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WO2013092314A1 - Dépôt d'alliages cuivre-étain-zinc à partir d'un électrolyte - Google Patents

Dépôt d'alliages cuivre-étain-zinc à partir d'un électrolyte Download PDF

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Publication number
WO2013092314A1
WO2013092314A1 PCT/EP2012/075113 EP2012075113W WO2013092314A1 WO 2013092314 A1 WO2013092314 A1 WO 2013092314A1 EP 2012075113 W EP2012075113 W EP 2012075113W WO 2013092314 A1 WO2013092314 A1 WO 2013092314A1
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WO
WIPO (PCT)
Prior art keywords
electrolyte
copper
range
tin
zinc
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.)
Ceased
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PCT/EP2012/075113
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English (en)
Inventor
Klaus Bronder
Uwe Manz
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.)
Umicore Galvanotechnik GmbH
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Umicore Galvanotechnik GmbH
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 Umicore Galvanotechnik GmbH filed Critical Umicore Galvanotechnik GmbH
Publication of WO2013092314A1 publication Critical patent/WO2013092314A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • 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
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper

Definitions

  • the present invention relates to a cyanide-free, pyrophosphate-free and phosphonic acid-free electrolyte and a process for the electrolytic deposition of a ternary alloy of the elements copper, tin and zinc.
  • the electrolyte and the process are characterized in that not only zinc (II) ions and stannate anions but also copper ions are present in the electrolyte used.
  • the copper and zinc ions are present in a particular molar ratio relative to one another.
  • the solderability of the resulting layer and possibly its mechanical strength are the critical properties of the layer to be produced.
  • the appearance of the layers is generally less important than their functionality for use in this field.
  • the decorative effect and also durability of the layer with an ideally unchanged appearance are the important target parameters in the production of bronze or brass layers on consumer goods.
  • Cyanide-free electrolytic baths for the deposition of brass layers may be found, for example, in EP 790332. There, not only the copper and zinc, which can be added as pyrophosphate salts to the electrolyte, but also metal polyphosphates are added to the electrolyte. Possible metal polyphosphates are pyrophosphate salts of sodium, potassium, magnesium or calcium. The deposition of copper-zinc-tin layers is not described here.
  • EP 1 146148 describes a cyanide-free copper-tin electrolyte which contains the reaction product of an amine and an epichlorohydrin in a molar ratio of 1 :1 and also a cationic surfactant.
  • the amine can be hexamethylene tetramine.
  • JP 10102278 and US 6416571 describe baths for the deposition of copper-tin alloys.
  • Cyanide-free electrolytic baths for the deposition of bronze layers are likewise adequately known.
  • WO 2009109271 reports that copper and tin can be deposited together from appropriate baths which have a large excess of pyrophosphate ions. All these teachings disclose exclusively the deposition of bronzes, i.e. copper-tin alloys.
  • a ternary alloy consisting of copper, tin and zinc from a cyanide-free electrolyte is disclosed, for example, in EP 21 16634.
  • a high concentration of pyrophosphate anions in the electrolyte but also a specific reaction product of hexamethylene tetramines and epichlorohydrin at a virtually neutral pH of the electrolyte are used.
  • US20010014407 mentions in passing the deposition of a ternary alloy of Cu/Sn/Zn on copper surfaces as corrosion protection. Relatively low-tin alloys are obtained from the pyrophosphate-containing electrolyte.
  • US20100147696 discloses the deposition of Cu-Zn-Sn alloy from electrolytes containing phosphonic acid. The deposition processes described here give white coatings which are, however, relatively low in zinc.
  • a cyanide-free electrolyte for the deposition of ternary copper-zinc-tin alloys is described in Thin Solid Films, 517 (2009) 251 1 -2514.
  • a layer which is not defined in more detail is deposited from an alkaline electrolyte containing the metals copper in the oxidation state +2, zinc in the oxidation state +2 and tin in the oxidation state +4.
  • the electrolyte described here is said to contain a ten-fold excess of tin and lead only to low-copper deposits.
  • EP 2037006 describes the electrolytic deposition of copper-tin-zinc alloys in a very particular atom ratio.
  • the layers deposited have a composition which is said to be close to the formula Cu2ZnSn.
  • the layers obtained in this way serve as base layer for the production of kesterite (CZTS or Cu2ZnSn(S,Se)4) which is a promising material for the production of photovoltaically active molecules (Solar Energy Materials & Solar Cells 201 1 , 95, 2136-2140; Chemical Physics Letters 201 1 , 501 , 619-622).
