WO2015093297A1 - Electrolytic etching method and electrolytic etching fluid - Google Patents

Electrolytic etching method and electrolytic etching fluid Download PDF

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WO2015093297A1
WO2015093297A1 PCT/JP2014/082072 JP2014082072W WO2015093297A1 WO 2015093297 A1 WO2015093297 A1 WO 2015093297A1 JP 2014082072 W JP2014082072 W JP 2014082072W WO 2015093297 A1 WO2015093297 A1 WO 2015093297A1
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electrolytic etching
etching solution
metal
noble metal
treated
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PCT/JP2014/082072
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French (fr)
Japanese (ja)
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クリストファー コルドニエ
本間　英夫
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学校法人関東学院
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F5/00—Electrolytic stripping of metallic layers or coatings
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids

Definitions

  • the present invention relates to an electrolytic etching method and an electrolytic etching solution, and in particular, to an electrolytic etching method and an electrolytic etching solution that can selectively etch a noble metal-containing metal film formed on a base material made of a base metal material such as aluminum. .
  • a recording medium such as a hard disk
  • a display device such as a liquid crystal display
  • a semiconductor device various materials such as a metal material are formed on a processing substrate using a sputtering apparatus or the like.
  • a PtCoCr film or the like is formed as a perpendicular magnetic recording layer of a recording medium by a sputtering method.
  • the recording density can be significantly improved as compared with the conventional in-plane magnetic recording system, it has been widely used in recent years as a recording layer of a recording medium such as a hard disk.
  • a sputtering apparatus generally, a chamber in which a processing substrate and a target are accommodated in a vacuum atmosphere, a sputtering gas supply means for supplying a sputtering gas into the chamber, and glow discharge using the target as one electrode are performed in the chamber.
  • plasma generating means for generating plasma.
  • a thin film can be formed on the surface of the substrate by causing the plasma cations generated in the chamber to collide with the target and depositing atoms (sputtered atoms) knocked out of the target on the surface of the substrate (for example, (See “Patent Document 1”).
  • sputtered atoms or the like may be scattered / diffused around the processing substrate during film formation and adhere / deposit on the inner wall of the chamber.
  • a shield plate is disposed in the chamber so as to surround the processing space, and sputtered atoms and the like scattered / diffused during film formation are attached / deposited on the shield plate, and deposited on the shield plate, whereby the inner wall of the chamber Etc. are protected.
  • the shield plate is periodically replaced, and the used shield plate is cleaned by etching or the like and reused.
  • a metal coating containing a noble metal such as Pt or Co, such as the PtCoCr film has high corrosion resistance, and it is difficult to completely remove it from the surface of the shield plate by etching.
  • the shield plate is made of a base metal material having low corrosion resistance such as aluminum, the surface of the shield plate is also eroded until the noble metal-containing metal coating is completely dissolved and removed from the surface of the shield plate, It becomes difficult to reuse the shield plate.
  • the present invention provides an electrolytic etching method and electrolytic etching capable of selectively etching a noble metal-containing metal film provided on the surface of a base material while maintaining the shape of the base material made of a base metal material such as aluminum. It is an object to provide a liquid.
  • the electrolytic etching method according to the present invention is an electrolytic etching method for removing, by etching, a material having a noble metal-containing metal coating on the surface of a base material made of a base metal material, and is represented by the following formula (1).
  • the material to be treated is immersed in an electrolytic etching solution containing a complexing agent of 1 g / L to 100 g / L and having a pH adjusted to 2 to 7, and the voltage is applied to the other electrode using the material to be treated as an anode. And an anodized film is formed on the surface of the substrate while etching the noble metal-containing metal film.
  • the base metal is preferably one or more of Al, Ti, Zr, Nb, Mo, Hf, Ta, and W.
  • the composition component of the electrolytic etching solution does not include a substance that acts as a chloride ion source.
  • the composition component of the electrolytic etching solution preferably contains a substance that acts as a potassium ion source.
  • the electrolytic etching solution according to the present invention is an electrolytic etching solution for removing, by etching, a material having a noble metal-containing metal coating on the surface of a base material made of a base metal material, and is represented by the following formula (1). It is characterized in that it contains 1 g / L to 100 g / L of a complexing agent and the pH is adjusted to 2 to 7.
  • an electrolytic etching solution having a pH of 2 to 6 containing the complexing agent represented by the formula (1) a voltage is applied between the treated material as an anode and another electrode.
  • the metal components constituting the noble metal-containing metal film can be stably held as a complex in the electrolytic etching solution.
  • an anodized film is formed on the surface of the base material, so that it is possible to prevent the surface of the base material made of a base metal material from eluting into the electrolytic etching solution.
  • a noble metal containing metal film can be physically peeled from the surface of a base material by forming an anodic oxide film on the surface of a base material. That is, according to the present invention, only the noble metal-containing metal film can be selectively etched from the surface of the base material while maintaining the shape of the base material.
  • the electrolytic etching method and the electrolytic etching solution according to the present invention are an electrolytic etching method and an electrolytic etching solution for removing a material to be processed having a noble metal-containing metal coating on the surface of a base material made of a base metal material. For example, it is possible to selectively etch only a metal film containing a noble metal that is a difficult-to-etch substance provided on the surface of the base material without eroding the surface of the base material made of aluminum or aluminum alloy.
  • the material to be treated is not particularly limited as long as it includes a noble metal-containing metal coating on the surface of a base material made of a base metal material.
  • the base metal is used as a term for a noble metal and refers to a metal that has a large ionization tendency and is not chemically stable. Specifically, it refers to alkali metal, alkaline earth metal, aluminum, iron, zinc, lead, etc., and the present invention forms an anodic oxide film that is insoluble in the electrolytic etching solution, particularly during the electrolytic etching described later. Suitable for base metals.
  • Examples of base metals that form an anodic oxide film insoluble in such an electrolytic etching solution include Al, Ti, Zr, Nb, Mo, Hf, Ta, and W.
  • a base metal material means these base metals themselves or the alloy which has these base metals as a main component.
  • the electrolytic etching method according to the present invention is suitable for a material to be processed having a noble metal-containing coating on the surface of a base material made of aluminum or an aluminum alloy.
  • Specific examples of the material to be processed include a shield plate used in the chamber of the above-described sputtering apparatus. That is, a shield plate made of aluminum or aluminum alloy on which a noble metal-containing metal film is formed can be used as the material to be processed. However, it is not limited to this used shield plate, and its use, shape, etc. are not particularly limited as long as it is a base material made of a base metal material having a noble metal-containing coating on the surface.
