CN1740399A - Method for the electrolytic deposition of copper - Google Patents
Method for the electrolytic deposition of copper Download PDFInfo
- Publication number
- CN1740399A CN1740399A CN200510092292.7A CN200510092292A CN1740399A CN 1740399 A CN1740399 A CN 1740399A CN 200510092292 A CN200510092292 A CN 200510092292A CN 1740399 A CN1740399 A CN 1740399A
- Authority
- CN
- China
- Prior art keywords
- ionogen
- copper
- preferred
- ethoxylate
- aforementioned
- 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.)
- Pending
Links
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
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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)
- Electroplating Methods And Accessories (AREA)
Abstract
The present invention relates to a method as well as and electrolyte for the electrolytic deposition of mat or half-glossy copper layers from an acid electrolyte in a pull-through device. The method according to the invention is operated with current densities comprises between 10A/dm2 and 100 A/dm2 and is suitable for depositing sufficiently thick copper layers in high-speed pull-through devices. The electrolyte according to the invention comprises apart from copper, alkyl sulfonic acid.
Description
Technical field
The present invention relates to be undertaken the method for the electrolytic deposition of tarnish or semi-gloss copper layer by acidic electrolyte bath.
Background technology
Acidic copper matter is used for the surface-coated of base material in many ways, to form functional or decorative coating on substrate surface.
Method for metallising to be used and ionogen to be used depend on type and the character for the treatment of metallized base material.Thus, metal and non-conductive base material all can be provided corresponding upper layer.
Especially, in the metallization such as the base material of wire, band or pipe, employed ionogen and method to be used must satisfy the particular requirement to stability and sedimentation velocity.Thereby, but above-mentioned drawn products for example often is to metallize in traction (pull-through) equipment at a high speed.In order to obtain the abundant metallization of substrate surface down in short duration of contact (high through-rate), must electroplate with high current density.
Usually the hydrosulphate (acid sulphate) that contains copper electrolytes is used for copper is deposited on described base material.Yet because this type of ionogen stability under high current density is not enough, thereby it is unsuitable for using in the high speed traction type equipment.
Summary of the invention
Thereby the purpose of this invention is to provide the method for electrodeposition that on substrate surface, carries out tarnish or semi-gloss copper layer by acidic electrolyte bath, described method is suitable for using in the high speed traction type equipment.In addition, the purpose of this invention is to provide the suitable ionogen that is used to implement this method.
Embodiment
This target realizes by the method for electrodeposition that is carried out tarnish or semi-gloss copper layer by acidic electrolyte bath on substrate surface, it is characterized in that the sedimentary current density that is used for layer is in about 10A/dm
2More than and 100A/dm
2Between, preferably be in 20A/dm
2And 80A/dm
2Between.According to the present invention, the temperature range of implementing this method is between 22 ℃ and 60 ℃, preferably is between 45 ℃ and 55 ℃.These processing condition are suitable for having the deposition of the copper layer of adequate thickness and soundness on metallized plastic or plastics in the high speed traction type equipment, described metallized plastic or plastics have been electroplate with copper layer as thin as a wafer in the preliminary step of this method.
About ionogen, this target of the present invention is to realize that by containing copper electrolytes it contains alkylsulphonic acid.This alkylsulphonic acid is preferably methylsulfonic acid, but presents all suitable use of every other sulfonic acid of enough stability under these processing condition.
Ionogen can contain the copper of vitriol, nitrate, halogenide, carboxylate form.In addition, ionogen contains the ethoxylate of q.s, is preferably beta naphthal ethoxylate [2-(2-naphthyl oxygen)-ethanol].In addition, ionogen contains the naphthalene condensation product (naphthalene condensation product) of the general formula I of q.s.
Wherein n is an integer.Ionogen can contain typical process materials in addition, and for example levelling agent and tensio-active agent also have its combination, because they are known in the literature.
Following embodiment has described according to ionogen of the present invention, and wherein the present invention is not limited to the implementation method of example.
Embodiment 1
Be used for carrying out the composition of the sedimentary aqueous electrolyte of copper at traction type equipment:
Copper: 40-90g/l, preferred 75g/l
Methylsulfonic acid: 50-130ml/l, preferred 90ml/l
Halide ions: 40-100mg/l, preferred 50mg/l
Beta naphthal ethoxylate: 5-30g/l, preferred 10g/l
Naphthalene condensation product: 0.001-1g/l, preferred 0.1g/l
Preferably, this ionogen contains muriate as halide ions.
Embodiment 2 shows the typical process condition that is used for the inventive method.
