EP0297306A1 - Aqueous acid bath for the galvanic deposition of brightening and leveling copper coatings - Google Patents

Aqueous acid bath for the galvanic deposition of brightening and leveling copper coatings Download PDF

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Publication number
EP0297306A1
EP0297306A1 EP88108876A EP88108876A EP0297306A1 EP 0297306 A1 EP0297306 A1 EP 0297306A1 EP 88108876 A EP88108876 A EP 88108876A EP 88108876 A EP88108876 A EP 88108876A EP 0297306 A1 EP0297306 A1 EP 0297306A1
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Prior art keywords
acid
liter
aqueous acid
acid bath
bath according
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EP88108876A
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German (de)
French (fr)
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EP0297306B1 (en
Inventor
Wolfgang Dahms
Hubert-Matthias Dr. Rer.Nat. Seidenspinner
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Atotech Deutschland GmbH and Co KG
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Schering AG
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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 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 reacted with diaalkylaminobenzoyl chloride to give the desired product.
  • 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.
  • 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. 5H2O) 20 - 250 g / liter, preferably 60-80 g / liter or 180-220 g / liter Sulfuric acid 50 - 350 g / liter, preferably 180-220 g / liter or 50-90 g / liter Sodium chloride 0.02 - 0.25 g / liter, preferably 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 - 1 2 A / dm2, preferably 2 - 4 A / dm2
  • Electrolysis 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.
  • a plated-through circuit is copper-plated for 50 minutes.
  • the plate looks greasy and shiny and has very strong defects at the edges of the borehole.

Abstract

An aqueous acidic bath for the electrodeposition of bright and level copper coatings contains at least one benzothiazonium compound of the general formula <IMAGE> in which R1 is C1-C5-alkyl, optionally substituted aryl or aralkyl, R2 is hydrogen, C1-C5-alkyl or C1-C5-alkoxy, R3 and R4 are each C1-C5-alkyl and X is an acid radical.

Description

Die Erfindung betrifft ein saures Bad zur galvanischen Abscheidung glänzender und eingeebneter Kupferüberzüge.The invention relates to an acid bath for the electrodeposition of shiny and leveled copper coatings.

Es ist seit langem bekannt, daß sauren, insbesondere den am meisten verbreite­ten, schwefelsauren Kupferelektrolyten bestimmte organische Substanzen in geringen Mengen zugesetzt werden können, um statt einer kristallin-matten Ab­scheidung glänzende Kupferüberzüge zu erhalten. Für diesen Zweck sind zum Beispiel bekanntgeworden Polyäthylenglycol, Thioharnstoff, Gelatine, Melasse, Kaffee-Extrakt, "basische" Farbstoffe und Thiophosphorsäureester, die jedoch keinerlei praktische Bedeutung mehr besitzen, da die Qualität der mit Ihnen er­haltenen Kupferüberzüge nicht den heutigen Anforderungen entsprechen. So sind die Überzüge entweder zu spröde oder sie besitzen einen zu geringen Glanz be­ziehungsweise fallen in bestimmten Stromdichtebereichen reliefartig aus.It has long been known that acidic, in particular the most widespread, sulfuric acid copper electrolytes, certain organic substances can be added in small amounts in order to obtain shiny copper coatings instead of a crystalline matt deposition. For this purpose, for example, polyethylene glycol, thiourea, gelatin, molasses, coffee extract, "basic" dyes and thiophosphoric acid esters have become known, but they no longer have any practical significance, since the quality of the copper coatings obtained with them does not meet today's requirements. For example, the coatings are either too brittle or have a low gloss or are relief-like in certain current density ranges.

Gemische verschiedener chemisch unterschiedlicher Inhibitoren mit Thioverbin­dung verbesserten die Kupferabscheidung:Mixtures of different chemically different inhibitors with thio compound improved the copper deposition:

