EP0554275A1 - Acid bath for copper plating, and a process using a bath of this type for this purpose. - Google Patents

Acid bath for copper plating, and a process using a bath of this type for this purpose.

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Publication number
EP0554275A1
EP0554275A1 EP91917496A EP91917496A EP0554275A1 EP 0554275 A1 EP0554275 A1 EP 0554275A1 EP 91917496 A EP91917496 A EP 91917496A EP 91917496 A EP91917496 A EP 91917496A EP 0554275 A1 EP0554275 A1 EP 0554275A1
Authority
EP
European Patent Office
Prior art keywords
naphthol
poly
ethoxylate
compounds
phenazonium
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.)
Granted
Application number
EP91917496A
Other languages
German (de)
French (fr)
Other versions
EP0554275B1 (en
Inventor
Wolfgang Dahms
Horst Westphal
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Atotech Deutschland GmbH and Co KG
Original Assignee
Schering AG
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Publication of EP0554275A1 publication Critical patent/EP0554275A1/en
Application granted granted Critical
Publication of EP0554275B1 publication Critical patent/EP0554275B1/en
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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

  • copper sulfate (CuS0. 4 5H 2 0)
  • customary brighteners, levelers or wetting agents can also be present in the bathroom.

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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)
  • Electrolytic Production Of Metals (AREA)

Abstract

The invention concerns an aqueous acid copper-electroplating bath and the use of the bath for the electrolytic deposition of copper.

