EP2620529B1 - Procédé de production de dépôts de cuivre mate - Google Patents

Procédé de production de dépôts de cuivre mate Download PDF

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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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EP12152390.6A
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German (de)
English (en)
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EP2620529A1 (fr
Inventor
Stefan Kretschmer
Dr. Philip Hartmann
Dr. Bernd Roelfs
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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Priority to PL12152390T priority Critical patent/PL2620529T3/pl
Application filed by Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Priority to ES12152390.6T priority patent/ES2478267T3/es
Priority to EP12152390.6A priority patent/EP2620529B1/fr
Priority to BR112014018114-4A priority patent/BR112014018114B1/pt
Priority to JP2014553641A priority patent/JP6086930B2/ja
Priority to CN201280068192.9A priority patent/CN104080955B/zh
Priority to US14/374,000 priority patent/US20150014177A1/en
Priority to CA2862141A priority patent/CA2862141C/fr
Priority to PCT/EP2012/073688 priority patent/WO2013110373A2/fr
Priority to KR1020147022888A priority patent/KR101979975B1/ko
Priority to TW101147026A priority patent/TWI526582B/zh
Publication of EP2620529A1 publication Critical patent/EP2620529A1/fr
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Publication of EP2620529B1 publication Critical patent/EP2620529B1/fr
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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)

  1. Procédé de dépôt d'un revêtement de cuivre mat comprenant, dans cet ordre, les étapes consistant à
    a. se procurer un substrat,
    b. déposer une première couche de cuivre sur le substrat à partir d'un premier électrolyte aqueux comprenant une source d'ions cuivre, au moins un acide et au moins un composé de polyéther, ledit premier électrolyte ne contenant pas de composé organique comprenant du soufre divalent, et
    c. déposer une deuxième couche de cuivre sur la première couche de cuivre à partir d'un deuxième électrolyte aqueux comprenant une source d'ions cuivre, au moins un acide, un premier additif contenant du soufre hydrosoluble choisi dans le groupe constitué par les dérivés alkyliques d'acide sulfonique et un deuxième additif contenant du soufre hydrosoluble choisi dans le groupe constitué par les dérivés aromatiques d'acide sulfonique,
    dans lequel une densité de courant est appliquée au substrat pendant l'étape b et c.
  2. Procédé de dépôt d'un revêtement de cuivre mat selon la revendication 1 dans lequel l'au moins un composé de polyéther dans le premier électrolyte est choisi dans le groupe constitué par les polyalkylène glycols et les polyglycérines.
  3. Procédé de dépôt d'un revêtement de cuivre mat selon l'une quelconque des revendications précédentes dans lequel l'au moins un composé de polyéther dans le premier électrolyte est choisi dans le groupe constitué par le poly(1,2,3-propanetriol), le poly(2,3-époxy-1-propanol) et les dérivés de ceux-ci.
  4. Procédé de dépôt d'un revêtement de cuivre mat selon l'une quelconque des revendications précédentes dans lequel l'au moins un composé de polyéther dans le premier électrolyte est choisi dans le groupe constitué par les composés répondant aux formules (1), (2) et (3) :
    Figure imgb0023
     dans laquelle n est un entier de 1 à 80 ;
    Figure imgb0024
     dans laquelle n est un entier > 1 et m est un entier > 1, à condition que n+m soit ≤ 30 ;
    Figure imgb0025
     dans laquelle n est un entier de 1 à 80 ;
    et dans lesquelles
    R6, R7, R8 et R9 sont identiques ou différents et sont choisis dans le groupe comprenant l'hydrogène et les groupes alkyle, acyle, phényle et benzyle.
  5. Procédé de dépôt d'un revêtement de cuivre mat selon la revendication 4 dans lequel le poids moléculaire des composés répondant aux formules (1), (2) et (3) va de 160 à 6000 g/mol.
  6. Procédé de dépôt d'un revêtement de cuivre mat selon l'une quelconque des revendications précédentes dans lequel la concentration de l'au moins un composé de polyéther dans le premier électrolyte va de 0,005 g/l à 5 g/l.
  7. Procédé de dépôt d'un revêtement de cuivre mat selon l'une quelconque des revendications précédentes dans lequel le premier additif contenant du soufre hydrosoluble dans le deuxième électrolyte est choisi dans le groupe constitué par les composés répondant aux formules (4) et (5) :
    R1S-(CH2)n-SO3R2 (4)
    R3SO3-(CH2)m-S-S-(CH2)m-SO3R3 (5)
    dans lesquelles
    R1 est choisi dans le groupe constitué par l'hydrogène, le méthyle, l'éthyle, le propyle, le butyle, le lithium, le sodium, le potassium et l'ammonium,
    n va de 1 à 6,
    R2 est choisi dans le groupe constitué par l'hydrogène, le méthyle, l'éthyle, le propyle, le butyle, le lithium, le sodium, le potassium et l'ammonium,
    R3 est choisi dans le groupe constitué par l'hydrogène, le méthyle, l'éthyle, le propyle, le butyle, le lithium, le sodium, le potassium et l'ammonium, et
    m va de 1 à 6.
  8. Procédé de dépôt d'un revêtement de cuivre mat selon l'une quelconque des revendications précédentes dans lequel la concentration du premier additif contenant du soufre hydrosoluble dans le deuxième électrolyte va de 0,0001 à 0,05 g/l.
  9. Procédé de dépôt d'un revêtement de cuivre mat selon l'une quelconque des revendications précédentes dans lequel le deuxième additif contenant du soufre hydrosoluble dans le deuxième électrolyte est choisi dans le groupe constitué par les composés répondant aux formules (6) et (7) :