Vorgeschlagen wurde der Zusatz von Polyalykliminen in Verbindung mit organi­schen Thioverbindungen (DE-PS 1246347) und Polyvinylverbindungen in Mischung mit sauerstoffhaltigen hochmolekularen Verbindungen und organischen insbeson­dere aromatischen Thioverbindungen (DE AS 15 21 062). Derartige Kupferelektro­lyte erlauben aber nicht den Einsatz höherer kathodischer Stromdichten, und die abgeschiedenen Kupferüberzüge können außerdem nur nach einer vorausgegangenen Zwischenbehandlung vernickelt werden. In der genannten DE AS 15 21 062 wird außerdem ein saures Kupferbad beschrieben, das neben einer polymeren sauer­stoffhaltigen Verbindung mit wasserlöslich machender Gruppe noch mindestens eine substituierte Phenazoniumverbindung gelöst enthält.It was proposed to add polyalyklimines in combination with organic thio compounds (DE-PS 1246347) and polyvinyl compounds in a mixture with oxygen-containing high-molecular compounds and organic, in particular aromatic thio compounds (DE AS 15 21 062). However, such copper electrolytes do not allow the use of higher cathodic current densities, and the deposited copper coatings can also only be nickel-plated after a previous intermediate treatment. In the aforementioned DE AS 15 21 062 an acidic copper bath is also described which, in addition to a polymeric oxygen-containing compound with a water-solubilizing group, also contains at least one substituted phenazonium compound in solution.

Bei diesen monomeren Phenazoniumverbindungen ist die anwendbare Stromdichte sowie das Alterungsverhalten nicht ausreichend. Weitere Veröffentlichungen ver­wenden die Kombination von organischen Thioverbindungen und nichtiogenen Netz­mitteln mit anderen Farbstoffen wie zum Beispiel Kristall-Violett (Eu-PS 71512), Methylviolett (DE PS 225584), Amiden (US PS 4181582), Phthalo­cyanin-De1ivaten mit Apo-Safranin (US PS 3420999).With these monomeric phenazonium compounds, the current density that can be used and the aging behavior are not sufficient. Other publications use the combination of organic thio compounds and noniogenic wetting agents with other dyes such as, for example, crystal violet (Eu-PS 71512), methyl violet (DE PS 225584), amides (US PS 4181582), phthalocyanine derivatives with apo-safranine (US PS 3420999).

Anstelle des Farbstoffes wurden auch undefinierte Umsetzungsprodukte von Poly­aminen mit Benzylchlorid (US PS 4110176) beziehungsweise Epichlorhydrin (EU PS 68807) oder solche mit Thioverbindungen und Acrylamid (EU PS 107109) vorgeschlagen.Instead of the dye, undefined reaction products of polyamines with benzyl chloride (US PS 4110176) or epichlorohydrin (EU PS 68807) or those with thio compounds and acrylamide (EU PS 107109) have also been proposed.

Sie ergeben alle ungleichmäßige Abscheidungen insbesondere in Kombination mit stickstoffhaltigen Thioverbindungen.They all result in non-uniform deposits, especially in combination with nitrogen-containing thio compounds.

Einen wesentlichen Fortschritt erbrachten Bäder, die polymere Phenazoniumver­bindungen (DE PS 2039831) enthielten. Sie finden hauptsächlich in Kombination mit nichtionogenen Netzmitteln und organischen Schwefelverbindungen Anwendung.Baths containing polymeric phenazonium compounds (DE PS 2039831) made significant progress. They are mainly used in combination with non-ionic wetting agents and organic sulfur compounds.

Nachteilig ist die hohe Einebnung im hohen Stromdichtebereich im Vergleich zur geringen Einebnung im niedrigen Bereich, was bei der Verkupferung von gedruck­ten Schaltungen zu Lochrandabflachungen an den Bohrlöchern führt. In der deko­rativen Kupferabscheidung machen sich die unterschiedlichen Bereiche in der Stromdichte unschön bemerkbar.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. In the decorative copper deposition, the different areas in the current density are noticeably noticeable.

Aufgabe dieser Erfindung ist es, diese Nachteile zu vermeiden und darüber hinaus die Einebnung und gleichmäßige Abscheidung im Bereich niedriger Strom­dichte zu verbessern.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.

Diese Aufgabe wird erfindungsgemäß durch ein saures Bad gemäß dem kennzeich­nenden Teil des Patentanspruchs gelöst.This object is achieved by an acid bath according to the characterizing part of the patent claim.

Vorteilhafte Weiterentwicklungen sind in den Unteransprüchen aufgeführt.Advantageous further developments are listed in the subclaims.

Zusätzlich können noch Einebner, wie zum Beispiel Thioharnstoffderivate oder polymere Phenazoniumverbindungen von Fall zu Fall die Einebnung im hohen Be­reich verbessern.In addition, levelers, such as thiourea derivatives or polymeric phenazonium compounds, can improve the leveling in the high range from case to case.

