene glycol dialkyl ethers are known per se or can be prepared by processes known per se by reacting polyalkylene glycols with an alkylating agent, e.g. Dimethyl sulfate or tert. Butene are made.
- an alkylating agent e.g. Dimethyl sulfate or tert. Butene are made.
- Table 1 shows examples of the polyalkylene glycol dialkyl ethers to be used according to the invention and their preferred use concentration listed: Table 1 Polyalkylene glycol dialkyl ether preferred concentration g / liter Dimethyl polyethylene glycol ether 0.1 - 5.0 Dimethyl polypropylene glycol ether 0.05-1.0 Di-tert-butyl polyethylene glycol ether 0.1 - 2.0 Stearly monomethyl polyethylene glycol ether 0.5 - 8.0 Nonylphenyl monomethyl polyethylene glycol ether 0.5 - 6.0 Polyethylene-polypropylene-dimethyl ether (mixed or block polymer) 0.02 - 5.0 Octyl monomethyl polyalkylene ether (copolymer or block polymer) 0.05-0.5 Dimethyl-bis (polyalkylene glycol) octylene ether (mixed or block polymer) 0.02 - 0.5 ⁇ -naphthol monomethyl polyethylene glycol ether 0.03 - 4.0
- At least one thio compound having a water-solubilizing group can be added to the compound according to the invention in order to obtain a shiny precipitate.
- Other additives such as nitrogen-containing thio compounds, polymeric nitrogen compounds and / or polymeric phenazonium compounds can also be added to the bath.
- Table 2 lists some common thio compounds with water-soluble groups and their preferred use concentration: Table 2 Thio compounds preferred concentration g / liter 3-mercaptopropan-1-sulfonic acid, sodium salt 0.002 - 0.1 Thiophosphoric acid-O-ethyl-bis- ( ⁇ -sulfopropyl) ester, disodium salt 0.01-0.15 Thiophosphoric acid tris ( ⁇ -sulfopropyl) ester, trisodium salt 0.02-0.15 Thioglycolic acid 0.001 - 0.005 Ethylene dithiodipropyl sulfonic acid, sodium salt 0.001 - 0.1 Bis- ( ⁇ -sulfopropyl) disulfide, disodium salt 0.001 - 0.05 Bis ( ⁇ -sulfopropyl) sulfide, disodium salt 0.01-0.15 O-ethyl-dithiocarbonic acid S- ( ⁇ -sulfopropyl) ester,
- Table 3 contains examples of nitrogen-containing thio compounds (so-called thiourea derivatives) and Table 4 for polymeric phenazonium compounds and Table 5 for polymeric nitrogen compounds.
- the basic composition of the bath according to the invention can vary within wide limits.
- An aqueous solution of the following composition is generally used: Copper sulfate (CuSO4 ⁇ 5H2O) preferably 20 - 250 g / liter 60 - 80 g / liter or 180 - 220 g / liter
- chloride ions 0.01 - 0.18 g / liter, 0.03-0.10 g / liter
- copper sulfate instead of copper sulfate, other copper salts can also be used, at least in part.
- Some or all of the sulfuric acid can be replaced by fluoroboric acid, methanesulfonic acid or other acids.
- the chloride ions are added as alkali chloride (eg sodium chloride) or in the form of hydrochloric acid pa. The addition of sodium chloride can be omitted in whole or in part if the additives already contain halogen ions.
- customary brighteners, levelers or wetting agents can also be present in the bathroom.
- the working conditions of the bath are as follows: PH value: ⁇ 1 Temperature: 15 ° C - 50 ° C, preferably 25 ° C - 40 ° C cath. Current density: 0.5 - 12 A / dm2, preferably 2-7 A / dm2
- the electrolyte movement takes place by blowing clean air in, so strongly that the electrolyte surface is in a strong flush.
- Copper with a content of 0.02 to 0.067% phosphorus is used as the anode.
- electrolyte temperature 30 ° C with a current density of 4 A / dm2 and movement by blowing in air, a well-leveled shiny copper coating is obtained.
- the electrolyte at the tub edge shows clear gelatinous polymer framing.
- the compound according to the invention polyethylene glycol dimethyl ether
- the electrolyte shows no polymer framing after aging.
- the electrolyte at the tub edge shows clear gelatinous polymer framing.
- the compound according to the invention polypropylene glycol dimethyl ether
- the electrolyte shows no polymer framing after aging.
- the electrolyte at the tub edge shows clear gelatinous polymer framing.
- the electrolyte shows no polymer framing after aging.
