EP0297306B1 - Bain aqueux acide pour le dépôt galvanique de revêtements en cuivre brillants et nivelés - Google Patents

Bain aqueux acide pour le dépôt galvanique de revêtements en cuivre brillants et nivelés Download PDF

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Publication number
EP0297306B1
EP0297306B1 EP88108876A EP88108876A EP0297306B1 EP 0297306 B1 EP0297306 B1 EP 0297306B1 EP 88108876 A EP88108876 A EP 88108876A EP 88108876 A EP88108876 A EP 88108876A EP 0297306 B1 EP0297306 B1 EP 0297306B1
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EP
European Patent Office
Prior art keywords
accordance
aqueous acid
acid bath
bath
acid
Prior art date
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Expired - Lifetime
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EP88108876A
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German (de)
English (en)
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EP0297306A1 (fr
Inventor
Wolfgang Dahms
Hubert-Matthias Dr. Rer.Nat. Seidenspinner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Atotech Deutschland GmbH and Co KG
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Schering AG
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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 and leveled copper coatings.
  • Baths containing polymeric phenazonium compounds made significant progress. They are mainly used in combination with non-ionic wetting agents and organic sulfur compounds.
  • the high leveling in the high current density range is disadvantageous in comparison to the low leveling in the low range, which leads to flattening of the edge of the holes in the drill holes when copper-plating printed circuits.
  • the different areas in the current density are noticeably noticeable.
  • the object of this invention is to avoid these disadvantages and also to improve the leveling and uniform deposition in the region of low current density.
  • levelers such as thiourea derivatives or polymeric phenazonium compounds, can improve the leveling in the high range from case to case.
  • the amounts in which the benzothiazolium compounds have to be added in order to achieve a significant improvement in the copper deposition are small and are about 0.0005 to 0.3 g / liter, preferably 0.002 to 0.05 g / liter.
  • Table 1 contains examples of substances to be used according to the invention and details of the preferred concentrations in the bath.
  • the benzothiazolium compounds are known per se or can be prepared, for example, as follows by processes known per se.
  • the corresponding benzothiazole derivative is alkylated on nitrogen, this ring is opened with hydrazine hydrate and converted to the desired product with diaalkylaminobenzoyl chloride.
  • Table III contains examples of organic nitrogen-free thio compounds with water-soluble groups for additional use as a component and their preferred use concentration:
  • the individual components of the copper bath according to the invention can generally advantageously be present in the ready-to-use bath within the following limit concentrations.
  • Thiazolium compound preferred 0.0005 - 0.3 g / liter 0.002-0.05 g / liter
  • Oxygen-containing, high molecular compounds preferably 0.005 - 20 g / liter 0.01 - 5 g / liter
  • Organic thio compounds with water solubilizing groups are preferred 0.0005 - 0.2 g / liter 0.001 - 0.03 g / liter
  • the basic composition of the bath according to the invention can vary within wide limits.
  • an aqueous solution of the following composition is used: Copper sulfate (CuSO4. 5H20) preferably 20 - 250 g / liter, 60 - 80 g / liter or 180 - 220 g / liter
  • CuSO4. 5H20 Copper sulfate
  • Sodium chloride preferably 0.02 - 0.25 g / liter, 0.05-0.12 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 addition of sodium chloride can be omitted in whole or in part if the additives already contain halogen ions.
  • the bathroom can also contain customary brighteners, levelers, such as thiourea derivatives or polymeric phenazonium compounds, and / or wetting agents.
  • the working conditions of the bath are as follows: PH value: ⁇ 1 Temperature: 15 - 45 ° C, preferably 25 ° C cath. Current density: 0.5 - 12 A / dm2, preferably 2 - 4 A / dm2
  • Electrolyte movement takes place by blowing clean air so strongly that the electrolyte surface is in a strong surge.
  • Copper with a content of 0.02 to 0.067% phosphorus is used as the anode.
  • the Hull cell contains shiny deposits at a current density above 0.8 A / dm2, whereas matt deposits are present at a current density below 0.8 A / dm2.
  • an electrolyte temperature of 27 ° C with a current density of 1 A / dm2 and air injection, shiny copper coatings are obtained, the leveling is only 27% with a layer thickness of 3.4 ⁇ m. If 0.01 g / liter of substance 1 (Table I) is added to the bath, the leveling increases to 35% under the same working conditions. So it increases by 30%.
  • a printed via circuit is copper-plated for 50 minutes.
  • the plate looks greasy and shiny and has very strong defects at the edges of the borehole.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electroplating Methods And Accessories (AREA)

