EP2620529B1 - Verfahren zur Herstellung von matten Kupferablagerungen - Google Patents
Verfahren zur Herstellung von matten Kupferablagerungen Download PDFInfo
- Publication number
- EP2620529B1 EP2620529B1 EP12152390.6A EP12152390A EP2620529B1 EP 2620529 B1 EP2620529 B1 EP 2620529B1 EP 12152390 A EP12152390 A EP 12152390A EP 2620529 B1 EP2620529 B1 EP 2620529B1
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- Prior art keywords
- group
- electrolyte
- deposition
- matt
- poly
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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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
Definitions
- the present invention relates to a method for deposition of matt copper deposits in the field of decorative coatings.
- Matt copper coatings in the field of decorative coatings are required as a surface finish for e.g. sanitary equipment.
- Another application of matt copper coatings is to replace matt nickel layers ("satin nickel") as an intermediate layer in decorative multilayer coating systems which becomes more demanding due to the toxicity of nickel.
- a homogeneous matt appearance is required for decorative metal layers.
- the homogeneity of the matt appearance can easily be achieved on substrates which have no complex shape because the current density distribution during electroplating of matt copper layers is within a narrow range.
- the current density during electroplating is within a wide range.
- Typical substrates having a complex shape which are to be coated with a matt copper coating are for example shower heads and automotive interior parts.
- matt copper layers Another requirement for matt copper layers is that their matt level should be adjustable in order to be able to manufacture copper layers having different matt levels.
- Plating bath compositions comprising at least one polyglycerine compound for producing matt copper layers during manufacture of printed circuit boards are disclosed in US 2004/0020783 A1 . It is neither possible to obtain a homogeneously matt copper deposit on a substrate having a complex shape nor to adjust the matt level of such a copper deposit when using the electrolyte disclosed therein.
- a dull plating method is disclosed in JP 8 134689 wherein a copper plating layer is first deposited by barrel electroplating, roughened by "emery power" and then a non-lustrous copper or nickel plating layer is deposited thereon.
- a multiple chemistry electrochemical plating method is disclosed in US 2004/0154926 A1 wherein a first copper layer is deposited from a first solution followed by electroplating a second copper layer from a second solution thereon.
- a method to improve copper electrochemical deposition is disclosed in US 2005/0045485 A1 wherein a first copper layer is deposited from a plating bath comprising a antiforming agent followed by electroplating a second copper layer thereon.
- the copper coatings obtained by the method according to the present invention have a homogeneous matt appearance on substrates having a complex shape.
- the matt appearance of the copper coating can be adjusted during deposition of the individual copper layers.
- the method for deposition of a matt copper coating comprises deposition of two individual copper layers onto a substrate from two individual copper electrolytes which are herein denoted first electrolyte from which the first copper layer is deposited and second electrolyte from which the second copper layer is deposited onto the first copper layer.
- the first electrolyte comprises a source of copper ions, at least one acid and at least one polyether compound.
- the first electrolyte does not contain an organic compound comprising divalent sulfur, e.g., sulfides, disulfides, thioles, and derivatives thereof.
- Copper ions are added to the first electrolyte in the form of a water-soluble copper salt or an aqueous solution thereof.
- the source of copper ions is selected from copper sulfate and copper methane sulfonate.
- the concentration of copper ions in the first electrolyte preferably ranges from 15 to 75 g/l, more preferably from 40 to 60 g/l.
- the at least one acid in the first electrolyte is selected from the group comprising sulfuric acid, fluoro boric acid and methane sulfonic acid.
- the concentration of the at least one acid in the first electrolyte preferably ranges from 20 to 400 g/I and more preferably from 40 to 300 g/I.
- sulfuric acid is used as the acid, it is preferably added in form of a 50 to 96 wt.-% solution. More preferably, sulphuric acid is added to the first electrolyte as a 50 wt.-% aqueous solution of sulfuric acid.
- the at least one polyether compound in the first electrolyte is selected from the group consisting of polyalkylene ethers and polyglycerine compounds.
- Suitable polyalkylene ethers are selected from the group consisting of polyethylene glycol, polypropylene glycol, stearylalcoholpolyglycolether, nonylphenolpolyglycolether, octanolpolyalkylenglcolether, octanediol-bis-(polyalkylenglycolether), poly(ethylenglycol- ran -propylenglycol), poly(ethylenglycol)- block -poly(propylenglycol)- block -poly(ethylenglycol) and poly-(propylenglycol)- block -poly(ethylenglycol)- block -poly(propylenglycol).
