EP1630258A1 - Method for the electrolytic deposition of copper - Google Patents
Method for the electrolytic deposition of copper Download PDFInfo
- Publication number
- EP1630258A1 EP1630258A1 EP05018241A EP05018241A EP1630258A1 EP 1630258 A1 EP1630258 A1 EP 1630258A1 EP 05018241 A EP05018241 A EP 05018241A EP 05018241 A EP05018241 A EP 05018241A EP 1630258 A1 EP1630258 A1 EP 1630258A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrolyte
- copper
- halide
- ethoxylate
- deposition
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000010949 copper Substances 0.000 title claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 230000008021 deposition Effects 0.000 title claims description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 12
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Substances CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- -1 halide ions Chemical class 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 239000007859 condensation product Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 description 9
- 238000000151 deposition Methods 0.000 description 8
- 238000001465 metallisation Methods 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BQPBZDSDFCDSAO-UHFFFAOYSA-N 2-naphthalen-2-yloxyethanol Chemical compound C1=CC=CC2=CC(OCCO)=CC=C21 BQPBZDSDFCDSAO-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 1
- 229910002535 CuZn Inorganic materials 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N OS(c1cccc2c1cccc2)(=O)=O Chemical compound OS(c1cccc2c1cccc2)(=O)=O PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 0 [*+]c(cc1)cc2c1c(*)ccc2* Chemical compound [*+]c(cc1)cc2c1c(*)ccc2* 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- LRPCLTPZMUIPFK-UHFFFAOYSA-N methane;sulfuric acid Chemical compound C.OS(O)(=O)=O LRPCLTPZMUIPFK-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Definitions
- the present invention relates to a process for the electrolytic deposition of a matte or semi-bright copper layer of an acidic electrolyte.
- Acid copper electrolytes are widely used for surface coating of substrates to form a functional or decorative coating on the substrate surfaces.
- the metallization process to be used as well as the electrolyte to be used depend on the type and nature of the substrate to be metallized. Thus, both metallic and non-conductive substrates can be equipped with corresponding surface layers.
- This object is achieved by a method for the electrolytic deposition of a matte or semi-glossy copper layer of an acidic electrolyte on a substrate, which is characterized in that for the deposition of the layer current densities between about greater than 10 and 100 A / dm 2 , preferably between 20 and 80 A / dm 2 are used.
- the process is carried out in a temperature range between 22 and 60 ° C, preferably between 45 and 55 ° C.
- the object of the invention is achieved by a copper-containing electrolyte containing an alkylsulfonic acid.
- the alkylsulfonic acid is preferably methanesulfonic acid, but all other sulfonic acids which have sufficient stability under the process conditions are also suitable.
- the electrolyte may be copper in the form of its sulfates, nitrates, halides; Have carboxylates.
- the electrolyte has a sufficient amount of an ethoxylate, preferably 2-naphthol ethoxylate [2- (2-naphthyloxy) ethanol], on.
- the electrolyte has a sufficient amount of a sulfur-containing naphthalene condensation product of the general formula I. where n is an integer.
- the electrolyte may additionally comprise typical adjuvants such as levelers and wetting agents known from the literature, also in combination.
- the electrolyte according to the invention is suitable, inter alia, for depositing intermediate layers on CuZn alloys, for minimizing whisker formation or for coating without intermediate rinsing in a tin sulfide methanesulfonic acid.
- the electrolyte has chloride as halide ions.
- Example 2 shows typical process conditions for the process according to the invention.
- methanesulfonic acid-based electrolytes show no disadvantages compared to sulfuric acid electrolytes in terms of percentage elongation.
- the required value for the percentage elongation in the tempered state is between 10% and 20%.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zur elektrolytischen Abscheidung einer matten oder halbglänzenden Kupferschicht aus einem sauren Elektrolyten.The present invention relates to a process for the electrolytic deposition of a matte or semi-bright copper layer of an acidic electrolyte.
Saure Kupferelektrolyten werden vielfältig zur Oberflächenbeschichtung von Substraten eingesetzt, um eine funktionale oder dekorative Beschichtung auf den Substratoberflächen zu bilden.Acid copper electrolytes are widely used for surface coating of substrates to form a functional or decorative coating on the substrate surfaces.
Das einzusetzende Metallisierungsverfahren sowie der einzusetzende Elektrolyt richten sich nach Art und Beschaffenheit des zu metallisierenden Substrats. So können sowohl metallische als auch nicht leitende Substrate mit entsprechenden Oberflächenschichten ausgerüstet werden.The metallization process to be used as well as the electrolyte to be used depend on the type and nature of the substrate to be metallized. Thus, both metallic and non-conductive substrates can be equipped with corresponding surface layers.