  • a correspondingly produced Cu2ZnSn layer is subsequently converted by reaction with sulphur or sulphur-containing compounds at elevated temperatures into the corresponding kesterite phase (e.g.: Thin Solid Films 2009, 517, 2465-2468).
  • sulphur or sulphur-containing compounds at elevated temperatures into the corresponding kesterite phase
  • Such a procedure is likewise addressed in EP 2037006.
  • the specific electrolytically produced Cu2ZnSn deposits are obtained from an electrolyte to which particular disubstituted benzene derivatives have been added.
  • the copper and zinc ions can be added as pyrophosphates to the electrolyte.
  • the tin is preferably used as stannate.
  • the electrolytes described for the deposition of the ternary alloy of copper, tin and zinc obviously all have only a low ability to deposit a desired ternary alloy composition of this type when, for example, specific additional additives are not added to the electrolyte or extremely high tin-IV concentrations are not present in the electrolyte.
  • the alkaline bath-stabilizing additives such as pyrophosphates, phosphonic acid or cyanides are also frequently used. The additional complexity caused thereby makes the production and processing of the electrolytes unattractive.
  • the electrolyte should ideally have a simple composition and be sufficiently stable.
  • the process and the electrolyte according to the invention should also be superior to the processes and electrolytes known from the prior art from ecological and economic points of view.
  • an aqueous, cyanide-free, pyrophosphate-free and phosphonic acid-free, basic electrolyte in which the proportion of copper in the alloy is in the range from 38 to 44% by weight, the proportion of tin is in the range from 34 to 42% by weight and the proportion of zinc is in the range from 16 to 26% by weight, which contains the metals copper and zinc to be deposited in ionically dissolved form and tin as water-soluble stannate salt and where the electrolyte has a molar ratio of copper ions to zinc ions in the range from 1 :1 to 1 :10, for the deposition of a ternary alloy leads, extremely surprisingly but no less advantageously, to achievement of the stated object.
  • the target alloy composition can also be achieved using the electrolyte described here when no stabilizing cyanides, pyrophosphates or phosphonic acid derivates are present in the electrolyte.
  • the electrolyte is stable, despite expectations. Any turbidity occurring will be redissolved with the addition of the water-soluble stannate salt and according to the invention it is possible to produce an appropriate deposit.
  • the electrolyte described here is further noteworthy for the fact that obviously no further substances which influence the deposition of the ternary alloy have to be added to the electrolyte in order to bring about an appropriately composed deposition of copper-zinc-tin.
  • reaction products of amines with epichlorohydrin as proposed in EP 21 16634 (mentioned at the outset) and the addition of disubstituted benzene derivatives known from EP 2037006 can be dispensed with.
  • the composition of the ternary alloy of copper, tin and zinc can obviously be controlled in a simple manner via the abovementioned features alone, as long as Sn is simultaneously present as Sn 4+ . This has not yet been proposed in the prior art.
  • the concentration of tin ions in the electrolyte is in a particular ratio relative to the copper ions present. It has proven advantageous for the molar ratio of Cu to Sn ions in the electrolyte to be 1 :2 to 1 :6, preferably 1 :3 to 1 :5 and particularly preferably around 1 :4.
  • the metals copper and zinc are present in ionically dissolved form in the present electrolyte.
  • the copper can be added in the form of divalent copper salts to the electrolyte.
  • Zinc will be present in the form of 2-valent ions in the electrolyte.
  • the molar ratio according to the invention of copper ions to zinc ions is preferably in the range from 1 :1 to 1 :6. Very particular preference is given to a value of about 1 :2.
  • the tin is added as stannate salt, i.e. in the 4-valent form, to the electrolyte. Such stannate salts are well known to those skilled in the art.
  • Particularly suitable stannate salts are, for example, sodium stannate and potassium stannate.
  • the ratios of the concentrations of copper and zinc ions relative to one another are critical in determining the composition of the alloy deposited. It is naturally also advantageous for the tin used to be present in an appropriate ratio to the copper and zinc ions in total.
  • the molar ratio of stannate salt used to the sum of copper and zinc ions should be 1 :1 - 5:1 , preferably 1 .5:1 - 3:1 and particularly preferably from 2:1 to 2.5:1 in each case based on the metals.