  • the noble metal-containing metal film may be a metal film made of a noble metal, a metal film made of a noble metal alloy, or the like, and the form is particularly limited as long as it is a metal film containing a noble metal. It is not a thing.
  • a noble metal refers to gold, silver, and a platinum group element (ruthenium, rhodium, palladium, osmium, iridium, platinum). Since these have a small ionization tendency and are resistant to acids, they correspond to so-called etching difficult substances.
  • the noble metal-containing metal film is not particularly limited as long as it is a metal film containing the above-mentioned noble metal, but as a noble metal-containing metal film suitable for applying the electrolytic etching method according to the present invention, CoCr-based alloy containing
  • the perpendicular magnetic recording layer of the perpendicular magnetic recording medium is composed of a PtCoCr film formed by a sputtering apparatus or the like, and such a PtCoCr film may be formed on an aluminum shield plate.
  • Electrolytic etching solution The electrolytic etching solution according to the present invention includes 1 g / L to 100 g / L of a complexing agent represented by the following formula (1), and has a pH of 2 to 7.
  • the electrolytic etching solution according to the present invention includes a complexing agent represented by the formula (1) described later, and may have any composition as long as the pH is 2 to 6, but is an acid solution described later.
  • it is preferable that the pH value is in the range of 2 to 6 and adjusted to a predetermined value by an electrolyte and / or a pH adjusting agent described later.
  • the pH value of the electrolytic etching solution is preferably within the range of 2 to 6 described above.
  • the value is more preferably in the range of 3 to 5, and the pH value is more preferably in the range of 3.5 to 4.5.
  • the electrolytic etching solution according to the present invention contains a complexing agent represented by the following formula (1) in a range of 1 g / L to 100 g / L, thereby forming a metal constituting a noble metal-containing metal film. It can form a complex with the component and can be stably held in the electrolytic etching solution.
  • n in the formula (1) is in the range of 1 ⁇ n ⁇ 7. This is because these compounds form better complexes with the noble metal components constituting the noble metal-containing metal coating, and these noble metal components can be stably retained in the electrolytic etching solution. If the value of n exceeds the above range, the viscosity of the electrolytic etching solution becomes high, and the diffusion coefficient of the electrolytic etching solution becomes small.
  • n 1 aminoethanethiol or the like can be suitably used.
  • X which is a terminal group may be either an amino group (—NH 2 ) or a thiol group (—SH), and an appropriate one can be selected according to the purpose.
  • the terminal group X is an amino group
  • the electrolytic etching rate is faster than when the terminal group X is a thiol group.
  • the terminal group X is an amino group
  • the terminal group X is a thiol group
  • the noble metal component which is easy to form a metal complex differs.
  • the terminal group X when the terminal group X is an amino group, it exhibits selective etching properties for Co, and when the terminal group is a thiol group, it exhibits selective etching properties for Pt. For this reason, it is preferable to select a more appropriate compound as appropriate according to the type of the noble metal component constituting the noble metal-containing film.
  • the content of the complexing agent in the electrolytic etching solution is 1 g / L to 100 g / L as described above. From the viewpoint of bringing the metal component and the complexing agent into good contact, the etching solution The content of the complexing agent is more preferably 20 g / L to 50 g / L.
  • the electrolytic etching solution according to the present invention is an acidic to weakly acidic solution having a pH of 2 to 6, and the above complexing agent, electrolyte, and acid solution obtained by dissolving various strong acids or weak acids in a solvent.
  • various components such as a pH adjuster can be added.
  • the composition component of the electrolytic etching solution does not include a substance that acts as a chloride ion source. This is because chloride ions are highly reactive with aluminum, which is a constituent material of the base material, and when the electrolytic etching method described later is applied, the surface of the base material may be eroded.
  • an acid solution other than an acid such as hydrochloric acid containing chlorine in the chemical formula and ionizing in an aqueous solution to generate chloride ions for example, a strong acid such as sulfuric acid or sulfonic acid, or a weak acid such as carbonic acid, nitric acid, or carboxylic acid can be used.
  • a strong acid such as sulfuric acid or sulfonic acid, or a weak acid such as carbonic acid, nitric acid, or carboxylic acid
  • the sulfonic acid alkylsulfonic acid such as methanesulfonic acid and ethanesulfonic acid, allylsulfonic acid and the like can be used.
  • the carboxylic acid may be an organic acid having at least one carboxy group, but is particularly preferably a monocarboxylic acid having one carboxy group.
  • a hydroxy acid such as lactic acid or glycolic acid having a hydroxy group in the vicinity of the carboxy group
  • the organic acid an ⁇ -hydroxycarboxylic acid represented by the following formula (2) is used. More preferably, it is used. What is necessary is just to select suitably 1 type or multiple types from the acid mentioned above according to the pH value of the electrolytic etching liquid to prepare. In particular, it is preferable to use alkylsulfonic acid and sulfuric acid in combination.
  • R 1 and R 2 are each hydrogen, a hydrocarbon having 1 to 4 carbon atoms, an alkylamine having 1 to 4 carbon atoms, or an alkyl ether having 1 to 4 carbon atoms.
  • R 1 and R 2 may be any of these, but it is not preferable that both the carbon number of R 1 and the carbon number of R 2 are 4.
  • the sum of the carbon number of R 1 and the carbon number of R 2 is more preferably 4 or less. This is because as the carbon number increases, the solubility in the electrolytic etching solution decreases.
  • Electrolyte and pH adjuster are also preferably not substances that act as a chloride ion source. That is, it is preferably a substance that acts as an anion source other than chloride ions.
  • the above-described acids that is, salts of sulfuric acid, sulfonic acid, carbonic acid, nitric acid, carboxylic acid, etc. are preferable.
  • An alkali salt such as a salt, potassium salt, sodium salt, rubidium salt or cesium salt is preferred, and a potassium salt is particularly preferred.
  • the pH value of the electrolytic etching solution can be set to a predetermined value between 2 and 6.
  • the electrolyte and the pH adjuster are not substances that act as a chloride ion source, but are preferably substances that act as a potassium ion source. That is, a potassium salt of a substance that acts as an anion source other than chloride ions is preferable. Specifically, potassium sulfate, potassium sulfonate, potassium carbonate, potassium nitrate, and potassium carboxylate are preferable. In addition, 1 type or multiple types of electrolyte and pH adjuster can respectively be used appropriately as appropriate.