Description

SAURES BAD ZUR GALVANISCHEN ABSCHEIDUNG VON KUPFERÜBERZÖGEN UND VERFAHREN UNTER VERWENDUNG DIESER KOMBINATION ACID BATH FOR THE GALVANIC DEPOSITION OF COPPER COATINGS AND METHOD USING THIS COMBINATION
Die Erfindung betrifft ein saures Bad zur galvanischen Abscheidung glänzender und eingeebneter Kupferüberzüge und die Verwendung.The invention relates to an acid bath for the electrodeposition of shiny and leveled copper coatings and the use.
Es ist seit langem bekannt, daß sauren, insbesondere den am mei¬ sten verbreiteten schwefelsauren Kupferelektrolyten bestimmte or¬ ganische Substanzen in geringen Mengen zugesetzt werden können, um statt einer kristallin-matten Abscheidung glänzende Kupferüberzüge zu erhalten. Für diesen Zweck werden zum Beispiel Polyäthylengly- σol, Thioharnstoff, Gelatine,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,
Melasse, Kaffee-Extrakt, "basische" Farbstoffe und Thiophosphor- säureester verwendet.Solche Bäder besitzen jedoch keinerlei prak¬ tische Bedeutung mehr, da die Qualität der erhaltenen Kupferüber¬ züge nicht den heutigen Anforderungen entspricht. So sind die Überzüge entweder zu spröde oder sie besitzen einen zu geringen Glanz bzw. fallen in bestimmten Stromdichtebereichen reliefartig aus.Molasses, coffee extract, "basic" dyes and thiophosphoric acid esters are used. However, such baths no longer have any practical significance, since the quality of the copper coatings obtained 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.
Bekannt ist der Zusatz von Polyalkyliminen in Verbindung mit orga¬ nischen Thioverbindungen (DE-PS 1246347) und PolyvinylVerbindungen in Mischung mit sauerstoffhaltigen hochmolekularen Verbindungen und organischen, insbesondere aromatischen Thioverbindungen (De-AS 1521062). Derartige Kupferelektrolyte erlauben aber nicht den Ein¬ satz höherer kathodischer Stromdichten, und die abgeschiedenen Kupferüberzüge können außerdem nur nach einer voarusgegangenen Zwischenbehandlung vernickelt werden. In der genannten DE-AS 1521062 wird außerdem ein saures Kupferbad beschrieben, das neben einer polymeren saurestoffhaltigen Verbindung mit hydrophiler Gruppe noch mindestsnes eine substituierte Phenazoniu verbindung gelöst enthält. Bei diesen monomeren Phenazoniumverbindungen ist die anwendbare Stromdiσhte sowie das Alterungsverhalten verbesserngswürdig. Wei¬ ter sind Kombinationen von organischen Thioverbindungen und nich- tionogenen Netzmitteln mit anderen Farbstoffen wie zum Beispiel Kristall-Violett (EP-PS 71512), Amiden (DE-PS 2746938), Phtha- locyanin-Derivaten mit Apo-Safranin (DE-PS 3420999) bekannt. Anstelle des Farbstoffes werden auch Undefinierte Umsetzungspro¬ dukte von Polyaminen mit Benzylchlorid (DE-PS 2541897) bzw. Epi- chlorhydrin (EU-PS 68807) oder solche mit Thioverbindungen und Aσrylamid (EU-PS 107109) verwendet.It is known to add polyalkylimines in conjunction 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 1521062). 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 an intermediate treatment. DE-AS 1521062 also describes an acidic copper bath which, in addition to a polymeric acid-containing compound having a hydrophilic group, also contains at least one substituted phenazoniu compound in solution. With these monomeric phenazonium compounds, the current current that can be used and the aging behavior are in need of improvement. Combinations of organic thio compounds and nonionic wetting agents with other dyes such as, for example, crystal violet (EP-PS 71512), amides (DE-PS 2746938), phthalocyanine derivatives with apo-safranin (DE-PS 3420999). Instead of the dye, undefined reaction products of polyamines with benzyl chloride (DE-PS 2541897) or epichlorohydrin (EU-PS 68807) or those with thio compounds and arylamide (EU-PS 107109) are also used.
Die bisher bekannten Bäder ergeben alle ungleichmäßige Abscheidun¬ gen; insbesondere die Kombination mit stickstoffhaltigen Thiover¬ bindungen.The previously known baths all result in uneven deposits; especially the combination with nitrogen-containing thio compounds.
Einen Fortschritt erbrachten Bäder, die polymere Phenazoniumver¬ bindungen (DE-PS 2039831) enthalten;diese finden hauptsächlich in Kombination mit nichtionogenen Netzmitteln und organischen Schwefelverbindungen Anwendung.Baths containing polymeric phenazonium compounds (DE-PS 2039831) have made progress and are mainly used in combination with nonionic wetting agents and organic sulfur compounds.