Claims (14)

  1. Bain aqueux acide pour la déposition électrolytique de couches de cuivre brillantes et lissées, caractérisé par une teneur en au moins un composé de benzothiazole de la formule générale
    Figure imgb0007
     dans laquelle
    R₁   représente du C₁-C₅-alkyle, le cas échéant de l'aryle ou de l'aralkyle substitués,
    R₂   représente de l'hydrogène, du C₁-C₅-alkyle ou du C₁-C₅-alkoxy,
    R₃ et R₄   représentent respectivement du C₁-C₅-alkyle et
    X   représente un résidu acide.
  2. Bain aqueux acide suivant revendication 1, où
    R₁   représente du méthyle, de l'éthyle, du n-propyle, du i-propyle, du phényle ou du benzyle,
    R₂   représente de l'hydrogène, du méthyle, de l'éthyle, du n-propyle ou du i-propyle,
    R₃   et R₄ représentent respectivement du méthyle, de l'éthyle, du n-propyle ou du i-propyle et
    X   représente un résidu acide.
  3. Bain aqueux acide suivant revendications 1 et 2, où le groupe R₂ est disposé en position 5 ou 6.
  4. Bain aqueux acide suivant revendications 1 et 2, où X représente un résidu de l'acide chlorhydrique, de l'acide sulfurique, de l'acide méthanesulfonique, de l'acide acétique, de l'acide toluènesulfonique ou de l'acide méthanesulfurique.
  5. Bain aqueux acide suivant revendications 1 à 4, contenant les composés de thiazole à des concentrations comprises entre 0,0005 et 0,3 g/litre, de préférence entre 0,002 et 0,05 g/litre.
  6. Bain aqueux acide suivant revendications 1 à 5, caractérisé en ce qu'il contient en plus au moins un composé oxygénifère à poids moléculaire élevé.
  7. Bain aqueux acide suivant revendication 6, contenant les composés suivants
    - alcool polyvinylique,
    - cellulose carboxyméthylique,
    - polyéthylène glycol,
    - polypropylène glycol,
    - polyglycol stéarate,
    - polyglycol oléate,
    - éther polyglycolique de l'alcool stéarylique,
    - éther polyglycolique du nonylphénol,
    - éther polyalkylène-glycolique de l'octanol,
    - octandiol-bis-(polyalkylène glycol éther),
    - polyoxypropylène glycol,
    - polyéthylène propylène glycol, ou
    - éther polyglycolique du β-naphthol.
  8. Bain aqueux acide suivant revendications 6 et 7, contenant les-dits composés oxygénifères à poids moléculaire élevé à des concentrations comprises entre 0,005 et 20 g/litre, de préférence entre 0,01 et 5 g/litre.
  9. Bain aqueux acide suivant revendications 1 à 5, caractérisé en ce qu'il contient en plus un composés organique thio non-azoté comprenant des groupes solubilisants dans l'eau.
  10. Bain aqueux acide suivant revendication 9, contenant les composés suivants
    - sel de sodium de l'acide mercapto-3-propane-sulfonique-1,
    - sel disodique du o-éthly-bis-(w-sulfopropyle) thiophosphate,
    - sel trisodique du tris-(w-sulfopropyle) thiophosphate,
    - acide thioglycolique,
    - sel de sodium de l'acide éthylène-di-thiodipropyle-sulfonique,
    - sel disodique de l'acide di-n-propylethio-éther-di-w-sulfonique,
    - sel disodique du bis(w-sulfopropyle)-disulfure,
    - sel disodique du bis(w-sulfobutyle)-disulfure,
    - sel de sodium du methyle-(w-sulfopropyle)-disulfure, ou
    - sel de sodium du methyle-(w-sulfobutyle)-trisulfure.
  11. Bain aqueux acide suivant revendications 9 et 10, contenant les-dits composés thio organiques non-azotés, comprenant des groupes solubilisants dans l'eau, à des concentrations comprises entre 0,0005 et 0,2 g/litre, de préférence entre 0,001 et 0,03 g/litre.
  12. Bain aqueux acide, caractérisé en ce qu'il contient des composés de thiazole suivant revendications 1 à 5, des composés oxygénifères à poids moléculaire élevé suivant revendications 6 à 8 et des composés thio organiques non-azotés comprenant des groupes solubilisants dans l'eau suivant revendications 9 à 11.
  13. Bain aqueux acide suivant revendication 12, caractérisé en ce que ce bain a un pH de moins de 1.
  14. Procédé pour la déposition électrolytique de couches de cuivre brillantes et lissées, caractérisé en ce que des bains à cuivre suivant revendications 1 à 13 sont utilisés à des températures comprises entre 15 et 45 °C et à des densités de courant comprises entre 0,5 et 12 A/dm².
EP88108876A 1987-06-30 1988-06-03 Bain aqueux acide pour le dépôt galvanique de revêtements en cuivre brillants et nivelés Expired - Lifetime EP0297306B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3721985 1987-06-30
DE19873721985 DE3721985A1 (de) 1987-06-30 1987-06-30 Waessriges saures bad zur galvanischen abscheidung glaenzender und eingeebneter kupferueberzuege