  • the electrolytic etching solution according to the present invention contains the complexing agent represented by the formula (1) within the range of 1 g / L to 100 g / L, and the pH is within the range of 2 to 6.
  • the above-mentioned acid, electrolyte, pH adjuster and the like can be included, but in addition to the above-described components, various components used as additives for an electrolytic etching solution such as a surfactant are the gist of the present invention. Of course, it may be used as a composition component without departing from the scope of the present invention.
  • the electrolytic etching method according to the present invention is an electrolytic etching method for removing a material to be processed having a noble metal-containing metal coating on the surface of a base material made of a base metal material, and is represented by the above-described formula (1).
  • a material to be treated is immersed in an electrolytic etching solution containing 1 g / L to 100 g / L of a complexing agent and having a pH of 2 to 7, and a voltage is applied between other electrodes using the material to be treated as an anode. Then, an anodic oxide film is formed on the surface of the base material while etching the noble metal-containing metal film.
  • FIG. 1 (a) schematically shows a cross section of a material to be processed.
  • the material to be treated shown in FIG. 1A is provided with a noble metal-containing metal film that is a physical vapor deposition film on the surface of a base material made of the above-mentioned base metal material.
  • the noble metal-containing metal film is a PtCoCr film formed on the surface of the substrate by sputtering.
  • This material to be treated is immersed in the above-described electrolytic etching solution, and a voltage is applied between the other material with the material to be treated as an anode.
  • the electrolysis temperature is higher because the electrolytic etching rate becomes faster.
  • the electrolysis temperature is too high, the anodic oxide film formed on the surface of the material to be treated may be dissolved, which is not preferable.
  • decomposition of the bath may occur, and an appropriate electrolytic reaction may not be performed, which is not preferable.
  • it is preferably 30 ° C. to 90 ° C., more preferably 50 ° C. to 80 ° C., and further preferably 65 ° C. to 75 ° C.
  • other electrolytic current densities and the like are preferably set to appropriate conditions for anodizing the metal material according to a material constituting the substrate, for example, a specific metal material such as aluminum.
  • the noble metal-containing metal film is removed from the surface of the base material, and an anodized film is formed on the exposed portion of the surface of the base material. .
  • an anodized film is formed on the entire surface of the substrate.
  • the noble metal-containing metal film provided on the surface of the base material is physically peeled from the surface of the base material by an anodized film formed at the interface between the base material and the noble metal-containing metal film. It is retained in the electrolysis solution as a complex.
  • the base metal-containing metal film containing noble metal such as Pt having high corrosion resistance provided on the surface of the aluminum base material having low corrosion resistance is eroded without eroding the surface of the base material. Only the noble metal-containing metal film can be selectively etched while maintaining the shape of the material.
  • Example 1 the following electrolytic etching solution of the composition with respect to 100 mL, a surface area of 1mm thick on an aluminum substrate 0.8856dm 2 PtCoCr sputtered film (surface area: 0.0320dm 2) to be formed
  • the treatment material was immersed and electrolytic etching was performed under the following conditions.
  • Example 2 electrolytic etching was performed in the same manner as in Example 1 except that aminoethanethiol was used in place of pentaethylenehexamine in the electrolytic etching solution of Example 1.
  • the element ratio of each metal component on the surface of the treated material after electrolytic etching is 100% for Al, and Pt, Co, and Cr are Both were 0%. From this, it was confirmed that according to the electrolytic etching method according to the present invention, it is possible to completely remove the noble metal-containing coating containing the noble metal which is a difficult etching substance from the surface of the material to be treated.
  • the element ratios of Al, Pt, Co, and Cr contained in the electrolytic etching solution were as follows.
  • Al contained in the electrolytic etching solution was 23.0%, Pt was 0.5%, and Co was 67.0% and Cr were 9.5%.
  • electrolytic etching was performed using the electrolytic etching solution of Example 2 containing aminoethanethiol as a complexing agent, Al contained in the electrolytic etching solution was 1.0%, Pt was 81.3%, Co Was 8.6%, and Cr was 9.1%.
  • Al was also detected in the electrolytic etching solution. Moreover, although it was trace amount, the deposit was also confirmed and Al was detected also from the deposit. However, considering that Al has a high ionization tendency and is a material that is extremely easily etched compared with noble metal components such as Pt and Co, according to the present invention, the surface of the member to be treated is effectively suppressed from being eluted. We can conclude that we were able to. Further, when the shape of the base material before and after the electrolytic etching was visually observed, it was confirmed that the shape of the base material did not change before and after the electrolytic etching, and the shape of the base material could be maintained.
  • an electrolytic etching solution having a pH of 2 to 6 containing the complexing agent represented by the formula (1) a voltage is applied between the treated material as an anode and another electrode.
  • the metal components constituting the noble metal-containing metal film can be stably held as a complex in the electrolytic etching solution.
  • an anodized film is formed on the surface of the base material, so that it is possible to prevent the surface of the base material made of a base metal material from eluting into the electrolytic etching solution.
  • a noble metal containing metal film can be physically peeled from the surface of a base material by forming an anodic oxide film on the surface of a base material. That is, according to the present invention, it is possible to selectively etch only the noble metal-containing metal film from the surface of the material to be processed while maintaining the shape of the base material. Therefore, the present invention can be suitably applied to the regeneration of the shield plate provided in the chamber of the physical vapor deposition apparatus.

Abstract

　The present invention addresses the problem of providing an electrolytic etching method and an electrolytic etching fluid by which it is possible to selectively etch only a metal film containing a precious metal from the surface of a material to be treated, in a state in which the shape of the material to be treated made of a base metal material is maintained. Provided is an electrolytic etching method for solving the above-mentioned problem, characterized in that the material to be treated is soaked in an electrolytic etching fluid including therein 1 to 100 g/L of a complexing agent represented by formula (1) below, the pH of the electrolytic etching fluid being adjusted to 2-7, a voltage is applied between the material to be treated and another electrode, with the material to be treated being the anode, thereby forming an anodic oxide film on the surface of the base material while etching the metal film containing a precious metal. In formula (1), 1 ≤ n ≤7 and X is an amino group or a thiol group.