  • the concentration ranges of the metal in the electrolyte can be selected by a person skilled in the art. It has been found to be advantageous for the ion concentration of copper to be in the range from 0.1 to 5 g/L of electrolyte, the concentration of tin to be in the range from 0.5 to 20 g/L of electrolyte and the ion concentration of zinc to be in the range from 0.2 to 15 g/L of electrolyte.
  • the concentration of copper is particularly preferably 0.3 - 2 g/L, very preferably 0.5 - 1 .0 g/L.
  • the concentration of zinc is particularly preferably 0.3 - 5 g/L, very preferably 0.5 - 2.0 g/L.
  • the concentration of tin is particularly preferably 2 - 10 g/L, very preferably 3.5 - 7.0 g/L.
  • Copper is present in a concentration of 0.5 - 1.0 g/L
  • Zinc is present in a concentration of 1.0 - 2.0 g/L
  • Tin is present in a concentration of 3.5 - 7.0 g/L
  • the copper and zinc ions are present in dissolved form in the electrolyte.
  • compounds of these metals to be deposited which are soluble in water under the reaction conditions indicated, it is possible to employ compounds selected from the group consisting of, carbonates, hydrogencarbonates, sulphites, sulphates, phosphates, nitrites, nitrates, halides, hydroxides, oxide-hydroxides, oxides and combinations thereof. Preference is given to using carbonate, hydrogencarbonates or sulphates. Very particular preference is given to the addition in the form of sulphate salt in this context.
  • the electrolyte is operated in the slightly to strongly alkaline range.
  • the pH of the electrolyte is preferably in the range from 8 to 13, more preferably from 8.5 to 12 and very particularly preferably from 9 to 1 1 .5.
  • the pH of the electrolyte according to the invention is especially preferably about 10-1 1.
  • Preferred buffer substances are salts of weak organic or inorganic acids selected from the group consisting of phosphoric acid and citric acid.
  • additives selected from the group consisting of monocarboxylic and dicarboxylic acids, alkanesulphonic acids, betaines and aromatic nitro compounds can be added to the electrolyte.
  • additives are adequately known for the present type of baths, in particular in the field of deposition of brass or bronze.
  • Such additives are particularly preferably selected from the group consisting of oxalic acid, tartaric acid, citric acid and salts thereof.
  • the present invention likewise provides a process for the electrolytic deposition of Cu- Zn-Sn alloy layers, in which the substrate to be coated is dipped as cathode into an electrolyte according to the invention and a flow of current is established between the anode and the cathode.
  • the embodiments of the electrolyte mentioned as preferred are analogously likewise preferred for the process.
  • the proportion of copper in the ternary alloy deposited is in the range from 38 to 44% by weight, the proportion of tin to be in the range from 34 to 42% by weight and the proportion of zinc to be in the range from 16 to 26% by weight.
  • Preference is likewise given to alloys containing 36 - 40% by weight of Sn, very preferably about 38% by weight.
  • the sum of the alloy constituents should be 100% by weight.
  • the alloy deposited should have a thickness of 0.4 - 5 ⁇ , preferably 0.5 - 3 ⁇ and very particularly preferably of 1 - 2 ⁇ .
  • the alloy composition can likewise change with the temperature prevailing during the electrolysis.
  • the electrolysis is therefore carried out in the range from 20 to 90°C, preferably from 30 to 60°C and very preferably about 45°C.
  • the composition of the ternary alloy of copper, tin and zinc can likewise change with the current density set during the electrolysis. It is advantageous to set a current density in the range from 0.1 to 5 ampere per square decimetre.
  • the current density is preferably from 0.2 to 1 .0 ampere per square centimetre, very preferably from 0.3 to 0.8 ampere per square centimetre.
  • As anode it is possible to use any electrode which comes into question for this purpose to a person skilled in the art.
  • insoluble anodes e.g. platinated titanium anodes or mixed metal oxide anodes.
  • soluble anodes composed of a material selected from the group consisting of electrolytic copper, phosphorus-containing copper, tin, tin-copper alloy, zinc-copper alloy and zinc- tin-copper alloy or combinations of these anodes are likewise advantageous.
  • the alloy composition achieved by means of electrolysis preferably very closely approximates that corresponding to the alloy base material in the material kesterite (Cu2ZnSnS4).
  • the layer produced by the process of the invention very preferably consists of a composition close to the formula Cu2ZnSn. From this, the desired compound Cu2ZnSn(SeS)4 (CZTS) is produced by action of sulphur, selenium and/or appropriate compounds using appropriate processes as discussed in the literature.
  • stannate salt itself serves as an adequate stabilizer for preventing zinc or copper compounds from precipitating out in the alkaline range. This was not to be expected in the light of the background of the known prior art.
  • the result is a ternary copper-tin-zinc alloy from a stable electrolyte.

