EP0448870A1 - System und Verfahren zum Ätzen mit alkalischen ammoniakalen Ätzlösungen und deren Regenerierung - Google Patents

System und Verfahren zum Ätzen mit alkalischen ammoniakalen Ätzlösungen und deren Regenerierung Download PDF

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Publication number
EP0448870A1
EP0448870A1 EP90313186A EP90313186A EP0448870A1 EP 0448870 A1 EP0448870 A1 EP 0448870A1 EP 90313186 A EP90313186 A EP 90313186A EP 90313186 A EP90313186 A EP 90313186A EP 0448870 A1 EP0448870 A1 EP 0448870A1
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Prior art keywords
etchant
etchant solution
working
solution
spent
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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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Application number
EP90313186A
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English (en)
French (fr)
Inventor
Raymond A. Letize
Bernd Gigas
Peter E. Kukanskis
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MacDermid Inc
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MacDermid Inc
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Publication date
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Publication of EP0448870A1 publication Critical patent/EP0448870A1/de
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    • 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 present invention relates to etchant baths for dissolution of metals and, more particularly, to a system and process for regenerating alkaline ammoniacal etchant solutions which have reached a degree of reduced etching ability, particularly as a consequence of increased concentration therein of etched metals.
  • etchants for copper are potentially useful in processes of this type, but considerations of undesired aggressiveness toward other metals and materials, and desired high copper etch rates, greatly narrow the range of commercially practical etchant solutions.
  • One class of etchant solutions which have of late been a subject of interest are alkaline ammoniacal etchant solutions, typically aqueous solutions of cupric sulfate, ammonium sulfate or like non-halogen ammonium salts, and sufficient ammonium hydroxide to adjust the pH of the solution to a value in the range of from about 8.0 to 10.0, preferably about 8.5 to 9.5.
  • working alkaline ammoniacal etchant solution which has been employed in the etching of copper in a suitable etching chamber is drawn off from the etching chamber as "spent etchant" and transferred to a spent etchant collection or storage vessel; spent etchant from the spent etchant storage vessel is drawn off therefrom to an electrolytic treatment vessel in which the spent etchant is electrolyzed to remove therefrom, in the form of elemental metal deposited on the cathode, at least a portion of the etched metals (e.g., copper) contained in the spent etchant as a consequence of its etching of copper; the so-treated spent etchant of reduced etched metal content is drawn off from the electrolytic treatment vessel as "fresh etchant" and transferred to a fresh etchant collection or storage vessel; and fresh etchant is withdrawn from the fresh etchant storage vessel and transferred to the etching chamber for admixture with the working alka
  • an oxygen-containing gas is employed to effect oxidation of cuprous ion to cupric ion, and ammonia is employed to maintain the appropriate pH in the working etchant solution.
  • ammonia is employed to maintain the appropriate pH in the working etchant solution.
  • oxygen and ammonia are at least periodically fed to the etching chamber containing the working alkaline ammoniacal etchant solution such that the appropriate pH is maintained therein and such that the cuprous species generated during the etching (i.e., by the reaction of the cupric species of the working solution with the metallic copper to be etched, in which the metal is oxidized (Cu0 ⁇ Cu+1) and the cupric species is correspondingly reduced (Cu+2 ⁇ Cu+1)) are oxidized back to the cupric (Cu+2) state.
  • this working solution is drawn off as spent etchant (having reduced etching ability because of the build-up therein of oxidized copper), it is then processed in the electrolytic treatment vessel to decrease its copper ion content (by reduction to copper metal at, and plating out onto, the cathode).
  • oxygen and ammonia are also liberated and the electrolyzed solution also may still have present cuprous ions. From this point, the electrolyzed solution can be transferred to the fresh etchant storage vessel, and from there to the etching chamber, without additions of ammonia and/or oxygen, relying on the fact that in the etching chamber, required additions of these gases to the entire working solution will in any event be made as needed.
  • additions of oxygen and/or ammonia could also be made to the electrolyzed solution before it is transferred to the etching chamber, e.g., in the fresh etchant storage vessel and/or at points between transfer into or out of that storage vessel.
  • At least a portion of the oxygen and/or ammonia additions made anywhere in the process can utilize as their source the gases liberated during electrolyzing.
  • Additives which are employed in the alkaline ammoniacal etchant solution as etch rate increasers e.g., small amounts of ammonium halide, water-soluble salts of anions containing sulfur or selenium or tellurium, organic thio compounds and, optionally, water-soluble salts of noble metals, as described in the earlier-mentioned U.S. Patent No. 4,784,785, generally are not regenerated as such in the process, and thus are periodically or continuously metered directly to the working etchant solution used in the etching chamber and/or to fresh etchant before it is transferred to the etching chamber.
  • nitrates may form during the electrolytic treatment, particularly when chloride-containing rate-increasing additives have been employed in the alkaline ammoniacal etchant solution. These nitrates generally have limited solubility in the alkaline ammoniacal etchant solution and, because of the closed nature of the overall etching and regenerating system, the nitrates will precipitate and progressively build up in the system as the overall process continues through etching and regeneration steps, unless the nitrates are maintained at appropriate low levels (i.e., below saturation levels at the temperatures of interest).