Description

電解エッチング方法及び電解エッチング液Electrolytic etching method and electrolytic etching solution
　本件発明は、電解エッチング方法及び電解エッチング液に関し、特に、アルミニウム等の卑金属材料からなる基材上に形成された貴金属含有金属被膜を選択的にエッチングすることのできる電解エッチング方法及び電解エッチング液に関する。 The present invention relates to an electrolytic etching method and an electrolytic etching solution, and in particular, to an electrolytic etching method and an electrolytic etching solution that can selectively etch a noble metal-containing metal film formed on a base material made of a base metal material such as aluminum. .
　ハードディスク等の記録媒体、液晶ディスプレイ等の表示装置、半導体装置等の各種製造工程では、スパッタリング装置等を用いて処理基板上に、金属材料等の各種材料を成膜する。例えば、近年、記録媒体の垂直磁気記録層として、ＰｔＣｏＣｒ膜等をスパッタリング法により成膜することが行われている。この垂直磁気記録方式によれば、従来の面内磁気記録方式と比較すると、記録密度の著しい向上を図ることができることから、近年、ハードディスク等の記録媒体の記録層として広く利用されている。 In various manufacturing processes such as a recording medium such as a hard disk, a display device such as a liquid crystal display, and a semiconductor device, various materials such as a metal material are formed on a processing substrate using a sputtering apparatus or the like. For example, in recent years, a PtCoCr film or the like is formed as a perpendicular magnetic recording layer of a recording medium by a sputtering method. According to this perpendicular magnetic recording system, since the recording density can be significantly improved as compared with the conventional in-plane magnetic recording system, it has been widely used in recent years as a recording layer of a recording medium such as a hard disk.
　ところで、スパッタリング装置では、一般に、処理基板及びターゲットを真空雰囲気下で収容するチャンバと、チャンバ内にスパッタガスを供給するスパッタガス供給手段と、ターゲットを一方の電極としてグロー放電を行うことによりチャンバ内にプラズマを発生させるプラズマ発生手段等を備えている。チャンバ内において発生させたプラズマの陽イオンをターゲットに衝突させ、ターゲットから叩き出された原子（スパッタ原子）を基板表面に堆積させることにより、基板の表面に薄膜を形成することができる（例えば、「特許文献１」参照）。 By the way, in a sputtering apparatus, generally, a chamber in which a processing substrate and a target are accommodated in a vacuum atmosphere, a sputtering gas supply means for supplying a sputtering gas into the chamber, and glow discharge using the target as one electrode are performed in the chamber. Are provided with plasma generating means for generating plasma. A thin film can be formed on the surface of the substrate by causing the plasma cations generated in the chamber to collide with the target and depositing atoms (sputtered atoms) knocked out of the target on the surface of the substrate (for example, (See “Patent Document 1”).
　このようなスパッタリング装置等の物理蒸着装置では、成膜中に処理基板の周囲にもスパッタ原子等が飛散／拡散し、チャンバの内壁等に付着／堆積する場合がある。このため、チャンバ内において、処理空間を囲むようにシールド板を配置し、成膜中に飛散／拡散したスパッタ原子等をシールド板に付着／堆積させ、シールド板に堆積させることにより、チャンバの内壁等を保護している。シールド板は定期的に交換され、使用済みのシールド板はエッチング等により清浄化されて、再利用される。 In such a physical vapor deposition apparatus such as a sputtering apparatus, sputtered atoms or the like may be scattered / diffused around the processing substrate during film formation and adhere / deposit on the inner wall of the chamber. For this reason, a shield plate is disposed in the chamber so as to surround the processing space, and sputtered atoms and the like scattered / diffused during film formation are attached / deposited on the shield plate, and deposited on the shield plate, whereby the inner wall of the chamber Etc. are protected. The shield plate is periodically replaced, and the used shield plate is cleaned by etching or the like and reused.
特開２００９－１２０９２５号公報JP 2009-120925 A
　しかしながら、例えば、上記ＰｔＣｏＣｒ膜のように、Ｐｔ、Ｃｏ等の貴金属を含む金属被膜は耐腐食性が高く、エッチングによりシールド板の表面から完全に除去するのは困難である。また、シールド板がアルミニウム等の耐腐食性の低い卑金属材料からなる場合、シールド板の表面から貴金属含有金属被膜が完全に溶解除去されるまでの間に、シールド板の表面も浸食されてしまい、シールド板を再利用することが困難になる。 However, for example, a metal coating containing a noble metal such as Pt or Co, such as the PtCoCr film, has high corrosion resistance, and it is difficult to completely remove it from the surface of the shield plate by etching. In addition, when the shield plate is made of a base metal material having low corrosion resistance such as aluminum, the surface of the shield plate is also eroded until the noble metal-containing metal coating is completely dissolved and removed from the surface of the shield plate, It becomes difficult to reuse the shield plate.
　そこで、本件発明は、アルミニウム等の卑金属材料からなる基材の形状を保持した状態で、基材の表面に設けられた貴金属含有金属被膜を選択的にエッチングすることができる電解エッチング方法及び電解エッチング液を提供することを課題とする。 Accordingly, the present invention provides an electrolytic etching method and electrolytic etching capable of selectively etching a noble metal-containing metal film provided on the surface of a base material while maintaining the shape of the base material made of a base metal material such as aluminum. It is an object to provide a liquid.
　本発明者等は、鋭意研究を行った結果、以下の電解エッチング方法及び電解エッチング液を採用することで上記課題を達成するに到った。 As a result of intensive studies, the present inventors have achieved the above-mentioned problems by employing the following electrolytic etching method and electrolytic etching solution.
　本件発明に係る電解エッチング方法は、卑金属材料からなる基材の表面に貴金属含有金属被膜を備える被処理材をエッチングにより除去するための電解エッチング方法であって、下記式（１）で表される錯化剤１ｇ／Ｌ～１００ｇ／Ｌを含み、ｐＨが２～７に調整された電解エッチング液に前記被処理材を浸漬し、当該被処理材を陽極として、他の電極との間で電圧を印加して、当該貴金属含有金属被膜をエッチングしながら、当該基材の表面に陽極酸化被膜を形成させることを特徴とする。 The electrolytic etching method according to the present invention is an electrolytic etching method for removing, by etching, a material having a noble metal-containing metal coating on the surface of a base material made of a base metal material, and is represented by the following formula (1). The material to be treated is immersed in an electrolytic etching solution containing a complexing agent of 1 g / L to 100 g / L and having a pH adjusted to 2 to 7, and the voltage is applied to the other electrode using the material to be treated as an anode. And an anodized film is formed on the surface of the substrate while etching the noble metal-containing metal film.