- Suitable polyglycerine compounds are selected from the group consisting of poly(1,2,3-propantriol), poly(2,3-epoxy-1-propanol) and derivatives thereof which are represented by formulae (1), (2) and (3): wherein
- Polyglycerine compounds are produced according to known methods. Indications on the conditions of production are disclosed in the following publications for example: Cosmet. Sci. Technol. Ser., glycerines, page 106 and US 3,945,894 . Further details on the syntheses of polyglycerine compounds according to formulae (1), (2) and (3) are disclosed in US 2004/0020783 A1 .
- the at least one polyether compound in the first electrolyte is selected from compounds according to formulae (1), (2) and (3).
- the concentration of the at least one polyether compound or all polyether compounds together in case more than one polyether compound is added preferably ranges from 0.005 g/l to 20 g/l, more preferably from 0.01 g/l to 5 g/l.
- the temperature of the first electrolyte is preferably adjusted to a value in the range of from 30 to 60°C, more preferably from 40 to 50 °C.
- the current density applied to the substrate during copper deposition from the first aqueous electrolyte preferably ranges from 0.5 to 5 A/dm 2 , more preferably from 1 to 3 A/dm 2 .
- the substrate is rinsed with water before depositing the second copper layer from the second electrolyte.
- Copper ions are added to the second electrolyte as a water-soluble copper salt or an aqueous solution thereof.
- the source of copper ions is selected from copper sulfate and copper methane sulfonate.
- the concentration of copper ions in the second electrolyte preferably ranges from 15 to 75 g/l, more preferably from 40 to 60 g/l.
- the at least one acid in the second electrolyte is selected from the group comprising sulfuric acid, fluoro boric acid and methane sulfonic acid.
- the concentration of the at least one acid in the second electrolyte preferably ranges from 20 to 400 g/I and more preferably from 40 to 300 g/l.
- sulfuric acid is used as the acid, it is added in form of a 50 to 96 wt.-% solution.
- sulfuric acid is added as a 50 wt.-% aqueous solution of sulfuric to the second electrolyte.
- the second electrolyte further comprises a first water-soluble sulfur-containing additive and a second water-soluble sulfur-containing additive.
- the first water-soluble sulfur-containing compound is an alkyl sulfonic acid derivative.
- the alkyl sulfonic acid derivative comprises divalent sulfur.
- the second water-soluble sulfur-containing compound is an aromatic sulfonic acid derivative.
- the aromatic sulfonic acid derivative comprises divalent sulfur.
- the first sulfur-containing additive is more preferably selected from the group consisting of compounds according to formulae (4) and (5): R 1 S-(CH 2 ) n -SO 3 R 2 (4) R 3 SO 3 -(CH 2 ) m -S-S-(CH 2 ) m -SO 3 R 3 (5) wherein
- the concentration of the first sulfur-containing additive in the second electrolyte preferably ranges from 0.0001 to 0.05 g/l, more preferably from 0.0002 to 0.025 g/l.
- the second sulfur-containing additive in the second electrolyte is more preferably selected from the group consisting of compounds according to formulae (6) and (7): R 4 S y -X-SO 3 M (6) wherein R 4 is selected from the group consisting of and hydrogen; X is selected from the group consisting of y is an integer from 1 to 4 and M is selected from the group consisting of hydrogen, sodium, potassium and ammonium; and wherein R 5 is selected from the group consisting of hydrogen, SH and SO 3 M and M is selected from the group consisting of hydrogen, sodium, potassium and ammonium.
- the second sulfur-containing additive is selected from compounds according to formula (6).
- the concentration of the second sulfur-containing additive in the second electrolyte preferably ranges from 0.005 to 1 g/l, more preferably from 0.01 to 0.25 g/l.
- the second electrolyte further comprises one or more carrier additive selected from the group consisting of polyvinylalcohol, carboxymethylcellulose, polyethylene glycol, polypropylene glycol, stearic acid polyglycolester, alkoxylated naphtoles, oleic acid polyglycolester, stearylalcoholpolyglycolether, nonylphenolpolyglycolether, octanolpolyalkylenglycolether, octanediol-bis-(polyalkylenglycolether), poly(ethylenglycol- ran -propylenglycol), poly(ethylenglycol)- block -poly(propylenglycol)- block -poly(ethylenglycol) and poly(propylenglycol)- block -poly(ethylenglycol)- block -poly(propylenglycol).