Die Mengen, in denen die Benzthiazolium-Verbindungen zugegeben werden müssen, um eine deutliche Verbesserung der Kupferabscheidung zu erzielen, sind gering und betragen etwa 0.0005 bis 0.3 g/Liter vorzugsweise 0.002 bis 0.05 g/Liter. Tabelle 1 enthält Beispiele für erfindungsgemäß zu verwendete Substanzen und Angaben über die bevorzugten Konzentrationen im Bad.

Figure imgb0001
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.
Figure imgb0001

Die Benzthiazolium-Verbindungen sind an sich bekannt oder können nach an sich bekannten Verfahren beispielsweise wie folgt hergestellt werden.The benzothiazolium compounds are known per se or can be prepared, for example, as follows by processes known per se.

Zunächst wird das entsprechende Benzthiazolderivat am Stickstoff alkyliert, dieser Ring mit Hydrazin-hydrat geöffnet und mit Diaalkylaminobenzoylchlorid zum gewünschten Produkt umgesetzt.First, the corresponding benzothiazole derivative is alkylated on nitrogen, this ring is opened with hydrazine hydrate and reacted with diaalkylaminobenzoyl chloride to give the desired product.

Herstellungsvorschrift für Verbindung Nr. 1Manufacturing instructions for compound no. 1

In einem 4-1-Drehhalskolben mit KPG-Rührer, Rückflußkühler und Tropftrichter mit Druckausgleich werden 587 g ( 3.20 mol) 4-Dimethylamino-benzoylchlorid in 2.4 1 Toluol suspendiert, auf 60° C erwärmt und unter Stickstoff in 30 min mit einer Lösung von 445 g (3,20 mol) N-Methyl-2-mercaptoanilin versetzt. Man rührt 1 h bei Siedetemperatur, läßt abkühlen und saugt das ausgefallene Produkt ab. Nach Waschen mit ca. 2 1 Toluol und Trocknen bei 50° C im Vakuum erhält man 940 g (96 % der Theorie) hellgelbes Pulver, das zwischen 180 und 220° C unter Zersetzung schmilzt.587 g (3.20 mol) of 4-dimethylamino-benzoyl chloride are suspended in 2.4 l of toluene, heated to 60 ° C. and under nitrogen in 30 minutes with a solution of 445 g (3.20 mol) of N-methyl-2-mercaptoaniline were added. The mixture is stirred at boiling temperature for 1 h, allowed to cool and the product which has precipitated is filtered off with suction. After washing with about 2 l of toluene and drying at 50 ° C. in vacuo, 940 g (96% of theory) of light yellow powder are obtained, which melts between 180 and 220 ° C. with decomposition.

Die folgende Tabelle II enthält Beispiele für sauerstoffhaltige, hochmolekulare Verbindungen zur Verwendung als zasätzliche Komponente und deren bevorzugte Anwendungskonzentrationen:

Figure imgb0002
The following Table II contains examples of oxygen-containing, high-molecular compounds for use as an additional component and their preferred use concentrations:
Figure imgb0002

Die folgende Tabelle III enthält Beispiele für organische stickstofffreie Thio­verbindungen mit wasserlöslichen Gruppen zur zusätzlichen Verwendung als Kom­ponente und deren bevorzugte Anwendungskonzentration:

Figure imgb0003
Figure imgb0004
 The following 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:
Figure imgb0003
Figure imgb0004

Die Einzelkomponenten des erfindungsgemäßen Kupferbades können im allgemeinen vorteilhaft innerhalb folgender Grenzkonzentrationen im anwendungsfertigen Bad enthalten sein.
Thiazolium-Verbindung      0.0005 - 0.3 g / Liter
vorzugsweise      0.002 - 0.05 g - / Liter
Sauerstoffhaltige, hochmolekulare Verbindungen      0.005 - 20 g / Liter
vorzugsweise      0.01 - 5 g / Liter
Organische Thioverbindungen mit wasserlöslich machenden Gruppen      0.0005 - 0.2 g / Liter
vorzugsweise      0.001 - 0.03 g / LiterThe 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 0.0005 - 0.3 g / liter
preferably 0.002 - 0.05 g - / liter
Oxygenated, high molecular compounds 0.005 - 20 g / liter
preferably 0.01 - 5 g / liter
Organic thio compounds with water-solubilizing groups 0.0005 - 0.2 g / liter
preferably 0.001-0.03 g / liter