Figure JPOXMLDOC01-appb-C000003
　但し、上記式（１）において、１≦ｎ≦７であり、Ｘはアミノ基又はチオール基である。
Figure JPOXMLDOC01-appb-C000003
However, in said formula (1), it is 1 <= n <= 7 and X is an amino group or a thiol group.
　本件発明に係る電解エッチング方法において、前記卑金属は、Ａｌ，Ｔｉ，Ｚｒ，Ｎｂ，Ｍｏ，Ｈｆ，Ｔａ又はＷのいずれか一種又は二種以上であることが好ましい。 In the electrolytic etching method according to the present invention, the base metal is preferably one or more of Al, Ti, Zr, Nb, Mo, Hf, Ta, and W.
　本件発明に係る電解エッチング方法において、前記電解エッチング液の組成成分には、塩化物イオン源として作用する物質は含まれないことが好ましい。 In the electrolytic etching method according to the present invention, it is preferable that the composition component of the electrolytic etching solution does not include a substance that acts as a chloride ion source.
　本件発明に係る電解エッチング方法において、前記電解エッチング液の組成成分には、カリウムイオン源として作用する物質が含まれることが好ましい。 In the electrolytic etching method according to the present invention, the composition component of the electrolytic etching solution preferably contains a substance that acts as a potassium ion source.
　本件発明に係る電解エッチング液は、卑金属材料からなる基材の表面に貴金属含有金属被膜を備える被処理材をエッチングにより除去するための電解エッチング液であって、下記式（１）で表される錯化剤１ｇ／Ｌ～１００ｇ／Ｌを含み、ｐＨが２～７に調整されたことを特徴とする。 The electrolytic etching solution according to the present invention is an electrolytic etching solution for removing, by etching, a material having a noble metal-containing metal coating on the surface of a base material made of a base metal material, and is represented by the following formula (1). It is characterized in that it contains 1 g / L to 100 g / L of a complexing agent and the pH is adjusted to 2 to 7.
Figure JPOXMLDOC01-appb-C000004
　但し、上記式（１）において、１≦ｎ≦７であり、Ｘはアミノ基又はチオール基である。
Figure JPOXMLDOC01-appb-C000004
However, in said formula (1), it is 1 <= n <= 7 and X is an amino group or a thiol group.
　本件発明によれば、式（１）で表される錯化剤を含むｐＨが２～６の電解エッチング液を用いて、当該被処理材を陽極として、他の電極との間で電圧を印加して、貴金属含有金属被膜をエッチングしながら、貴金属含有金属被膜を構成する金属成分を電解エッチング液中で錯体として安定に保持することができる。これと同時に、基材の表面が露出した場合、基材の表面に陽極酸化被膜が形成されるため、卑金属材料からなる基材の表面が電解エッチング液に溶出するのを防止することができる。また、基材の表面に陽極酸化被膜を形成することにより、基材の表面から貴金属含有金属被膜を物理的に剥離することができる。すなわち、本件発明によれば、基材の形状を保持した状態で、基材の表面から貴金属含有金属被膜のみを選択的にエッチングすることができる。 According to the present invention, using an electrolytic etching solution having a pH of 2 to 6 containing the complexing agent represented by the formula (1), a voltage is applied between the treated material as an anode and another electrode. Thus, while etching the noble metal-containing metal film, the metal components constituting the noble metal-containing metal film can be stably held as a complex in the electrolytic etching solution. At the same time, when the surface of the base material is exposed, an anodized film is formed on the surface of the base material, so that it is possible to prevent the surface of the base material made of a base metal material from eluting into the electrolytic etching solution. Moreover, a noble metal containing metal film can be physically peeled from the surface of a base material by forming an anodic oxide film on the surface of a base material. That is, according to the present invention, only the noble metal-containing metal film can be selectively etched from the surface of the base material while maintaining the shape of the base material.
本件発明に係る電解エッチング方法の手順を説明するための模式図である。It is a schematic diagram for demonstrating the procedure of the electrolytic etching method which concerns on this invention.
　以下、本件発明に係る電解エッチング方法及び電解エッチング液の実施の形態を説明する。 Hereinafter, embodiments of the electrolytic etching method and the electrolytic etching solution according to the present invention will be described.
　まず、本件発明の概要について説明する。本件発明に係る電解エッチング方法及び電解エッチング液は、卑金属材料からなる基材の表面に貴金属含有金属被膜を備える被処理材を除去するための電解エッチング方法及び電解エッチング液であり、本件発明によれば、アルミニウム製又はアルミニウム合金製の基材の表面を浸食することなく、当該基材の表面に設けられたエッチング難物質である貴金属を含有する金属被膜のみを選択的にエッチングすることができる。 First, the outline of the present invention will be described. The electrolytic etching method and the electrolytic etching solution according to the present invention are an electrolytic etching method and an electrolytic etching solution for removing a material to be processed having a noble metal-containing metal coating on the surface of a base material made of a base metal material. For example, it is possible to selectively etch only a metal film containing a noble metal that is a difficult-to-etch substance provided on the surface of the base material without eroding the surface of the base material made of aluminum or aluminum alloy.