- carrier additive selected from the group consisting of
- the concentration of the optional carrier additive in the second electrolyte preferably ranges from 0.005 g/l to 5 g/l, more preferably from 0.01 g/l to 3 g/l.
- the temperature of the second electrolyte is preferably adjusted to a value in the range of from 20 to 50 °C, most preferably of from 25 to 30°C.
- the current density applied to the substrate during copper deposition from the second aqueous electrolytes preferably ranges from 0.5 to 5 A/dm 2 , more preferably from 1 to 3 A/dm 2 .
- the matt level of the copper surface may be tailored by adjusting the thicknesses of the first and second copper layer by simple experimentation. A more matt appearance may be achieved with a thinner second copper layer, whereas a less matt appearance may be achieved with a thicker second copper layer.
- ABS acrylnitrile-butadiene-styrol-copolymer
- brass substrates having a complex shape were used throughout all examples.
- ABS substrates were etched in chromic acid, activated with a palladium containing colloid and metallised by electroless plating of nickel from an acidic hypophosphite-based electrolyte prior to copper deposition.
- the brass substrates were degreased prior to deposition of copper.
- the copper surface obtained has a homogenous technical gloss which is not desired for decorative applications.
- a first layer of copper was deposited onto ABS and brass substrates having a complex shape from the electrolyte used in example 2. Thereon, a second copper layer was deposited from the electrolyte used in example 1.
- a first copper layer was deposited onto ABS and brass substrates having a complex shape from the electrolyte used in example 1.
- the second electrolyte did not contain a second sulfur-containing additive selected from compounds according to formulae (6) and (7).
- the resulting copper surface has a non-homogeneous matt appearance which is not acceptable for decorative applications.
- a first copper layer was deposited onto ABS and brass substrates having a complex shape from the electrolyte used in example 1.
- the second electrolyte did not contain a first sulfur-containing additive selected from compounds according to formulae (4) and (5).
- the copper surface obtained has a matt appearance with burnt areas (shady black appearance) which is not acceptable for decorative applications.
- the first copper layer was deposited onto the ABS and brass substrates from the electrolyte used in Example 1.
- the second copper layer was deposited thereon from the electrolyte used in Example 2.
- the copper surface obtained has a homogeneous matt appearance which is desired for decorative applications.
- the first copper layer was deposited from a first electrolyte comprising 80 g/l CuSO 4 ⁇ 5H 2 O, 240 g/l sulfuric acid, and 1 g/l polyethylene glycol.
- the second copper layer was deposited thereon from the electrolyte used in Example 2.
- Example 1 First and second electrolytes used in Examples 1 to 6.
- Example 1* Example 2*
- Example 3* Example 4*
- Example 6 Example 7
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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)
Claims (13)
- Verfahren zum Abscheiden einer matten Kupferbeschichtung, umfassend, in dieser Reihenfolge, die Schrittea. Bereitstellen eines Substrats,b. Abscheiden einer ersten Kupferschicht aus einem ersten wässrigen Elektrolyten, der eine Quelle von Kupferionen, wenigstens eine Säure und wenigstens eine Polyetherverbindung umfasst, auf das Substrat, wobei der erste Elektrolyt keine organische Verbindung, die zweiwertigen Schwefel umfasst, enthältundc. Abscheiden einer zweiten Kupferschicht aus einem zweiten wässrigen Elektrolyten, der eine Quelle von Kupferionen, wenigstens eine Säure, einen ersten wasserlöslichen Schwefel-enthaltenden Zusatzstoff, ausgewählt aus der Gruppe bestehend aus Alkylsulfonsäurederivaten, und einen zweiten wasserlöslichen Schwefel-enthaltenden Zusatzstoff, ausgewählt aus der Gruppe bestehend aus aromatischen Sulfonsäurederivaten, umfasst, auf die erste Kupferschicht,wobei bei den Schritten b. und c. eine Stromdichte an das Substrat angelegt wird.
- Verfahren zum Abscheiden einer matten Kupferbeschichtung gemäß Anspruch 1, wobei die wenigstens eine Polyetherverbindung in dem ersten Elektrolyten ausgewählt ist aus der Gruppe bestehend aus Polyalkylenglycolen und Polyglycerinen.
- Verfahren zum Abscheiden einer matten Kupferbeschichtung gemäß einem der vorstehenden Ansprüche, wobei die wenigstens eine Polyetherverbindung in dem ersten Elektrolyten ausgewählt ist aus der Gruppe bestehend aus Poly(1,2,3-propantriol), Poly(2,3-epoxy-1-propanol) und Derivaten davon.