Insbesondere bei der Metallisierung von Substraten wie Draht, Band oder Rohr werden an den eingesetzten Elektrolyt und das einzusetzende Verfahren besondere Ansprüche hinsichtlich der Stabilität und Abscheidungsgeschwindigkeit gestellt. So werden zum Beispiel die oben genannten Streckprodukte häufig in Hochgeschwindigkeitsdurchzugsanlagen metallisiert. Um trotz kurzer Kontaktzeit (hohe Durchsatzgeschwindigkeit) eine hinreichende Metallisierung der Substratoberflächen zu erreichen, muß mit hohen Stromdichten elektrolytisch aufmetallisiert werden.In particular, in the metallization of substrates such as wire, tape or tube special demands are made in terms of stability and deposition rate of the electrolyte used and the method to be used. For example, the above-mentioned stretch products are often metallized in high-speed pass through equipment. Despite a short contact time (high throughput rate) sufficient metallization of To reach substrate surfaces must be metallized electrolytically with high current densities.
Üblicherweise werden saure, sulfathaltige Kupferelektrolyten zur Abscheidung von Kupfer auf den beschriebenen Substraten eingesetzt. Solche Elektrolyten sind jedoch aufgrund ihrer unzureichenden Stabilität bei hohen Stromdichten nicht zum Einsatz in Hochgeschwindigkeitsdurchzugsanlagen geeignet.Usually, acid, sulfate-containing copper electrolytes are used to deposit copper on the described substrates. However, such electrolytes are not suitable for use in high-speed pass-through systems due to their insufficient stability at high current densities.
Es ist daher eine Aufgabe der vorliegenden Erfindung, ein Verfahren zur elektrolytischen Abscheidung einer matten oder halbglänzenden Kupferschicht aus einem sauren Elektrolyten auf einer Substratoberfläche zur Verfügung zu stellen, welches geeignet ist in Hochgeschwindigkeitsdurchzugsanlagen eingesetzt zu werden. Darüber hinaus ist es die Aufgabe der Erfindung einen geeigneten Elektrolyten für die Durchführung des Verfahrens bereitzustellen.It is therefore an object of the present invention to provide a process for the electrodeposition of a matte or semi-bright copper layer of an acidic electrolyte on a substrate surface which is suitable for use in high-speed pass-through equipment. Moreover, it is the object of the invention to provide a suitable electrolyte for carrying out the method.
Gelöst wird diese Aufgabe durch ein Verfahren zur elektrolytischen Abscheidung einer matten oder halbglänzenden Kupferschicht aus einem sauren Elektrolyten auf einem Substrat, welches dadurch gekennzeichnet ist, dass zur Abscheidung der Schicht Stromdichten zwischen ungefähr größer 10 und 100 A/dm2, bevorzugt zwischen 20 und 80 A/dm2 eingesetzt werden. Erfindungsgemäß wird das Verfahren in einem Temperaturbereich zwischen 22 und 60°C, bevorzugt zwischen 45 und 55°C, durchgeführt. Diese Verfahrensbedingungen sind geeignet, um Kupferschichten hinreichender Dicke und Festigkeit in Hochgeschwindigkeitsdurchzugsanlagen auf metallischen oder im Vorfeld zu diesem Verfahren anschlagsverkupferten Kunststoffen abzuscheiden. This object is achieved by a method for the electrolytic deposition of a matte or semi-glossy copper layer of an acidic electrolyte on a substrate, which is characterized in that for the deposition of the layer current densities between about greater than 10 and 100 A / dm 2 , preferably between 20 and 80 A / dm 2 are used. According to the invention, the process is carried out in a temperature range between 22 and 60 ° C, preferably between 45 and 55 ° C. These process conditions are suitable for depositing copper layers of sufficient thickness and strength in high-speed pass-through systems on metallic or impact-doped plastics prior to this process.
Bezüglich des Elektrolyten wird die Aufgabe der Erfindung durch einen kupferhaltigen Elektrolyten gelöst, welcher eine Alkylsulfonsäure enthält. Vorzugsweise handelt es sich bei der Alkylsulfonsäure um Methansulfonsäure, jedoch sind auch alle anderen Sulfonsäuren geeignet, welche unter den Verfahrensbedingungen eine hinreichende Stabilität aufweisen.With respect to the electrolyte, the object of the invention is achieved by a copper-containing electrolyte containing an alkylsulfonic acid. The alkylsulfonic acid is preferably methanesulfonic acid, but all other sulfonic acids which have sufficient stability under the process conditions are also suitable.
