EP4001472A1 - Verfahren zur herstellung eines elektroplattierten produktes durch abscheiden einer unterschicht, einer diffusionssperrschicht und einer deckschicht auf der oberfläche eines substrats und so hergestelltes elektroplattiertes produkt - Google Patents

Verfahren zur herstellung eines elektroplattierten produktes durch abscheiden einer unterschicht, einer diffusionssperrschicht und einer deckschicht auf der oberfläche eines substrats und so hergestelltes elektroplattiertes produkt Download PDF

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Publication number
EP4001472A1
EP4001472A1 EP20207754.1A EP20207754A EP4001472A1 EP 4001472 A1 EP4001472 A1 EP 4001472A1 EP 20207754 A EP20207754 A EP 20207754A EP 4001472 A1 EP4001472 A1 EP 4001472A1
Authority
EP
European Patent Office
Prior art keywords
indium
underlayer
electroplated product
layer
top layer
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.)
Withdrawn
Application number
EP20207754.1A
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English (en)
French (fr)
Inventor
Coline Nelias
Stefano BEGLIOMINI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Coventya SpA
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Coventya SpA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Coventya SpA filed Critical Coventya SpA
Priority to EP20207754.1A priority Critical patent/EP4001472A1/de
Priority to CN202180073859.3A priority patent/CN116368267A/zh
Priority to EP21810021.2A priority patent/EP4244409A1/de
Priority to PCT/EP2021/081685 priority patent/WO2022101474A1/en
Publication of EP4001472A1 publication Critical patent/EP4001472A1/de
Withdrawn legal-status Critical Current

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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
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins
    • 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
    • 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/46—Electroplating: Baths therefor from solutions of silver
    • 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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • 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
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50