Die Grundzusammensetzung des erfindungsgemäßen Bades kann in weiten Grenzen schwanken. Im allgemeinen wird eine wässrige Lösung folgender Zusammensetzung benutzt:
Kupfersulfat (CuSO₄ . 5H₂O)      20 - 250 g / Liter,
vorzugsweise      60 - 80 g / Liter oder 180 - 220 g / Liter
Schwefelsäure      50 - 350 g / Liter,
vorzugsweise      180 - 220 g / Liter oder 50 - 90 g / Liter
Natriumchlorid      0.02 - 0.25 g / Liter,
vorzugsweise      0.05 - 0.12 g / LiterThe basic composition of the bath according to the invention can vary within wide limits. In general, an aqueous solution of the following composition is used:
Copper sulfate (CuSO₄. 5H₂O) 20 - 250 g / liter,
preferably 60-80 g / liter or 180-220 g / liter
Sulfuric acid 50 - 350 g / liter,
preferably 180-220 g / liter or 50-90 g / liter
Sodium chloride 0.02 - 0.25 g / liter,
preferably 0.05 - 0.12 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 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 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, wie zum Beispiel Thioharnstoffderivate oder polymere Phenazoniumverbindungen, und/oder Netzmittel enthalten sein.In addition, the bathroom can also contain customary brighteners, levelers, such as thiourea derivatives or polymeric phenazonium compounds, and / or wetting agents.

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 - 45°C, vorzugsweise 25° C
kath. Stromdichte : 0.5 - 1 2 A/dm², vorzugsweise 2 - 4 A/dm²The working conditions of the bath are as follows:
pH value: <1
Temperature: 15 - 45 ° C, preferably 25 ° C
cath. Current density: 0.5 - 1 2 A / dm², preferably 2 - 4 A / dm²

Elektrolyltbewegung erfolgt durch Einblasen von sauberer Luft, so stark, Daß die Elektrolytoberfläche in starker Wallung sich befindet.Electrolysis movement takes place by blowing clean air so strongly that the electrolyte surface is in a strong surge.

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
80 g/Liter Kupfersulfat (CuSo₄.5H₂O)
180 g/Liter Schwefelsäure konz.
0.08 g/Liter Natriumchlorid
werden als Glanzbilder
0.6 g/Liter Polypropylenglycol und
0.02 g/Liter 3-Mercaptopropan-sulfonsäure, Natriumsalz
zugegeben. Bei einer Elektrolyttemperatur von 30° C enthält man in der Hull-­Zelle bei einer Stromdichte oberhalb 0.8 A/dm² glänzende Abscheidungen, bei einer Stromdichte unterhalb 0.8 A/dm² dagegen matte Abscheidungen.A copper bath of the composition
80 g / liter copper sulfate (CuSo₄.5H₂O)
180 g / liter sulfuric acid conc.
0.08 g / liter sodium chloride
are used as glossy pictures
0.6 g / liter polypropylene glycol and
0.02 g / liter 3-mercaptopropanesulfonic acid, sodium salt
admitted. At an electrolyte temperature of 30 ° C, 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.

Setzt man dem Bad
0.02 g/Liter Verbindung Nr. 1 oder
0.01 g/Liter Verbindung Nr. 2 oder
0.01 g/Liter Verbindung Nr. 3 oder
0.02 g/Liter Verbindung Nr. 4 oder
0.04 g/Liter Verbindung Nr. 5 oder
0.01 g/Liter Verbindung Nr. 6 oder
0.01 g/Liter Verbindung Nr.7 aus Tabelle I
zu, so ist der gesamte Stromdichtebereich auf dem Hull-Zellen-Prüfblech glän zend.If you put the bathroom
0.02 g / liter of compound No. 1 or
0.01 g / liter of compound No. 2 or
0.01 g / liter of compound No. 3 or
0.02 g / liter of compound No. 4 or
0.04 g / liter of compound No. 5 or
0.01 g / liter of compound No. 6 or
0.01 g / liter of compound No. 7 from Table I
closed, the entire current density range on the Hull cell test plate is shiny.