　ここで、本件発明において被処理材とは、卑金属材料からなる基材の表面に貴金属含有金属被膜を備えるものであれば特に限定されるものではない。本件発明において、卑金属とは、貴金属に対する語として用いており、イオン化傾向が大きく、化学的に安定ではない金属を指す。具体的には、アルカリ金属、アルカリ土類金属、アルミニウム、鉄、亜鉛、鉛などを指し、本件発明は、特に、後述する電解エッチングの際に、電解エッチング液に不溶の陽極酸化被膜を形成する卑金属に好適である。このような電解エッチング液に不溶の陽極酸化被膜を形成する卑金属として、Ａｌ，Ｔｉ，Ｚｒ，Ｎｂ，Ｍｏ，Ｈｆ，Ｔａ、Ｗ等を挙げることができる。また、卑金属材料とは、これらの卑金属自体又はこれらの卑金属を主成分とする合金を意味する。特に、本件発明に係る電解エッチング方法は、アルミニウム又はアルミニウム合金からなる基材の表面に貴金属含有被膜を備えた被処理材に好適である。被処理材として、具体的には、上述したスパッタリング装置のチャンバ内で用いられたシールド板を挙げることができる。すなわち、貴金属含有金属被膜が成膜されたアルミニウム製又はアルミニウム合金製のシールド板を被処理材とすることができる。しかしながら、この使用済みのシールド板に限定されるものではなく、表面に貴金属含有被膜を備える卑金属材料からなる基材であれば、その用途や形状等が特に限定されるものではない。 Here, in the present invention, the material to be treated is not particularly limited as long as it includes a noble metal-containing metal coating on the surface of a base material made of a base metal material. In the present invention, the base metal is used as a term for a noble metal and refers to a metal that has a large ionization tendency and is not chemically stable. Specifically, it refers to alkali metal, alkaline earth metal, aluminum, iron, zinc, lead, etc., and the present invention forms an anodic oxide film that is insoluble in the electrolytic etching solution, particularly during the electrolytic etching described later. Suitable for base metals. Examples of base metals that form an anodic oxide film insoluble in such an electrolytic etching solution include Al, Ti, Zr, Nb, Mo, Hf, Ta, and W. Moreover, a base metal material means these base metals themselves or the alloy which has these base metals as a main component. In particular, the electrolytic etching method according to the present invention is suitable for a material to be processed having a noble metal-containing coating on the surface of a base material made of aluminum or an aluminum alloy. Specific examples of the material to be processed include a shield plate used in the chamber of the above-described sputtering apparatus. That is, a shield plate made of aluminum or aluminum alloy on which a noble metal-containing metal film is formed can be used as the material to be processed. However, it is not limited to this used shield plate, and its use, shape, etc. are not particularly limited as long as it is a base material made of a base metal material having a noble metal-containing coating on the surface.
　また、貴金属含有金属被膜とは、貴金属からなる金属被膜であってもよいし、貴金属合金からなる金属被膜等であってもよく、貴金属を含有する金属被膜であれば特にその形態が限定されるものではない。また、本件発明において、貴金属とは、金、銀及び白金族元素（ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金）を指す。これらはイオン化傾向が小さく、酸に強いため、いわゆるエッチング難物質に該当する。 The noble metal-containing metal film may be a metal film made of a noble metal, a metal film made of a noble metal alloy, or the like, and the form is particularly limited as long as it is a metal film containing a noble metal. It is not a thing. Moreover, in this invention, a noble metal refers to gold, silver, and a platinum group element (ruthenium, rhodium, palladium, osmium, iridium, platinum). Since these have a small ionization tendency and are resistant to acids, they correspond to so-called etching difficult substances.
　本件発明において、貴金属含有金属被膜は、上記貴金属を含有する金属被膜であれば特に限定されるものではないが、本件発明に係る電解エッチング方法を適用することが好適な貴金属含有金属被膜として、貴金属を含有するＣｏＣｒ系合金が挙げられる。例えば、垂直磁気記録媒体の垂直磁気記録層は、スパッタリング装置等により成膜されるＰｔＣｏＣｒ被膜から構成されており、アルミニウム製のシールド板にはこのようなＰｔＣｏＣｒ被膜が形成されている場合がある。このような場合も本件発明に係る電解エッチング液を用いて、後述する電解エッチング方法を適用することにより、アルミニウム製のシールド板の表面を浸食することなく、シールド板の表面からＰｔＣｏＣｒ被膜のみを剥離することが可能になる。以下、電解エッチング液、電解エッチング方法の順に説明する。 In the present invention, the noble metal-containing metal film is not particularly limited as long as it is a metal film containing the above-mentioned noble metal, but as a noble metal-containing metal film suitable for applying the electrolytic etching method according to the present invention, CoCr-based alloy containing For example, the perpendicular magnetic recording layer of the perpendicular magnetic recording medium is composed of a PtCoCr film formed by a sputtering apparatus or the like, and such a PtCoCr film may be formed on an aluminum shield plate. Even in such a case, only the PtCoCr film is peeled off from the surface of the shield plate without eroding the surface of the shield plate made of aluminum by applying the electrolytic etching method described later using the electrolytic etching solution according to the present invention. It becomes possible to do. Hereinafter, the electrolytic etching solution and the electrolytic etching method will be described in this order.
１．電解エッチング液
　本件発明に係る電解エッチング液は、下記式（１）で表される錯化剤１ｇ／Ｌ～１００ｇ／Ｌを含み、ｐＨが２～７であることを特徴とする。本件発明に係る電解エッチング液は、後述する式（１）で表される錯化剤を含み、ｐＨが２～６であればどのような組成であってもよいが、後述する酸溶液であり、且つ、後述する電解質及び／又はｐＨ調整剤によりｐＨの値が２～６の範囲内であって、所定の値に調整されたものとすることが好ましい。 1. Electrolytic etching solution The electrolytic etching solution according to the present invention includes 1 g / L to 100 g / L of a complexing agent represented by the following formula (1), and has a pH of 2 to 7. The electrolytic etching solution according to the present invention includes a complexing agent represented by the formula (1) described later, and may have any composition as long as the pH is 2 to 6, but is an acid solution described later. In addition, it is preferable that the pH value is in the range of 2 to 6 and adjusted to a predetermined value by an electrolyte and / or a pH adjusting agent described later.
　ここで、当該電解エッチング液のｐＨの値が２未満である場合、基材の表面に陽極酸化被膜を形成したとしても、当該陽極酸化被膜及び基材の構成材料であるアルミニウム又はアルミニウム合金が溶解するため好ましくない。一方、ｐＨの値が６を超える場合、電解エッチング速度が遅くなりすぎ、工業的な処理工程で当該エッチング処理を採用することが難しくなるため好ましくない。基材を浸食することなく、工業的な処理工程で採用可能な電解エッチング速度とするという観点から、電解エッチング液のｐＨの値は上述の２～６の範囲内であることが好ましく、ｐＨの値は３～５の範囲内であることがより好ましく、ｐＨの値は３．５～４．５の範囲内であることがさらに好ましい。
　以下、当該電解エッチング液の各組成毎に説明する。 Here, when the pH value of the electrolytic etching solution is less than 2, even if an anodized film is formed on the surface of the base material, aluminum or an aluminum alloy as a constituent material of the anodized film and the base material is dissolved. Therefore, it is not preferable. On the other hand, when the pH value exceeds 6, the electrolytic etching rate becomes too slow, and it is difficult to employ the etching process in an industrial process, which is not preferable. From the viewpoint of achieving an electrolytic etching rate that can be employed in industrial processing steps without eroding the substrate, the pH value of the electrolytic etching solution is preferably within the range of 2 to 6 described above. The value is more preferably in the range of 3 to 5, and the pH value is more preferably in the range of 3.5 to 4.5.