- Verfahren zum Abscheiden einer matten Kupferbeschichtung gemäß einem der vorstehenden Ansprüche, wobei die wenigstens eine Polyetherverbindung in dem ersten Elektrolyten ausgewählt ist aus der Gruppe bestehend aus Verbindungen gemäß den Formeln (1), (2) und (3):
und wobei
R6, R7, R8 und R9 gleich oder verschieden sind und ausgewählt sind aus der Gruppe umfassend Wasserstoff, Alkyl, Acyl, Phenyl und Benzyl. - Verfahren zum Abscheiden einer matten Kupferbeschichtung gemäß Anspruch 4, wobei das Molekulargewicht der Verbindungen gemäß den Formeln (1), (2) und (3) im Bereich von 160 bis 6000 g/mol liegt.
- Verfahren zum Abscheiden einer matten Kupferbeschichtung gemäß einem der vorstehenden Ansprüche, wobei die Konzentration der wenigstens einen Polyetherverbindung in dem ersten Elektrolyten im Bereich von 0,005 g/l bis 5 g/l liegt.
- Verfahren zum Abscheiden einer matten Kupferbeschichtung gemäß einem der vorstehenden Ansprüche, wobei der erste wasserlösliche Schwefel-enthaltende Zusatzstoff in dem zweiten Elektrolyten ausgewählt ist aus der Gruppe bestehend aus Verbindungen gemäß den Formeln (4) und (5):
R1S-(CH2)n-SO3R2 (4)
R3SOs-(CH2)m-S-S-(CH2)m-SO3R3 (5)
wobei
R1 ausgewählt ist aus der Gruppe bestehend aus Wasserstoff, Methyl, Ethyl, Propyl, Butyl, Lithium, Natrium, Kalium und Ammonium,
n im Bereich von 1 bis 6 liegt,
R2 ausgewählt ist aus der Gruppe bestehend aus Wasserstoff, Methyl, Ethyl, Propyl, Butyl, Lithium, Natrium, Kalium und Ammonium,
R3 ausgewählt ist aus der Gruppe bestehend aus Wasserstoff, Methyl, Ethyl, Propyl, Butyl, Lithium, Natrium, Kalium und Ammonium und
m im Bereich von 1 bis 6 liegt. - Verfahren zum Abscheiden einer matten Kupferbeschichtung gemäß einem der vorstehenden Ansprüche, wobei die Konzentration des ersten wasserlöslichen Schwefel-enthaltenden Zusatzstoffs in dem zweiten Elektrolyten im Bereich von 0,0001 bis 0,05 g/l liegt.
- Verfahren zum Abscheiden einer matten Kupferbeschichtung gemäß einem der vorstehenden Ansprüche, wobei der zweite wasserlösliche Schwefel-enthaltende Zusatzstoff in dem zweiten Elektrolyten ausgewählt ist aus der Gruppe bestehend aus Verbindungen gemäß den Formeln (6) und (7):
R4Sy-X-SO3M (6)
wobei R4 ausgewählt ist aus der Gruppe bestehend aus
X ausgewählt ist aus der Gruppe bestehend aus - Verfahren zum Abscheiden einer matten Kupferbeschichtung gemäß einem der vorstehenden Ansprüche, wobei die Konzentration des zweiten wasserlöslichen Schwefel-enthaltenden Zusatzstoffs in dem zweiten Elektrolyten im Bereich von 0,005 bis 1 g/l liegt.
- Verfahren zum Abscheiden einer matten Kupferbeschichtung gemäß einem der vorstehenden Ansprüche, wobei der zweite Elektrolyt ferner wenigstens einen Träger-Zusatzstoff umfasst.
- Verfahren zum Abscheiden einer matten Kupferbeschichtung gemäß Anspruch 11, wobei der wenigstens eine Träger-Zusatzstoff ausgewählt ist aus der Gruppe bestehend aus Polyvinylalkohol, Carboxymethylcellulose, Polyethylenglycol, Polypropylenglycol, Stearinsäurepolyglycolester, alkoxylierten Naphtolen, Oleinsäurepolyglycolester, Stearylalkoholpolyglycolether, Nonylphenolpolyglycolether, Octanolpolyalkylenglycolether, Octandiolbis(polyalkylenglycolether), Poly(ethylenglycol-ran-propylenglycol), Poly(ethylenglycol)-block-poly(propylenglycol)-block-poly(ethylenglycol) und Poly(propylenglycol)-block-poly(ethylenglycol)-block-poly(propylenglycol).
