EP0011800B1 - Verfahren zum Ätzen von Oberflächen aus Kupfer oder Kupferlegierungen - Google Patents

Verfahren zum Ätzen von Oberflächen aus Kupfer oder Kupferlegierungen Download PDF

Info

Publication number
EP0011800B1
EP0011800B1 EP79104575A EP79104575A EP0011800B1 EP 0011800 B1 EP0011800 B1 EP 0011800B1 EP 79104575 A EP79104575 A EP 79104575A EP 79104575 A EP79104575 A EP 79104575A EP 0011800 B1 EP0011800 B1 EP 0011800B1
Authority
EP
European Patent Office
Prior art keywords
etching solution
copper
iron
etching
anode
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
Application number
EP79104575A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0011800A1 (de
Inventor
Wolfgang Faul
Leander Fürst
Bertel Prof. Dr. Kastening
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.)
Forschungszentrum Juelich GmbH
Original Assignee
Forschungszentrum Juelich GmbH
Kernforschungsanlage Juelich 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 Forschungszentrum Juelich GmbH, Kernforschungsanlage Juelich GmbH filed Critical Forschungszentrum Juelich GmbH
Priority to AT79104575T priority Critical patent/ATE652T1/de
Publication of EP0011800A1 publication Critical patent/EP0011800A1/de
Application granted granted Critical
Publication of EP0011800B1 publication Critical patent/EP0011800B1/de
Expired legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/46—Regeneration of etching compositions