Hereinafter, each composition of the electrolytic etching solution will be described.
（１）錯化剤
本件発明に係る電解エッチング液は、下記式（１）で表される錯化剤を１ｇ／Ｌ～１００ｇ／Ｌの範囲で含むことにより、貴金属含有金属被膜を構成する金属成分と錯体を形成して電解エッチング液中に安定に保持することができる。 (1) Complexing agent The electrolytic etching solution according to the present invention contains a complexing agent represented by the following formula (1) in a range of 1 g / L to 100 g / L, thereby forming a metal constituting a noble metal-containing metal film. It can form a complex with the component and can be stably held in the electrolytic etching solution.
Figure JPOXMLDOC01-appb-C000005
　但し、上記式（１）において、１≦ｎ≦７であり、Ｘはアミノ基又はチオール基である。
Figure JPOXMLDOC01-appb-C000005
However, in said formula (1), it is 1 <= n <= 7 and X is an amino group or a thiol group.
　上記式（１）で表され、式（１）中のｎが１≦ｎ≦７の範囲内である化合物であれば、いずれであってもよい。これらの化合物は、上記貴金属含有金属被膜を構成する貴金属成分とより良好に錯体を形成し、電解エッチング液中にこれらの貴金属成分を安定に保持することができるためである。ｎの値が上記範囲を超えると、電解エッチング液の粘性が高くなり、電解エッチング液の拡散係数が小さくなるため好ましくない。また、本件発明において、例えば、末端基がアミノ基である場合、上記式（１）中のｎは３≦ｎ≦６であることがより好ましく、ｎ＝５のペンタエチレンヘキサミンを錯化剤として用いることがより好ましい。また、末端基がチオール基である場合、ｎ＝１のアミノエタンチオールなどを好適に用いることができる。 Any compound may be used as long as it is represented by the above formula (1) and n in the formula (1) is in the range of 1 ≦ n ≦ 7. This is because these compounds form better complexes with the noble metal components constituting the noble metal-containing metal coating, and these noble metal components can be stably retained in the electrolytic etching solution. If the value of n exceeds the above range, the viscosity of the electrolytic etching solution becomes high, and the diffusion coefficient of the electrolytic etching solution becomes small. In the present invention, for example, when the terminal group is an amino group, n in the above formula (1) is more preferably 3 ≦ n ≦ 6, and n = 5 pentaethylenehexamine is used as a complexing agent. More preferably, it is used. In addition, when the terminal group is a thiol group, n = 1 aminoethanethiol or the like can be suitably used.
　また式（１）において末端基であるＸは、アミノ基（－ＮＨ２）及びチオール基（－ＳＨ）のいずれであってもよく、目的に応じて適宜適切なものを選択することができる。末端基Ｘがアミノ基である場合、末端基Ｘがチオール基である場合と比較すると電解エッチング速度が速くなる。また、末端基Ｘがアミノ基である場合と、末端基Ｘがチオール基である場合には、金属錯体を形成しやすい貴金属成分が異なる。例えば、末端基Ｘがアミノ基である場合、Ｃｏに対する選択エッチング性を示し、末端基がチオール基である場合、Ｐｔに対する選択エッチング性を示す。このため、貴金属含有被膜を構成する貴金属成分の種類に応じて、適宜、より適切な化合物を選択することが好ましい。 In the formula (1), X which is a terminal group may be either an amino group (—NH 2 ) or a thiol group (—SH), and an appropriate one can be selected according to the purpose. When the terminal group X is an amino group, the electrolytic etching rate is faster than when the terminal group X is a thiol group. Moreover, when the terminal group X is an amino group, when the terminal group X is a thiol group, the noble metal component which is easy to form a metal complex differs. For example, when the terminal group X is an amino group, it exhibits selective etching properties for Co, and when the terminal group is a thiol group, it exhibits selective etching properties for Pt. For this reason, it is preferable to select a more appropriate compound as appropriate according to the type of the noble metal component constituting the noble metal-containing film.
　当該電解エッチング液中における当該錯化剤の含有量は、上述のとおり、１ｇ／Ｌ～１００ｇ／Ｌであるが、上記金属成分と錯化剤とを良好に接触させるという観点から、当該エッチング液中における錯化剤の含有量は２０ｇ／Ｌ～５０ｇ／Ｌであることがより好ましい。 The content of the complexing agent in the electrolytic etching solution is 1 g / L to 100 g / L as described above. From the viewpoint of bringing the metal component and the complexing agent into good contact, the etching solution The content of the complexing agent is more preferably 20 g / L to 50 g / L.
（２）酸
　本件発明に係る電解エッチング液は、ｐＨは２～６の酸性～弱酸性の溶液であり、各種強酸又は弱酸を溶媒に溶解させた酸溶液に対して、上記錯化剤、電解質、ｐＨ調整剤等の各種成分を添加したものとすることができる。ここで、当該電解エッチング液の組成成分には、塩化物イオン源として作用する物質が含まれないことが好ましい。塩化物イオンは基材の構成材料であるアルミニウムに対する反応性が高く、後述する電解エッチング方法を適用したときに、基材の表面を浸食する恐れが生じるためである。 (2) Acid The electrolytic etching solution according to the present invention is an acidic to weakly acidic solution having a pH of 2 to 6, and the above complexing agent, electrolyte, and acid solution obtained by dissolving various strong acids or weak acids in a solvent. In addition, various components such as a pH adjuster can be added. Here, it is preferable that the composition component of the electrolytic etching solution does not include a substance that acts as a chloride ion source. This is because chloride ions are highly reactive with aluminum, which is a constituent material of the base material, and when the electrolytic etching method described later is applied, the surface of the base material may be eroded.