            R4Sy X-SO3     (6)

    dans laquelle R4 est choisi dans le groupe constitué par
    Figure imgb0026
     et l'hydrogène ;
    X est choisi dans le groupe constitué par
    Figure imgb0027
     y est un entier valant de 1 à 4 ; et
    M est choisi dans le groupe constitué par l'hydrogène, le sodium, le potassium et l'ammonium ; et
    Figure imgb0028
     dans laquelle R5 est choisi dans le groupe constitué par H, SH et SO3M et M est choisi dans le groupe constitué par l'hydrogène, le sodium, le potassium et l'ammonium.
  10. Procédé de dépôt d'un revêtement de cuivre mat selon l'une quelconque des revendications précédentes dans lequel la concentration du deuxième additif contenant du soufre hydrosoluble dans le deuxième électrolyte va de 0,005 à 1 g/l.
  11. Procédé de dépôt d'un revêtement de cuivre mat selon l'une quelconque des revendications précédentes dans lequel le deuxième électrolyte comprend en outre au moins un additif de support.
  12. Procédé de dépôt d'un revêtement de cuivre mat selon la revendication 11 dans lequel l'au moins un additif de support est choisi dans le groupe constitué par l'alcool polyvinylique, la carboxyméthylcellulose, le polyéthylène glycol, le polypropylène glycol, l'ester de polyglycol d'acide stéarique, les naphtoles alcoxylés, l'ester de polyglycol d'acide oléique, l'éther de polyglycol d'alcool stéarylique, l'éther de polyglycol de nonylphénol, l'éther de polyalkylène glycol d'octanol, le bis-(éther de polyalkylène glycol) d'octanediol, le poly(éthylène glycol-ran-propylène glycol), le poly(éthylène glycol)-bloc-poly(propylène glycol)-bloc-poly(éthylène glycol) et le poly(propylène glycol)-bloc-poly(éthylène glycol)-bloc-poly(propylène glycol).
  13. Procédé de dépôt d'un revêtement de cuivre mat selon les revendications 11 et 12 dans lequel la concentration de l'au moins un additif de support dans le deuxième électrolyte va de 0,005 g/l à 5 g/l.
EP12152390.6A 2012-01-25 2012-01-25 Procédé de production de dépôts de cuivre mate Active EP2620529B1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
ES12152390.6T ES2478267T3 (es) 2012-01-25 2012-01-25 Método para producir depósitos de cobre mate
EP12152390.6A EP2620529B1 (fr) 2012-01-25 2012-01-25 Procédé de production de dépôts de cuivre mate
PL12152390T PL2620529T3 (pl) 2012-01-25 2012-01-25 Sposób wytwarzania matowych warstw miedzianych
JP2014553641A JP6086930B2 (ja) 2012-01-25 2012-11-27 つや消し銅めっきの製造方法
CN201280068192.9A CN104080955B (zh) 2012-01-25 2012-11-27 制造无光泽铜沉积的方法
US14/374,000 US20150014177A1 (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
CA2862141A CA2862141C (fr) 2012-01-25 2012-11-27 Procede de production de depots de cuivre mat
PCT/EP2012/073688 WO2013110373A2 (fr) 2012-01-25 2012-11-27 Procédé de production de dépôts de cuivre mat
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