Zwar ist es Stand der Technik, nichtionogene Netzmittel den sauren Kupferbädern zuzusetzen, die Entfernung der feinen Rauheit gelang damit jedoch nicht.Although it is state of the art to add nonionic wetting agents to the acidic copper baths, the removal of the fine roughness was not successful.
Die Verwendung von ß-Naphthol-Polyglycoläther als Zusatz eines Kupferbades wird in der DE-OS 37 21 985 (Beispiel 2) offenbart, jedoch nicht in der Kombination mit stickstoffhaltigen Thioverbin¬ dungen und/oder polymeren Phenazoniumverbindungen.The use of β-naphthol polyglycol ether as an additive to a copper bath is disclosed in DE-OS 37 21 985 (example 2), but not in combination with nitrogen-containing thio compounds and / or polymeric phenazonium compounds.
In der DE-PS 3104108 wid ein Fluorboratbad beschrieben, das ß- Naphtholäthoxylat in Kombination mit einem Phthalocyanin-Farbstoff enthält. Der Elektrolyt selbst zeigt nur eine mäßige Einebnung im Vergelich zu polymeren Phenazoniumverbindungen. Nachteilig bei diesen Bädern ist bei hoher Einebnung eine feine Rauheit (Pittings, Nodules) auf der Schicht, welche das dekorative Aussehen besonders großflächiger Teile empfindlich stört. Diese Rauheit rührt nicht von Schwebeteilchen im Elektrolyten her, son¬ dern beruht auf einer gestörten Abscheidung in der kathodischen Doppelschicht. Diese tritt besonders bei stickstoffhaltigen Schwefelverbindungen (sog. Thioharnstoffderivaten) und bei Phenazoniumverbindungen auf.DE-PS 3104108 describes a fluoroborate bath which contains β-naphthol ethoxylate in combination with a phthalocyanine dye. The electrolyte itself shows only a moderate leveling in comparison to polymeric phenazonium compounds. A disadvantage of these baths is the high leveling of a fine roughness (pittings, nodules) on the layer, which sensitively disturbs the decorative appearance of particularly large parts. This roughness is not due to floating particles in the electrolyte, but is due to a disturbed deposition in the cathodic double layer. This occurs particularly with nitrogen-containing sulfur compounds (so-called thiourea derivatives) and with phenazonium compounds.
Aufgabe dieser Erfindung ist es, diese beschriebenen Nachteile zu vermeiden und darüber hinaus die vorteilhafte Einebnung nicht zu verschlechtern.The object of this invention is to avoid the disadvantages described and, moreover, not to deteriorate the advantageous leveling.
Diese Aufgabe wird erfindungsgemäß durch ein saures Bad gelöst, das mindestens eine Mischung bestehend aus β-Naphtholalkoxylate der allgemeinen Formel IThis object is achieved according to the invention by an acid bath containing at least one mixture consisting of β-naphthol alkoxylates of the general formula I.
CH20)ln-HCH 2 0) ln -H
in der n = 0 - 50, vorzugsweise 10 - 25, und m = 0 - 50, vorzugs¬ weise 0 - 10, bedeuten, wobei n + m .3 ist, Thioharnstoff oder Thioharnstoffderivat und/oder polymere Phenazoniumverbindung ent¬ hält. in which n = 0-50, preferably 10-25, and m = 0-50, preferably 0-10, where n + m .3 contains thiourea or thiourea derivative and / or polymeric phenazonium compound.
Als ß-Naphtholalkoxylate der allgemeinen Formel I eignen sich be¬ sonders Verbindungen derParticularly suitable as β-naphthol alkoxylates of the general formula I are compounds of the
Tabelle 1 ß-Naphthol-tetracosa(äthoxylat) n- 24; m = 0 ß-Napthol-eicosa(äthoxylat) n= 20; m = 0 ß-Naphthol-octadeca(äthoxylat) n= 18; m = 0 ß-Naphthol-hexadeca(äthoxylat) n= 16; = 0 ß-Naphthol-tetradeca(äthoxylat) n= 14; m = 0 ß-Naphthol-trideca(äthoxylat) n= 13; m = 0 ß-Naphthol-dodeca(äthoxylat) n= 12; m = 0 ß-Naphthol-deca(äthoxylat) n= 10; m = 0 ß-Naphthol-octa(äthoxylat) n= 8; m = 0 ß-Naphthol-hexa(äthoxylat) n= 6; m = 0 ß-Naphthol-tetracosa(propoxylat) n= 0, m = 24 ß-Naphthol-tetraσosa(äthoxy)- n=24; m = 1- mono(propoxylat)*) ß-Naphthol-octadeca(äthoxy)- n= 20; m = 2 di(propoxylat)*) ß-Naphthol-mono(propoxy)- n= 24; m == 1 tetracosa(äthoxylat)*) ß-Naphthol-di(prpoxy)- n= 20; m = 2 octadeca(äthoxylat)*)Table 1 β-naphthol tetracosa (ethoxylate) n-24; m = 0 β-napthol eicosa (ethoxylate) n = 20; m = 0 β-naphthol octadeca (ethoxylate) n = 18; m = 0 β-naphthol hexadeca (ethoxylate) n = 16; = 0 β-naphthol tetradeca (ethoxylate) n = 14; m = 0 ß-naphthol trideca (ethoxylate) n = 13; m = 0 β-naphthol dodeca (ethoxylate) n = 12; m = 0 β-naphthol deca (ethoxylate) n = 10; m = 0 β-naphthol octa (ethoxylate) n = 8; m = 0 β-naphthol hexa (ethoxylate) n = 6; m = 0 ß-naphthol tetracosa (propoxylate) n = 0, m = 24 ß-naphthol tetraσosa (ethoxy) - n = 24; m = 1-mono (propoxylate) *) β-naphthol octadeca (ethoxy) - n = 20; m = 2 di (propoxylate) *) β-naphthol mono (propoxy) - n = 24; m == 1 tetracosa (ethoxylate) *) ß-naphthol-di (prpoxy) - n = 20; m = 2 octadeca (ethoxylate) *)
