EP0598763B1 - Acid bath for the galvanic deposition of copper, and the use of such a bath - Google Patents

Acid bath for the galvanic deposition of copper, and the use of such a bath Download PDF

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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
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Prior art keywords
aqueous
bath according
phenazonium
poly
acidic bath
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EP92916259A
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German (de)
French (fr)
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EP0598763A1 (en
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Wolfgang Dahms
Horst Westphal
Michael Jonat
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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    • 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.

Abstract

PCT No. PCT/DE92/00605 Sec. 371 Date Apr. 6, 1994 Sec. 102(e) Date Apr. 6, 1994 PCT Filed Jul. 22, 1992 PCT Pub. No. WO93/03204 PCT Pub. Date Feb. 18, 1993.An aqueous acid bath for the galvanic deposition of bright, ductile and smooth copper coats which is suitable for decorative purposes as well as for strengthening the conductors of printed circuits. The bath is characterized by a content of polyalkylene glycol ether. When combined with thio compounds containing water-soluble groups, these additions produce an electrolyte with excellent stability. Polymeric phenazonium compounds, polymeric nitrogen compounds and/or thio compounds containing nitrogen may also be successfully combined, in addition, depending on the desired properties.

Description

Die Erfindung betrifft ein saures Bad zur galvanischen Abscheidung glänzender, duktiler und eingeebneter Kupferüberzüge und die Verwendung dieser Kombination. Das erfindungsgemäße Bad kann sowohl zur Verstärkung der Leiterbahnen von gedruckten Schaltungen als auch auf dem dekorativen Sektor eingesetzt werden.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.

Es ist seit langem bekannt, daß galvanischen Kupferbädern organische Substanzen zugesetzt werden, um glänzende Abscheidungen zu erzielen. Die zahlreichen für diesen Zweck bereits bekannten Verbindungen, wie zum Beispiel Thioharnstoff, Gelatine, Melasse, Kaffee-Extrakt, "basische" Farbstoffe und Thiophosphorsäureester, besitzen jedoch keinerlei praktische Bedeutung mehr, da die Qualität der mit ihnen erhaltenen Kupferüberzüge - besonders bezüglich des gleichmäßigen Aussehens, der Härte und der Bruchelongation - nicht den heutigen Anforderungen entsprechen.It has been known for a long time that organic substances are added to galvanic copper baths in order to achieve shiny deposits. However, the numerous compounds already known for this purpose, such as, for example, thiourea, gelatin, molasses, coffee extract, "basic" dyes and thiophosphoric acid esters, are no longer of any practical importance since the quality of the copper coatings obtained with them - particularly with regard to their uniform appearance , hardness and elongation at break - do not meet today's requirements.

Zum Stand der Technik zählen Bäder, die eine Mischung von sauerstoffhaltigen hochmolekularen Verbindungen mit organischen, insbesondere aromatischen Thioverbindungen (DE-AS 1521062), enthalten. Diese zeigen aber unbefriegende Ergebnisse bezüglich Metallstreuung und/oder Einebnung.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.

Zur Verbesserung wird in der DE-AS 2039831 ein saures Kupferbad beschrieben, das neben einer polymeren sauerstoffhaltigen Verbindung und einer Thioverbindung mit wasserlösliche Gruppe noch mindestens einen Farbstoff aus der Reihe der polymeren Phenazoniumverbindungen gelöst enthält. Weitere Arbeiten beschreiben die Kombination von organischen Thioverbindungen und polymeren sauerstoffhaltigen Verbindungen mit anderen Farbstoffen wie zum Beispiel Kristall-Violett (EP-PS 071512) oder PhthalocyaninDerivaten mit Apo-Safranin (DE-PS 3420999) oder eine Kombination mit Amiden (DE-PS 2746938).For improvement, 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) .

Nachteilig bei der Verwendung üblicher sauerstoffhaltiger hochmolekularer Verbindungen ist die Stabilität im Elektrolyten. Bei normaler Anwendung Zersetzen sich diese genannten Verbindungen während der Elektrolyse langsam zur wasserunlöslichen Polymeren, die sich immer mehr im Elektrolyten anreichern, an den Wandungen als Gallerte ausrahmen und schließlich auf der Ware selbst ablagern, so daß die Ware mit Fehlstellen behaftet und so unbrauchbar wird. Diese Zersetzung wird extrem verstärkt, wenn die Badtemperatur über 28 °C ansteigt.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.

