EP0737760B1 - Bain de dépôt électrolytique de platine - Google Patents

Bain de dépôt électrolytique de platine Download PDF

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Publication number
EP0737760B1
EP0737760B1 EP96102799A EP96102799A EP0737760B1 EP 0737760 B1 EP0737760 B1 EP 0737760B1 EP 96102799 A EP96102799 A EP 96102799A EP 96102799 A EP96102799 A EP 96102799A EP 0737760 B1 EP0737760 B1 EP 0737760B1
Authority
EP
European Patent Office
Prior art keywords
acid
platinum
electroplating bath
complex
bath
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.)
Expired - Lifetime
Application number
EP96102799A
Other languages
German (de)
English (en)
Other versions
EP0737760A1 (fr
Inventor
Werner Kuhn
Wolfgang Zilske
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.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
Degussa Huels AG
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
Priority claimed from DE19547900A external-priority patent/DE19547900C2/de
Application filed by Degussa GmbH, Degussa Huels AG filed Critical Degussa GmbH
Publication of EP0737760A1 publication Critical patent/EP0737760A1/fr
Application granted granted Critical
Publication of EP0737760B1 publication Critical patent/EP0737760B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals

Definitions

  • the invention relates to a galvanic platinum bath, especially for the deposition of thick layers, the 5 to 30 Contains g / l of platinum as an amine sulfamato complex and a pH value less than 1.
  • Electrodeposition of platinum acidic and alkaline baths based on platinum (II) - and Platinum (IV) compounds are used.
  • the main types of bath contain diamminodinitritoplatinum (II) (P salt), Sulfatodinitritoplatinic acid (DNA) or Hexahydroxoplatinic acid, or its alkali salts.
  • the types of baths mentioned are mainly only suitable for Deposition of thin platinum layers of a few ⁇ m.
  • the Deposition of thick layers for technical applications a general problem with platinum. Either the layers have high internal tensions, become cracked and burst even on, or the electrolytes are insufficient stable and decompose during the long electrolysis times relatively quickly.
  • From DE-PS 11 82 924 is an acid bath for galvanic Deposition of platinum coatings known from a aqueous solution of a complex dinitroplatinate (II) compound exists and has a pH below 2.
  • complex platinum compound can also Dinitrosulfamato complex can be used. After own Information can only be obtained with these platinum baths Layer thicknesses up to 25 ⁇ m. Layers over 25 ⁇ m tend to Tear and are therefore not suitable for many applications.
  • the P salt is reacted with a large excess of sulfamic acid, NH 2 SO 3 H, so that a diluted bath with 6-20 g / l platinum and 20 Contains -100 g / l sulfamic acid (amidosulfuric acid).
  • this electrolyte is only stable as long as the bath is in operation. Thick layers can only be obtained without cracks with a matt surface.
  • Galvanic platinum bath especially for thicker deposition Develop layers that are 5 to 30 g / l platinum Contains amminsulfamato complex and a pH of has less than 1, with which also layer thicknesses over 100 ⁇ m can be deposited without cracks, smooth and shiny and that is stable even when not in use.
  • Electrolyte at most 5 g / l free amidosulfuric acid (Sulfamic acid) and 20 to 400 g / l of a strong acid contains a pH of less than 1.
  • the strong acid is sulfuric acid, Methanesulfonic acid or perchloric acid used.
  • Besides can also use other mineral acids, such as fluorosulfuric acid or fluoroboric acid, alkanesulfonic acids, such as Methane disulfonic acid, ethanesulfonic acid, Hydroxiethan sulfonic acid and homologues, or perfluorinated Alkanesulfonic acids, such as trifluoromethanesulfonic acid or Pentafluoroethanesulfonic acid, and perfluorocarboxylic acids, such as Trifluoroacetic acid can be used.
  • mineral acids such as fluorosulfuric acid or fluoroboric acid
  • alkanesulfonic acids such as Methane disulfonic acid, ethanesulfonic acid, Hydroxiethan sulfonic acid and homologues
  • perfluorinated Alkanesulfonic acids such as trifluoromethanesulf
  • electrolyte is additional Contains 0.01 to 0.2 g / l of a fluorosurfactant as a wetting agent.
  • amminsulfamato complex Product from the reaction of 1 mol of P salt (Platinum diamminodinitrito complex) with 4 to 6 mol Amidosulfuric acid is used.
  • the bath may also contain 0.01-0.2 g / l of a fluorosurfactant to suppress spray. It is operated at a temperature between 60 and 90 ° C and at current densities of 1-4 A / dm 2 .
  • the platinum amine sulfamato complex solution was found in the strongly acidic bath without free amidosulfuric acid as surprisingly stable.
  • the bathroom showed even with long ones Electrolysis times no precipitation. In the Separation of the platinum liberated sulfamate becomes rapid does not hydrolyze and accumulate in the electrolyte.
  • the platinum coatings deposited from these baths are crack-free, glossy and ductile even with layer thicknesses above 100 ⁇ m.
  • a galvanic platinum bath is prepared as follows: 80 ml of sulfuric acid (97%) are diluted in approx. 600 ml of water. 16 g of platinum in the form of the platinum amine sulfamato complex solution and 0.1 g of a fluorosurfactant are added to this solution. After filling with water, 1 l of the finished bath is obtained. At a bath temperature of 80 ° C and a current density of 2 A / dm 2 , a part made of silver is coated while rotating. After approx. 13 hours, an approx. 120 ⁇ m thick, shiny platinum layer has deposited evenly. After removing the silver with nitric acid, diluted 1: 1, a stable, crack-free platinum foil is obtained.