Definitions

  • the invention relates to a method for etching surfaces made of copper or copper alloys by means of an acidic etching solution containing an oxidizing agent, which after removal of the copper surface flows through an anode and cathode-containing electrolytic cell, the etched-off copper being deposited on the cathode .
  • etching solution The removal of surfaces consisting of copper or containing copper by means of an etching solution is known for the production of printed circuits, plastic plates which are copper-clad on one or both sides being etched off after covering the surfaces forming the circuit with a protective layer with the remaining part of the copper cladding .
  • the etching solutions are also used to form the surface of printing rollers. In order to make the processes economical, the used etching solutions are regenerated and reprocessed. The etched-off copper contained in the etching solution is recovered.
  • Electrochemical processes are suitable for continuous reprocessing of the etching solution, the etching solution being introduced into an electrolysis cell, the anode of which is regenerated by the oxidizing agent used for the etching.
  • iron (III) chloride is used as the etchant
  • the iron (l-1) chloride formed during the etching is oxidized to iron (III) chloride.
  • etching solutions containing copper (II) chloride as an oxidizing agent can be regenerated.
  • the copper (I) chloride contained in the electrolyte solution after the copper surface has been removed is converted back to copper (II) chloride at the anode of the electrolytic cell.
  • the disadvantage here is the development of chlorine at the anode, which leads to considerable pollution of the environment and to the consumption of the oxidizing agent.
  • the anode compartment contains a sodium hydroxide solution.
  • the sodium hydroxide serves to absorb the chlorine which develops at the anode during the regeneration of the etching solution.
  • a disadvantage when using iron (III) chloride or copper (II) chloride as the etching solution containing the oxidizing agent is, moreover, the attack by the oxidizing agent of the materials used for the construction of the etching systems, provided that these do not consist of acid-resistant materials such as plastics which, however, are not temperature resistant.
  • the object of the invention is to provide a method for chemical etching of metallic surfaces, in which chlorine development at the anode is prevented in a simple manner and in which the components of the apparatus are no longer attacked chemically even at higher temperatures.
  • the copper should also be able to be deposited in solid form when the etching solution is regenerated.
  • iron compounds which form iron (III) sulfate at the anode when the etching solution flows through the electrolysis cell.
  • Electrically conductive carbon particles are added to the etching solution. Coal particles characterized in patent claims 4 to 7 are particularly suitable. The carbon particles are suspended in the etching solution. When flowing through the electrolysis cell, the carbon particles charge at the anode and transfer electrical charge to the copper surface to be processed. When the particles touch the copper layer, metal ions dissolve, so that the surface is electrochemically removed in addition to chemical etching with iron (III) sulfate. The copper ions in solution are deposited on the cathode of the electrolytic cell.
  • the method according to the invention therefore enables the copper layers to be removed with a circulating etching solution with immediate recovery of the deposited copper on the cathode without the development of chlorine * .
  • the etching solution containing iron (III) sulfate also enables the use of stainless steel for the construction of the apparatus.
  • FIG. 1 The copper removal as a function of the iron content of the etching solution is shown in FIG. 2.
  • Figure 3 shows the current yield achieved as a function of copper and iron content in the solution 4, the laser manure ü transmission in the electrolysis cell.
  • the device has an etching chamber 1 and an electrolysis cell 2, between which an etching solution 3 is circulated.
  • the etching solution is applied to the surface of a workpiece 5 to be processed by means of a spray nozzle 4.
  • the used etching solution flows to the bottom of the etching chamber 1. From there it is sucked off by a solvent pump 7 via a suction line 6 and pumped into the electrolytic cell 2.
  • a diaphragm or an ion exchange membrane 10 is inserted between the anode 8 and the cathode 9 in the electrolysis cell and separates the cathode space 11 of the electrolysis cell from the anode space 12.
  • the anode 8 consists of graphite and is designed as a tube through which the etching solution flows.
  • the wall of the graphite tube has openings 14; in order to bring the etching solution to the diaphragm or the ion exchange membrane and to enable the ion exchange between the anode space 12 and the cathode space 11.
  • Copper is deposited on the cathode 9, and the oxidizing agent of the etching solution is regenerated on the anode.
  • the recycled etching solution flows back from the anode compartment 12 via a pressure line 15 to the etching chamber 1.
  • An aqueous, sulfuric acid, iron (III) sulfate solution is used as the etching solution.
  • Electrically conductive carbon particles in a concentration in the range between 50 and 250 g / l of etching solution can be suspended in the circulating etching solution.
  • the diaphragm or the ion exchange membrane 10 used in the electrolysis cell is impermeable to the carbon particles.
  • the carbon particles are positively charged at the anode 8 of the electrolytic cell and transport electrical charge to the copper surface of the workpiece 5 to be machined. In addition to chemical etching, copper is then also removed electrochemically, the carbon particles releasing their charge.
  • the etching rate is increased considerably by adding activated carbon powder particles.
  • the current yield decreases with increasing iron content in the etching solution, measured in g fur.
  • the copper content in the etching solution measured in g Cu / l, and the current density maintained in the electrolysis cell, measured in A / dm 2 , counteract this.
  • the higher the copper content and the higher the current density the higher the current efficiency.
  • the functions shown in FIG. 3, which show the dependence of the current yield on iron content in the etching solution, apply to constant values of copper content and current density. If the current efficiency reaches the value O, copper deposition no longer takes place at the cathode.
  • Curve I in the diagram shows the charge transfer for a sulfuric acid, but iron-free, etching solution which contains 15% by weight of activated carbon powder in suspended form.
  • Curve II shows the charge transfer for a sulfuric acid etching solution with iron (III) sulfate in a concentration corresponding to 10 g Fe / 1 etching solution.
  • the charge transfer for the etching solution with 15% by weight of activated carbon powder and iron (III) sulfate in a concentration corresponding to 10 g Fe / l finally shows curve 111.
  • the diagram shows that with a sulfuric acid, iron (III) - Sulphate-containing etching solution, in which activated carbon powder particles are suspended, surprisingly high values can be achieved for the charge transfer in the electrolysis cell.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Crushing And Grinding (AREA)
  • Manufacture And Refinement Of Metals (AREA)
EP79104575A 1978-11-22 1979-11-19 Verfahren zum Ätzen von Oberflächen aus Kupfer oder Kupferlegierungen Expired EP0011800B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT79104575T ATE652T1 (de) 1978-11-22 1979-11-19 Verfahren zum aetzen von oberflaechen aus kupfer oder kupferlegierungen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2850542A DE2850542C2 (de) 1978-11-22 1978-11-22 Verfahren zum Ätzen von Oberflächen aus Kupfer oder Kupferlegierungen
DE2850542 1978-11-22

Publications (2)

Publication Number Publication Date
EP0011800A1 EP0011800A1 (de) 1980-06-11
EP0011800B1 true EP0011800B1 (de) 1982-02-03

Family

ID=6055278

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79104575A Expired EP0011800B1 (de) 1978-11-22 1979-11-19 Verfahren zum Ätzen von Oberflächen aus Kupfer oder Kupferlegierungen

Country Status (8)