- Verfahren zum Abscheiden einer matten Kupferbeschichtung gemäß Ansprüchen 11 und 12, wobei die Konzentration des wenigstens einen Träger-Zusatzstoffs in dem zweiten Elektrolyten im Bereich von 0,005 g/l bis 5 g/l liegt.
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12152390.6A EP2620529B1 (de) | 2012-01-25 | 2012-01-25 | Verfahren zur Herstellung von matten Kupferablagerungen |
ES12152390.6T ES2478267T3 (es) | 2012-01-25 | 2012-01-25 | Método para producir depósitos de cobre mate |
PL12152390T PL2620529T3 (pl) | 2012-01-25 | 2012-01-25 | Sposób wytwarzania matowych warstw miedzianych |
PCT/EP2012/073688 WO2013110373A2 (en) | 2012-01-25 | 2012-11-27 | Method for producing matt copper deposits |
BR112014018114-4A BR112014018114B1 (pt) | 2012-01-25 | 2012-11-27 | Método para a produção de depósitos de cobre mate |
JP2014553641A JP6086930B2 (ja) | 2012-01-25 | 2012-11-27 | つや消し銅めっきの製造方法 |
CA2862141A CA2862141C (en) | 2012-01-25 | 2012-11-27 | Method for producing matt copper deposits |
US14/374,000 US20150014177A1 (en) | 2012-01-25 | 2012-11-27 | Method for producing matt copper deposits |
CN201280068192.9A CN104080955B (zh) | 2012-01-25 | 2012-11-27 | 制造无光泽铜沉积的方法 |
KR1020147022888A KR101979975B1 (ko) | 2012-01-25 | 2012-11-27 | 무광 구리 성막물의 제조 방법 |
TW101147026A TWI526582B (zh) | 2012-01-25 | 2012-12-12 | 製造無光澤銅沈積之方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12152390.6A EP2620529B1 (de) | 2012-01-25 | 2012-01-25 | Verfahren zur Herstellung von matten Kupferablagerungen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2620529A1 EP2620529A1 (de) | 2013-07-31 |
EP2620529B1 true EP2620529B1 (de) | 2014-04-30 |
Family
ID=47226182
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12152390.6A Active EP2620529B1 (de) | 2012-01-25 | 2012-01-25 | Verfahren zur Herstellung von matten Kupferablagerungen |
Country Status (11)
Country | Link |
---|---|
US (1) | US20150014177A1 (de) |
EP (1) | EP2620529B1 (de) |
JP (1) | JP6086930B2 (de) |
KR (1) | KR101979975B1 (de) |
CN (1) | CN104080955B (de) |
BR (1) | BR112014018114B1 (de) |
CA (1) | CA2862141C (de) |
ES (1) | ES2478267T3 (de) |
PL (1) | PL2620529T3 (de) |
TW (1) | TWI526582B (de) |
WO (1) | WO2013110373A2 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA3119028A1 (en) | 2018-11-07 | 2020-05-14 | Coventya, Inc. | Satin copper bath and method of depositing a satin copper layer |
US11384446B2 (en) | 2020-08-28 | 2022-07-12 | Macdermid Enthone Inc. | Compositions and methods for the electrodeposition of nanotwinned copper |
KR20240034865A (ko) * | 2021-08-05 | 2024-03-14 | 맥더미드 엔쏜 인코포레이티드 | 나노쌍정 구리의 전착을 위한 조성물 및 방법 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2360892A1 (de) * | 1972-12-14 | 1974-06-20 | M & T Chemicals Inc | Waessriges saures galvanisches kupferbad |
US4009087A (en) * | 1974-11-21 | 1977-02-22 | M&T Chemicals Inc. | Electrodeposition of copper |
US3945894A (en) | 1975-04-11 | 1976-03-23 | Oxy Metal Industries Corporation | Bath composition and method of electrodepositing utilizing the same |
JPH04139787A (ja) * | 1990-09-28 | 1992-05-13 | Fujitsu Ltd | プリント配線板の電解メッキ方法 |
DE4324995C2 (de) * | 1993-07-26 | 1995-12-21 | Demetron Gmbh | Cyanidisch-alkalische Bäder zur galvanischen Abscheidung von Kupfer-Zinn-Legierungsüberzügen |
JP2915305B2 (ja) * | 1994-11-04 | 1999-07-05 | 有限会社カネヒロ・メタライジング | つや消しメッキ方法および検針器対応つや消しメッキ方法 |