+) Misch- oder Blockpolymerisat+) Mixed or block polymer
Als stickstoffhaltige Thioverbindungen finden Thioharnstoff und Thioharnstoffderivate sowie S- und N-haltige heterocyclische Ver¬ bindungen Anwendung. Thiourea and thiourea derivatives and S- and N-containing heterocyclic compounds are used as nitrogen-containing thio compounds.
Tabelle 2 enthält Beispiele für stickstoffhaltige Thioverbindunge (sog. Thioharnstoffderivate) und Tabelle 3 für polymere Phenazoni umverbindungen.Table 2 contains examples of nitrogen-containing thio compounds (so-called thiourea derivatives) and Table 3 for polymeric phenazone compounds.
Tabelle 2Table 2
ThioharnstoffThiourea
N-AcetylthioharnstoffN-acetylthiourea
N-TrifluoroaσetythioharnstoffN-trifluoroacetythiourea
N-ÄthylthioharnstoffN-ethylthiourea
N-CyanoacetylthioharnstoffN-cyanoacetylthiourea
N-Allylthioharnstoff o-TolylthioharnstoffN-allylthiourea o-tolylthiourea
N,N'-ButylenthioharnstoffN, N'-butylene thiourea
Thiazolidinthiol(2)Thiazolidin thiol (2)
4-Thiazolinthiol(2)4-thiazolinethiol (2)
Imidazolidinthiol(2) (N,N'-Äthylenthioharnstoff)Imidazolidinthiol (2) (N, N'-ethylene thiourea)
4-Methyl-2-pyrimidinthiol4-methyl-2-pyrimidine thiol
2-Thiouracil2-thiouracil
Tabelle 3Table 3
Poly(6-methyl-7-dimethylamino-5-phenyl-phenazoniumsulfat) Poly(2-methyl-7-diäthylamino-5-phenyl-phenazoniumchlorid) Poly(2-methyl-7-dimethylaraino-5-phenyl-phenazoniumsulfat) Poly(5-methyl-7-dimethylamino-phenazoniumacetat) Poly(2-methyl-7-anilino-5-phenyl-phenazoniumsulfat) Poly(2-methyl-7-dimethylamino-phenazoniumsulfat) Poly(7-methylamino-5-phenyl-phenazoniumacetat) Poly(7-äthylamino-2,5-diphenyl-phenazoniumchlorid) Poly(2,8-dimethyl-7-diäthylamino-5-p-tolyl- phenazoniumchlorid)Poly (6-methyl-7-dimethylamino-5-phenyl-phenazonium sulfate) poly (2-methyl-7-diethylamino-5-phenyl-phenazonium chloride) poly (2-methyl-7-dimethylaraino-5-phenyl-phenazonium sulfate) poly ( 5-methyl-7-dimethylamino-phenazonium acetate) poly (2-methyl-7-anilino-5-phenyl-phenazonium sulfate) poly (2-methyl-7-dimethylamino-phenazonium sulfate) 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-phenazoniumsulfat) Poly(2,8-dimethyl-7-amino-5-phenyl-phenazoniumsulfat) Poly(7-Dimethylamino-5-phenyl-phenazoniumchlorid) Für die erfindungsgemäßen Lösungen lassen sich auch Gemische der in den Tabellen 1,2 und 3 aufgeführten Verbindungen einsetzen.Poly (2,5,8-triphenyl-7-dimethylamino-phenazonium sulfate) poly (2,8-dimethyl-7-amino-5-phenyl-phenazonium sulfate) poly (7-dimethylamino-5-phenyl-phenazonium chloride) Mixtures of the compounds listed in Tables 1, 2 and 3 can also be used for the solutions according to the invention.
Die bevorzugte Menge, in der das ß-Naphtholäthoxylat zugegeben werden muß, um eine deutliche Verbesserung der Kupferabscheidung zu erzielen, beträgt etwa 0,005 bis 3 g/Liter vorzugsweise 0,01 bis 0,25 g/Liter.The preferred amount in which the β-naphthol ethoxylate must be added in order to achieve a significant improvement in the copper deposition is approximately 0.005 to 3 g / liter, preferably 0.01 to 0.25 g / liter.
Die ß-Naphtholäthoxylate sind bekannt oder können nach an sich be¬ kannten Verfahren durch Umsetzen von ß - Naphthol mit Äthylenoxyd und/oder Propylenoxyd hergestellt werden.The β-naphthol ethoxylates are known or can be prepared by processes known per se by reacting β-naphthol with ethylene oxide and / or propylene oxide.
Die Einzelkomponenten des erfindungsgemäβen Kupferbades können im allgemeinen vorteilhaft innerhalb folgender Grenzkonzentrationen im anwendungsfertigen Bad enthalten sein:The 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:
Übliche Sauerstoffhaltige, hochmolekulare Verbindungen 0,005 - 20 g/Liter vorzugsweise 0,01 - 5 g/LiterUsual oxygen-containing, high molecular compounds 0.005-20 g / liter, preferably 0.01-5 g / liter
Übliche organische Thiover¬ bindungen mit hydrophilen GruppenConventional organic thio compounds with hydrophilic groups
0,0005 - 0,2 g/Liter0.0005 - 0.2 g / liter
vorzugsweise 0,001 - 0,03 g/Literpreferably 0.001-0.03 g / liter
Übliche stickstoffhaltige ThioverbindungenUsual nitrogen-containing thio compounds
(sog. Thioharnstoffderivate) und/oder polymere Phenazoniumverbindungen 0,0001 - 0,50 g/Liter(so-called thiourea derivatives) and / or polymeric phenazonium compounds 0.0001 - 0.50 g / liter
