EP2604727A1 - Electrolytic bath for the deposition of a gold copper alloy - Google Patents
Electrolytic bath for the deposition of a gold copper alloy Download PDFInfo
- Publication number
- EP2604727A1 EP2604727A1 EP12195269.1A EP12195269A EP2604727A1 EP 2604727 A1 EP2604727 A1 EP 2604727A1 EP 12195269 A EP12195269 A EP 12195269A EP 2604727 A1 EP2604727 A1 EP 2604727A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bath
- gold
- per liter
- bath according
- tellurium
- 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.)
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- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 8
- 230000008021 deposition Effects 0.000 title description 6
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 claims abstract description 18
- 239000010931 gold Substances 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 17
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 26
- 239000000080 wetting agent Substances 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 4
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- IQXHAJSMTNDJGA-UHFFFAOYSA-O azanium;gold(1+);dicyanide Chemical compound [NH4+].[Au+].N#[C-].N#[C-] IQXHAJSMTNDJGA-UHFFFAOYSA-O 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- ICAIHGOJRDCMHE-UHFFFAOYSA-O ammonium cyanide Chemical compound [NH4+].N#[C-] ICAIHGOJRDCMHE-UHFFFAOYSA-O 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 229940044654 phenolsulfonic acid Drugs 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000004285 Potassium sulphite Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000337 buffer salt Substances 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 3
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 2
- VYWYYJYRVSBHJQ-UHFFFAOYSA-N 3,5-dinitrobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 VYWYYJYRVSBHJQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- BFPJYWDBBLZXOM-UHFFFAOYSA-L potassium tellurite Chemical compound [K+].[K+].[O-][Te]([O-])=O BFPJYWDBBLZXOM-UHFFFAOYSA-L 0.000 description 2
- SITVSCPRJNYAGV-UHFFFAOYSA-L tellurite Chemical compound [O-][Te]([O-])=O SITVSCPRJNYAGV-UHFFFAOYSA-L 0.000 description 2
- 150000003497 tellurium Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOBZQAFUBBVPEO-UHFFFAOYSA-N [Cu](C#N)C#N.[K] Chemical compound [Cu](C#N)C#N.[K] GOBZQAFUBBVPEO-UHFFFAOYSA-N 0.000 description 1
- NGRSIWGPWLJMKS-UHFFFAOYSA-N [Na].N#C[Cu]C#N Chemical compound [Na].N#C[Cu]C#N NGRSIWGPWLJMKS-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- KPQDSKZQRXHKHY-UHFFFAOYSA-N gold potassium Chemical compound [K].[Au] KPQDSKZQRXHKHY-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- VOADVZVYWFSHSM-UHFFFAOYSA-L sodium tellurite Chemical compound [Na+].[Na+].[O-][Te]([O-])=O VOADVZVYWFSHSM-UHFFFAOYSA-L 0.000 description 1
- VMDSWYDTKFSTQH-UHFFFAOYSA-N sodium;gold(1+);dicyanide Chemical compound [Na+].[Au+].N#[C-].N#[C-] VMDSWYDTKFSTQH-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XHGGEBRKUWZHEK-UHFFFAOYSA-L tellurate Chemical compound [O-][Te]([O-])(=O)=O XHGGEBRKUWZHEK-UHFFFAOYSA-L 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
- C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
Definitions
- the invention is based on an electrolytic bath for depositing a gold-copper alloy having the features specified in the preamble of claim 1.
- a gold-copper alloy having the features specified in the preamble of claim 1.
- Such a bath is from the EP 0 384 679 B1 known.
- Object of the present invention is therefore to show an improved way how gold copper alloys can be deposited without the addition of cadmium.
- tellurium is used as an addition of an alkaline cyanide bath for the electrolytic deposition of gold-copper alloys, preferably in a concentration of 0.001 to 10 g of tellurium per liter of bath liquid, in particular 0.005 to 2 g of tellurium per liter bath liquid.
- the tellurium is preferably used in the form of an IV- or VI-valent tellurium salt, for example tellurium or tellurite.