Aufgabe dieser Erfindung ist es, diese Nachteile zu vermeiden.The object of this invention is to avoid these disadvantages.

Diese Aufgabe wird erfindungsgemäß durch ein saures Bad gelöst, das mindestens einen Polyalkylenglycoldialkyläther der allgemeinen Formel

Figure imgb0001

enthält, in der n = 8 - 800, vorzugsweise 14 - 90, und m = 0 - 50, vorzugsweise 0 - 20, R¹ ein niedriges Alkyl C₁ bis C₄, R² eine aliphatische Kette oder einen aromatischen Rest und a entweder 1 oder 2 bedeuten .This object is achieved according to the invention by an acid bath containing at least one polyalkylene glycol dialkyl ether of the general formula
Figure imgb0001
contains, in which n = 8-800, preferably 14-90, and m = 0-50, preferably 0-20, R¹ is a lower alkyl C₁ to C₄, R² is an aliphatic chain or an aromatic radical and a is either 1 or 2 .

Die Menge, in der der Polyalkylengylcoldialkyläther zugegeben werden kann, um eine deutliche Verbesserung der Kupferabscheidung zu erzielen, beträgt etwa 0,005 bis 30 g/Liter; vorzugsweise 0,02 bis 8,0 g/Liter. Die relative Molmasse kann zwischen 500 und 35000 g/mol betragen; vorzugsweise 800 bis 4000 g/mol.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.

Die Polyalkylenglycoldialkyläther sind an sich bekannt oder können nach an sich bekannten Verfahren durch Umsetzen von Polyalkylenglykolen mit einem Alkylierungsmittel, wie z.B. Dimethylsulfat oder tert. Buten hergestellt werden.The 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.

In der Tabelle 1 sind Beispiele der erfindungsgemäß zu verwendenden Polyalkylenglycoldialkyläther sowie ihre bevorzugte Anwendungskonzentration aufgeführt: Tabelle 1 Polyalklenglycoldialkyläther bevorzugte Konzentration g/Liter Dimethyl-polyäthylenglycoläther 0,1 - 5,0 Dimethyl-polypropylenglycoläther 0,05 - 1,0 Di-tert.-butyl-polyäthylenglycoläther 0,1 - 2,0 Stearly-monomethyl-polyäthylenglycoläther 0,5 - 8,0 Nonylphenyl-monomethyl-polyäthylenglycoläther 0,5 - 6,0 Polyäthylen-polypropylen-dimethyläther (Misch- oder Blockpolymerisat) 0,02 - 5,0 Octyl-monomethyl-polyalkylenäther (Misch- oder Blockpolymerisat) 0,05 - 0,5 Dimethyl-bis(polyalkylenglykol)octylenäther (Misch- oder Blockpolymerisat) 0,02 - 0,5 β-Naphthol-monomethyl-polyäthylenglycoläther 0,03 - 4,0 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 β-naphthol monomethyl polyethylene glycol ether 0.03 - 4.0

Zu der erfindungsgemäßen Verbindung können, um glänzende Niederschlage zu erhalten, zumindestens eine Thioverbindung mit wasserlöslichmachender Gruppe zugesetzt werden. Weitere Zusätze, wie stickstoffhaltige Thioverbindungen, polymere Stickstoffverbindungen und/oder polymere Phenazoniumverbindungen können ebenfalls dem Bad zugesetzt werden.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.

Diese Einzelkomponenten des erfindungsgemäßen Kupferbades können im allgemeinen vorteilhaft innerhalb folgender Grenzkonzentrationen im anwendungsfertigen Bad enthalten sein: Übliche organische Thioverbindungen mit wasserlöslichen Gruppen 0,0005 - 0,4 g/Liter vorzugsweise 0,001 - 0,15 g/Liter These individual components of the copper bath according to the invention can in general advantageously be present in the ready-to-use bath within the following limit concentrations: Common organic thio compounds with water soluble groups 0.0005 - 0.4 g / liter preferably 0.001 - 0.15 g / liter

In der Tabelle 2 sind einige übliche Thioverbindungen mit wasserlöslichen Gruppen sowie ihre bevorzugte Anwendungskonzentration aufgeführt: Tabelle 2 Thioverbindungen bevorzugte Konzentration g/Liter 3-Mercaptopropan-1-sulfonsäure, Natriumsalz 0,002 - 0,1 Thiophosphorsäure-O-äthyl-bis-(ω-sulfopropyl)-ester, Dinatriumsalz 0,01 - 0,15 Thiophosphorsäure-tris-(ω-sulfopropyl)-ester, Trinatriumsalz 0,02 - 0,15 Thioglycolsäure 0,001 - 0,005 Äthylendithiodipropylsulfonsäure, Natriumsalz 0,001 - 0,1 Bis-(ω-sulfopropyl)-disulfid, Dinatriumsalz 0,001 - 0,05 Bis-(ω-sulfopropyl)-sulfid, Dinatriumsalz 0,01 - 0,15 O-Äthyl-dithiokohlensäure-S-(ω-sulfopropyl)-ester, Kaliumsalz 0,002 - 0,05 3(Benzthiazolyl-2-thio)-propylsulfonsäure, Natriumsalz 0,005 - 0,1 Bis-(ω-sulfohydroxypropyl)-disulfid, Dinatriumsalz 0,003 - 0,04 Bis-(ω-sulfobutyl)-disulfid, Dinatriumsalz 0,004 - 0,04 Bis(p-sulfophenyl)-disulfid, Dinatriumsalz 0,004 - 0,04 Methyl-(ω-sulfopropyl)-disulfid, Dinatriumsalz 0,007 - 0,08 Methyl-(ω-sulfopropyl)-trisulfid, Dinatriumsalz 0,005 - 0,03 Übliche stickstoffhaltige Thioverbindungen (sog. Thioharnstoffderivate) und/oder polymere Phenazoniumverbindungen und/oder polymere Stickstoffverbindungen 0,0001 - 0,50 g/Liter vorzugsweise 0,0005 - 0,04 g/Liter 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- (ω-sulfopropyl) ester, disodium salt 0.01-0.15 Thiophosphoric acid tris (ω-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- (ω-sulfopropyl) disulfide, disodium salt 0.001 - 0.05 Bis (ω-sulfopropyl) sulfide, disodium salt 0.01-0.15 O-ethyl-dithiocarbonic acid S- (ω-sulfopropyl) ester, potassium salt 0.002 - 0.05 3 (benzothiazolyl-2-thio) propyl sulfonic acid, sodium salt 0.005-0.1 Bis (ω-sulfohydroxypropyl) disulfide, disodium salt 0.003 - 0.04 Bis (ω-sulfobutyl) disulfide, disodium salt 0.004 - 0.04 Bis (p-sulfophenyl) disulfide, disodium salt 0.004 - 0.04 Methyl (ω-sulfopropyl) disulfide, disodium salt 0.007 - 0.08 Methyl (ω-sulfopropyl) trisulfide, disodium salt 0.005 - 0.03 Usual nitrogen-containing thio compounds (so-called thiourea derivatives) and / or polymeric phenazonium compounds and / or polymeric nitrogen compounds 0.0001 - 0.50 g / liter preferably 0.0005 - 0.04 g / liter

Tabelle 3 enthält Beispiele für stickstoffhaltige Thioverbindungen (sog. Thioharnstoffderivate) und Tabelle 4 für polymere Phenazoniumverbindungen und Tabelle 5 für polymere Stickstoffverbindungen.