  • steps are taken to at least periodically remove a sufficient portion of these nitrates from the system by drawing off solution from any appropriate stage in the overall process (e.g., from the etching chamber or spent etchant storage vessel or fresh etchant storage vessel, etc.), treating the drawn off portion to eliminate or at least reduce the nitrate content thereof (e.g., by crystallization), and then returning the so-treated solution back to an appropriate step in the overall system.
  • this nitrate reduction is effected by at least periodic treatment of a portion of the working alkaline ammoniacal etchant solution drawn off from the etch chamber.
  • the system and process according to the invention are designed ultimately to maintain the alkaline ammoniacal etchant solution at an essentially constant composition, and preferably one which ensures efficient and rapid etching.
  • a high degree of dependable consistency becomes inherent in the process as it is used in the etching of a large quantity of copper-coated substrates.
  • residence times established for particular substrates having generally uniform amounts of copper thereon to be etched can be dependably adhered to over the course of etching a large number of such substrates without undue concern for compositional changes in the etchant which might lead to insufficient etching in the predetermined residence time.
  • efficient regeneration of the etchant leads to greatly improved process economics.
  • the system steps are designed and arranged such that draw off from the etchant solution for regeneration and replenishment thereof can occur at regulated periodic intervals or continuously, thereby maintaining an essentially constant etching composition. So too, the use of storage vessels for spent etchant and for fresh etchant permits these solutions to be accumulated and, thus, enables regeneration to be conducted essen tially independent of the etching process.
  • the system and process of the present invention preferably is operated in conjunction with sensors or meters for on-stream measuring of relevant parameters of the system (e.g., pH, dissolved oxygen, specific gravity, level sensors and the like) and associated controls responsive as necessary to those measured characteristics of the system.
  • relevant parameters of the system e.g., pH, dissolved oxygen, specific gravity, level sensors and the like
  • the system and process of the invention have particular reference to alkaline ammoniacal etchant solutions used in copper etching, and particularly such solutions whose fundamental components are non-halogen cupric and ammonium salts having oxygen in their anion, such as cupric sulfate and ammonium sulfate, and most particularly those solutions containing the rate-increasing additives as set forth in U.S. Patent No. 4,784,785.
  • working alkaline ammoniacal etchant solution is contacted with the substrates to be etched at etching chamber 10 .
  • the etching process can be an immersion etching process, in which case substrates are immersed in the working etchant bath in a suitable vessel, or alternatively a spray etching process, in which case the etchant is supplied to a suitable spraying apparatus (not shown) contained in an appropriately-sized vessel for spraying onto the substrate and for collecting the run-off of the spraying process. Provision can be made for recirculation of run-off etchant back to the spraying apparatus within the etching chamber 10 .
  • the etching process will be carried out at working bath temperatures in the range of from room temperature to about 130°F.
  • a predetermined portion of the working etchant solution in etching chamber 10 is drawn off therefrom as spent etchant through line 15 (e.g., by pump 16 ) and into spent etchant storage vessel 20 in which it can be accumulated and then drawn off for further processing (regeneration) as needed.
  • a portion of spent etchant from spent etchant storage vessel 20 is drawn off therefrom, through line 25 (e.g., via pump 26 ), to electrolytic processing station 30 .
  • the electrolyzing station 30 can be any suitable vessel or parallel sets of vessels containing appropriate anode and cathode elements connected to a rectifier and operated at current densities effective to plate out in metallic form, onto the cathode, at least a portion of the etched metals (copper) contained in the spent etchant solution.
  • gaseous oxygen and ammonia will be produced and liberated and, as described hereinafter, can be vented off and used at other stages in the process for oxidizing cuprous ions to cupric ions and for maintaining suitable operating pH (e.g., between about 8 to 10) in the working etchant bath.
  • the fresh etchant from electrolyzing station 30 now of reduced etched metal content, is drawn off at line 35 (e.g., via pump 36 ) to fresh etchant storage vessel 40 , where it can be accumulated until needed.
  • fresh etchant is drawn off through line 45 (e.g., via pump 46 ) to etching chamber 10 for admixture there with working alkaline ammoniacal etchant solution.
  • oxygen per se or an oxygen-containing gas
  • ammonia for maintaining the pH of the working bath.
  • oxygen and ammonia are added directly to the working etchant solution in etching chamber 10 , as for example through porous diaphragm tubes or pipes arranged therein or at inlets thereto, fed by source lines 101 and 102, respectively.
  • cuprous ions formed in the oxidation of the copper metal being etched and in the corresponding reduction of the cupric ions in the working solution are wholly or partially oxidized to the desired Cu+2 state, and the appropriate operating pH is maintained in the working solution.
  • these feeds of oxygen and ammonia directly to the solution in etching chamber 10 a portion of the working solution (distinct from that portion drawn off as spent etchant) can at least periodically be drawn off from etching chamber 10 , treated in a separate draw-off vessel with oxygen and/or ammonia as necessary, and then returned to the working bath in the etching chamber 10 .
  • the spent etchant after it has been electrolyzed, with oxygen and/or ammonia, at a point prior to its return to the etching chamber 10 for admixture with working etchant solution.
  • one convenient place for such treatment is in fresh etchant storage vessel 40 , where the fresh etchant therein can be admixed with ammonia and/or oxygen as necessary (shown generally as 42 ).