Definitions

  • the present invention refers to a method for preparing an electroplated product by depositing an underlayer, a barrier diffusion layer and a top layer on a surface of a substrate comprising or consisting of copper or a copper or copper alloy layer wherein the underlayer comprises or consists of a precious metal selected from the group consisting of Au, Ag, Pd, Rh, Ru, Pt and alloys thereof and the top layer comprises or consists of a precious metal selected from the group consisting of Au, Ag, Pd, Rh, Ru, Pt and alloys thereof.
  • the underlayer and the top layer are separated by a barrier diffusion layer comprising or consisting of Indium or an alloy of Indium. This barrier layer prevents the interdiffusion between the underlayer and the top layer.
  • the present invention also refers to an electroplated product obtainable by such a method.
  • the common electroplating sequence comprises a deposition of an underlayer of acid copper on the surface of the substrate to ensure a proper levelling of the substrate roughness followed subsequently by a white bronze layer of 2 to 5 ⁇ m and a thin palladium based layer of a thickness from 0.2 to 0.5 ⁇ m to stop the diffusion of the top precious metal layer, mainly gold or a gold alloy, into the copper or copper alloy underlayer, and most importantly to prevent the diffusion of copper into the precious metal layer.
  • the present bronze technology mainly uses cyanide as a complexing agent to enable the co-deposition of a ternary alloy of copper, tin and zinc, which is also efficient as a copper diffusion barrier.
  • indium on copper can lead to two different problems based on the thickness of the deposit. If the deposit has a low thickness, it could raise doubts for the operator about the presence of the deposit on the surface because of his 'translucid' aspect. A higher thickness could lead to many defects on the deposit, up to obtaining a dull deposit which is unacceptable for aesthetic reasons.
  • EP°3°540°097°A1 discloses electroplated products having a combination of layers used to provide a diffusion barrier layer under a precious metal top layer on a substrate comprising a copper-based material and/or a copper-based underlayer, such that the layer or combination of layers prevents or retards the migration of copper into the precious metal layer or the opposite.
  • the diffusion barrier layer comprises indium or an indium alloy.
  • EP°2°139°012°A1 discloses a silver-coated material for a movable contact component includes an electrically conductive base member that is comprised of copper or a copper alloy; an underlayer that is comprised of nickel or a nickel alloy to coat on the electrically conductive base member; an intermediate layer that is comprised of palladium, or a palladium alloy, or a silver tin alloy, to coat on the underlayer; and an outermost surface layer that is comprised of silver or a silver alloy, and that is formed on the intermediate layer.
  • US°2013/0224515°A1 discloses a thin indium metal layer that is electroplated onto silver to prevent silver tarnishing.
  • the indium and silver composite has high electrical conductivity.
  • EP°3°359°710°A1 discloses a process for deposition of indium or indium alloys and an article obtained by the process, wherein the process comprises the steps:
  • the plating of indium on a precious metal lead to a bright lucid and white deposit. It was further found that this underlayer permits to increase the thickness of the indium barrier while maintaining the brightness. Furthermore, the bath can be operated more easily due to the fact that the electroplating bath is less sensible to parameter variations. It was found out that by using a precious metal underlayer under an indium diffusion barrier layer the barrier properties of the indium diffusion layer can be improved significantly.
  • the electroplating bath of step b) has a pH in the range of 1 to 14, preferably from 2 to 11, and more preferably from 4 to 10.
  • the at least one source of indium ions is selected from the group consisting of indium sulfate, indium chloride, indium acetate, indium sulfamate and combinations or mixtures thereof.
  • the concentration of the at least one source of indium ions of the electroplating bath of step b) is from 0,1 to 20 g/L, preferably from 0,2 to 15 g/L, more preferably from 0,3 to 10 g/L, and even more preferably from 0,5 to 10 g/L.
  • the electroplating bath of step b) contains conductive salts in order to spread the indium distribution throughout the required current density range.
  • the conductive salts are selected and balanced to not only act as a conductive salt but also as a buffering agent.
  • the conductive salts/buffering agents are preferably selected from the group consisting of citrates (e.g. sodium or potassium citrate or their corresponding acidic version), formates (e.g. sodium formate or the corresponding acidic version), pyrophosphates (e.g. tetrapotassium pyrophosphate) and gluconates (e.g. sodium or potassium gluconate), nitrate, carbonate, borate and combinations or mixtures thereof.
  • the electroplating bath of step b) comprises 30 to 600 g/L, more preferably 40 to 500 g/L, and most preferably 100 to 400 g/L of the at least one conductive salt.
  • a concentration in this range is suitable for keeping the pH of the inventive electroplating solution constant for many turnovers (TOs) of the electroplating solution.
  • the brightness of the indium deposit is preferably controlled by adding a surfactant to the electroplating bath of step b).
  • the surfactant acts as a wetting agent and reduces the surface tension to allow indium deposition.
  • the surfactants may belong to the amphoteric family and are selected from the group consisting of propionic amino acids, propionic imino acids, quaternary alkyl betaines or sulfo-betains.