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Application Number Priority Date Filing Date Title
EP12152390.6A EP2620529B1 (fr) 2012-01-25 2012-01-25 Procédé de production de dépôts de cuivre mate

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EP2620529A1 EP2620529A1 (fr) 2013-07-31
EP2620529B1 true EP2620529B1 (fr) 2014-04-30

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EP (1) EP2620529B1 (fr)
JP (1) JP6086930B2 (fr)
KR (1) KR101979975B1 (fr)
CN (1) CN104080955B (fr)
BR (1) BR112014018114B1 (fr)
CA (1) CA2862141C (fr)
ES (1) ES2478267T3 (fr)
PL (1) PL2620529T3 (fr)
TW (1) TWI526582B (fr)
WO (1) WO2013110373A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
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WO2020096906A1 (fr) 2018-11-07 2020-05-14 Coventya, Inc. Bain de cuivre satiné et procédé de dépôt d'une couche de cuivre satiné
US11384446B2 (en) 2020-08-28 2022-07-12 Macdermid Enthone Inc. Compositions and methods for the electrodeposition of nanotwinned copper
JP2024530122A (ja) * 2021-08-05 2024-08-16 マクダーミッド エンソン インコーポレイテッド ナノ双晶銅の電着のための組成物及び方法

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA739310B (en) * 1972-12-14 1974-11-27 M & T Chemicals Inc Electrode position of copper
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
US6679983B2 (en) * 2000-10-13 2004-01-20 Shipley Company, L.L.C. Method of electrodepositing copper
US6649038B2 (en) * 2000-10-13 2003-11-18 Shipley Company, L.L.C. Electroplating method
BR0114600B1 (pt) * 2000-10-19 2011-04-05 banho de revestimento eletrolìtico de cobre e processo de eletroposição de uma camada fosca de cobre.
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
EP2143828B1 (fr) * 2008-07-08 2016-12-28 Enthone, Inc. Electrolyte et procédé de dépôt d'une couche de métal 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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BR112014018114A2 (fr) 2017-06-20
KR101979975B1 (ko) 2019-09-03
BR112014018114A8 (pt) 2017-07-11
JP2015510038A (ja) 2015-04-02
JP6086930B2 (ja) 2017-03-01
CA2862141A1 (fr) 2013-08-01
WO2013110373A2 (fr) 2013-08-01
BR112014018114B1 (pt) 2020-09-01
CA2862141C (fr) 2020-03-10
TWI526582B (zh) 2016-03-21
WO2013110373A3 (fr) 2014-04-24
TW201333274A (zh) 2013-08-16
US20150014177A1 (en) 2015-01-15
PL2620529T3 (pl) 2014-09-30
KR20140119123A (ko) 2014-10-08
CN104080955A (zh) 2014-10-01
EP2620529A1 (fr) 2013-07-31
ES2478267T3 (es) 2014-07-21
CN104080955B (zh) 2016-03-23

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