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)
- Electroplating Methods And Accessories (AREA)
- Chemically Coating (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4126502A DE4126502C1 (es) | 1991-08-07 | 1991-08-07 | |
| DE4126502 | 1991-08-07 | ||
| PCT/DE1992/000605 WO1993003204A1 (de) | 1991-08-07 | 1992-07-22 | Saures bad zur galvanischen abscheidung von kupfer und dessen verwendung |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0598763A1 EP0598763A1 (de) | 1994-06-01 |
| EP0598763B1 true EP0598763B1 (de) | 1995-12-13 |
Family
ID=6438067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92916259A Expired - Lifetime EP0598763B1 (de) | 1991-08-07 | 1992-07-22 | Saures bad zur galvanischen abscheidung von kupfer und dessen verwendung |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5433840A (es) |
| EP (1) | EP0598763B1 (es) |
| JP (1) | JP3121346B2 (es) |
| AT (1) | ATE131546T1 (es) |
| CA (1) | CA2115062C (es) |
| DE (2) | DE4126502C1 (es) |
| ES (1) | ES2082486T3 (es) |
| WO (1) | WO1993003204A1 (es) |
Families Citing this family (45)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5849171A (en) * | 1990-10-13 | 1998-12-15 | Atotech Deutschland Gmbh | Acid bath for copper plating and process with the use of this combination |
| JP3313277B2 (ja) * | 1995-09-22 | 2002-08-12 | 古河サーキットフォイル株式会社 | ファインパターン用電解銅箔とその製造方法 |
| US6460548B1 (en) * | 1997-02-14 | 2002-10-08 | The Procter & Gamble Company | Liquid hard-surface cleaning compositions based on specific dicapped polyalkylene glycols |
| WO1998036042A1 (en) * | 1997-02-14 | 1998-08-20 | The Procter & Gamble Company | Liquid hard-surface cleaning compositions based on specific dicapped polyalkylene glycols |
| US5863410A (en) * | 1997-06-23 | 1999-01-26 | Circuit Foil Usa, Inc. | Process for the manufacture of high quality very low profile copper foil and copper foil produced thereby |
| WO2000010200A1 (en) * | 1998-08-11 | 2000-02-24 | Ebara Corporation | Wafer plating method and apparatus |
| WO2000014306A1 (en) * | 1998-09-03 | 2000-03-16 | Ebara Corporation | Method for plating substrate and apparatus |
| US6444110B2 (en) * | 1999-05-17 | 2002-09-03 | Shipley Company, L.L.C. | Electrolytic copper plating method |
| JP2001073182A (ja) * | 1999-07-15 | 2001-03-21 | Boc Group Inc:The | 改良された酸性銅電気メッキ用溶液 |
| EP1207730B1 (en) * | 1999-08-06 | 2009-09-16 | Ibiden Co., Ltd. | Electroplating solution, method for fabricating multilayer printed wiring board using the solution, and multilayer printed wiring board |
| LU90532B1 (en) * | 2000-02-24 | 2001-08-27 | Circuit Foil Luxembourg Trading Sarl | Comosite copper foil and manufacturing method thereof |
| US6491806B1 (en) | 2000-04-27 | 2002-12-10 | Intel Corporation | Electroplating bath composition |
| US6361673B1 (en) | 2000-06-27 | 2002-03-26 | Ga-Tek Inc. | Electroforming cell |
| US6679983B2 (en) * | 2000-10-13 | 2004-01-20 | Shipley Company, L.L.C. | Method of electrodepositing copper |
| US7074315B2 (en) | 2000-10-19 | 2006-07-11 | Atotech Deutschland Gmbh | Copper bath and methods of depositing a matt copper coating |
| DE10058896C1 (de) * | 2000-10-19 | 2002-06-13 | Atotech Deutschland Gmbh | Elektrolytisches Kupferbad, dessen Verwendung und Verfahren zur Abscheidung einer matten Kupferschicht |
| US6797146B2 (en) * | 2000-11-02 | 2004-09-28 | Shipley Company, L.L.C. | Seed layer repair |
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| US6911068B2 (en) * | 2001-10-02 | 2005-06-28 | Shipley Company, L.L.C. | Plating bath and method for depositing a metal layer on a substrate |
| US6736954B2 (en) * | 2001-10-02 | 2004-05-18 | Shipley Company, L.L.C. | Plating bath and method for depositing a metal layer on a substrate |
| US6652731B2 (en) | 2001-10-02 | 2003-11-25 | Shipley Company, L.L.C. | Plating bath and method for depositing a metal layer on a substrate |
| EP1310582A1 (en) * | 2001-11-07 | 2003-05-14 | Shipley Company LLC | Process for electrolytic copper plating |
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| DE60336539D1 (de) * | 2002-12-20 | 2011-05-12 | Shipley Co Llc | Methode zum Elektroplattieren mit Umkehrpulsstrom |
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| TWI400365B (zh) | 2004-11-12 | 2013-07-01 | Enthone | 微電子裝置上的銅電沈積 |