Figure imgb0002
Figure imgb0003
Figure imgb0004
 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.
Figure imgb0002
Figure imgb0003
Figure imgb0004

Die Grundzusammensetzung des erfindungsgemäßen Bades kann in weiten Grenzen schwanken. Im allgemeinen wird eine wässrige Lösung folgender Zusammensetzung benutzt: Kupfersulfat (CuSO₄ · 5H₂O) vorzugsweise 20 - 250 g/Liter 60 - 80 g/Liter oder 180 - 220 g/Liter Schwefelsäure vorzugsweise 50 - 350 g/Liter 180 - 220 g/Liter oder 50 - 90 g/Liter Chloridionen vorzugsweise 0,01 - 0,18 g/Liter, 0,03 - 0,10 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 generally used: Copper sulfate (CuSO₄ · 5H₂O) preferably 20 - 250 g / liter 60 - 80 g / liter or 180 - 220 g / liter Preferably sulfuric acid 50 - 350 g / liter 180 - 220 g / liter or 50 - 90 g / liter Preferably chloride ions 0.01 - 0.18 g / liter, 0.03-0.10 g / liter

Anstelle von Kupfersulfat können zumindest teilweise auch andere Kupfersalze benutzt werden. Auch die Schwefelsäure kann teilweise oder ganz durch Fluoroborsäure, Methansulfonsäure oder andere Säuren ersetzt werden. Die Chloridionen werden als Alkali chlorid (z.B. Natriumchlorid) oder in Form von Salzsäure p.a. zugesetzt. Die Zugabe von Natriumchlorid kann ganz oder teilweise entfallen, wenn in den Zusätzen bereits Halogenionen enthalten sind.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.

Außerdem können im Bad auch zusätzlich übliche Glanzbildner, Einebner oder Netzmittel enthalten sein.In addition, customary brighteners, levelers or wetting agents can also be present in the bathroom.

Zur Herstellung des erfindungsgemäßen Bades werden die Einzelkomponenten der Grundzusammensetzung hinzugefügt.To produce the bath according to the invention, the individual components of the basic composition are added.

Die Arbeitsbedingungen des Bades sind wie folgt: pH-Wert: < 1 Temperatur: 15°C - 50°C, vorzugsweise 25°C - 40°C kath. Stromdichte: 0,5 - 12 A/dm², vorzugsweise 2-7 A/dm² 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

Die Elektrolytbewegung erfolgt durch Einblasen von sauberer Luft, und zwar so stark, daß sich die Elektrolytoberfläche in starker Wallung befindet.The electrolyte movement takes place by blowing clean air in, so strongly that the electrolyte surface is in a strong flush.

Als Anode wird Kupfer mit einem Gehalt von 0,02 bis 0,067 % Phosphor verwendet.Copper with a content of 0.02 to 0.067% phosphorus is used as the anode.

Die folgenden Beispiele dienen zur Erläuterung der Erfindung:The following examples serve to illustrate the invention:

BEISPIEL 1EXAMPLE 1

Einem Kupferbad der Zusammensetzung
   200,0 g/Liter Kupfersulfat (CuSO₄.5 H₂O)
   65,0 g/Liter Schwefelsäure
   0,12 g/Liter Natriumchlorid
werden als Glanzbildner
   0,2 g/Liter Polyäthylenglycol,
   0,01 g/Liter Bis-(ω-sulfopropyl)-disufid, Dinatriumsalz,
und 0,02 g/Liter polymeres 7-Dimethylamino-5-phenylphenazonium-chlorid
zugegeben. Man erhält bei einer Elektrolyttemperatur von 30 °C mit einer Stromdichte von 4 A/dm² und Bewegung durch Lufteinblasung einen gut eingeebneten glänzenden Kupferüberzug.A copper bath of the composition
200.0 g / liter copper sulfate (CuSO₄.5 H₂O)
65.0 g / liter sulfuric acid
0.12 g / liter sodium chloride
are used as brighteners
0.2 g / liter polyethylene glycol,
0.01 g / liter bis- (ω-sulfopropyl) disufide, disodium salt,
and 0.02 g / liter polymeric 7-dimethylamino-5-phenylphenazonium chloride
admitted. At an electrolyte temperature of 30 ° C with a current density of 4 A / dm² and movement by blowing in air, a well-leveled shiny copper coating is obtained.

Wird nun der Elektrolyt einer Dauerbelastung von 500 Ah/l unterzogen, wobei die während der Elektrolyse verbrauchten Glanzbildner auf Sollwerte ergänzt werden, so zeigt der Elektrolyt am Wannenrand deutliche gallertartige Polymerausrahmungen.If the electrolyte is now subjected to a permanent load of 500 Ah / l, with the brightening agents used during the electrolysis being supplemented to set values, the electrolyte at the tub edge shows clear gelatinous polymer framing.