- a bath according to the invention contains in a liter of bath liquid at least 1 g of gold as cyanide complex and at least 4 g of copper as cyanide complex and at least 0.001 g of tellurium, preferably at least 0.005 g of tellurium, and brightener in the form of a soluble mono-, di- and / or trinitro compound.
- the bath may contain other additives, such as wetting agents, conductive and / or buffer salts.
- the gold, copper and tellurium content of a bath according to the invention can be varied within wide limits, for example, the bath in one liter of bath liquid 1 g to 20 g of gold.
- the bath contains at least 3 grams of gold per liter of bath fluid to allow for greater rates of deposition.
- the bath does not contain more than 8 grams of gold per liter of bath fluid since higher gold concentrations are not economical.
- the copper concentration of the bath may be for example between 4 g and 100 g per liter, preferably at least 10 g of copper per liter, in particular at least 20 g of copper per liter.
- the bath does not contain more than 70 g of copper per liter, in particular not more than 50 g of copper per liter, for example 30 g to 35 g of copper per liter of bath liquid.
- the tellurium content should not exceed 10 g per liter of bath fluid.
- the bath contains less than 2 g of tellurium, in particular less than 1 g of tellurium per liter of bath liquid. Very good results are achieved, for example, with a tellurium content of 0.005 g to 0.2 g of tellurium per liter of bath liquid.
- Both gold and copper are present in a bath according to the invention as cyanide complexes.
- the gold may be contained in the bath, for example, as a potassium-gold-cyanide complex, a sodium-gold-cyanide complex and / or an ammonium-gold-cyanide complex.
- the copper may be contained as potassium copper cyanide complex, sodium copper cyanide complex and / or ammonium gold cyanide complex.
- the bath according to the invention is preferably an alkaline bath, in particular an alkaline cyanide bath.
- the pH of the bath is preferably from 9.0 to 12.0, more preferably from 10 to 11.0.
- the bath according to the invention may additionally contain free cyanide, for example potassium cyanide, sodium cyanide and / or ammonium cyanide.
- the bath preferably contains at least 8 g of free cyanide per liter of bath liquid, more preferably at least 15 per liter of bath liquid.
- the bath does not contain more than 50 g of free cyanide per liter of bath liquid, especially not more than 25 g per liter of bath liquid.
- the tellurium preferably has the oxidation number IV or IV in a bath according to the invention.
- the tellurium can be added to the bath as a soluble IV- or VI-valent tellurium salt, for example in the form of tellurate or tellurite, preferably an alkalitellurate or alkalitellurite.
- Particularly suitable are water- or alkali-soluble tellurites, such as sodium tellurite or potassium tellurite.
- sulfite is dissolved in the bath, for example potassium sulfite, sodium sulfite and / or ammonium sulfite.
- the addition of sulfite improves the ductility of the deposited gold-copper layers.
- the bath contains at least 0.1 g, more preferably at least 5 g of sulfite per liter of bath liquid.
- a content of more than 50 g per liter of bath liquid can lead to undesirable precipitations. Therefore, the bath preferably contains at most 50 g of sulfite per liter of bath liquid, more preferably not more than 15 g per liter.
- the bath can be added in the electroplating usual Leitsalze and / or buffer salts.
- Particularly suitable are ammonium, sodium, and potassium salts, for example, the phosphoric acids, oxicarboxylic acids, sulfuric acid, hydrochloric acid, carbonic acid, sulfamic acid, phosphoric acid, acetic acid, boric acid or trinitrineacetic acid and derivatives thereof.
- the content of guide and buffer salts can be varied within wide limits. In general, amounts of from 5 g to 300 g per liter of bath liquid are particularly economical.
- brighteners are not absolutely necessary in galvanic baths, they are usually added to improve the gloss of the deposited layers.
- particularly suitable brighteners are soluble nitro compounds, for example mono-, di- and trinitro compounds of phenol or benzenesulfonic acid.
- the bath preferably contains at least 0.01 g of brightener per liter, more preferably at least 0.1 g of brightener per liter of bath liquid. More than 10 g of brightener per liter of bath liquid are generally not economical. Therefore, the bath preferably contains no more than 1 g of brightener per liter, more preferably not more than 0.5 g per liter of bath liquid.