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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)

Abstract

La présente invention concerne un électrolyte sans cyanure, sans pyrophosphate et sans acide phosphonique, et un procédé de dépôt électrolytique d'un alliage ternaire des éléments cuivre, étain et zinc. L'électrolyte et le procédé sont caractérisés en ce que non seulement des ions zinc (II) et des ions cuivre, mais aussi des anions stannate sont présents dans l'électrolyte employé. Les ions cuivre et zinc sont présents dans un rapport molaire particulier l'un par rapport à l'autre.
PCT/EP2012/075113 2011-12-21 2012-12-11 Dépôt d'alliages cuivre-étain-zinc à partir d'un électrolyte Ceased WO2013092314A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011121798.7 2011-12-21
DE201110121798 DE102011121798B4 (de) 2011-12-21 2011-12-21 Elektrolyt und Verfahren zur elektrolytischen Abscheidung von Cu-Zn-Sn-Legierungsschichten und Verfahren zur Herstellung einer Dünnschichtsolarzelle

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WO2013092314A1 true WO2013092314A1 (fr) 2013-06-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013226297B3 (de) * 2013-12-17 2015-03-26 Umicore Galvanotechnik Gmbh Wässriger, cyanidfreier Elektrolyt für die Abscheidung von Kupfer-Zinn- und Kupfer-Zinn-Zink-Legierungen aus einem Elektrolyten und Verfahren zur elektrolytischen Abscheidung dieser Legierungen
CN106119911A (zh) * 2016-08-21 2016-11-16 无锡瑾宸表面处理有限公司 稳定型电镀液
EP3540097A1 (fr) 2018-03-13 2019-09-18 COVENTYA S.p.A. Produits galvanisés et bain électrolytique approprié pour fournir de tels produits

Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
AT514818B1 (de) * 2013-09-18 2015-10-15 W Garhöfer Ges M B H Ing Abscheidung von Cu, Sn, Zn-Beschichtungen auf metallischen Substraten
DE102021117095A1 (de) 2021-07-02 2023-01-05 Umicore Galvanotechnik Gmbh Bronzeschichten als Edelmetallersatz
DE202021004169U1 (de) 2021-07-02 2022-12-07 Umicore Galvanotechnik Gmbh Bronzeschicht als Edelmetallersatz in Smart Cards

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EP2116634A1 (fr) 2008-05-08 2009-11-11 Umicore Galvanotechnik GmbH Electrolyte de cuivre-zinc modifié et procédé de déposition de couches de bronze
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JPH10102278A (ja) 1996-09-30 1998-04-21 Nippon New Chrome Kk 銅−スズ合金メッキ用ピロリン酸浴
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EP2116634A1 (fr) 2008-05-08 2009-11-11 Umicore Galvanotechnik GmbH Electrolyte de cuivre-zinc modifié et procédé de déposition de couches de bronze
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013226297B3 (de) * 2013-12-17 2015-03-26 Umicore Galvanotechnik Gmbh Wässriger, cyanidfreier Elektrolyt für die Abscheidung von Kupfer-Zinn- und Kupfer-Zinn-Zink-Legierungen aus einem Elektrolyten und Verfahren zur elektrolytischen Abscheidung dieser Legierungen
WO2015091201A1 (fr) 2013-12-17 2015-06-25 Umicore Galvanotechnik Gmbh Dépôt d'alliages cuivre-étain et cuivre-étain-zinc à partir d'un électrolyte
CN106119911A (zh) * 2016-08-21 2016-11-16 无锡瑾宸表面处理有限公司 稳定型电镀液
EP3540097A1 (fr) 2018-03-13 2019-09-18 COVENTYA S.p.A. Produits galvanisés et bain électrolytique approprié pour fournir de tels produits
WO2019175270A1 (fr) 2018-03-13 2019-09-19 Coventya S.P.A. Produits électroplaqués et bain d'électroplacage pour obtenir lesdits produits

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DE102011121798B4 (de) 2013-08-29

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