Setzt man dagegen anstelle des Polyäthylenglycols die erfindungsgemäße Verbindung, Polyäthylenglycoldimethyläther in der gleichen Menge dem Elektrolyten zu, so zeigt der Elektrolyt nach der Alterung keine Polymerausrahmungen.If, on the other hand, the compound according to the invention, polyethylene glycol dimethyl ether, is added to the electrolyte in the same amount instead of the polyethylene glycol, the electrolyte shows no polymer framing after aging.

BEISPIEL 2EXAMPLE 2

Einem Kupferbad der Zusammensetzung
   80 g/Liter Kupfersulfat (CuSO₄·5 H₂O)
   180 g/Liter Schwefelsäure konz.
   0,08 g/Liter Natriumchlorid
werden als Glanzbildner
   0,6 g/Liter Polypropylenglycol,
   0,02 g/Liter 3-Mercaptopropan-1-sulfonsäure, Natriumsalz
und 0,003 g/Liter N-Acetylthioharnstoff
zugegeben. Bei einer Elektrolyttemperatur von 30 °C enthält man auf gekratztem Kupferlaminat bei einer Stromdichte von 2 A/dm² glänzende Abscheidungen.A copper bath of the composition
80 g / liter copper sulfate (CuSO₄.5 H₂O)
180 g / liter sulfuric acid conc.
0.08 g / liter sodium chloride
are used as brighteners
0.6 g / liter polypropylene glycol,
0.02 g / liter 3-mercaptopropan-1-sulfonic acid, sodium salt
and 0.003 g / liter of N-acetylthiourea
admitted. At an electrolyte temperature of 30 ° C there are shiny deposits on scraped copper laminate with a current density of 2 A / dm².

Wird nun der Elektrolyt einer Dauerbelastung von 500 Ah/l unterzogen, wobei die während der Elektrolyse verbrauchten Glanzbildner auf Sollwerte ergänzt werden, so zeigt der Elektrolyt am Wannenrand deutliche gallertartige Polymerausrahmungen.If the electrolyte is now subjected to a permanent load of 500 Ah / l, with the brightening agents used during the electrolysis being supplemented to set values, the electrolyte at the tub edge shows clear gelatinous polymer framing.

Setzt man dagegen anstelle des Polypropylenglycols die erfindungsgemäße Verbindung, Polypropylenglycoldimethyläther in der gleichen Menge dem Elektrolyten zu, so zeigt der Elektrolyt nach der Alterung keine Polymerausrahmungen.If, on the other hand, the compound according to the invention, polypropylene glycol dimethyl ether, is added to the electrolyte in the same amount instead of the polypropylene glycol, the electrolyte shows no polymer framing after aging.

BEISPIEL 3EXAMPLE 3

Einem Kupferbad der Zusammensetzung
   80 g/Liter Kupfersulfat (CuSO₄·5 H₂O)
   200 g/Liter Schwefelsäure konz.
   0,06 g/Liter Natriumchlorid
werden als Glanzbildner
   0,4 g/Liter Octyl-polyalkyläther und
   0,01 g/Liter Bis-(ω-sulfopropyl)-sulfid, Dinatriumsalz und
   0,01 g/Liter Polyacrylsäureamid
zugegeben. Bei einer Elektrolyttemperatur von 30 °C enthält man auf gekratztem Kupferlaminat bei einer Stromdichte von 2 A/dm² glänzende Abscheidungen.A copper bath of the composition
80 g / liter copper sulfate (CuSO₄.5 H₂O)
200 g / liter sulfuric acid conc.
0.06 g / liter sodium chloride
are used as brighteners
0.4 g / liter octyl polyalkyl ether and
0.01 g / liter of bis (ω-sulfopropyl) sulfide, disodium salt and
0.01 g / liter polyacrylic acid amide
admitted. At an electrolyte temperature of 30 ° C there are shiny deposits on scraped copper laminate with a current density of 2 A / dm².