- Wetting agents may be added to the bath.
- Suitable wetting agents ie additives which promote wetting, are, for example, complex organic phosphate esters or sulfate esters, polyethylene fatty alcohol esters and sodium lauryl sulfate.
- the bath preferably contains at least 0.05 g of wetting agent per liter of bath liquid, more preferably at least 0.5 g per liter of bath liquid. Wetting agent concentrations of more than 5 g per liter are generally not economical. Therefore, the bath preferably contains no more than 5 g wetting agent per liter, more preferably no more than 1 g wetting agent per liter bath liquid.
- the bath can be operated even at low temperatures of only 35 ° C. Therefore, low-melting wax models can be directly coated after prior metallization, which can be done for example by means of a conductive wax.
- the bath temperature can also be much higher, for example, up to 80 ° C. Particularly high deposition rates are possible with bath temperatures of 65 ° C to 75 ° C.
- the bath is preferably operated with current densities of 0.2 A / dm 2 to 2.0 A / dm 2 , more preferably with current densities of 0.7 A / dm 2 to 1.3 A / dm 2 .
- a gold-copper layer electrodeposited by use of a bath according to the invention may contain, for example, 0.1% by weight of tellurium or more.
- a gold-copper layer according to the invention preferably contains not more than 5% by weight, more preferably not more than 2% by weight, of tellurium.
- the ratio between gold and copper can be adjusted in a gold-copper layer according to the invention by varying the gold and copper contents.
- a gold-copper layer according to the invention preferably contains more than 50% by weight of gold, more preferably more than 70% by weight. Alloy constituents customary for gold-copper alloys may be present in a layer according to the invention. Preferably, however, the layer does not contain any other alloy components except gold, copper and tellurium.
- a pH of 10.5 and a current density of 1.2 A / dm, 2 ductile, shiny layers with a layer thickness of up to a few hundred micrometers can be deposited.
- the layer produced in this way contains 75% by weight of gold, 24.5% by weight of copper and 0.5% by weight of tellurium.
Landscapes
- 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
Description
Die Erfindung geht aus von einem elektrolytischen Bad zum Abscheiden einer Goldkupferlegierung mit den im Oberbegriff des Anspruchs 1 angegebenen Merkmalen. Ein solches Bad ist aus der
Um Goldkupferlegierungen mit gutem Glanz und guter Duktilität abzuscheiden, werden üblicherweise galvanische Bäder verwendet, die Kadmium enthalten. Die auf diese Weise erzeugten Schichten enthalten deshalb einige Gewichtsprozent Kadmium. Kadmium ist als giftiges Schwermetall jedoch problematisch. Besser ist in dieser Hinsicht ein tellurhaltiges Bad, das aus der
Aufgabe der vorliegenden Erfindung ist es deshalb, einen verbesserten Weg aufzuzeigen, wie Goldkupferlegierungen auch ohne Zusatz von Kadmium abgeschieden werden können.Object of the present invention is therefore to show an improved way how gold copper alloys can be deposited without the addition of cadmium.
Diese Aufgabe wird erfindungsgemäß durch ein elektrolytisches Bad mit den im Anspruch 1 angegebenen Merkmalen gelöst. Vorteilhafte Weiterbildungen der Erfindung sind Gegenstand von Unteransprüchen.This object is achieved by an electrolytic bath with the features specified in claim 1. Advantageous developments of the invention are the subject of dependent claims.