  • one convenient means for effecting these additions is to vent the gases formed in the electrolysis (oxygen, ammonia) directly to the fresh etchant contained in fresh etchant storage vessel 40 (e.g., via line 43 ), either in lieu of or in addition to adds of oxygen and/or ammonia to the fresh etchant storage vessel 40 by other distinct means (e.g., porous tubes or pipes 42 ).
  • fresh etchant from the electrolyzing step can be treated with oxygen and/or ammonia at a separate station either before being fed to, or after leaving, the fresh etchant vessel 40 .
  • a separate station for delivering oxygen and/or ammonia to portions of working solution drawn off from etching chamber 10 for treatment and return to the etching chamber, as previously described.
  • all or a portion of the mixed gases liberated in the electrolyzing step can instead be vented directly to the etching chamber 10 for supplying oxygen and ammonia to the working etchant solution therein.
  • copper and/or ammonium nitrates or complexes thereof may form as a consequence of electrolytic treatment of the spent etchant, a tendency which appears more pronounced when chloride-containing rate-enhancing additives are used in the working alkaline ammoniacal solution. If permitted to build up as the overall process continues in its etching and regeneration steps, and given the fact that the overall system is essentially a closed one, these nitrates eventually will exceed saturation levels in etcher 10 (or in other equipment) and form precipitates therein causing problems of interference with and/or clogging of apparatus associated with the etcher, as well as the general problem of solids build-up requiring interruption of the process to effect removal.
  • means are provided for eliminating or at least reducing the content of these nitrates at any one or more appropriate stages in the overall system.
  • the means for effecting removal of these nitrates is by crystallization and still further by crystallization treatment of a portion of working etchant solution at least periodically drawn off from the etching chamber 10 .
  • crystallization unit 60 is employed to cool portions of working etchant solution, drawn off from etching chamber 10 via line 64 , to temperatures at which nitrate solubility is reduced as compared to that in the working etchant solution, thereby encouraging and effecting precipitation of at least a portion of the nitrates as solids in the crystallization unit.
  • the so-treated etchant solution now of reduced nitrate concentration, is returned as working etchant solution to etching chamber 10 via line 65 where it intermixes with solution having an elevated temperature relative to the crystallization unit, and thus an increased capacity for solubilizing nitrates, thereby substantially eliminating precipitation of nitrates in etching chamber 10 .
  • the crystallization unit 60 can be of any appropriate type or construction, so long as its capacity, efficiency and cooling coil area are sufficient to effect the required temperature drop for the amount of etchant solution required to be drawn off from the etching chamber 10 so as to maintain nitrates at below saturation levels.
  • the removal of nitrates can be conducted by treatment of other solutions in the process, e.g., spent etchant or fresh etchant drawn off from their respective storage vessels for such treatment.
  • control unit 100 is used primarily to assimilate information regarding the specific gravity of the working etchant bath in etching chamber 10 as a measure of the amount of copper etched and the corresponding depletion of active components in the working bath.
  • control unit 100 can assimilate information regarding the quantity and specific gravity of spent etchant solution drawn off from etching chamber 10 via line 15 as additional data for use in indicating the amount of copper etched by the working solution and the depletion of active compounds.
  • control unit 100 can be used to activate, as necessary, transfer means (shown as pump 12 in the accompanying drawing) for delivering to etcher 10 appropriate quantities of fresh additives.
  • transfer means shown as pump 12 in the accompanying drawing
  • control unit 100 is used to activate transfer (e.g., via pump 46 ) of an appropriate quantity of fresh etchant from fresh etch storage vessel 40 for delivery to etching chamber 10 to replenish the working etchant solution therein.
  • a substantially equal volume of the working etchant solution (as spent etchant) is drawn off from etching chamber 10 , via overflow or pumping (e.g., pump 16 ), to spent etchant storage vessel 20 .
  • Spent etchant in vessel 20 can be accumulated (and, if necessary heated) until such time as it is necessary to deliver a portion thereof to the electrolyzing unit 30 and thereafter to fresh etchant storage vessel 40 .
  • Spent etchant in the electrolyzer 30 can be monitored by specific gravity and/or amp-hours and/or residence time therein, to determine when a sufficient quantity of etched copper has been removed therefrom in the form of metallic copper deposited on the cathode.
  • controller 200 which responsively actuates transfer (via pump 36 ) of the so-processed solution to the fresh etchant storage vessel 40 and refilling of the electrolytic cell with a quantity of spent etchant from spent etchant storage vessel 20 (via pump 26 ).
  • Additional controls can be employed in the system, most notably those assimilating information from meters reading pH and dissolved oxygen, for responsively actuating and regulating ammonia (e.g., anhydrous ammonia) and oxygen additions.
  • ammonia e.g., anhydrous ammonia
  • the various storage vessels e.g., for spent etchant and/or for fresh etchant
  • the system of the invention is best operated as a feed and bleed type system where additions of replenished working etchant solution from fresh etchant storage vessel 40 trigger corresponding draw off of spent etchant and regeneration of spent etchant.
  • An important feature of the invention is that regeneration can be carried out and continued independent of the etching process, so that fresh etchant can be built up for reserve in its storage vessel 40 and spent etchant can correspondingly be depleted from its vessel 20 .
  • the system is arranged to be responsive even to substantial periodic replenishment and draw-off demands without being restricted in this regard by capacity- and/or rate-limiting steps (e.g., electrolysis of spent etchant).
EP90313186A 1990-03-21 1990-12-05 System und Verfahren zum Ätzen mit alkalischen ammoniakalen Ätzlösungen und deren Regenerierung Withdrawn EP0448870A1 (de)