Embodiment 2
Be used on base material, carrying out the sedimentary processing condition of tarnish or semi-gloss copper layer by ionogen of the present invention:
Base material: brass
Temperature: 25 ℃
Current density: 10A/dm
2
Pulling speed: 50m/min
The thickness of copper layer: 5 μ m
Aspect elongation, methylsulfonic acid type ionogen is compared with the sulfuric acid type ionogen and is not shown disadvantage.
Methylsulfonic acid sulfuric acid
Embodiment 1 7.54 6.43
2 6.96 5.24
3 6.96 7.12
4 6.84 5.42
5 9.74 6.04
φ 7.6 6.05
Max. 9.74 7.12 not tempering
1 13.37 14.3
2 17.28 17.65
3 13.92 17.92
4 9.28 13.6
5 15.66 10.65
φ 13.9 14.82
Max. 17.28 17.92 tempering
Claims (8)
1. on base material, carry out the method for the electrolytic deposition of tarnish or semi-gloss copper layer by acidic electrolyte bath, it is characterized in that the sedimentary current density that is used for layer is set at about 10A/dm
2And 100A/dm
2Between, be preferably 20A/dm
2And 80A/dm
2Between.
2. according to the method for claim 1, the enforcement temperature that it is characterized in that described method is between 22 ℃ and 60 ℃, is preferably between 45 ℃ and 55 ℃.
3. according at least one method in the aforementioned claim, it is characterized in that described method implements being used for the traction type equipment that electrolysis applies.
4. be used for implementing the ionogen of the method for at least one of aforementioned claim, it is characterized in that described ionogen contains following component at least: copper, alkylsulphonic acid, halide ions, ethoxylate and naphthalene condensation product.
5. according to the ionogen of claim 4, it is characterized in that described ionogen contains the beta naphthal ethoxylate as ethoxylate.
6. according to one or multinomial ionogen of claim 4 and 5, it is characterized in that described ionogen contains chloride ion as halogenide.
7. be used for implementing the ionogen of the method for at least one of aforementioned claim, it is characterized in that described ionogen contains following component at least:
-copper: 40-90g/l, preferred 75g/l
-methylsulfonic acid: 50-130ml/l, preferred 90ml/l
-halide ions: 40-100mg/l, preferred 50mg/l
-ethoxylate: 5-30g/l, preferred 10g/l
-naphthalene condensation product: 0.001-1g/l, preferred 0.1g/l.
8. according to one or the multinomial ionogen of claim 4-7, it is characterized in that described ionogen contains the copper of at least one compounds form in vitriol, nitrate, halogenide, the carboxylate salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004041701A DE102004041701A1 (en) | 2004-08-28 | 2004-08-28 | Process for the electrolytic deposition of metals |
| DE102004041701.6 | 2004-08-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1740399A true CN1740399A (en) | 2006-03-01 |
Family
ID=35395909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200510092292.7A Pending CN1740399A (en) | 2004-08-28 | 2005-08-26 | 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102995075A (en) * | 2011-09-09 | 2013-03-27 | 罗门哈斯电子材料有限公司 | Low internal stress copper electroplating method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009041097A (en) * | 2007-08-10 | 2009-02-26 | Rohm & Haas Electronic Materials Llc | Copper plating method |
| US10128022B1 (en) * | 2017-10-24 | 2018-11-13 | Northrop Grumman Systems Corporation | Lightweight carbon nanotube cable comprising a pair of plated twisted wires |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2525942A (en) * | 1945-06-29 | 1950-10-17 | Standard Oil Co | Electrodepositing bath and process |
| 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 |
| 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 |
| US6491806B1 (en) * | 2000-04-27 | 2002-12-10 | Intel Corporation | Electroplating bath composition |
| 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 |
| US6676823B1 (en) * | 2002-03-18 | 2004-01-13 | Taskem, Inc. | High speed acid copper plating |
| ES2531163T3 (en) * | 2002-10-11 | 2015-03-11 | Enthone | Procedure and electrolyte for galvanic deposition of bronzes |
| 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
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102995075A (en) * | 2011-09-09 | 2013-03-27 | 罗门哈斯电子材料有限公司 | Low internal stress copper electroplating method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4283256B2 (en) | 2009-06-24 |
| DE102004041701A1 (en) | 2006-03-02 |
| EP1630258A1 (en) | 2006-03-01 |
| US20060049058A1 (en) | 2006-03-09 |
| EP1630258B1 (en) | 2013-02-27 |
| ES2402688T3 (en) | 2013-05-07 |
| JP2006063450A (en) | 2006-03-09 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20060301 |