Bereits die Verwendung sehr kleine Mengen Tellur ermöglicht die Abscheidung von duktilen, glänzenden Goldkupferschichten, so dass auf den Einsatz von Kadmium verzichtet werden kann. Die Erfindung ermöglicht also die Abscheidung kadmiumfreier Goldkupferschichten durch Einsatz eines kadmiumfreien galvanischen Bades. Erfindungsgemäß wird Tellur als Zusatz eines alkalischen Cyanidbades zum elektrolytischen Abscheiden von Goldkupferlegierungen verwendet, bevorzugt in einer Konzentration von 0,001 bis 10 g Tellur pro Liter Badflüssigkeit, insbesondere 0,005 bis 2 g Tellur pro Liter Badflüssigkeit. Bevorzugt wird das Tellur in Form eines IV- oder VI-wertigen Tellursalzes, beispielsweise Tellurat oder Tellurit verwendet.Already using very small amounts of tellurium allows the deposition of ductile, shiny gold copper layers, so that the use of cadmium can be dispensed with. Thus, the invention enables the deposition of cadmium-free gold copper layers by using a cadmium-free galvanic bath. According to the invention, tellurium is used as an addition of an alkaline cyanide bath for the electrolytic deposition of gold-copper alloys, preferably in a concentration of 0.001 to 10 g of tellurium per liter of bath liquid, in particular 0.005 to 2 g of tellurium per liter bath liquid. The tellurium is preferably used in the form of an IV- or VI-valent tellurium salt, for example tellurium or tellurite.
Ein erfindungsgemäßes Bad enthält in einem Liter Badflüssigkeit wenigstens 1 g Gold als Cyanidkomplex und wenigstens 4 g Kupfer als Cyanidkomplex sowie wenigstens 0,001 g Tellur, vorzugsweise wenigstens 0,005 g Tellur, und Glanzbildner in Form einer löslichen Mono-, Di- und/oder Trinitroverbindung. Zusätzlich kann das Bad weitere Zusätze enthalten, beispielsweise Netzmittel, Leit- und/oder Puffersalze.A bath according to the invention contains in a liter of bath liquid at least 1 g of gold as cyanide complex and at least 4 g of copper as cyanide complex and at least 0.001 g of tellurium, preferably at least 0.005 g of tellurium, and brightener in the form of a soluble mono-, di- and / or trinitro compound. In addition, the bath may contain other additives, such as wetting agents, conductive and / or buffer salts.
Der Gold-, Kupfer- und Tellurgehalt eines erfindungsgemäßen Bades kann in weiten Grenzen variiert werden, beispielsweise kann das Bad in einem Liter Badflüssigkeit 1 g bis 20 g Gold. Bevorzugt enthalt das Bad wenigstens 3 g Gold pro Liter Badflüssigkeit, um größere Abscheideraten zu ermöglichen. Bevorzugt enthält das Bad nicht mehr als 8 g Gold pro Liter Badflüssigkeit, da höhere Goldkonzentrationen nicht wirtschaftlich sind. Die Kupferkonzentration des Bades kann beispielsweise zwischen 4 g und 100 g pro Liter betragen, bevorzugt sind wenigstens 10 g Kupfer pro Liter, insbesondere wenigstens 20 g Kupfer pro Liter. Besonders vorteilhaft ist es, wenn das Bad nicht mehr als 70 g Kupfer pro Liter, insbesondere nicht mehr als 50 g Kupfer pro Liter enthält, beispielsweise 30 g bis 35 g Kupfer pro Liter Badflüssigkeit. Der Tellurgehalt sollte 10 g pro Liter Badflüssigkeit nicht übersteigen. Bevorzugt enthält das Bad weniger als 2 g Tellur, insbesondere weniger als 1 g Tellur pro Liter Badflüssigkeit. Sehr gute Ergebnisse werden beispielsweise mit einem Tellurgehalt von 0,005 g bis 0,2 g Tellur pro Liter Badflüssigkeit erzielt.The gold, copper and tellurium content of a bath according to the invention can be varied within wide limits, for example, the bath in one liter of bath liquid 1 g to 20 g of gold. Preferably, the bath contains at least 3 grams of gold per liter of bath fluid to allow for greater rates of deposition. Preferably, the bath does not contain more than 8 grams of gold per liter of bath fluid since higher gold concentrations are not economical. The copper concentration of the bath may be for example between 4 g and 100 g per liter, preferably at least 10 g of copper per liter, in particular at least 20 g of copper per liter. It is particularly advantageous if the bath does not contain more than 70 g of copper per liter, in particular not more than 50 g of copper per liter, for example 30 g to 35 g of copper per liter of bath liquid. The tellurium content should not exceed 10 g per liter of bath fluid. Preferably, the bath contains less than 2 g of tellurium, in particular less than 1 g of tellurium per liter of bath liquid. Very good results are achieved, for example, with a tellurium content of 0.005 g to 0.2 g of tellurium per liter of bath liquid.