BEISPIEL 2EXAMPLE 2

Einem Kupferbad folgender Zusammensetzung
60 g/Liter Kupfersulfat (CuSO₄.5H₂O)
220 g/Liter Schwefelsäure konz.
0.1 g/Liter Natriumchlorid
werden
1.0 g/Liter BNaphthol -polyglycoläther und
0.01 g/Liter Bis (w-sulfohydroxypropyl)disulfid. Dinatriumsalz zugegeben.A copper bath with the following composition
60 g / liter copper sulfate (CuSO₄.5H₂O)
220 g / liter sulfuric acid conc.
0.1 g / liter sodium chloride
will
1.0 g / liter BNaphthol polyglycol ether and
0.01 g / liter bis (w-sulfohydroxypropyl) disulfide. Disodium salt added.

Bei einer mittleren Stromdichte von 2 A/dm² wird eine gedruckte, nach der Additivtechnik verkupferte Schaltung 60 Minuten verstärkt. Hierbei zeigen sich um die Bohrlöcher matte abgeflachte Höfe, die nach dem Verzinnen deutliche Risse aufweisen.At an average current density of 2 A / dm², a printed circuit, copper-plated using the additive technology, is amplified for 60 minutes. This shows matte, flattened courtyards around the boreholes, which show marked cracks after tinning.

Setzt man dem Bad außerdem 0.02 g/Liter Verbindung 7 aus Tabelle I zu, so sind die Bohrlöcher auch nach dem Verzinnen einwandfrei.If 0.02 g / liter of compound 7 from Table I is also added to the bath, the boreholes are perfect even after tinning.

BEISPIEL 3EXAMPLE 3

Einem Kupferbad der Zusammensetzung
200.0 g/Liter Kupfersulfat (CuSO₄ .5 H₂O)
65.0 g/Liter Schwefelsäure
0.2 g/Liter Natriumchlorid
werden als Glanzbildner 0.2 g/Liter Polyäthylenglycol 0.01 g/Liter Bis (w-sul­fopropyl)-disulfid. Dinatriumsalz, und
0.02 g/Liter polymeres 7-Dimethylamino-5-phenyl-phenazomium-chlorid
zugegeben. Bei einer Elektrolyttemperatur von 27°C erhält man bei einer Stromdichte von 1 A/dm² und Lufteinblasung zwar glänzende Kupferüberzüge, die Einebnung beträgt bei einer Schichtdicke von 3.4 µm nur 27%. Gibt man dem Bad zusätzlich 0.01 g/Liter der Subszanz 1 (Tabelle I) zu, so steigt die Einebnung unter gleichen Arbeitsbedingungen auf 35% an. Sie erhöht sich also um 30%.A copper bath of the composition
200.0 g / liter copper sulfate (CuSO₄ .5 H₂O)
65.0 g / liter sulfuric acid
0.2 g / liter sodium chloride
are used as brighteners 0.2 g / liter of polyethylene glycol 0.01 g / liter of bis (w-sulfopropyl) disulfide. Disodium salt, and
0.02 g / liter of polymeric 7-dimethylamino-5-phenylphenazomium chloride
admitted. At 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 µm. If you add 0.01 g / liter of Subszanz 1 (Table I) to the bath, the leveling increases to 35% under the same working conditions. So it increases by 30%.

BEISPIEL 4EXAMPLE 4

Einem Kupferbad folgender Zusammensetzung
80 g/Liter Kupfersulfat (CuSO₄ . 5 H₂O)
200 g/Liter Schwefelsäure, konz.
0.06 g/Liter Natriumchlorid
werden
0.4 g/Liter Oktanolpolyalkylenglykoläther
0.01 g/Liter Di-n-propylthioäther-di-w-sulfonsäure, Dinatriumsalz und
0.01 g/Liter polymeres 7-Dimethylamino-5-phelyl-phenazoniumchlorid zugegeben.A copper bath with the following composition
80 g / liter copper sulfate (CuSO₄. 5 H₂O)
200 g / liter sulfuric acid, conc.
0.06 g / liter sodium chloride
will
0.4 g / liter octanol polyalkylene glycol ether
0.01 g / liter di-n-propylthioether-di-w-sulfonic acid, disodium salt and
0.01 g / liter of polymeric 7-dimethylamino-5-phelyl-phenazonium chloride was added.

Bei einer mittleren Stromdichte von 2.4 A/dm² wird eine gedruckte durchkontak­tierte Schaltung 50 Minuten verkupfert. Die Platte sieht speckig glänzend aus und hat sehr starke Fehlstellen an den Bohrlochkanten.With an average current density of 2.4 A / dm², a plated-through circuit is copper-plated for 50 minutes. The plate looks greasy and shiny and has very strong defects at the edges of the borehole.