Wird nun der Elektrolyt einer Dauerbelastung von 500 Ah/l unterzogen, wobei die während der Elektrolyse verbrauchten Glanzbildner auf Sollwerte ergänzt werden, so zeigt der Elektrolyt am Wannenrand deutliche gallertartige Polymerausrahmungen.If the electrolyte is now subjected to a permanent load of 500 Ah / l, with the brightening agents used during the electrolysis being supplemented to set values, the electrolyte at the tub edge shows clear gelatinous polymer framing.

Setzt man dagegen anstelle des Octyl-polyalkylglycols die erfindungsgemäße Verbindung, Octyl-monomethyl-polyalkylglycols in der gleichen Menge dem Elektrolyten zu, so zeigt der Elektrolyt nach der Alterung keine Polymerausrahmungen.On the other hand, if instead of the octyl polyalkyl glycol, the compound according to the invention, octyl monomethyl polyalkyl glycol, is added to the electrolyte in the same amount, the electrolyte shows no polymer framing after aging.

BEISPIEL 4EXAMPLE 4

Eine Kupferfolie von 40 »m, die aus einem Kupferbad der Zusammensetzung
   80 g/Liter Kupfersulfat (CuSO₄.5 H₂O)
   200 g/Liter Schwefelsäure konz.
   0,06 g/Liter Natriumchlorid
abgeschieden wurde, zeigt eine Bruchelongation von 4,2 %. Nachdem in dem Elektrolyten
   0,4 g/Liter Dimethyl-polyalkyläther
gelöst wurden, zeigt eine unter gleichen Bedingungen abgeschiedene Folie 12,3 % Bruchelongation.A copper foil of 40 »m made from a copper bath of the composition
80 g / liter copper sulfate (CuSO₄.5 H₂O)
200 g / liter sulfuric acid conc.
0.06 g / liter sodium chloride
was separated, shows a fracture elongation of 4.2%. After in the electrolyte
0.4 g / liter dimethyl polyalkyl ether
a film deposited under the same conditions shows 12.3% elongation at break.

Claims (18)

  1. Aqueous, acidic bath for the galvanic deposition of shiny and smooth copper coatings, containing polyalkylene glycol dialkyl ethers of the general formula
    Figure imgb0006
     in which n = 8 - 800, m = 0 - 50, R¹ is a low alkyl C₁ to C₄, R² is an aliphatic chain or aromatic residue and a=1 or 2.
  2. Aqueous, acidic bath according to claim 1, containing polyalkylene glycol dialkyl ethers or mixtures thereof in concentrations of between 0.005 and 30 g/litre.
  3. Aqueous, acidic bath according to claims 1 and 2, containing
    dimethyl-polyethyleneglycol ethers,
    di-tert.-butyl-polyethyleneglycol ethers,
    stearyl-monomethyl-polyethyleneglycol ethers,
    nonylphenyl-monomethyl-polyethyleneglycol ethers,
    polyethylene-polypropylene-dimethylglycol ethers,
    octyl-monomethyl-polyalkylene ethers,
    dimethyl-bis(polyalkyleneglycol) octylene ethers and/or
    β-naphthol-monomethyl-polyethyleneglycol ethers.
  4. Aqueous, acidic bath according to claims 1 to 3, additionally containing a thio compound or a mixture of a plurality of thio compounds.
  5. Aqueous, acidic bath according to claim 4, containing
    3-mercaptopropane-1-sulphonic acid, sodium salt,
    thiophosphoric acid-O-ethyl-bis-(ω-sulphopropyl)-esters, disodium salt,
    thiophosphoric acid-tris-(ω-sulphopropyl)-esters, trisodium salt,
    thioglycol acid,
    ethylene dithiodipropylsulphonic acid, sodium salt,
    bis-(ω-sulphopropyl)-disulphide, disodium salt,
    bis-(ω-sulphopropyl)-sulphide, disodium salt,
    O-ethyl-dithiocarbonic acid-S-(ω-sulphopropyl)-esters, potassium salt,
    3(benzthiazolyl-2-thio)-propylsulphonic acid, sodium salt,
    bis-(ω-sulphohydroxypropyl)-disulphide, disodium salt,
    bis-(ω-sulphobutyl)-disulphide, disodium salt,
    bis-(p-sulphophenyl)-disulphide, disodium salt,
    methyl-(ω-sulphopropyl)-disulphide, disodium salt
    and/or
    methyl-(ω-sulphopropyl)-trisulphide, disodium salt.
  6. Aqueous, acidic bath according to claims 4 and 5, containing thio compounds in concentrations of between 0.0005 and 0.4 g/litre.
  7. Aqueous, acidic bath according to claims 1 to 6, characterised by an additional content of at least one polymeric phenazonium compound.
  8. Aqueous, acidic bath according to claim 7, containing
    poly(6-methyl-7-dimethylamino-5-phenyl phenazonium sulphate),
    poly(2-methyl-7-diethylamino-5-phenyl phenazonium chloride),
    poly(2-methyl-7-dimethylamino-5-phenyl phenazonium sulphate),
    poly(5-methyl-7-dimethylamino-phenazonium acetate),
    poly(2-methyl-7-anilino-5-phenyl phenazonium sulphate),
    poly(2-methyl-7-dimethylamino-phenazonium sulphate),
    poly(7-methylamino-5-phenyl phenazonium acetate),
    poly(7-ethylamino-2,5-diphenyl phenazonium chloride),
    poly(2,8-dimethyl-7-diethylamino-5-p-tolyl phenazonium chloride),
    poly(2,5,8-triphenyl-7-dimethylamino-phenazonium sulphate),
    poly(2,8-dimethyl-7-amino-5-phenyl phenazonium sulphate) and/or
    poly(7-dimethylamino-5-phenyl phenazonium chloride).
  9. Aqueous, acidic bath according to claims 7 and 8, containing polymeric phenazonium compounds in concentrations of between 0.0001 and 0.5 g/litre.
  10. Aqueous, acidic bath according to claims 1 to 6, characterised by an additional content of at least one thiourea derivative.
  11. Aqueous, acidic bath according to claim 10, containing
    N-acetylthiourea,
    N-trifluoroacetylthiourea,
    N-ethylthiourea,
    N-cyanoacetylthiourea,
    N-allylthiourea,
    o-tolylthiourea,
    N,N'-butylenethiourea,
    thiazolidine thiol(2),
    4-thiazolidine thiol(2),
    imidazolidine thiol(2) (N,N'-ethylenethiourea),
    4-methyl-2-pyrimidine thiol and/or 2-thiouracil.
  12. Aqueous, acidic bath according to claims 10 and 11, containing thiourea derivative in concentrations of between 0.0001 and 0.5 g/litre.
  13. Aqueous, acidic bath according to claims 1 to 6, characterised by an additional content of at least one polymeric nitrogen compound.
  14. Aqueous, acidic bath according to claim 13, containing
    polyethyleneimine,
    polyethyleneimide,
    polyacrylicacidamide,
    polypropyleneimine,
    polybutyleneimine,
    N-methylpolyethyleneimine,
    N-acetylpolyethyleneimine and/or
    N-butylpolyethyleneimine.
  15. Aqueous, acidic bath according to claims 13 and 14, containing polymeric nitrogen compounds in concentrations of between 0.0001 and 0.05 g/litre.
  16. Aqueous, acidic bath, characterised by a content of polyalkylene glycol dialkyl ethers according to claims 1 to 3 and thio compounds according to claims 4 to 6.
  17. Use of the bath according to at least one of claims 1 to 16 for reinforcing conductor paths of printed circuits.
  18. Use of the bath according to at least one of claims 1 to 16 for the production of shiny and smooth copper coatings.
EP92916259A 1991-08-07 1992-07-22 Acid bath for the galvanic deposition of copper, and the use of such a bath Expired - Lifetime EP0598763B1 (en)

Applications Claiming Priority (3)

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DE4126502A DE4126502C1 (en) 1991-08-07 1991-08-07
DE4126502 1991-08-07
PCT/DE1992/000605 WO1993003204A1 (en) 1991-08-07 1992-07-22 Acid bath for the galvanic deposition of copper, and the use of such a bath

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WO (1) WO1993003204A1 (en)

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ES2082486T3 (en) 1996-03-16
CA2115062C (en) 2005-11-22
US5433840A (en) 1995-07-18
WO1993003204A1 (en) 1993-02-18
ATE131546T1 (en) 1995-12-15
DE59204703D1 (en) 1996-01-25
JPH07505187A (en) 1995-06-08

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