Sowohl Gold als auch Kupfer liegen in einem erfindungsgemäßen Bad als Cyanidkomplexe vor. Das Gold kann in dem Bad beispielsweise als Kalium-Gold-Cyanidkomplex, Natrium-Gold-Cyanidkomplex und/oder Ammonium-Gold-Cyanidkomplex enthalten sein. Ebenso kann beispielsweise das Kupfer als KaliumKupfer-Cyanidkomplex, Natrium-Kupfer-Cyanidkomplex und/oder Ammonium-Gold-Cyanidkomplex enthalten sein.Both gold and copper are present in a bath according to the invention as cyanide complexes. The gold may be contained in the bath, for example, as a potassium-gold-cyanide complex, a sodium-gold-cyanide complex and / or an ammonium-gold-cyanide complex. Likewise, for example, the copper may be contained as potassium copper cyanide complex, sodium copper cyanide complex and / or ammonium gold cyanide complex.
Das erfindungsgemäße Bad ist bevorzugt ein alkalisches Bad, insbesondere ein alkalisch-cyanidisches Bad. Der pH-Wert des Bades beträgt bevorzugt von 9,0 bis 12,0, besonderes bevorzugt von 10, bis 11,0.The bath according to the invention is preferably an alkaline bath, in particular an alkaline cyanide bath. The pH of the bath is preferably from 9.0 to 12.0, more preferably from 10 to 11.0.
Das erfindungsgemäße Bad kann zusätzlich freies Cyanid enthalten, beispielsweise Kaliumcyanid, Natriumcyanid und/oder Ammoniumcyanid. Bevorzugt enthält das Bad wenigstens 8 g freies Cyanid pro Liter Badflüssigkeit, besonders bevorzugt wenigstens 15 pro Liter Badflüssigkeit. Bevorzugt enthält das Bad aber nicht mehr als 50 g freies Cyanid pro Liter Badflüssigkeit, besonders nicht mehr als 25 g pro Liter Badflüssigkeit.The bath according to the invention may additionally contain free cyanide, for example potassium cyanide, sodium cyanide and / or ammonium cyanide. The bath preferably contains at least 8 g of free cyanide per liter of bath liquid, more preferably at least 15 per liter of bath liquid. Preferably, however, the bath does not contain more than 50 g of free cyanide per liter of bath liquid, especially not more than 25 g per liter of bath liquid.
Das Tellur hat in einem erfindungsgemäßen Bad bevorzugt die Oxidationszahl IV oder IV. Das Tellur kann dem Bad als ein lösliches IV- oder VI-wertiges Tellursalz zugegeben werden, beispielsweise in Form von Tellurat oder Tellurit, bevorzugt ein Alkalitellurat oder Alkalitellurit. Geeignet sind insbesondere wasser- oder alkalilösliche Tellurite wie Natriumtellurit oder Kaliumtellurit.The tellurium preferably has the oxidation number IV or IV in a bath according to the invention. The tellurium can be added to the bath as a soluble IV- or VI-valent tellurium salt, for example in the form of tellurate or tellurite, preferably an alkalitellurate or alkalitellurite. Particularly suitable are water- or alkali-soluble tellurites, such as sodium tellurite or potassium tellurite.
Eine vorteilhafte Weiterbildung der Erfindung sieht vor, dass in dem Bad Sulfit gelöst ist, beispielsweise Kaliumsulfit, Natriumsulfit und/oder Ammoniumsulfit. Durch die Zugabe von Sulfit lässt sich die Duktilität der abgeschiedenen Goldkupferschichten verbessern. Bevorzugt enthält das Bad wenigstens 0,1 g, besonders bevorzugt wenigstens 5 g Sulfit pro Liter Badflüssigkeit. Ein Gehalt von mehr als 50 g pro Liter Badflüssigkeit kann zu unerwünschten Ausscheidungen führen. Bevorzugt enthält das Bad deshalb höchstens 50 g Sulfit pro Liter Badflüssigkeit, besonders bevorzugt nicht mehr als 15 g pro Liter.An advantageous development of the invention provides that sulfite is dissolved in the bath, for example potassium sulfite, sodium sulfite and / or ammonium sulfite. The addition of sulfite improves the ductility of the deposited gold-copper layers. Preferably, the bath contains at least 0.1 g, more preferably at least 5 g of sulfite per liter of bath liquid. A content of more than 50 g per liter of bath liquid can lead to undesirable precipitations. Therefore, the bath preferably contains at most 50 g of sulfite per liter of bath liquid, more preferably not more than 15 g per liter.
Dem Bad können in der Galvanotechnik übliche Leitsalze und/oder Puffersalze zugegeben sein. Besonders geeignet sind Ammonium-, Natrium-, und Kaliumsalze, beispielsweise der Phosphorsäuren, Oxicarbonsäuren, Schwefelsäure, Salzsäure, Kohlensäure, Sulfaminsäure, Phosphorsäure, Essigsäure, Borsäure oder Trinitrinessigsäure und deren Derivate. Der Gehalt an Leit- und Puffersalzen kann in weiten Grenzen variiert werden. Besonders wirtschaftlich sind im Allgemeinen Mengen von 5 g bis 300 g pro Liter Badflüssigkeit.The bath can be added in the electroplating usual Leitsalze and / or buffer salts. Particularly suitable are ammonium, sodium, and potassium salts, for example, the phosphoric acids, oxicarboxylic acids, sulfuric acid, hydrochloric acid, carbonic acid, sulfamic acid, phosphoric acid, acetic acid, boric acid or trinitrineacetic acid and derivatives thereof. The content of guide and buffer salts can be varied within wide limits. In general, amounts of from 5 g to 300 g per liter of bath liquid are particularly economical.
Glanzbildner sind in galvanischen Bädern zwar nicht unbedingt erforderlich, werden aber in der Regel zugegeben, um den Glanz der abgeschiedenen Schichten zu verbessern. Für ein erfindungsgemäßes Bad sind als Glanzbildner insbesondere Iösliche Nitroverbindungen geeignet, beispielsweise Mono-, Di-, und Trinitroverbindungen des Phenols oder der Benzolsulfonsäure. Bevorzugt enthält das Bad wenigstens 0,01 g Glanzbildner pro Liter, besonders bevorzugt wenigstens 0,1 g Glanzbildner pro Liter Badflüssigkeit. Mehr als 10 g Glanzbildner pro Liter Badflüssigkeit sind in der Regel nicht wirtschaftlich. Bevorzugt enthält das Bad deshalb nicht mehr als 1 g Glanzbildner pro Liter, besonders bevorzugt nicht mehr als 0,5 g pro Liter Badflüssigkeit.Although brighteners are not absolutely necessary in galvanic baths, they are usually added to improve the gloss of the deposited layers. For a bath according to the invention, particularly suitable brighteners are soluble nitro compounds, for example mono-, di- and trinitro compounds of phenol or benzenesulfonic acid. The bath preferably contains at least 0.01 g of brightener per liter, more preferably at least 0.1 g of brightener per liter of bath liquid. More than 10 g of brightener per liter of bath liquid are generally not economical. Therefore, the bath preferably contains no more than 1 g of brightener per liter, more preferably not more than 0.5 g per liter of bath liquid.
Dem Bad können Netzmittel zugesetzt sein. Als Netzmittel, also Zusätze, welche die Benetzung fördern, eignen sich beispielsweise komplexe organische Phosphat-, oder Sulfatester, Polyethylenfettalkoholester sowie Natriumlaurylsulfat. Bevorzugt enthält das Bad wenigstens 0,05 g Netzmittel pro Liter Badflüssigkeit, besonders bevorzugt wenigstens 0,5 g pro Liter Badflüssigkeit. Netzmittelkonzentrationen von mehr als 5 g pro Liter sind im Allgemeinen nicht wirtschaftlich. Bevorzugt enthält das Bad deshalb nicht mehr als 5 g Netzmittel pro Liter, besonders bevorzugt nicht mehr als 1 g Netzmittel pro Liter Badflüssigkeit.Wetting agents may be added to the bath. Suitable wetting agents, ie additives which promote wetting, are, for example, complex organic phosphate esters or sulfate esters, polyethylene fatty alcohol esters and sodium lauryl sulfate. The bath preferably contains at least 0.05 g of wetting agent per liter of bath liquid, more preferably at least 0.5 g per liter of bath liquid. Wetting agent concentrations of more than 5 g per liter are generally not economical. Therefore, the bath preferably contains no more than 5 g wetting agent per liter, more preferably no more than 1 g wetting agent per liter bath liquid.
Das Bad kann schon bei niedrigen Temperaturen von nur 35°C betrieben werden. Deshalb können niedrig schmelzende Wachsmodelle nach vorheriger Metallisierung, welche beispielsweise mittels eines Leitwachses erfolgen kann, direkt beschichtet werden. Die Badtemperatur kann aber auch wesentlich höher sein und beispielsweise bis zu 80°C betragen. Besonders hohe Abscheideraten sind mit Badtemperaturen von 65°C bis 75°C möglich.The bath can be operated even at low temperatures of only 35 ° C. Therefore, low-melting wax models can be directly coated after prior metallization, which can be done for example by means of a conductive wax. The bath temperature can also be much higher, for example, up to 80 ° C. Particularly high deposition rates are possible with bath temperatures of 65 ° C to 75 ° C.
Das Bad wird bevorzugt mit Stromdichten von 0,2 A/dm2 bis 2,0 A/dm2 betrieben, besonders bevorzugt mit Stromdichten von 0,7 A/dm2 bis 1,3 A/dm2.The bath is preferably operated with current densities of 0.2 A / dm 2 to 2.0 A / dm 2 , more preferably with current densities of 0.7 A / dm 2 to 1.3 A / dm 2 .
Eine durch Verwendung eines erfindungsgemäßen Bades galvanisch abgeschiedene Goldkupferschicht kann beispielsweise 0,1 Gew.-% Tellur oder mehr enthalten. Bevorzugt enthält eine erfindungsgemäße Goldkupferschicht nicht mehr als 5 Gew.-%, besonders bevorzugt nicht mehr als 2 Gew.-% Tellur. Das Verhältnis zwischen Gold und Kupfer kann in einer erfindungsgemäßen Goldkupferschicht durch Variation des Gold- und des Kupfergehalts eingestellt werden. Bevorzugt enthält eine erfindungsgemäße Goldkupferschicht mehr als 50 Gew.-% Gold, besonders bevorzugt mehr als 70 Gew.-% Für Goldkupferlegierungen gebräuchliche Legierungsbestandteile können in einer erfindungsgemäßen Schicht enthalten sein. Bevorzugt enthält die Schicht aber außer Gold, Kupfer und Tellur keine weiteren Legierungsbestandteile.A gold-copper layer electrodeposited by use of a bath according to the invention may contain, for example, 0.1% by weight of tellurium or more. A gold-copper layer according to the invention preferably contains not more than 5% by weight, more preferably not more than 2% by weight, of tellurium. The ratio between gold and copper can be adjusted in a gold-copper layer according to the invention by varying the gold and copper contents. A gold-copper layer according to the invention preferably contains more than 50% by weight of gold, more preferably more than 70% by weight. Alloy constituents customary for gold-copper alloys may be present in a layer according to the invention. Preferably, however, the layer does not contain any other alloy components except gold, copper and tellurium.
Nachstehend ist ein Beispiel für eine gut geeignete Badzusammensetzung angegeben:
- Ein Liter Badflüssigkeit enthält in wässriger Lösung 3 g bis 8 g Gold als Kaliumgold-l-Cyanid, 30 g bis 35 g Kupfer als Kaliumkupfer-I-Cyanid, 16 g bis 24 g freies Kaliumcyanid, 10 g bis 30 g Kaliumsulfit, 20 g bis 50 g Kaliumcarbonat, 20 g bis 50 g Dikaliumphosphat, 0,2 g bis 0,4 g 3,5-Dinitrobenzoesäure, 35 mg bis 100 mg Tellur als Kaliumtellurit, 0,5 g bis 1 g Natrium-Lauryl-Metaphosphat, 10 mg bis 5 g Nitrophenol.