Ersetzt man das polymere Produkt durch 0.01 g/Liter der Verbindung 4 aus Ta­belle I, so ist die Schaltung glänzend und hat gute Bohrlochkanten.If you replace the polymer product with 0.01 g / liter of compound 4 from Table I, the circuit is shiny and has good borehole edges.

Claims (15)

1. Wässriges saures Bad zur galvanischen Abscheidung glänzender und eingeeb­neter Kupferüberzüge, gekennzeichnet durch einen Gehalt an mindestens ei­ner Benzthiazonium-Verbindung der allgemeinen Formel
Figure imgb0005
 in der
R₁ C₁-C₅-Alkyl, gegebenenfalls substituiertes Aryl oder Aralkyl,
R₂ Wasserstoff, C₁-C₅-Alkyl oder C₁-C₅-Alkoxy,
R₃ und R₄ jeweils C₁-C₅-Alkyl und
X einen Säurerest darstellen.1. Aqueous acid bath for the electrodeposition of shiny and leveled copper coatings, characterized by a content of at least one benzothiazonium compound of the general formula
Figure imgb0005
 in the
R₁ C₁-C₅ alkyl, optionally substituted aryl or aralkyl,
R₂ is hydrogen, C₁-C₅-alkyl or C₁-C₅-alkoxy,
R₃ and R₄ are each C₁-C₅ alkyl and
X represents an acid residue. 2. Wässriges saures Bad gemäß Anspruch 1, worin
R₁ Methyl, Äthyl, n-Propyl, i-Propyl, Phenyl oder Benzyl,
R₂ Wasserstoff, Methyl, Ätyhl, n-Propyl oder i-Propyl,
R₃ und R₄ jeweils Methyl, Äthyl, n-Propyl oder i-Propyl und
X einen Säurerest darstellen.2. An aqueous acid bath according to claim 1, wherein
R₁ is methyl, ethyl, n-propyl, i-propyl, phenyl or benzyl,
R₂ is hydrogen, methyl, ethyl, n-propyl or i-propyl,
R₃ and R₄ are each methyl, ethyl, n-propyl or i-propyl and
X represents an acid residue. 3. Wässriges saures Bad gemäß Ansprüchen 1 und 2, worin die R₂-Gruppe in 5-oder 6-Stellung angeordnet ist.3. Aqueous acid bath according to claims 1 and 2, wherein the R₂ group is arranged in the 5 or 6 position. 4. Wässriges saures Bad gemäß Ansprüchen 1 und 2, worin X einen Rest der Salz­säure, Schwefelsäure, Methansulfonsäure, Essigsäure, Toluolsulfonsäure oder Methanschwefelsäure darstellt.4. Aqueous acid bath according to claims 1 and 2, wherein X represents a residue of hydrochloric acid, sulfuric acid, methanesulfonic acid, acetic acid, toluenesulfonic acid or methanesulfuric acid. 5. Wässriges saures Bad gemäß Ansprüchen 1 bis 4, enthaltend die Thiazonium-­Verbindungen in Konzentrationen von 0.0005 bis 0.3 g/Liter, vorzugsweise 0.002 bis 0.25 g/Liter.5. Aqueous acid bath according to claims 1 to 4, containing the thiazonium compounds in concentrations of 0.0005 to 0.3 g / liter, preferably 0.002 to 0.25 g / liter. 6. Wässriges saures Bad gemäß Ansprüchen 1 bis 5, gekennzeichnet durch einen zusätzlichen Gehalt an mindestens einer sauerstoffhaltigen hochmolekularen Verbindung.6. Aqueous acid bath according to claims 1 to 5, characterized by an additional content of at least one oxygen-containing high molecular compound. 7. Wässriges saures Bad gemäß Anspruch 6, enthaltend
Polyvinylalkohol,
Carboxymethylcellulose,
Polyäthylenglycol,
Polypropylenglycol,
Stearinsäure-Polyglycolester,
Ölsäure-Polyglycolester,
Stearyalkohol-Polyglycoläther,
Nonylphenol-Polyglycoläther,
Oktanolpolyalkylenglycoläther,
Oktandiol-bis-(polyalkylenglycoläther),
Polyoxypropylenglycol,
Polyäthylen-propylenglycol oder
β-Naphthol-Polyglycoläther.7. Aqueous acid bath according to claim 6, containing
Polyvinyl alcohol,
Carboxymethyl cellulose,
Polyethylene glycol,
Polypropylene glycol,
Stearic acid polyglycol ester,
Oleic acid polyglycol ester,
Steary alcohol polyglycol ether,
Nonylphenol polyglycol ether,
Octanol polyalkylene glycol ether,
Octane diol bis (polyalkylene glycol ether),
Polyoxypropylene glycol,
Polyethylene propylene glycol or