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)

Claims (4)

  1. Bain de dépôt électrolytique de platine servant à précipiter des couches épaisses, bain qui contient 5 à 30 grammes par litre de platine sous la forme d'un complexe d'aminosulfamate et présente un pH d'une valeur inférieure à 1,
    caractérisé en ce que
    l'électrolyte contient au maximum 5 grammes par litre d'acide amidosulfurique et 20 à 400 grammes par litre d'un acide fort avec un pH d'une valeur inférieure à 1.
  2. Bain de dépôt électrolytique de platine selon la revendication 1,
    caractérisé en ce que
    l'on utilise comme acide fort de l'acide sulfurique, de l'acide méthanosulfonique ou de l'acide perchlorique.
  3. Bain de dépôt électrolytique de platine selon la revendication 1 ou 2,
    caractérisé en ce que
    il contient 0,01 à 0,2 gramme par litre d'un dérivé tensioactif du fluor en tant qu'agent mouillant.
  4. Bain de dépôt électrolytique de platine selon la revendication 1,
    caractérisé en ce que
    l'on utilise comme complexe d'aminosulfamate le produit résultant de la décomposition d'un mol de diamino-dinitrito-platine (II) avec 4 à 6 mol d'acide amidosulfurique.
EP96102799A 1995-04-15 1996-02-24 Bain de dépôt électrolytique de platine Expired - Lifetime EP0737760B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19514253 1995-04-15
DE19514253 1995-04-15
DE19547900A DE19547900C2 (de) 1995-04-15 1995-12-21 Galvanisches Platinbad
DE19547900 1995-12-21

Publications (2)

Publication Number Publication Date
EP0737760A1 EP0737760A1 (fr) 1996-10-16
EP0737760B1 true EP0737760B1 (fr) 2000-04-19

Family

ID=26014434

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96102799A Expired - Lifetime EP0737760B1 (fr) 1995-04-15 1996-02-24 Bain de dépôt électrolytique de platine

Country Status (3)

Country Link
US (1) US5620583A (fr)
EP (1) EP0737760B1 (fr)
JP (1) JPH08319595A (fr)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6294425B1 (en) 1999-10-14 2001-09-25 Samsung Electronics Co., Ltd. Methods of forming integrated circuit capacitors by electroplating electrodes from seed layers
US20020000380A1 (en) * 1999-10-28 2002-01-03 Lyndon W. Graham Method, chemistry, and apparatus for noble metal electroplating on a microelectronic workpiece
KR100331570B1 (ko) 2000-06-13 2002-04-06 윤종용 전기도금법을 이용한 반도체 메모리 소자의 커패시터제조방법
US7150820B2 (en) * 2003-09-22 2006-12-19 Semitool, Inc. Thiourea- and cyanide-free bath and process for electrolytic etching of gold
US20050230262A1 (en) * 2004-04-20 2005-10-20 Semitool, Inc. Electrochemical methods for the formation of protective features on metallized features
FR2974582A1 (fr) * 2011-04-27 2012-11-02 Commissariat Energie Atomique Procede de croissance de particules metalliques par electrodeposition avec inhibition in situ
GB201200482D0 (en) * 2012-01-12 2012-02-22 Johnson Matthey Plc Improvements in coating technology
US10612149B1 (en) 2019-09-05 2020-04-07 Chow Sang Sang Jewellery Company Limited Platinum electrodeposition bath and uses thereof
DE102020007789A1 (de) * 2020-12-18 2022-06-23 Umicore Galvanotechnik Gmbh Stabilisierung der Abscheiderate von Platinelektrolyten
TWI784601B (zh) * 2021-01-08 2022-11-21 日商Ｅｅｊａ股份有限公司 鉑電鍍浴及鍍鉑製品
JP7695086B2 (ja) * 2021-01-08 2025-06-18 Ｅｅｊａ株式会社 白金電解めっき浴および白金めっき製品
DE102021107826A1 (de) 2021-03-29 2022-09-29 Umicore Galvanotechnik Gmbh Platinelektrolyt
TWI876427B (zh) * 2022-08-04 2025-03-11 英商強生麥特公司 製造包含鉑(ii)錯合物之電鍍溶液之方法及藉由其生產之鉑電鍍溶液
DE102024113591A1 (de) 2024-05-15 2025-11-20 Umicore Galvanotechnik Gmbh Verfahren zur Herstellung einer Platinlösung zur elektrolytischen Abscheidung von Platin und Platinlegierungen, Elektrolyt und dessen Verwendung

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL123540C (fr) * 1958-08-06
GB8821005D0 (en) * 1988-09-07 1988-10-05 Johnson Matthey Plc Improvements in plating
JPH04297592A (ja) * 1991-03-25 1992-10-21 Tanaka Kikinzoku Kogyo Kk 白金電気メッキ浴

Also Published As

Publication number Publication date
US5620583A (en) 1997-04-15
EP0737760A1 (fr) 1996-10-16
JPH08319595A (ja) 1996-12-03

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