Country Link
US (1) US4265722A (enrdf_load_stackoverflow)
EP (1) EP0011800B1 (enrdf_load_stackoverflow)
JP (1) JPS5573872A (enrdf_load_stackoverflow)
AT (1) ATE652T1 (enrdf_load_stackoverflow)
AU (1) AU527609B2 (enrdf_load_stackoverflow)
BE (1) BE893883Q (enrdf_load_stackoverflow)
CA (1) CA1152939A (enrdf_load_stackoverflow)
DE (1) DE2850542C2 (enrdf_load_stackoverflow)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4416725A (en) * 1982-12-30 1983-11-22 International Business Machines Corporation Copper texturing process
DE3539886A1 (de) * 1985-11-11 1987-05-14 Hoellmueller Maschbau H Verfahren und vorrichtung zum aetzen eines zumindest teilweise aus metall, vorzugsweise kupfer, bestehenden aetzguts
US4879045A (en) * 1986-01-13 1989-11-07 Eggerichs Terry L Method and apparatus for electromagnetically treating a fluid
US5531874A (en) * 1994-06-17 1996-07-02 International Business Machines Corporation Electroetching tool using localized application of channelized flow of electrolyte
GB2293390A (en) * 1994-09-20 1996-03-27 British Tech Group Simultaneous etchant regeneration and metal deposition by electrodialysis
DE19850530A1 (de) * 1998-11-03 2000-05-25 Eilenburger Elektrolyse & Umwelttechnik Gmbh Kreislaufverfahren zum Beizen von Kupfer und Kupferlegierungen
US6656370B1 (en) * 2000-10-13 2003-12-02 Lenora Toscano Method for the manufacture of printed circuit boards
DE10059743A1 (de) * 2000-12-01 2002-06-20 Rolf Hempelmann Verfahren zur Katalysatorabscheidung
SE519898C2 (sv) * 2001-09-10 2003-04-22 Obducat Ab Sätt att etsa koppar på kort samt anordning och elektrolyt för utförande av sättet
DE10326767B4 (de) * 2003-06-13 2006-02-02 Atotech Deutschland Gmbh Verfahren zur Regenerierung von eisenhaltigen Ätzlösungen zur Verwendung beim Ätzen oder Beizen von Kupfer oder Kupferlegierungen sowie eine Vorrichtung zur Durchführung desselben
US20050067378A1 (en) * 2003-09-30 2005-03-31 Harry Fuerhaupter Method for micro-roughening treatment of copper and mixed-metal circuitry
CN103924243A (zh) * 2013-01-11 2014-07-16 上海飞凯光电材料股份有限公司 一种蚀刻液组合物
EP2754732B1 (en) * 2013-01-15 2015-03-11 ATOTECH Deutschland GmbH Aqueous composition for etching of copper and copper alloys
JP6684395B1 (ja) 2018-06-28 2020-04-22 古河電気工業株式会社 銅合金板材及び銅合金板材の製造方法並びに銅合金板材を用いたコネクタ
CN108866572A (zh) * 2018-08-27 2018-11-23 苏碧云 一种铁置换铜电解槽
CN111809184B (zh) * 2020-07-15 2022-03-04 深圳市祺鑫环保科技有限公司 再生子液回用方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3033793A (en) * 1958-08-13 1962-05-08 Photo Engravers Res Inc Powderless etching of copper photoengraving plates
US3622478A (en) * 1960-11-14 1971-11-23 Gen Electric Continuous regeneration of ferric sulfate pickling bath
SU438729A1 (ru) * 1970-07-17 1975-01-23 Предприятие П/Я А-7125 Способ регенерации сернокислых и хлористых травильных растворов железа
US3974050A (en) * 1971-10-12 1976-08-10 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Method of and apparatus for processing the surface of bodies
US3788915A (en) * 1972-02-09 1974-01-29 Shipley Co Regeneration of spent etchant
US4153531A (en) * 1976-08-21 1979-05-08 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Apparatus for electrochemically processing metallic surfaces
DE2641905C2 (de) * 1976-09-17 1986-03-20 Geb. Bakulina Galina Aleksandrovna Batova Verfahren zur Regenerierung verbrauchter Ätzlösungen
DE2655137C2 (de) * 1976-12-04 1978-06-08 Kernforschungsanlage Juelich Gmbh, 5170 Juelich Verfahren zur elektrochemischen Bearbeitung metallischer Oberflächen