  • the surfactant is preferably selected from the group consisting of betain, aminobetain, imidazoline, cocoamidopropyl betaine, N,N-dimethyl-N-(3-cocoamidopropyl)-N-(2-hydroxy-3-sulfopropyl) ammonium betain, N,N-dimethyl-N-octadecyl-N-(3-sulfopropyl)ammonium betaine, N,N-dimethyl-N-dodecyl-N-(3-sulfopropyl)ammonium betaine and combinations or mixtures thereof.
  • the electroplating bath in step b) comprises preferably from 0.01 to 5 g/L, more preferably from 0.01 to 1.5 g/L of the surfactant.
  • the indium ions may be complexed in solution by a complexing agent.
  • the complexing agent is preferably selected from the group consisting of carbohydrates, amino acids, imino acids, sulfur compounds, sugar alcohols, and combinations or mixtures thereof. More preferably, the complexing agent is selected from the group consisting of sorbitol, mannitol, gluconate, erithrytol, xylitol, nitrilotriacetic acid, cysteine, iminodiacetic acid, triethanolamine and combinations or mixtures thereof. Said complexing agents were found to be perfectly suited for complexing indium ions.
  • the electroplating bath of step b) comprises preferably from 0.5 to 100 g/L, preferably from 1 to 75 g/L, most preferably from 2.5 to 50 g/L, and in particular from 5 to 35 g/L of the complexing agent.
  • a concentration in these ranges is sufficient for complexing the indium ions which are comprised in the inventive electroplating solution.
  • a concentration of complexing agent under 0.5 g/L was found to be detrimental and not able to stabilize the bath at the required pH.
  • electroplating baths with non-complexed indium show a lack of stability at pH above 2 and that the stability is considerably improved with the use of appropriated complexing agents.
  • the sequence of steps a) to c) is not interrupted by any further deposition steps with the consequence that the layers electroplated in step a) to c) abut to each other.
  • the at least one source of the precious metal ion in the electroplating bath of step a) is at least one source of Au and/or Ag ion.
  • the at least one source of the precious metal ion in the electroplating bath of step c) is selected from the group consisting of at least one source of Au, Ag, Pd, Pt ions or combinations thereof, preferably of Au and/or Ag ions.
  • a passivation or a lacquer or a finishing agent layer is deposited on the top layer.
  • the step d) comprises dipping the product obtained in step c) in a chemical solution.
  • an electroplated product comprising a substrate comprising copper or having a copper coating on which with an underlayer comprising or consisting of a precious metal selected from the group consisting of Au, Ag, Pd, Rh, Ru, Pt and alloys thereof and a top layer comprising or consisting of a precious metal selected from the group consisting of Au, Ag, Pd, Rh, Ru, Pt and alloys thereof is deposited.
  • the underlayer and the top layer are separated by a barrier diffusion layer comprising or consisting of Indium or an alloy of Indium with the material of the top layer which prevents the interdiffusion between the underlayer and the top layer.
  • the underlayer has a thickness of 10 to 500 nm, preferably 25 to 400 nm and more preferably 40 to 300 nm.
  • the diffusion barrier layer has a thickness of 1 to 500 nm, preferably 25 to 300 nm and more preferably 50 to 250 nm.
  • the top layer has a thickness of 1 to 500 nm, preferably 3 to 400 nm and more preferably 5 to 300 nm.
  • the top layer consists of a precious metal selected from the group consisting of Au, Ag, Pd, Pt and its alloys, preferably of Au, Ag and its alloys.
  • the first layer consists of gold or gold alloy.
  • a passivation or a lacquer or a finishing agent layer on the top layer.
  • CIE Lab measurement were performed with Minolta CM-503i spectrophotometer. Illuminant used was Daylight D65 (6500K) with reflective component included (sci). Observer was set at standard (10°) and the measurements were performed in the Color space CIE L*a*b*.
  • the GDOES values were measured on a GD-Profiler 2 from Horiba using the software QUANTUM V2.08.
  • the Pressure was set at 650 Pa, Power at 35 W, without Pulse, the Module Voltage 6V and the Phase Voltage 5V.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 6 Layer 1 Copper Copper Copper Copper Copper Copper Copper Copper 10 - 15 ⁇ m 10 - 15 ⁇ m 10 - 15 ⁇ m 10 - 15 ⁇ m 10 - 15 ⁇ m 10 - 15 ⁇ m
  • Layer 2 Gold Indium Indium Gold Gold Gold 0.25 ⁇ m 75 nm 75 nm 50 nm 50 nm 0.1 ⁇ m
  • Layer 3 Gold Indium Indium Indium 0.25 ⁇ m 0.1 ⁇ m 0.1 ⁇ m 0.15 ⁇ m
  • Layer 4 Gold Gold 0.25 ⁇ m 0.25 ⁇ m ⁇ L* -25 1 -2 2 -2 -1 ⁇ a* 17 4 0 2 1 0 ⁇ b* 35 7 -1 23 1 -1
  • Fig.1 confirms that after heating treatment, the copper diffuses in gold reaching the surface.
  • Fig.10 evidences that by choosing a gold top layer the barrier effect can be improved.
EP20207754.1A 2020-11-16 2020-11-16 Verfahren zur herstellung eines elektroplattierten produktes durch abscheiden einer unterschicht, einer diffusionssperrschicht und einer deckschicht auf der oberfläche eines substrats und so hergestelltes elektroplattiertes produkt Withdrawn EP4001472A1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP20207754.1A EP4001472A1 (de) 2020-11-16 2020-11-16 Verfahren zur herstellung eines elektroplattierten produktes durch abscheiden einer unterschicht, einer diffusionssperrschicht und einer deckschicht auf der oberfläche eines substrats und so hergestelltes elektroplattiertes produkt
CN202180073859.3A CN116368267A (zh) 2020-11-16 2021-11-15 用于通过在衬底表面上沉积底层、扩散阻挡层和顶层来制备电镀产品的方法以及这样制备的电镀产品
EP21810021.2A EP4244409A1 (de) 2020-11-16 2021-11-15 Verfahren zur herstellung eines elektroplattierten produktes durch abscheidung einer unterschicht, diffusionsbarriereschicht und deckschicht auf der oberfläche
PCT/EP2021/081685 WO2022101474A1 (en) 2020-11-16 2021-11-15 Method for preparing an electroplated product by depositing an underlayer, diffusion barrier layer and top layer on the surface of a substrate and such prepared electroplated product