vorzugsweise 0,0005 - 0,04 g/Liter Die Grundzusammensetzung des erfindungsgemäßen Bades kann in wei¬ ten Grenzen schwanken. Im allgemeinen wird eine wässrige Lösung folgender Zusammensetzung benutzt:preferably 0.0005-0.04 g / liter The 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:
Kupfersulfat (CuS04. 5H20) vorzugsweisePreferably copper sulfate (CuS0. 4 5H 2 0)
Schwefelsäure vorzugsweise 180 - 220 g/Liter oder 50 - 90 g/Litersulfuric acid preferably 180-220 g / liter or 50-90 g / liter
Natriumchlorid 0,02 - 0,25 g/Liter, vorzugsweise 0,05 - 0,12 g/LiterSodium 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 Säu¬ ren 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 also 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 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 Einzelkom¬ ponenten 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:The working conditions of the bath are as follows:
pH-Wert: < 1pH: <1
Temperatur: 15βC - 45βC, vorzugsweise 20"C - 30°CTemperature: 15 β C - 45 β C, preferably 20 "C - 30 ° C
kath. Stromdichte. 0,5 - 12 A/dm2, vorzugsweise 2-4 A/dm2 cath. Current density. 0.5 - 12 A / dm 2 , preferably 2-4 A / dm 2
Die Elektrolytbewegung wird durch Einblasen von Luft erreicht. Als Anode wird Kupfer mit einem Gehalt von 0,02 bis 0,067 % Phos¬ phor verwendetThe electrolyte movement is achieved by blowing in air. Copper with a content of 0.02 to 0.067% phosphorus is used as the anode
Die Erfindung beinhaltet auch Verfahren unter Verwendung der er¬ findungsgemäßen Bäder gemäß den Patentansprüchen.The invention also includes methods using the baths according to the invention according to the patent claims.
Die folgenden Beispiele dienen zur Erläuterung der Erfindung:The following examples serve to illustrate the invention:
BEISPIEL 1EXAMPLE 1
Einem Kupferbad der ZusammensetzungA copper bath of the composition
200,0 g/Liter Kupfersulfat (CuS04.5 H20) 65,0 g/Liter Schwefelsäure200.0 g / liter copper sulfate (CuS0 4 .5 H 2 0) 65.0 g / liter sulfuric acid
0,2 g/Liter Natriumchlorid0.2 g / liter sodium chloride
werden als Glanzbildnerare used as brighteners
0,2 g/Liter Polyäthylenglycol,0.2 g / liter polyethylene glycol,
0,01 g/Liter Bis-(w-sulfopropyl)-disufid, Dinatriumsal0.01 g / liter bis (w-sulfopropyl) disufide, disodium sal
und 0,02 g/Liter polymeres 7-Dimethylamino-5-phenyl- phenazonium-σhloridand 0.02 g / liter of polymeric 7-dimethylamino-5-phenylphenazonium chloride
zugegeben. Bei einer Elektrolyttemperatur von 27 aC erhält man be einer Stromdichte von 4 A/dm2 und Lufteinblasung einen gut ein¬ geebneten glänzenden Kupferüberzug, der auf poliertem Messingblec beim genauen Hinsehen feine Rauhigkeiten (Pittings) zeigt.admitted. At an electrolyte temperature of 27 a C and with a current density of 4 A / dm 2 and air injection, a well-leveled shiny copper coating is obtained, which shows a fine roughness (pitting) on a polished brass sheet when you look closely.
Gibt man dem Bad zusätzlich 0,025 g/Liter der erfindungsgemäßen Substanz der allgemeinen Formel I mit n = 12 und m = 0 zu, so is die Abscheidung spiegelglänzend und gut eingeebnet. Man erkennt keine Fehlstellen. BEISPIEL 2If 0.025 g / liter of the substance of the general formula I according to the invention with n = 12 and m = 0 is additionally added to the bath, the deposition is mirror-like and well leveled. You can see no defects. EXAMPLE 2
Eine Kupferbad der ZusammensetzungA copper bath of the composition
80 g/Liter Kupfersulfat (CuS0 .5 H20)80 g / liter copper sulfate (CuS0 .5 H 2 0)
180 g/Liter Schwefelsäure konz.180 g / liter sulfuric acid conc.
0,08 g/Liter Natriumchlorid0.08 g / liter sodium chloride
werden als Glanzbildnerare used as brighteners
0,6 g/Liter Polypropylenglycol und0.6 g / liter polypropylene glycol and
0,02 g/Liter 3-Mercaptopropan-l-sulfonsäure, Natriumsal und0.02 g / liter 3-mercaptopropane-l-sulfonic acid, sodium salt and
0,003 g/Liter N-Acetylthioharnstoff0.003 g / liter of N-acetylthiourea
zugegeben. Bei einer Elektrolyttemperatur von 30 °C enthält man auf gekratztem Kupferlaminat bei einer Stromdichte von 2 A/dm2 glänzende Abscheidungen, bei der feine Rauhigkeiten (Pittings) sichtbar sind.admitted. At an electrolyte temperature of 30 ° C, scratched copper laminate with a current density of 2 A / dm contains 2 shiny deposits with fine roughness (pittings) visible.
Setzt man dem Bad 0,05 g/Liter der erfindungsgemäßen Substanz der allgemeinen Formel I mit n = 24 und = 0 zu, so ist der Kupferüberzug blank und enthält keine Störungen. If 0.05 g / liter of the substance of the general formula I according to the invention with n = 24 and = 0 is added to the bath, the copper coating is bare and contains no defects.