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US49688890A 1990-03-21 1990-03-21
US496888 1990-03-21

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993009267A1 (de) * 1991-11-09 1993-05-13 Hans Höllmüller Maschinenbau GmbH & Co. Verfahren zur regeneration eines ammoniakalischen ätzmittels sowie vorrichtung zur durchführung dieses verfahrens
FR2712607A1 (fr) * 1993-11-18 1995-05-24 Elochem Aetztechnik Gmbh Procédé accéléré de rongeage et de séparation des métaux dans les installations de rongeage en milieu ammoniacal.
FR2854905A1 (fr) * 2003-05-16 2004-11-19 Airbus France Procede de recuperation du cuivre d'une solution de gravure ammoniacale usee et de regeneration d'un sel d'ammonium
WO2007055670A1 (fr) * 2005-11-11 2007-05-18 Eve Recycling Sarl Procede de recyclage de solution de gravure pour le traitement des cartes imprimees
CN110172701A (zh) * 2019-05-08 2019-08-27 深圳市祺鑫天正环保科技有限公司 酸性蚀刻液再生回用系统
CN114752940B (zh) * 2022-04-21 2024-02-06 盛隆资源再生（无锡）有限公司 一种碱性含铜蚀刻废液的回收方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030012087A (ko) * 2001-07-30 2003-02-12 일성기계공업 주식회사 섬유가공시 발생되는 암모니아 가스의 재사용을 위한설비시스템
RU2622072C1 (ru) * 2016-01-11 2017-06-09 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Пензенский государственный университет" (ФГБОУ ВПО "Пензенский государственный университет") Способ утилизации отработанного медно-аммиачного раствора