| US20070158199A1 (en) * | 2005-12-30 | 2007-07-12 | Haight Scott M | Method to modulate the surface roughness of a plated deposit and create fine-grained flat bumps |
| US20070178697A1 (en) * | 2006-02-02 | 2007-08-02 | Enthone Inc. | Copper electrodeposition in microelectronics |
| DE502007005345D1 (de) | 2006-03-30 | 2010-11-25 | Atotech Deutschland Gmbh | Elektrolytisches verfahren zum füllen von löchern und vertiefungen mit metallen |
| JP2007327127A (ja) * | 2006-06-09 | 2007-12-20 | Daiwa Fine Chemicals Co Ltd (Laboratory) | 銀めっき方法 |
| US7905994B2 (en) | 2007-10-03 | 2011-03-15 | Moses Lake Industries, Inc. | Substrate holder and electroplating system |
| US8262894B2 (en) | 2009-04-30 | 2012-09-11 | Moses Lake Industries, Inc. | High speed copper plating bath |
| EP2547731B1 (en) * | 2010-03-18 | 2014-07-30 | Basf Se | Composition for metal electroplating comprising leveling agent |
| US8735580B2 (en) | 2010-09-24 | 2014-05-27 | Andrew M. Krol | Method of producing polymeric phenazonium compounds |
| US8691987B2 (en) | 2010-09-24 | 2014-04-08 | Andrew M. Krol | Method of producing polymeric phenazonium compounds |
| CN103422079B (zh) * | 2012-05-22 | 2016-04-13 | 比亚迪股份有限公司 | 一种化学镀铜液及其制备方法 |
| EP2735627A1 (en) * | 2012-11-26 | 2014-05-28 | ATOTECH Deutschland GmbH | Copper plating bath composition |
| JP2017503929A (ja) * | 2013-11-25 | 2017-02-02 | エンソン インコーポレイテッド | 銅の電析 |
| DE102014208733A1 (de) * | 2014-05-09 | 2015-11-12 | Dr. Hesse Gmbh & Cie Kg | Verfahren zum elektrolytischen Abscheiden von Kupfer aus Wasser basierenden Elektrolyten |
| JP6733314B2 (ja) * | 2015-09-29 | 2020-07-29 | 三菱マテリアル株式会社 | 高純度銅電解精錬用添加剤と高純度銅製造方法 |
| KR20210094558A (ko) * | 2018-11-07 | 2021-07-29 | 코벤트야 인크. | 새틴 구리조 및 새틴 구리층 침착 방법 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA633957A (en) * | 1962-01-02 | Unipak Cartons Ltd. | Container carton and cellular structure therefor | |
| NL291575A (es) * | 1962-04-16 | |||
| DE1293749B (de) * | 1965-04-24 | 1969-04-30 | Hoechst Ag | Verfahren zur Aufarbeitung der bei der Herstellung von Sorbinsaeure durch thermische Polyesterspaltung entstandenen waessrigen Polyglykoldialkylaetherloesung |
| DE2039831C3 (de) * | 1970-06-06 | 1979-09-06 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Saures Bad zur galvanischen Abscheidung glänzender Kupferüberzüge |
| US3804729A (en) * | 1972-06-19 | 1974-04-16 | M & T Chemicals Inc | Electrolyte and process for electro-depositing copper |
| 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 |
| FR2510145B1 (fr) * | 1981-07-24 | 1986-02-07 | Rhone Poulenc Spec Chim | Additif pour bain de cuivrage electrolytique acide, son procede de preparation et son application au cuivrage des circuits imprimes |
| AU554236B2 (en) * | 1983-06-10 | 1986-08-14 | Omi International Corp. | Electrolyte composition and process for electrodepositing copper |
| DE3722778A1 (de) * | 1987-07-09 | 1989-03-09 | Raschig Ag | Polyalkylenglykol-naphthyl-3-sulfopropyl- diether und deren salze, verfahren zur herstellung dieser verbindungen und ihre verwendung als netzmittel in der galvanotechnik |
| US5328589A (en) * | 1992-12-23 | 1994-07-12 | Enthone-Omi, Inc. | Functional fluid additives for acid copper electroplating baths |
-
1991
- 1991-08-07 DE DE4126502A patent/DE4126502C1/de not_active Expired - Fee Related
-
1992
- 1992-07-22 WO PCT/DE1992/000605 patent/WO1993003204A1/de active IP Right Grant
- 1992-07-22 JP JP05503171A patent/JP3121346B2/ja not_active Expired - Lifetime
- 1992-07-22 EP EP92916259A patent/EP0598763B1/de not_active Expired - Lifetime
- 1992-07-22 DE DE59204703T patent/DE59204703D1/de not_active Expired - Lifetime
- 1992-07-22 AT AT92916259T patent/ATE131546T1/de active
- 1992-07-22 ES ES92916259T patent/ES2082486T3/es not_active Expired - Lifetime
- 1992-07-22 CA CA002115062A patent/CA2115062C/en not_active Expired - Fee Related
- 1992-07-22 US US08/193,016 patent/US5433840A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE4126502C1 (es) | 1993-02-11 |
| JP3121346B2 (ja) | 2000-12-25 |
| WO1993003204A1 (de) | 1993-02-18 |
| JPH07505187A (ja) | 1995-06-08 |
| US5433840A (en) | 1995-07-18 |
| ES2082486T3 (es) | 1996-03-16 |
| ATE131546T1 (de) | 1995-12-15 |
| DE59204703D1 (de) | 1996-01-25 |
| CA2115062C (en) | 2005-11-22 |
| CA2115062A1 (en) | 1993-02-18 |
| EP0598763A1 (de) | 1994-06-01 |
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