Claims

PATENTANSPRÜCHE PATENT CLAIMS
1. Wässriges saures Bad zur galvanischen Abscheidung glänzender und eingeebneter Kupferüberzüge enthaltend mindestens eine Mi¬ schung bestehend aus ß-Naphtholalkoxylat der allgemeinen Formel I1. Aqueous acid bath for the electrodeposition of shiny and leveled copper coatings containing at least one mixture consisting of β-naphthol alkoxylate of the general formula I
CH20)ra-H ~CH 2 0) ra -H ~
in der n= 0-50 und m = 0 - 50 bedeuten, wobei n + m > 3 ist; Thio¬ harnstoff oder Thioharnstoffderivat und/oder polymere Phenazoniu verbindung.in which n = 0-50 and m = 0-50, where n + m> 3; Thio urea or thiourea derivative and / or polymeric phenazoniu compound.
2. Bad gemäß Anspruch 1, enthaltend als ß-Naphtholalkoxylat der allgemeinen Formel I2. Bath according to claim 1, containing as ß-naphthol alkoxylate of the general formula I.
ß-Naphthol-tetracos ( thoxylat) ß-Naphthol-eicosa(äthoxylat) ß-Naphthol-octadeca(äthoxylat) ß-Naphthol-hexadeca(äthoxylat) ß-Naphthol-tetradeca(äthoxylat) ß-Naphthol-trideca(äthoxylat) ß-Naphthol-dodeca(äthoxylat) ß-Naphthol-deca(äthoxylat) ß-Naphthol-octa(äthoxylat) ß-Naphthol-hexa(äthoxylat) ß-Naphthol-tetracosa(propoxylat) ß-Naphthol-tetracosa(äthoxy)- mono(propoxylat) ß-Naphthol-octadeca(äthoxy)-di(proxylat) ß-Naphthol-mono(propoxy)-tetracosa(äthoxylat) ß-Napththol-di(propoxy)-octadeca(äthoxalyt) oder Gemische dieser Verbindungen.ß-naphthol-tetracos (thoxylate) ß-naphthol-eicosa (ethoxylate) ß-naphthol-octadeca (ethoxylate) ß-naphthol-hexadeca (ethoxylate) ß-naphthol-tetradeca (ethoxylate) ß-naphthol-ethoxylate Naphthol-dodeca (ethoxylate) ß-naphthol-deca (ethoxylate) ß-naphthol-octa (ethoxylate) ß-naphthol-hexa (ethoxylate) ß-naphthol-tetracosa (propoxylate) ß-naphthol-tetraoxy-mono ) ß-Naphthol-octadeca (ethoxy) -di (proxylate) ß-naphthol-mono (propoxy) -tetracosa (ethoxylate) ß-naphthol-di (propoxy) -octadeca (ethoxy analyte) or mixtures of these compounds.
3. Bad gemäß Anspruch 1 oder 2, enthaltend ß-Naphtholalkoxylat der allgemeinen Formel I in Konzentrationen von 0,005 bis 3 g/Liter. 4. Bad gemäß Anspruch 1, enthaltend als Thioharnstoffderivat N-Aσetylthioharnstoff,3. Bath according to claim 1 or 2, containing β-naphthol alkoxylate of the general formula I in concentrations of 0.005 to 3 g / liter. 4. Bath according to claim 1, containing as thiourea derivative N-acetylthiourea,
N-TrifluoroacetythioharnstoffN-trifluoroacetythiourea
N-ÄthylthioharnstoffN-ethylthiourea
N-Cyanoacety1thioharnstoffN-cyanoacety1thiourea
N-Allylthioharnstoff o-TolylthiohanrnstoffN-allylthiourea o-tolylthiourea
N,N*-ButylenthioharnstoffN, N * -butylene thiourea
Thiazolidinthiol(2)Thiazolidin thiol (2)
4-Thiazolinthiol(2)4-thiazolinethiol (2)
Imidazolidinthiol(2) (N,N*-Äthylenthioharnstoff)Imidazolidinethiol (2) (N, N * ethylene thiourea)
4-Methyl-2-pyrimidinthiol4-methyl-2-pyrimidine thiol
2-Thiouracil oder Gemische dieser Verbindungen.2-thiouracil or mixtures of these compounds.
5. Bad gemäß Anspruch 1 oder 4, enthaltend Thioharnstoff oder Thi¬ oharnstoffderivate in Konzentrationen von 0,0001 bis 0,5 g/Liter. 5. Bath according to claim 1 or 4, containing thiourea or thiourea derivatives in concentrations of 0.0001 to 0.5 g / liter.
6. Bad gemäß Anspruch 1 enthaltend als polymere Phenazoniumver- bindung6. Bath according to claim 1 containing as a polymeric phenazonium compound
Poly(6-methyl-7-dimethylamino-5-phenyl-phenazoniumsulfat) Poly(2-methyl-7-diäthylamino-5-phenyl-phenazoniumchlorid) Poly(2-methyl-7-dimethylamino-5-phenyl-phenazoniumsulfat) Poly(5-methyl-7-dimethylamino-phenazoniumacetat)Poly (6-methyl-7-dimethylamino-5-phenyl-phenazonium sulfate) poly (2-methyl-7-diethylamino-5-phenyl-phenazonium chloride) poly (2-methyl-7-dimethylamino-5-phenyl-phenazonium sulfate) poly ( 5-methyl-7-dimethylamino-phenazonium acetate)
Poly(2-methyl-7-anilino-5-phenyl-phenazoniumsulfat)Poly (2-methyl-7-anilino-5-phenylphenazonium sulfate)
Poly(2-methyl-7-dimethylamino-phenazoniumsulfat)Poly (2-methyl-7-dimethylamino-phenazonium sulfate)
Poly(7-methylamino-5-phenyl-phenazoniumacetat)Poly (7-methylamino-5-phenylphenazonium acetate)
Poly(7-äthylamino-2,5-diphenyl-phenazoniumchlorid)Poly (7-ethylamino-2,5-diphenyl-phenazonium chloride)
Poly(2,8-dimethyl-7-diäthylamino-5-p-tolyl-phenazoniumchlorid)Poly (2,8-dimethyl-7-diethylamino-5-p-tolyl-phenazonium chloride)
Poly(2,5,8-triphenyl-7-dimethylamino-phenazoniumsulfat)Poly (2,5,8-triphenyl-7-dimethylaminophenazonium sulfate)