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20207754.1A EP4001472A1 (de) 2020-11-16 2020-11-16 Verfahren zur herstellung eines elektroplattierten produktes durch abscheiden einer unterschicht, einer diffusionssperrschicht und einer deckschicht auf der oberfläche eines substrats und so hergestelltes elektroplattiertes produkt

Publications (1)

Publication Number Publication Date
EP4001472A1 true EP4001472A1 (de) 2022-05-25

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EP20207754.1A Withdrawn EP4001472A1 (de) 2020-11-16 2020-11-16 Verfahren zur herstellung eines elektroplattierten produktes durch abscheiden einer unterschicht, einer diffusionssperrschicht und einer deckschicht auf der oberfläche eines substrats und so hergestelltes elektroplattiertes produkt
EP21810021.2A Pending EP4244409A1 (de) 2020-11-16 2021-11-15 Verfahren zur herstellung eines elektroplattierten produktes durch abscheidung einer unterschicht, diffusionsbarriereschicht und deckschicht auf der oberfläche

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EP21810021.2A Pending EP4244409A1 (de) 2020-11-16 2021-11-15 Verfahren zur herstellung eines elektroplattierten produktes durch abscheidung einer unterschicht, diffusionsbarriereschicht und deckschicht auf der oberfläche

Country Status (3)

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EP (2) EP4001472A1 (de)
CN (1) CN116368267A (de)
WO (1) WO2022101474A1 (de)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3367754A (en) * 1965-02-03 1968-02-06 Gen Dynamics Corp Electronic transmission material and method of fabrication
EP2139012A1 (de) 2007-03-27 2009-12-30 The Furukawa Electric Co., Ltd. Silberbeschichtetes material für eine bewegliche kontaktkomponente und verfahren zur herstellung eines solchen silberbeschichteten materials
US20130224515A1 (en) 2012-02-29 2013-08-29 Rohm And Haas Electronic Materials Llc Method of preventing silver tarnishing
WO2015000010A1 (de) * 2013-07-05 2015-01-08 Ing. W. Garhöfer Gesellschaft M.B.H. Elektrolytbad sowie objekte bzw. artikel, die mithilfe des bades beschichtet werden
EP3359710A1 (de) 2015-10-06 2018-08-15 ATOTECH Deutschland GmbH Verfahren zur abscheidung von indium oder einer indiumlegierung und artikel
EP3540097A1 (de) 2018-03-13 2019-09-18 COVENTYA S.p.A. Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3367754A (en) * 1965-02-03 1968-02-06 Gen Dynamics Corp Electronic transmission material and method of fabrication
EP2139012A1 (de) 2007-03-27 2009-12-30 The Furukawa Electric Co., Ltd. Silberbeschichtetes material für eine bewegliche kontaktkomponente und verfahren zur herstellung eines solchen silberbeschichteten materials
US20130224515A1 (en) 2012-02-29 2013-08-29 Rohm And Haas Electronic Materials Llc Method of preventing silver tarnishing
WO2015000010A1 (de) * 2013-07-05 2015-01-08 Ing. W. Garhöfer Gesellschaft M.B.H. Elektrolytbad sowie objekte bzw. artikel, die mithilfe des bades beschichtet werden
EP3359710A1 (de) 2015-10-06 2018-08-15 ATOTECH Deutschland GmbH Verfahren zur abscheidung von indium oder einer indiumlegierung und artikel
EP3540097A1 (de) 2018-03-13 2019-09-18 COVENTYA S.p.A. Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte

Also Published As

Publication number Publication date
EP4244409A1 (de) 2023-09-20
WO2022101474A1 (en) 2022-05-19
CN116368267A (zh) 2023-06-30

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