β-naphthol polyglycol ether. 8. Wässriges saures Bad gemäß Ansprüchen 6 und 7, enthaltend die sauerstoff­haltigen hochmolekularen Verbindungen in Konzentrationen von 0.005 bis 20 g / Liter, vorzugsweise 0.01 bis 5 g/Liter.8. Aqueous acid bath according to claims 6 and 7, containing the oxygen-containing high molecular compounds in concentrations of 0.005 to 20 g / liter, preferably 0.01 to 5 g / liter. 9. Wässriges saures Bad gemäß Ansprüchen 1 bis 5 gekennzeichnet durch einen zusätzlichen Gehalt an einer organischen stickstofffreien Thioverbindung mit wasserlöslich machenden Gruppen.9. Aqueous acid bath according to claims 1 to 5 characterized by an additional content of an organic nitrogen-free thio compound with water-solubilizing groups. 10. Wässriges saures Bad gemäß Anspruch 9, enthaltend
3-Mercaptopropan-1-sulfonsäure, Natriumsalz
Thiophosphorsäure-0-äthyl-bis-(w-sulfopropyl)-ester,Dinatriumsalz,
Thiophosphorsäure-tris-(w-sulfopropyl)-ester, Trinatriumsalz,
Thioglycolsäure,
Äthylendithiodipropylsulfonsäure, Natriumsalz
Di-n-propythioäther-di-w-sulfonsäure, Dinatriumsalz,
Bis(w-sulfopropyl)disulfid, Dinatriumsalz,
Bis(w-sulfohydroxypropyl)disulfid, Dinatriumsalz,
Bis(w-sulfobutyl)disulfid, Dinatriumsalz,
Methyl-(w-sulfopropyl)disulfid, Natriumsalz oder
Methyl-(w-sulfobutyl)trisulfid, Natriumsalz.10. Aqueous acid bath according to claim 9, containing
3-mercaptopropan-1-sulfonic acid, sodium salt
Thiophosphoric acid-0-ethyl-bis- (w-sulfopropyl) ester, disodium salt,
Thiophosphoric acid tris (w-sulfopropyl) ester, trisodium salt,
Thioglycolic acid,
Ethylene dithiodipropyl sulfonic acid, sodium salt
Di-n-propythioether-di-w-sulfonic acid, disodium salt,
Bis (w-sulfopropyl) disulfide, disodium salt,
Bis (w-sulfohydroxypropyl) disulfide, disodium salt,
Bis (w-sulfobutyl) disulfide, disodium salt,
Methyl (w-sulfopropyl) disulfide, sodium salt or
Methyl (w-sulfobutyl) trisulfide, sodium salt. 11. Wässriges saures Bad gemäß Ansprüchen 9 und 10, enthaltend die organischen stickstofffreien Thioverbindungen mit wasserlöslich machenden Gruppen in Konzentrationen von 0,0005 bis 0.2 g/Liter, vorzugsweise 0.001 bis 0.3 g/Liter.11. Aqueous acid bath according to claims 9 and 10, containing the organic nitrogen-free thio compounds with water-solubilizing groups in concentrations of 0.0005 to 0.2 g / liter, preferably 0.001 to 0.3 g / liter. 12. Wässriges saures Bad, gekennzeichnet durch einen Gehalt an Thiazoniumver­bindungen gemäß Ansprüchen 1 bis 5, sauerstoffhaltigen hochmolekularen Ver­bindungen gemäß Ansprüchen 6 bis 8 und organischen stickstofffreien Thio­verbindungen mit wasserlöslich machenden Gruppen gemäß Ansprüchen 9 bis 11.12. Aqueous acid bath, characterized by a content of thiazonium compounds according to claims 1 to 5, oxygen-containing high molecular compounds according to claims 6 to 8 and organic nitrogen-free thio compounds with water-solubilizing groups according to claims 9 to 11. 13. Wässriges saures Bad gemäß Anspruch 12, dadurch gekennzeichnet, daß dieses einen pH-Wert <1 aufweist.13. Aqueous acid bath according to claim 12, characterized in that it has a pH <1. 14. Verfahren zur galvanischen Abscheidung glänzender und eingeebneter Kupfer­überzüge, dadurch gekennzeichnet, daß galvanische Kupferbäder gemäß den Ansprüchen 1 bis 13 bei Temperaturen von 15 bis 45° C und Stromdichten von 0.5 bis 12 A/dm² verwendet werden.14. A method for the galvanic deposition of shiny and leveled copper coatings, characterized in that galvanic copper baths according to claims 1 to 13 are used at temperatures of 15 to 45 ° C and current densities of 0.5 to 12 A / dm². 15. Glänzende und eigeebnete Kupferüberzüge hergestellt nach dem Verfahren gemäß Anspruch 14.15. Shiny and self-leveling copper coatings produced by the method according to claim 14.
EP88108876A 1987-06-30 1988-06-03 Aqueous acid bath for the galvanic deposition of brightening and leveling copper coatings Expired - Lifetime EP0297306B1 (en)