Publications (2)

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EP0297306A1 EP0297306A1 (fr) 1989-01-04
EP0297306B1 true EP0297306B1 (fr) 1993-01-20

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EP88108876A Expired - Lifetime EP0297306B1 (fr) 1987-06-30 1988-06-03 Bain aqueux acide pour le dépôt galvanique de revêtements en cuivre brillants et nivelés

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Country Link
EP (1) EP0297306B1 (fr)
JP (1) JPH01100292A (fr)
AT (1) AT396946B (fr)
DE (2) DE3721985A1 (fr)
ES (1) ES2045013T3 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5051154A (en) * 1988-08-23 1991-09-24 Shipley Company Inc. Additive for acid-copper electroplating baths to increase throwing power
JPH04120692A (ja) * 1990-09-11 1992-04-21 Koatsu Gas Kogyo Kk 感知器試験装置
DE4032864A1 (de) * 1990-10-13 1992-04-16 Schering Ag Saures bad zur galvanischen abscheidung von kupferueberzuegen und verfahren unter verwendung dieser kombination
DE4133299A1 (de) * 1991-10-08 1993-04-15 Basf Lacke & Farben Kathodisch anscheidbarer elektrotauchlack
US5252196A (en) * 1991-12-05 1993-10-12 Shipley Company Inc. Copper electroplating solutions and processes
DE10000090A1 (de) * 2000-01-04 2001-08-30 Elfo Ag Sachseln Sachseln Verfahren zum Herstellen einer mehrlagigen Planarspule
EP1348320A1 (fr) * 2001-01-04 2003-10-01 Elmicron AG Procede de fabrication de structures electroconductrices
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
US7153408B1 (en) * 2006-04-13 2006-12-26 Herdman Roderick D Copper electroplating of printing cylinders
EP2568063A1 (fr) * 2011-09-09 2013-03-13 Rohm and Haas Electronic Materials LLC Procédé d'électrodéposition de cuivre à faible contrainte interne

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5817272A (ja) * 1981-07-20 1983-02-01 Yamatake Honeywell Co Ltd 調節弁用アクチユエ−タ
JPS59501829A (ja) * 1982-09-30 1984-11-01 リ−ロ−ナル　インコ−ポレ−テツド 電気銅メッキ液
US4490220A (en) * 1982-09-30 1984-12-25 Learonal, Inc. Electrolytic copper plating solutions

Also Published As

Publication number Publication date
EP0297306A1 (fr) 1989-01-04
AT396946B (de) 1993-12-27
ES2045013T3 (es) 1994-01-16
JPH01100292A (ja) 1989-04-18
DE3721985A1 (de) 1989-01-12
ATA166488A (de) 1993-05-15
DE3877633D1 (de) 1993-03-04

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