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0144742A1 (de) * 1983-11-08 1985-06-19 Forschungszentrum Jülich Gmbh Verfahren und Anlage zum Regenerieren einer ammoniakalischen Ätzlösung
DE3608516A1 (de) * 1986-03-14 1987-09-17 Markus Maria Dipl In Bringmann Vorrichtung zum kontinuierlichen elektrolytischen regenerieren einer zumindest teilweise verbrauchten kupfertetraminkomplex-aetzloesung
EP0117068B1 (de) * 1983-01-20 1988-03-23 The Electricity Council Verfahren und Vorrichtung zum Ätzen von Kupfer
DE3738022A1 (de) * 1987-11-09 1989-05-18 Holzer Walter Verfahren zur regenerierung von alkalischen aetzmitteln und vorrichtungen zur ausuebung des verfahrens

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0117068B1 (de) * 1983-01-20 1988-03-23 The Electricity Council Verfahren und Vorrichtung zum Ätzen von Kupfer
EP0144742A1 (de) * 1983-11-08 1985-06-19 Forschungszentrum Jülich Gmbh Verfahren und Anlage zum Regenerieren einer ammoniakalischen Ätzlösung
DE3608516A1 (de) * 1986-03-14 1987-09-17 Markus Maria Dipl In Bringmann Vorrichtung zum kontinuierlichen elektrolytischen regenerieren einer zumindest teilweise verbrauchten kupfertetraminkomplex-aetzloesung
DE3738022A1 (de) * 1987-11-09 1989-05-18 Holzer Walter Verfahren zur regenerierung von alkalischen aetzmitteln und vorrichtungen zur ausuebung des verfahrens

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993009267A1 (de) * 1991-11-09 1993-05-13 Hans Höllmüller Maschinenbau GmbH & Co. Verfahren zur regeneration eines ammoniakalischen ätzmittels sowie vorrichtung zur durchführung dieses verfahrens
FR2712607A1 (fr) * 1993-11-18 1995-05-24 Elochem Aetztechnik Gmbh Procédé accéléré de rongeage et de séparation des métaux dans les installations de rongeage en milieu ammoniacal.
DE4339320A1 (de) * 1993-11-18 1995-05-24 Elochem Aetztechnik Gmbh Verfahren zum beschleunigten Ätzen und Abscheiden von Metallen in ammoniakalischen Ätzanlagen
GB2283983A (en) * 1993-11-18 1995-05-24 Elochem Aetztechnik Gmbh Controlling the nitrate content of ammoniacal etching agent by electrolytic regeneration of used agent and recycling
GB2283983B (en) * 1993-11-18 1997-07-02 Elochem Aetztechnik Gmbh Process for the accelerated etching and refining of metals in ammoniacal etching systems
FR2854905A1 (fr) * 2003-05-16 2004-11-19 Airbus France Procede de recuperation du cuivre d'une solution de gravure ammoniacale usee et de regeneration d'un sel d'ammonium
WO2004104269A1 (fr) * 2003-05-16 2004-12-02 Airbus France Procede de recuperation du cuivre d'une solution de gravure ammoniacale usee et de regeneration d'un sel d'ammonium
WO2007055670A1 (fr) * 2005-11-11 2007-05-18 Eve Recycling Sarl Procede de recyclage de solution de gravure pour le traitement des cartes imprimees
CN110172701A (zh) * 2019-05-08 2019-08-27 深圳市祺鑫天正环保科技有限公司 酸性蚀刻液再生回用系统
CN110172701B (zh) * 2019-05-08 2021-02-09 深圳市祺鑫环保科技有限公司 酸性蚀刻液再生回用系统
CN114752940B (zh) * 2022-04-21 2024-02-06 盛隆资源再生（无锡）有限公司 一种碱性含铜蚀刻废液的回收方法

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CA2029444A1 (en) 1991-09-22
JPH05279875A (ja) 1993-10-26

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