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DE19873721985 DE3721985A1 (en) 1987-06-30 1987-06-30 AQUEOUS ACID BATH FOR GALVANIC DEPOSITION OF GLOSSY AND LEVELED COPPER COATINGS
DE3721985 1987-06-30

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AT (1) AT396946B (en)
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Publication number Priority date Publication date Assignee Title
EP0440027A2 (en) * 1990-01-29 1991-08-07 Shipley Company Inc. Additive for acid-copper electroplating baths to increase throwing power
EP0536638A2 (en) * 1991-10-08 1993-04-14 BASF Lacke + Farben AG Cathodically depositable electrophoresis paint
US5252196A (en) * 1991-12-05 1993-10-12 Shipley Company Inc. Copper electroplating solutions and processes

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JPH04120692A (en) * 1990-09-11 1992-04-21 Koatsu Gas Kogyo Kk Sensor testing device
DE4032864A1 (en) * 1990-10-13 1992-04-16 Schering Ag ACIDIC BATH FOR THE GALVANIC DEPOSITION OF COPPER COVERS AND METHODS USING THIS COMBINATION
DE10000090A1 (en) * 2000-01-04 2001-08-30 Elfo Ag Sachseln Sachseln Electrical connecting element production method has embossed substrate provided with selectively etched conductive galvanic coating
WO2002054840A1 (en) * 2001-01-04 2002-07-11 Elmicron Ag Method for producing electroconductive structures
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 (en) * 2011-09-09 2013-03-13 Rohm and Haas Electronic Materials LLC Low internal stress copper electroplating method

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EP0107109A2 (en) * 1982-09-30 1984-05-02 LeaRonal, Inc. Electrolytic copper plating solutions and a method for their application
EP0163131A2 (en) * 1984-04-27 1985-12-04 LeaRonal, Inc. An acid copper electroplating solution as well as a method of electroplating

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EP0107109A2 (en) * 1982-09-30 1984-05-02 LeaRonal, Inc. Electrolytic copper plating solutions and a method for their application
EP0163131A2 (en) * 1984-04-27 1985-12-04 LeaRonal, Inc. An acid copper electroplating solution as well as a method of electroplating

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0440027A2 (en) * 1990-01-29 1991-08-07 Shipley Company Inc. Additive for acid-copper electroplating baths to increase throwing power
EP0440027A3 (en) * 1990-01-29 1991-11-06 Shipley Company Inc. Additive for acid-copper electroplating baths to increase throwing power
EP0536638A2 (en) * 1991-10-08 1993-04-14 BASF Lacke + Farben AG Cathodically depositable electrophoresis paint
EP0536638A3 (en) * 1991-10-08 1993-05-26 Basf Lacke + Farben Ag Cathodically depositable electrophoresis paint
US5252196A (en) * 1991-12-05 1993-10-12 Shipley Company Inc. Copper electroplating solutions and processes

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ES2045013T3 (en) 1994-01-16
DE3877633D1 (en) 1993-03-04
ATA166488A (en) 1993-05-15
EP0297306B1 (en) 1993-01-20
AT396946B (en) 1993-12-27
DE3721985A1 (en) 1989-01-12

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