Der Elektrolyt kann Kupfer in Form seiner Sulfate, Nitrate, Halogenide; Carboxylate aufweisen. Darüber hinaus weist der Elektrolyt eine hinreichende Menge eines Ethoxylats, vorzugsweise 2-Naphtholethoxylat [2-(2-Naphthyloxy)-ethanol], auf. Des weiteren weist der Elektrolyt eine hinreichende Menge eines schwefelhaltigen Naphthalinkondensationsproduktes der allgemeinen Formel I
wobei n eine ganze Zahl ist, auf. Der Elektrolyt kann zusätzlich typische Hilfsstoffe wie aus der Literatur bekannte Einebner und Netzmittel, auch in Kombination, aufweisen.The electrolyte may be copper in the form of its sulfates, nitrates, halides; Have carboxylates. In addition, the electrolyte has a sufficient amount of an ethoxylate, preferably 2-naphthol ethoxylate [2- (2-naphthyloxy) ethanol], on. Furthermore, the electrolyte has a sufficient amount of a sulfur-containing naphthalene condensation product of the general formula I.
where n is an integer. The electrolyte may additionally comprise typical adjuvants such as levelers and wetting agents known from the literature, also in combination.
Der erfindungsgemäße Elektrolyt ist unter anderem zur Abscheidung von Zwischenschichten auf CuZn-Legierungen, zur Minimierung der Whiskerbildung oder zur Beschichtung ohne Zwischenspülung in einem methansulfonsauren Zinnbad geeignet.The electrolyte according to the invention is suitable, inter alia, for depositing intermediate layers on CuZn alloys, for minimizing whisker formation or for coating without intermediate rinsing in a tin sulfide methanesulfonic acid.
Die nachfolgenden Beispiele beschreiben erfindungsgemäße Elektrolyten, wobei sich die Erfindung jedoch nicht auf die Ausführungsbeispiele beschränken läßt.The following examples describe electrolytes according to the invention, although the invention can not be limited to the exemplary embodiments.
Zusammensetzung eines wäßrigen Elektrolyten zur Kupferabscheidung in einer Durchzugsanlage:
Vorzugsweise weist der Elektrolyt als Halogenidionen Chlorid auf.Preferably, the electrolyte has chloride as halide ions.
Beispiel 2 zeigt typische Verfahrensbedingungen für das erfindungsgemäße Verfahren.Example 2 shows typical process conditions for the process according to the invention.
Verfahrensbedingungen zur Abscheidung von matten oder halbglänzenden Kupferschichten auf einem Substrat aus einem erfindungsgemäßen Elektrolyten:
Die Methansulfonsäure basierenden Elektrolyten zeigen im Vergleich mit schwefelsauren Elektrolyten in Bezug auf die prozentuale Elongation keine Nachteile.
Der geforderte Wert für die prozentuale Elongation liegt im getemperten Zustand zwischen 10 % und 20 %.The required value for the percentage elongation in the tempered state is between 10% and 20%.
Claims (8)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004041701A DE102004041701A1 (en) | 2004-08-28 | 2004-08-28 | Process for the electrolytic deposition of metals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1630258A1 true EP1630258A1 (en) | 2006-03-01 |
| EP1630258B1 EP1630258B1 (en) | 2013-02-27 |
Family
ID=35395909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP05018241A Active EP1630258B1 (en) | 2004-08-28 | 2005-08-23 | Method for the electrolytic deposition of copper |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20060049058A1 (en) |
| EP (1) | EP1630258B1 (en) |
| JP (1) | JP4283256B2 (en) |
| CN (1) | CN1740399A (en) |
| DE (1) | DE102004041701A1 (en) |
| ES (1) | ES2402688T3 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009041097A (en) * | 2007-08-10 | 2009-02-26 | Rohm & Haas Electronic Materials Llc | Copper plating method |
| EP2568063A1 (en) * | 2011-09-09 | 2013-03-13 | Rohm and Haas Electronic Materials LLC | Low internal stress copper electroplating method |
| US10128022B1 (en) * | 2017-10-24 | 2018-11-13 | Northrop Grumman Systems Corporation | Lightweight carbon nanotube cable comprising a pair of plated twisted wires |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4036711A (en) * | 1975-12-18 | 1977-07-19 | M & T Chemicals Inc. | Electrodeposition of copper |
| US4134803A (en) * | 1977-12-21 | 1979-01-16 | R. O. Hull & Company, Inc. | Nitrogen and sulfur compositions and acid copper plating baths |
| US6491806B1 (en) * | 2000-04-27 | 2002-12-10 | Intel Corporation | Electroplating bath composition |
| US6676823B1 (en) * | 2002-03-18 | 2004-01-13 | Taskem, Inc. | High speed acid copper plating |
| EP1408141A1 (en) * | 2002-10-11 | 2004-04-14 | Enthone Inc. | Process for galvanic deposition of bronze |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2525942A (en) * | 1945-06-29 | 1950-10-17 | Standard Oil Co | Electrodepositing bath and process |
| US4347108A (en) * | 1981-05-29 | 1982-08-31 | Rohco, Inc. | Electrodeposition of copper, acidic copper electroplating baths and additives therefor |
| US5051154A (en) * | 1988-08-23 | 1991-09-24 | Shipley Company Inc. | Additive for acid-copper electroplating baths to increase throwing power |
| US5849171A (en) * | 1990-10-13 | 1998-12-15 | Atotech Deutschland Gmbh | Acid bath for copper plating and process with the use of this combination |
| DE4032864A1 (en) * | 1990-10-13 | 1992-04-16 | Schering Ag | ACIDIC BATH FOR THE GALVANIC DEPOSITION OF COPPER COVERS AND METHODS USING THIS COMBINATION |
| US5385661A (en) * | 1993-09-17 | 1995-01-31 | International Business Machines Corporation | Acid electrolyte solution and process for the electrodeposition of copper-rich alloys exploiting the phenomenon of underpotential deposition |
| DE4338148C2 (en) * | 1993-11-04 | 1997-01-30 | Atotech Deutschland Gmbh | Process for the electrolytic deposition of dull and pimple-free copper layers with high elongation at break on substrate surfaces |
| US6284309B1 (en) * | 1997-12-19 | 2001-09-04 | Atotech Deutschland Gmbh | Method of producing copper surfaces for improved bonding, compositions used therein and articles made therefrom |
| US6444110B2 (en) * | 1999-05-17 | 2002-09-03 | Shipley Company, L.L.C. | Electrolytic copper plating method |
| US6605204B1 (en) * | 1999-10-14 | 2003-08-12 | Atofina Chemicals, Inc. | Electroplating of copper from alkanesulfonate electrolytes |
| KR100366631B1 (en) * | 2000-09-27 | 2003-01-09 | 삼성전자 주식회사 | Electrolyte for copper plating comprising polyvinylpyrrolidone and electroplating method for copper wiring of semiconductor devices using the same |
| US6776893B1 (en) * | 2000-11-20 | 2004-08-17 | Enthone Inc. | Electroplating chemistry for the CU filling of submicron features of VLSI/ULSI interconnect |
| US20030066756A1 (en) * | 2001-10-04 | 2003-04-10 | Shipley Company, L.L.C. | Plating bath and method for depositing a metal layer on a substrate |
| US6843852B2 (en) * | 2002-01-16 | 2005-01-18 | Intel Corporation | Apparatus and method for electroless spray deposition |
| US20060260948A2 (en) * | 2005-04-14 | 2006-11-23 | Enthone Inc. | Method for electrodeposition of bronzes |
-
2004
- 2004-08-28 DE DE102004041701A patent/DE102004041701A1/en not_active Withdrawn
-
2005
- 2005-08-23 ES ES05018241T patent/ES2402688T3/en active Active
- 2005-08-23 EP EP05018241A patent/EP1630258B1/en active Active
- 2005-08-24 JP JP2005243009A patent/JP4283256B2/en active Active
- 2005-08-26 CN CN200510092292.7A patent/CN1740399A/en active Pending
- 2005-08-29 US US11/214,421 patent/US20060049058A1/en not_active Abandoned
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4036711A (en) * | 1975-12-18 | 1977-07-19 | M & T Chemicals Inc. | Electrodeposition of copper |
| US4134803A (en) * | 1977-12-21 | 1979-01-16 | R. O. Hull & Company, Inc. | Nitrogen and sulfur compositions and acid copper plating baths |
| US6491806B1 (en) * | 2000-04-27 | 2002-12-10 | Intel Corporation | Electroplating bath composition |
| US6676823B1 (en) * | 2002-03-18 | 2004-01-13 | Taskem, Inc. | High speed acid copper plating |
| EP1408141A1 (en) * | 2002-10-11 | 2004-04-14 | Enthone Inc. | Process for galvanic deposition of bronze |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4283256B2 (en) | 2009-06-24 |
| DE102004041701A1 (en) | 2006-03-02 |
| US20060049058A1 (en) | 2006-03-09 |
| EP1630258B1 (en) | 2013-02-27 |
| ES2402688T3 (en) | 2013-05-07 |
| JP2006063450A (en) | 2006-03-09 |
| CN1740399A (en) | 2006-03-01 |
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