Poly(2,8-diraethyl-7-amino-5-phenyl-phenazoniumsulfat)Poly (2,8-diraethyl-7-amino-5-phenylphenazonium sulfate)
Poly(7-Dimethylamino-5-phenyl-phenazoniumchlorid) oder Gemische dieser Verbindungen.Poly (7-dimethylamino-5-phenyl-phenazonium chloride) or mixtures of these compounds.
7. Bad gemäß Anspruch l oder 6, enthaltend polymere Phenazonium¬ verbindungen in Konzentrationen von 0,0001 bis 0,5 g/Liter.7. Bath according to claim 1 or 6, containing polymeric phenazonium compounds in concentrations of 0.0001 to 0.5 g / liter.
8. Bad gemäß Anspruch l gekennzeichnet durch einen zusätzlichen Gehalt an mindestens einer sauerstoffhaltigen hochmolekularen Ver¬ bindung. 8. Bath according to claim 1, characterized by an additional content of at least one oxygen-containing high molecular compound.
9. Bad gemäß Anspruch 8, enthaltend Polyvinylalkohol Carboxymethylcellulose Polyäthylenglycol Polypropylenglycol Stearinsäure-Polyglycolester Ölsäure-Polyglycolester Stearylalkohol-Polyglycoläther Nonylphenyol-Polyglycoläther Oktonalpolyalkylenglycoläther Oktandiol-bis(polyalkylenglycoläther) Polyoxypropylenglycol Polyäthylen-propylenglycol oder Gemische dieser Verbindungen.9. Bath according to claim 8, containing polyvinyl alcohol carboxymethyl cellulose, polyethylene glycol, polypropylene glycol, stearic acid, polyglycol ester, oleic acid, polyglycol ester, stearyl alcohol, polyglycol ether, nonylphenyol, polyglycol ether, octonal polyalkylene glycol ether, octane diol bis (polyalkylene glycol ether), polyhylene glycol compounds, polyoxypropylene glycol compounds and polyoxypropylene glycol compounds.
10. Bad gemäß Anspruch 9, enthaltend Sauerstoffhaltige hochmo¬ lekulare Verbindungen in Konzentrationen von 0,005 bis 20 g/Liter.10. Bath according to claim 9, containing oxygen-containing high molecular compounds in concentrations of 0.005 to 20 g / liter.
11. Bad gemäß Anspruch 1, gekennzeichnet durch einen zusätzlichen Gehalt an einer organischen stickstofffreien Thioverbindung mit wasserlöslichen hydrophilen Gruppen.11. Bath according to claim 1, characterized by an additional content of an organic nitrogen-free thio compound with water-soluble hydrophilic groups.
12. Bad gemäß Anspruch 11, enthaltend12. Bath according to claim 11, containing
3-Merσaptopropan-1-sulfonsäure, Natriumsalz3-Merσaptopropan-1-sulfonic acid, sodium salt
Thiophosphorsäure-θ-äthyl-bis-(w-sulfopropyl)-ester, DinatriumsalzThiophosphoric acid θ-ethyl bis (w-sulfopropyl) ester, disodium salt
Thiophosphorsäure-tris-(w-sulfopropyl)-ester, TrinatriumsalzThiophosphoric acid tris (w-sulfopropyl) ester, trisodium salt
Äthylendithiodipropylsulfonsäure, NatriumsalzEthylene dithiodipropyl sulfonic acid, sodium salt
Di-n-propylthioäther-di-w-sulfonsäure, DinatriumsalzDi-n-propylthioether-di-w-sulfonic acid, disodium salt
Bis-(w-sulfopropyl)disulfid, DinatriumsalzBis (w-sulfopropyl) disulfide, disodium salt
Bis(w-sulfohydroxypropyl)disulfid, DinatriumsalzBis (w-sulfohydroxypropyl) disulfide, disodium salt
Bis(w-sulfobutyl)disulfid, DinatriumsalzBis (w-sulfobutyl) disulfide, disodium salt
Methyl-(w-sulfopropyl)disulfid, NatriumsalzMethyl (w-sulfopropyl) disulfide, sodium salt
Methyl-(w-sulfobutyl)trisulfid, Natriumsalz oder Gemische dieser Verbindungen. Methyl (w-sulfobutyl) trisulfide, sodium salt or mixtures of these compounds.
13. Bad gemäß Anspruch 12, enthaltend die organischen stickstoff¬ freien Thioverbindungen mit wasserlöslichen hydrophilen Gruppen i Konzentrationen von 0,0005 bis 0,2 g/Liter.13. Bath according to claim 12, containing the organic nitrogen-free thio compounds with water-soluble hydrophilic groups i concentrations of 0.0005 to 0.2 g / liter.
14. Verwendung des Bades nach mindestens einem der Ansprüche 1-13 zur galvanischen Abscheidung von Kupfer. 14. Use of the bath according to at least one of claims 1-13 for the galvanic deposition of copper.
EP91917496A 1990-10-13 1991-10-11 Acid bath for copper plating, and a process using a bath of this type for this purpose Expired - Lifetime EP0554275B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4032864 1990-10-13
DE4032864A DE4032864A1 (en) 1990-10-13 1990-10-13 ACIDIC BATH FOR THE GALVANIC DEPOSITION OF COPPER COVERS AND METHODS USING THIS COMBINATION
PCT/DE1991/000811 WO1992007116A1 (en) 1990-10-13 1991-10-11 Acid bath for copper plating, and a process using a bath of this type for this purpose