- One liter of bath liquid contains in aqueous solution 3 g to 8 g of gold as potassium-gold 1-cyanide, 30 g to 35 g of copper as potassium copper-1-cyanide, 16 g to 24 g of free potassium cyanide, 10 g to 30 g of potassium sulfite, 20 g to 50 g of potassium carbonate, 20 g to 50 g of dipotassium phosphate, 0.2 g to 0.4 g of 3,5-dinitrobenzoic acid, 35 mg to 100 mg of tellurium as potassium tellurite, 0.5 g to 1 g of sodium lauryl metaphosphate, 10 mg to 5 g of nitrophenol.
Mit diesem Bad können bei 70 °C Badtemperatur, einem pH-Wert von 10,5 und einer Stromdichte von 1,2 A/dm2 duktile, glänzende Schichten mit einer Schichtdicke von bis zu einigen hundert Mikrometer abgeschieden werden. Die auf diese Weise erzeugte Schicht enthält 75 Gew.-% Gold, 24,5 Gew.-% Kupfer und 0,5 Gew.-% Tellur.With this bath, at a bath temperature of 70 ° C., a pH of 10.5 and a current density of 1.2 A / dm, 2 ductile, shiny layers with a layer thickness of up to a few hundred micrometers can be deposited. The layer produced in this way contains 75% by weight of gold, 24.5% by weight of copper and 0.5% by weight of tellurium.
Claims (14)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE201110056318 DE102011056318B3 (en) | 2011-12-13 | 2011-12-13 | Electrolytic bath for depositing a gold-copper alloy |
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| Publication Number | Publication Date |
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| EP2604727A1 true EP2604727A1 (en) | 2013-06-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP12195269.1A Withdrawn EP2604727A1 (en) | 2011-12-13 | 2012-12-03 | Electrolytic bath for the deposition of a gold copper alloy |
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| EP (1) | EP2604727A1 (en) |
| DE (2) | DE102011056318B3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113260738A (en) * | 2019-02-07 | 2021-08-13 | 意大利菲美特有限公司 | Rose gold alloy, production method and use |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2723910A1 (en) * | 1976-06-01 | 1977-12-15 | Systeme De Traitements De Surf | ADDITIONAL MIXTURE FOR ELECTROLYSIS BATTERIES |
| GB2053276A (en) * | 1979-06-14 | 1981-02-04 | Aliprandini P | Electrodeposition of gold alloy |
| EP0384679A1 (en) * | 1989-02-20 | 1990-08-29 | Engelhard Corporation | Electrolytic deposition of gold-containing alloys |
| US6126807A (en) * | 1999-04-30 | 2000-10-03 | Lucent Technologies Inc. | Process for making sodium gold sulfite solution |
-
2011
- 2011-12-13 DE DE201110056318 patent/DE102011056318B3/en active Active
-
2012
- 2012-01-31 DE DE201220100317 patent/DE202012100317U1/en not_active Expired - Lifetime
- 2012-12-03 EP EP12195269.1A patent/EP2604727A1/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2723910A1 (en) * | 1976-06-01 | 1977-12-15 | Systeme De Traitements De Surf | ADDITIONAL MIXTURE FOR ELECTROLYSIS BATTERIES |
| GB2053276A (en) * | 1979-06-14 | 1981-02-04 | Aliprandini P | Electrodeposition of gold alloy |
| EP0384679A1 (en) * | 1989-02-20 | 1990-08-29 | Engelhard Corporation | Electrolytic deposition of gold-containing alloys |
| EP0384679B1 (en) | 1989-02-20 | 1994-08-17 | Engelhard Corporation | Electrolytic deposition of gold-containing alloys |
| US6126807A (en) * | 1999-04-30 | 2000-10-03 | Lucent Technologies Inc. | Process for making sodium gold sulfite solution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113260738A (en) * | 2019-02-07 | 2021-08-13 | 意大利菲美特有限公司 | Rose gold alloy, production method and use |
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| DE202012100317U1 (en) | 2012-02-29 |
| DE102011056318B3 (en) | 2013-04-18 |
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