DE19540011C2 (de) * | 1995-10-27 | 1998-09-10 | Lpw Chemie Gmbh | Verfahren zur galvanischen Abscheidung von blendfreien Nickel- oder Nickellegierungsniederschlägen |
DE19653681C2 (de) * | 1996-12-13 | 2000-04-06 | Atotech Deutschland Gmbh | Verfahren zur elektrolytischen Abscheidung von Kupferschichten mit gleichmäßiger Schichtdicke und guten optischen und metallphysikalischen Eigenschaften und Anwendung des Verfahrens |
US6649038B2 (en) * | 2000-10-13 | 2003-11-18 | Shipley Company, L.L.C. | Electroplating method |
US6679983B2 (en) * | 2000-10-13 | 2004-01-20 | Shipley Company, L.L.C. | Method of electrodepositing copper |
JP3899313B2 (ja) * | 2000-10-19 | 2007-03-28 | アトーテヒ ドイッチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング | 銅浴および無光沢銅被膜の電着方法 |
US20040154926A1 (en) * | 2002-12-24 | 2004-08-12 | Zhi-Wen Sun | Multiple chemistry electrochemical plating method |
US20050045485A1 (en) * | 2003-09-03 | 2005-03-03 | Taiwan Semiconductor Manufacturing Co. Ltd. | Method to improve copper electrochemical deposition |
DE10354760A1 (de) * | 2003-11-21 | 2005-06-23 | Enthone Inc., West Haven | Verfahren zur Abscheidung von Nickel und Chrom(VI)freien metallischen Mattschichten |
ES2615337T3 (es) * | 2008-07-08 | 2017-06-06 | Enthone, Inc. | Electrolito y método para depositar una capa metálica mate |
DE102008033174B3 (de) * | 2008-07-15 | 2009-09-17 | Enthone Inc., West Haven | Cyanidfreie Elektrolytzusammensetzung zur galvanischen Abscheidung einer Kupferschicht und Verfahren zur Abscheidung einer kupferhaltigen Schicht |
JP5823665B2 (ja) * | 2009-02-20 | 2015-11-25 | 株式会社大和化成研究所 | めっき浴及びそれを用いためっき方法 |
KR101141923B1 (ko) * | 2009-12-28 | 2012-05-07 | 한밭대학교 산학협력단 | 이중 전기도금법을 이용한 전기도금법 및 이로부터 형성되는 금속 박막 |
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2012
- 2012-01-25 EP EP12152390.6A patent/EP2620529B1/de active Active
- 2012-01-25 PL PL12152390T patent/PL2620529T3/pl unknown
- 2012-01-25 ES ES12152390.6T patent/ES2478267T3/es active Active
- 2012-11-27 US US14/374,000 patent/US20150014177A1/en not_active Abandoned
- 2012-11-27 CN CN201280068192.9A patent/CN104080955B/zh active Active
- 2012-11-27 KR KR1020147022888A patent/KR101979975B1/ko active IP Right Grant
- 2012-11-27 CA CA2862141A patent/CA2862141C/en active Active
- 2012-11-27 BR BR112014018114-4A patent/BR112014018114B1/pt active IP Right Grant
- 2012-11-27 JP JP2014553641A patent/JP6086930B2/ja active Active
- 2012-11-27 WO PCT/EP2012/073688 patent/WO2013110373A2/en active Application Filing
- 2012-12-12 TW TW101147026A patent/TWI526582B/zh active
Also Published As
Publication number | Publication date |
---|---|
US20150014177A1 (en) | 2015-01-15 |
WO2013110373A2 (en) | 2013-08-01 |
PL2620529T3 (pl) | 2014-09-30 |
JP6086930B2 (ja) | 2017-03-01 |
BR112014018114A2 (de) | 2017-06-20 |
ES2478267T3 (es) | 2014-07-21 |
CA2862141A1 (en) | 2013-08-01 |
TW201333274A (zh) | 2013-08-16 |
TWI526582B (zh) | 2016-03-21 |
CA2862141C (en) | 2020-03-10 |
CN104080955B (zh) | 2016-03-23 |
KR20140119123A (ko) | 2014-10-08 |
BR112014018114B1 (pt) | 2020-09-01 |
EP2620529A1 (de) | 2013-07-31 |
WO2013110373A3 (en) | 2014-04-24 |
JP2015510038A (ja) | 2015-04-02 |
CN104080955A (zh) | 2014-10-01 |
BR112014018114A8 (pt) | 2017-07-11 |
KR101979975B1 (ko) | 2019-09-03 |
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