Also Published As

Publication number Publication date
DE2850542A1 (de) 1980-06-04
JPS636632B2 (enrdf_load_stackoverflow) 1988-02-10
EP0011800A1 (de) 1980-06-11
US4265722A (en) 1981-05-05
ATE652T1 (de) 1982-02-15
DE2850542C2 (de) 1982-07-01
JPS5573872A (en) 1980-06-03
AU527609B2 (en) 1983-03-10
BE893883Q (fr) 1982-11-16
AU5309379A (en) 1980-05-29
CA1152939A (en) 1983-08-30

Similar Documents

Publication Publication Date Title
EP0011800B1 (de) Verfahren zum Ätzen von Oberflächen aus Kupfer oder Kupferlegierungen
DE2850564C2 (de) Verfahren und Vorrichtung zum Regenerieren einer Kupfer(II)-Chlorid und/oder Eisen(III)-Chlorid enthaltenden Ätzlösung in einer Elektrolysezelle
DE2537757C3 (de) Verfahren zum Wiederverwenden einer Ätzlösung
DE68920615T2 (de) Verfahren zur Regenerierung eines Permanganatbeizbades.
DE69219063T2 (de) Verfahren zum Regenerieren von Ätzmitteln
DE3141949A1 (de) Verfahren zur kontinuierlichen regeneration von eisentrichloridloesungen
DE1094245B (de) Bleidioxyd-Elektrode zur Verwendung bei elektrochemischen Verfahren
DE602004009572T2 (de) Verfahren zur regeneration von eisenhaltigen ätzlösungen zur verwendung beim ätzen oder beizen von kupfer oder kupferlegierungen und vorrichtung zur durchführung des verfahrens
DE2008766B2 (de) Verfahren zum regenerieren einer kupferhaltigen aetzloesung insbesondere fuer die herstellung von gedruckten schaltungen
DE2641905C2 (de) Verfahren zur Regenerierung verbrauchter Ätzlösungen
EP0240589B1 (de) Verfahren zur Regenerierung eines stromlosen Verkupferungsbades und Vorrichtung zur Durchführung desselben
DE69010271T2 (de) Regenerierung von verbrauchten Ferrichlorid-Ätzmitteln.
DE4407448C2 (de) Elektrolyseverfahren zum Regenerieren einer Eisen-III-Chlorid- oder Eisen-III-Sulfatlösung, insbesondere zum Sprühätzen von Stahl
WO2000026440A2 (de) Kreislaufverfahren zum beizen von kupfer und kupferlegierungen
DE19532784C2 (de) Elektrolyseverfahren zum Regenerieren verbrauchter Eisen-III-chlorid- oder Eisen-III-sulfat-Ätzlösungen
EP0011801B1 (de) Verfahren zur elektrochemischen Bearbeitung metallischer Oberflächen
DE3324450A1 (de) Ammoniumsulfathaltige aetzloesung sowie verfahren zur regeneration der aetzloesung
EP0141905B1 (de) Verfahren zur elektrochemischen Kompensation der Luftoxidation bei der elektrochemischen Regenerierung von chloridhaltigen Kupferätzlösungen
DE4218916C2 (de) Verwendung einer Gitteranode zur elektrolytische Entgiftung oder Regeneration einer Cyanid enthaltenden wäßrigen Lösung
EP0638522A1 (de) Verfahren zum Abbau von oxidierbaren und reduzierbaren Verbindungen in Prozess-und Abwässern
DE4229917C1 (en) Electrolytic bath for meter coating - has sec. anode contg. alkaline or ammonium soln. with acid added to electrolyte to compensate for pH rise
DE4118725A1 (de) Verfahren und vorrichtung zur vollstaendigen regeneration von aetzloesungen
DE3245474C2 (enrdf_load_stackoverflow)
DE19646945A1 (de) Verfahren und Vorrichtung zur Aufarbeitung oder Regenerierung von Ätzbädern
DD294513A5 (de) Verfahren zum aufarbeiten von kupfer(i)chloridhaltigen elektrolyten

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH FR GB IT NL SE

17P Request for examination filed

Effective date: 19801031

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE CH FR GB IT NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19820203

REF Corresponds to:

Ref document number: 652

Country of ref document: AT

Date of ref document: 19820215

Kind code of ref document: T

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19841231

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19861008

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19871130

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Effective date: 19881119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19881120

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19890601

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
EUG Se: european patent has lapsed

Ref document number: 79104575.0

Effective date: 19890725

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19971103

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19971117

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19971125

Year of fee payment: 19

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981130

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19981119

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990730

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT