EP3540097A1 - Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte - Google Patents

Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte Download PDF

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Publication number
EP3540097A1
EP3540097A1 EP18161575.8A EP18161575A EP3540097A1 EP 3540097 A1 EP3540097 A1 EP 3540097A1 EP 18161575 A EP18161575 A EP 18161575A EP 3540097 A1 EP3540097 A1 EP 3540097A1
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Prior art keywords
indium
gold
copper
electroplated product
group
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EP18161575.8A
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English (en)
French (fr)
Inventor
Coline Nelias
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Coventya SpA
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Coventya SpA
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Priority to EP18161575.8A priority Critical patent/EP3540097A1/de
Priority to EP19709513.6A priority patent/EP3765658B1/de
Priority to PCT/EP2019/056328 priority patent/WO2019175270A1/en
Priority to ES19709513T priority patent/ES2970912T3/es
Publication of EP3540097A1 publication Critical patent/EP3540097A1/de
Withdrawn legal-status Critical Current

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    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • 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
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight 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
    • 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
    • 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

Definitions

  • the present invention relates to 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.
  • the present invention refers a method for preparing such an electroplated product.
  • the common electroplating sequence comprises electroplating on the substrate a first layer of acid copper to ensure a proper levelling of the substrate roughness followed by a white bronze layer of 2 to 5 ⁇ m and by 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.
  • WO2016/166330 A1 describes an electroplated product with a precious metal finishing layer that has an improved corrosion and abrasion resistance.
  • the electroplated product comprises two electroplated copper alloy layers having a different copper concentration (e.g. white bronze and yellow bronze). Another advantage of the electroplated product is that the use of allergenic nickel or expensive palladium intermediate layers against copper migration can be dispensed with.
  • WO2017/055553 A1 describes an electroplating bath for electrochemical deposition of a novel Cu-Sn-Zn-Pd alloy on a substrate.
  • the novel alloy is characterized by improved corrosion resistance but is based on cyanide media.
  • the metal indium is nowadays used mainly for photovoltaic applications due to its high thermal conductivity ( ⁇ 82 W/mK). It also has other unique physical properties which make it very useful in numerous industries. For example, it is sufficiently soft such that it is readily deformed and fills microstructures between two mating parts, has a low melting temperature (156° C). Such properties recommend indium for various uses in the electronics and related industries.
  • WO2015/000010 A1 describes a bath for the cathodic deposition of ternary bronze alloys.
  • the electrolyte composition comprises indium as a third metallic alloying constituent.
  • a ternary copper-tin-indium alloy is deposited directly on an optional copper layer.
  • EP 1 930 478 A1 teaches an electrolyte composition as well as a method for the deposition of another quaternary copper alloy on a substrate.
  • the electrolyte composition comprises besides the alloying metals copper, tin and zinc, at least one metal from the group consisting of indium and gallium providing white bronze layers free of noxious heavy metals.
  • the previously mentioned documents are based on baths containing cyanide. Cyanide based solutions have several disadvantages associated with the high toxicity of the electrolyte, difficulties associated with storage and transportation of the cyanide salts and solutions, and costs associated with the wastewater treatments.
  • Several attempts have been made to formulate cyanide free ternary bronze to substitute the dangerous complexing agent but none of them fulfils the market requirements to prevent the gold and copper inter diffusion as well as to maintain a bright and shiny aspect of the electroplated layers.
  • WO2004/035875 A3 refers to a method for bronze galvanic coating which consists of metallizing a substrate to be coated by its immersion into an acidic electrolyte which contains at least tin and copper ions.
  • the acidic electrolyte used for bronze coating is also disclosed.
  • WO2013/092314 cites an aqueous alkaline electrolyte, which is cyanide-free, pyrophosphate-free and phosphonic acid-free for depositing a ternary alloy comprising copper and tin present in dissolved form and zinc present as a zinc salt.
  • KR1168215 B1 teaches a copper-tin alloy plating film, a non-cyanide-based copper-tin alloy plating bath, and a plating method using the same. However, the deposit was not a barrier to copper diffusion.
  • the US 2,458,839 A teaches a bath which comprises at least 20 g/L of indium. However, with such high concentrations that no thin bright layers can be provided.
  • WO2009/097360 A1 describes an electroplating solution for the deposition of a pure indium film on a conductive surface useful in fabricating electronic devices.
  • the indium electroplating solutions are used to deposit indium films which are compositionally pure, uniform, substantially free of defects and smooth. Such films can be plated with almost 100% plating efficiency.
  • sub-micron thick indium layers are described. Such indium layers are used in fabrication of electronic devices such as thin film solar cells.
  • EP 2 123 799 B1 teaches a method to prevent silver from tarnishing by electroplating a thin indium metal layer onto a silver substrate.
  • the indium and silver composite has high electrical conductivity.
  • WO2017/060216 A1 teaches a process for indium or indium alloy deposition and for the formation of very smooth and glossy indium or indium alloy layers and their use in electronic and semiconductor devices, in particular interconnections used in electronic and semiconductor industries such as flip chips, tape automated bonding and the like.
  • a method for preparing an electroplated product by electroplating a substrate comprising the following steps:
  • indium has been found to be an efficient copper diffusion barrier, able with very low thickness to prevent copper migration to the top gold layer and thus preventing the article from undesirable change of colour.
  • the indium in the diffusion barrier layer which is deposited between the copper or copper alloy underlayer and the precious metal or precious metal alloy top layer, can migrate into the precious metal top layer, but prevents the interdiffusion between the underlayer and the top layer.
  • an underlayer consisting of copper or a copper alloy is obtained by electrodeposition from a copper electroplating solution.
  • This copper electroplating solution is generally very acidic as it contains up to 60 g/L of 98% sulfuric acid. It produces a bright deposit with high levelling characteristics. The deposits are free of pits even at high thicknesses.
  • the electroplated copper thicknesses can vary from 5 to 60 ⁇ m depending on the substrate and the targeted properties.
  • the function of the top layer consisting of a precious metal selected from the group consisting of Au, Ag, Pd, Rh, Ru, Pt and its alloys is highly decorative, it must be of a constant colour and give a very uniform and generally bright aspect to the final item.
  • the thickness is generally low due to the cost of the precious metals used. It typically varies between 0.05 ⁇ m up to 5 ⁇ m preferably between 0.1 and 1 ⁇ m. It is absolutely necessary that the top layer colour and aspects are not affected by the copper underlayer. In the absence of a proper diffusion barrier, the interdiffusion of the copper or copper rich underlayer and the top finishing layer will lead to a non-acceptable finish of the part upon ageing or storage. That is why it is so important to provide an intermediate layer that prevents the interdiffusion of the copper rich underlayer and the precious metal top layer.
  • the electroplating bath of step b) preferably has a pH in the range of 1 to 14, more preferably of 2 to 11, and most preferably of 4 to 10.
  • the at least one source of indium ion in the electroplating bath of step b) is preferably selected from the group consisting of indium sulfate, indium chloride, indium acetate, indium sulfamate and its combinations or mixtures. Considering the cost of this valuable metal, the source of indium ion should be affordable.
  • the bath has a concentration of indium as a metal of 0.1 to 20 g/L, preferably 0.2 to 15 g/L, more preferably 0.3 to 10 g/L, most preferably 0.5 to 7 g/L.
  • a concentration in these ranges is sufficient to obtain the suitable aspect of the indium thin layer.
  • a concentration of indium above 20 g/L was found to be detrimental to maintain brightness and thickness distribution.
  • the electroplating bath 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), formiates (e.g. sodium formiate or the corresponding acidic version), pyrophosphates (e.g. tetrapotassium pyrophosphate) and gluconates (e.g. sodium or potassium gluconate) and combinations or mixtures thereof.
  • the at least one conductive salt has a concentration of 30 to 500 g/L, more preferably 50 to 300 g/L, and most preferably 100 to 200 g/L.
  • 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 controlled by the introduction of a surfactant.
  • the surfactant acts as a wetting agent and reduces the surface tension to allow indium electroplating.
  • 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 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 surfactant concentration according to the invention is preferably from 0.1 to 5 g/L, more preferably from 0.5 to 1.5 g/L.
  • 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 concentration of the complexing agent in the bath is 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. 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.
  • the diffusion barrier layer consists of an alloy of indium with the material of the top layer, which is preferably gold.
  • Such a diffusion barrier layer of gold and indium allows to strongly reduce copper migration.
  • the electroplating bath comprises at least one source of gold ions, preferably selected from the group consisting of potassium gold (I) cyanide , sodium gold(I) sulphite, potassium gold(III) cyanide , gold (III) chloride and tetrachloroaurates(III), gold(I) thioglycerol and gold(I) and gold(III) hydantoin complexes, and combinations or mixtures thereof.
  • a source of gold ions preferably selected from the group consisting of potassium gold (I) cyanide , sodium gold(I) sulphite, potassium gold(III) cyanide , gold (III) chloride and tetrachloroaurates(III), gold(I) thioglycerol and gold(I) and gold(III) hydantoin complexes, and combinations or mixtures thereof.
  • the concentration of the at least one source of gold is preferably from 0.5 to 10 g/L, more preferably from 1 to 5 g/L and most preferably from 2.5 to 3.5 g/L.
  • the concentration of indium in the electroplating bath is preferably from 0.1 to 20 g/L, more preferably from 0.2 to 15 g/L and most preferably from 0.25 to 0.75 g/L.
  • steps a) to c) is not interrupted by further deposition steps with the consequence that the layers electroplated in step a) to c) abut to each other.
  • an electroplated product which comprises a substrate which is coated with an underlayer consisting of copper or a copper alloy and a top layer consisting 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 diffusion barrier layer consisting of indium or an alloy of indium with the material of the top layer
  • the diffusion barrier layer has preferably a thickness of 10 to 200 nm, more preferably 25 to 150 nm and most preferably 50 to 100 nm. It has been determined that a thickness of the indium intermediate layer of less than 50 nm does not prevent the diffusion of copper into the gold. A thickness above 200 nm leads to poor brightness and presents a powdering aspect.
  • the diffusion barrier layer comprises an gold indium alloy, preferably with 90 to 95 % by weight of gold and 5 to 10 % by weight of indium.
  • the electroplated products are preferably selected from the group consisting of jewelry, leather goods, spectacle frame, fashion, watch, trinkets and/or lock industry.
  • the copper plated panels were then plated with various subsequent layers using different electrolytes.
  • GDOES measurements GDOES (glow discharge optical emission spectrometry) principle
  • the sample forms the cathode and a thin (4 mm diameter) copper tube forms the anode.
  • a small O-ring separates the anode from the cathode.
  • High-purity argon is pumped into the anode chamber.
  • a high voltage (DC or RF) between sample and anode ionizes the argon to produce a glow discharge plasma.
  • the excited argon ions bombard the electroplated product sample and cause uniform sputtering of the sample surface. Atoms ejected are then excited by the argon plasma, and finally relax to their fundamental energy level, emitting a characteristic X-ray photon.
  • Emitted photons whose energy is characteristic of the energy level of a chemical element, are then collected by photomultipliers.
  • the intensity of each emission depends on the concentration of the element in the sample.
  • the recorded signals are processed to obtain the distribution of the elements according to the erosion time.
  • GDOES provides a depth profiling analysis of solids like metals, powders, polymers, glasses and ceramics (in the present case: depth profiling of electroplated substrates).
  • GDOES GDOES-like e.g. C, N and O.
  • the spectrum obtained represents the qualitative intensity of the metallic signal variation depending on time of sputtering in s.
  • Figs. 4 to 9 give the GDOES depth profiles for the different electroplated products of Examples 1 to 6 before and after the heat treatment at 180°C for 24 hours.
  • concentration of each chemical element Au, Cu, In and optionally Sn and Zn for reference is shown (y-axis for intensity) as a function of the distance from the surface of the finishing layer towards the base material of the electroplated product (x-axis for erosion time).
  • Table 2 Samples analyzed by GDOES analysis Copper thickness 15 ⁇ m 15 ⁇ m 15 ⁇ m 15 ⁇ m 15 ⁇ m 15 ⁇ m 15 ⁇ m Layer 1 GOLD White bronze Indium Indium Gold-Indium alloy %Au 95 %In 5 Gold-Indium alloy %Au 90 %In 10 Thickness layer 1 0,5 ⁇ m 3 ⁇ m 100 nm 100 nm 0,5 ⁇ m 0,5 ⁇ m Layer 2 - GOLD GOLD GOLD - - Thickness layer 2 - 0,5 ⁇ m 0,5 ⁇ m 0,5 ⁇ m - - REF example Comparative EX 1 Comparative EX 2 EX 3 EX 4 EX 5 EX 6 REF Figure (without thermal treatment) 4a 5a 6a 7a 8a 9a REF Figure (with thermal treatment) 4b 5b 6b 7b 8b 9b
  • Fig. 5a is the profile of a sample reported in Example 2 before heat treatment. We can see that each layer is well-defined, and no copper is present in the gold layer.
  • Example 3 according to the present invention the following sequence was used on the reference brass panels:
  • Example 3 From Example 3 according to the invention, it can be seen from Fig. 6a that the thin intermediate layer of indium is located between the copper and the top gold top layer.
  • the resulting top layer is an alloy of gold and indium that contains only very little if any copper. Obviously, copper migration to the surface was inhibited.
  • the top layer is composed of an Au-In alloy as a cover layer for the Cu under layer (and the substrate). It appears, therefore, that In can be employed as a copper diffusion barrier between a copper or copper alloy substrate and a gold surface layer in a way similar to the action of a nickel or palladium barrier commonly used until recently.
  • Example 5 according to the present invention the following sequence was used on the reference brass panels:
  • Example 5 according to the present invention the following sequence was used on the reference brass panels:
  • the gold-indium alloy (Au 90-95 % : In 5-10 %) layer can strongly reduce the copper migration during the thermal treatment procedure.
  • the interface between the copper layer and the gold-indium alloys is well defined in both cases and no copper migration is observed from the bottom copper layer.

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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)
EP18161575.8A 2018-03-13 2018-03-13 Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte Withdrawn EP3540097A1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP18161575.8A EP3540097A1 (de) 2018-03-13 2018-03-13 Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte
EP19709513.6A EP3765658B1 (de) 2018-03-13 2019-03-13 Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte
PCT/EP2019/056328 WO2019175270A1 (en) 2018-03-13 2019-03-13 Electroplated products and electroplating bath for providing such products
ES19709513T ES2970912T3 (es) 2018-03-13 2019-03-13 Productos galvanizados y baño de galvanoplastia para proporcionar dichos productos

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EP18161575.8A EP3540097A1 (de) 2018-03-13 2018-03-13 Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte

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EP19709513.6A Active EP3765658B1 (de) 2018-03-13 2019-03-13 Elektroplattierte produkte und elektroplattierungsbad zur bereitstellung solcher produkte

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022101474A1 (en) * 2020-11-16 2022-05-19 Coventya S.P.A. 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
CN114540895A (zh) * 2022-03-01 2022-05-27 九牧厨卫股份有限公司 一种杀菌灰色复合镀层及其制备方法和灰色杀菌产品

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114525553B (zh) * 2022-03-01 2023-05-30 九牧厨卫股份有限公司 一种蓝白色复合镀层及其制备方法和蓝白色杀菌产品

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WO2017055553A1 (en) 2015-09-30 2017-04-06 Coventya S.P.A. Electroplating bath for electrochemical deposition of a cu-sn-zn-pd alloy, method for electrochemical deposition of said alloy, substrate comprising said alloy and uses of the substrate
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US2458839A (en) 1944-04-19 1949-01-11 Indium Corp America Electrodeposition of indium and its alloys
US3367754A (en) * 1965-02-03 1968-02-06 Gen Dynamics Corp Electronic transmission material and method of fabrication
WO2004035875A2 (de) 2002-10-11 2004-04-29 Enthone Inc. Verfahren zur galvanischen abscheidungvon bronzen
EP1930478A1 (de) 2006-12-06 2008-06-11 Enthone, Inc. Zusammensetzung eines Elektrolyten und Verfahren zur Beschichtung von quaternären Kupferlegierungen
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CN114540895B (zh) * 2022-03-01 2023-05-30 九牧厨卫股份有限公司 一种杀菌灰色复合镀层及其制备方法和灰色杀菌产品

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