Publications (2)

Publication Number Publication Date
EP0554275A1 true EP0554275A1 (en) 1993-08-11
EP0554275B1 EP0554275B1 (en) 1994-12-14

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JP (1) JPH06501986A (en)
AT (1) ATE115651T1 (en)
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WO (1) WO1992007116A1 (en)

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DE10261852B3 (en) * 2002-12-20 2004-06-03 Atotech Deutschland Gmbh Mixture of di-, tri- and other oligomeric phenazinium compounds, used in copper electroplating bath for decorative plating or plating circuit board or semiconductor substrate, is prepared from monomer by diazotization and boiling
DE10337669B4 (en) * 2003-08-08 2006-04-27 Atotech Deutschland Gmbh Aqueous, acid solution and process for the electrodeposition of copper coatings and use of the solution
DE102004041701A1 (en) * 2004-08-28 2006-03-02 Enthone Inc., West Haven Process for the electrolytic deposition of metals
US7282602B2 (en) * 2004-09-21 2007-10-16 Bionumerik Pharmaceuticals, Inc. Medicinal disulfide salts
JP5659411B2 (en) * 2006-01-27 2015-01-28 奥野製薬工業株式会社 Additive for electrolytic copper plating solution using phosphorous copper as anode, electrolytic copper plating solution and electrolytic copper plating method
DE102014208733A1 (en) 2014-05-09 2015-11-12 Dr. Hesse Gmbh & Cie Kg Process for the electrolytic deposition of copper from water-based electrolytes
JP7064115B2 (en) 2016-08-15 2022-05-10 アトテック ドイチュラント ゲー・エム・ベー・ハー ウント コー． カー・ゲー Acidic aqueous composition for electrolytic copper plating

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WO1992007116A1 (en) 1992-04-30
EP0554275B1 (en) 1994-12-14
DE59103933D1 (en) 1995-01-26
DE4032864C2 (en) 1993-01-07
CA2093924A1 (en) 1992-04-14
CA2093924C (en) 2002-02-05
ES2066477T3 (en) 1995-03-01
DE4032864A1 (en) 1992-04-16
ATE115651T1 (en) 1994-12-15
JPH06501986A (en) 1994-03-03

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