　具体的には、化学式中に塩素を含む塩酸等の酸であって、水溶液中で電離して塩化物イオンを生成する酸以外の酸溶液とすることが好ましい。このような酸として、例えば、硫酸やスルホン酸等の強酸、炭酸、硝酸、カルボン酸等の弱酸を用いることができる。スルホン酸としては、メタンスルホン酸やエタンスルホン酸等のアルキルスルホン酸、アリルスルホン酸等を用いることができる。また、カルボン酸は、少なくとも一つのカルボキシ基を有する有機酸であればよいが、特に、カルボキシ基を一つ有するモノカルボン酸であることが好ましい。さらに、カルボン酸として、カルボキシ基の近傍にヒドロキシ基を有する乳酸やグリコール酸等のヒドロキシ酸を用いてもよく、特に、有機酸としては下記式（２）で表されるα－ヒドロキシカルボン酸を用いることがより好ましい。調製する電解エッチング液のｐＨ値に応じて、上述した酸の中から一種又は複数種を適宜選択すればよい。特に、アルキルスルホン酸と、硫酸とを併用することが好ましい。 Specifically, it is preferable to use an acid solution other than an acid such as hydrochloric acid containing chlorine in the chemical formula and ionizing in an aqueous solution to generate chloride ions. As such an acid, for example, a strong acid such as sulfuric acid or sulfonic acid, or a weak acid such as carbonic acid, nitric acid, or carboxylic acid can be used. As the sulfonic acid, alkylsulfonic acid such as methanesulfonic acid and ethanesulfonic acid, allylsulfonic acid and the like can be used. The carboxylic acid may be an organic acid having at least one carboxy group, but is particularly preferably a monocarboxylic acid having one carboxy group. Further, as the carboxylic acid, a hydroxy acid such as lactic acid or glycolic acid having a hydroxy group in the vicinity of the carboxy group may be used. In particular, as the organic acid, an α-hydroxycarboxylic acid represented by the following formula (2) is used. More preferably, it is used. What is necessary is just to select suitably 1 type or multiple types from the acid mentioned above according to the pH value of the electrolytic etching liquid to prepare. In particular, it is preferable to use alkylsulfonic acid and sulfuric acid in combination.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　但し、上記式（２）において、Ｒ１ 及びＲ２はそれぞれ水素、炭素数が１～４の炭化水素、炭素数が１～４のアルキルアミン又は炭素数が１～４のアルキルエーテルである。Ｒ１ 及びＲ２はこれらのいずれであってもよいが、Ｒ１ の炭素数と、Ｒ２の炭素数とが共に４であることは好ましくない。また、Ｒ１ の炭素数と、Ｒ２の炭素数との和が４以下であることがより好ましい。炭素数が増加すると、電解エッチング液に対する溶解性が低下するためである。 In the above formula (2), R 1 and R 2 are each hydrogen, a hydrocarbon having 1 to 4 carbon atoms, an alkylamine having 1 to 4 carbon atoms, or an alkyl ether having 1 to 4 carbon atoms. R 1 and R 2 may be any of these, but it is not preferable that both the carbon number of R 1 and the carbon number of R 2 are 4. The sum of the carbon number of R 1 and the carbon number of R 2 is more preferably 4 or less. This is because as the carbon number increases, the solubility in the electrolytic etching solution decreases.
（３）電解質及びｐＨ調整剤
　電解質及びｐＨ調整剤についても、塩化物イオン源として作用する物質ではないことが好ましい。すなわち、塩化物イオン以外のアニオン源として作用する物質であることが好ましく、例えば、上述した酸、すなわち、硫酸、スルホン酸、炭酸、硝酸、カルボン酸等の塩であることが好ましく、これらのリチウム塩、カリウム塩、ナトリウム塩、ルビジウム塩、セシウム塩などのアルカリ塩であることが好ましく、カリウム塩であることが特に好ましい。具体的には、電解質としては、硫酸カリウム、メタンスルホン酸カリウム等を用いることが好ましい。一方、ｐＨ調整剤としては、炭酸、硝酸又はカルボン酸のアルカリ塩を用いることが好ましく、これらのカリウム塩であることがより好ましい。これら電解質及びｐＨ調整剤の量を適宜調整することにより、電解エッチング液のｐＨの値を２～６の間の所定の値にすることができる。 (3) Electrolyte and pH adjuster The electrolyte and pH adjuster are also preferably not substances that act as a chloride ion source. That is, it is preferably a substance that acts as an anion source other than chloride ions. For example, the above-described acids, that is, salts of sulfuric acid, sulfonic acid, carbonic acid, nitric acid, carboxylic acid, etc. are preferable. An alkali salt such as a salt, potassium salt, sodium salt, rubidium salt or cesium salt is preferred, and a potassium salt is particularly preferred. Specifically, it is preferable to use potassium sulfate, potassium methanesulfonate, or the like as the electrolyte. On the other hand, as a pH adjuster, it is preferable to use an alkali salt of carbonic acid, nitric acid or carboxylic acid, and more preferably a potassium salt thereof. By appropriately adjusting the amounts of the electrolyte and the pH adjuster, the pH value of the electrolytic etching solution can be set to a predetermined value between 2 and 6.
　また、電解質及びｐＨ調整剤は、塩化物イオン源として作用する物質ではないと共に、カリウムイオン源として作用する物質であることが好ましい。すなわち、塩化物イオン以外のアニオン源として作用する物質のカリウム塩であることが好ましい。具体的には、硫酸カリウム、スルホン酸カリウム、炭酸カリウム、硝酸カリウム、カルボン酸カリウムであることが好ましい。なお、電解質及びｐＨ調整剤はそれぞれ一種又は複数種を適宜、適切なものを用いることができる。 In addition, the electrolyte and the pH adjuster are not substances that act as a chloride ion source, but are preferably substances that act as a potassium ion source. That is, a potassium salt of a substance that acts as an anion source other than chloride ions is preferable. Specifically, potassium sulfate, potassium sulfonate, potassium carbonate, potassium nitrate, and potassium carboxylate are preferable. In addition, 1 type or multiple types of electrolyte and pH adjuster can respectively be used appropriately as appropriate.
（４）その他
　本件発明に係る電解エッチング液は、上述したとおり、式（１）で表される錯化剤を１ｇ／Ｌ～１００ｇ／Ｌの範囲内で含むと共に、ｐＨが２～６の範囲内であればよく、上記酸、電解質、ｐＨ調整剤などを含むことができるが、上述した成分以外にも界面活性剤等の電解エッチング液の添加剤として使用される各種成分は本件発明の趣旨を逸脱しない範囲において組成成分として用いてよいのは勿論である。 (4) Others As described above, the electrolytic etching solution according to the present invention contains the complexing agent represented by the formula (1) within the range of 1 g / L to 100 g / L, and the pH is within the range of 2 to 6. The above-mentioned acid, electrolyte, pH adjuster and the like can be included, but in addition to the above-described components, various components used as additives for an electrolytic etching solution such as a surfactant are the gist of the present invention. Of course, it may be used as a composition component without departing from the scope of the present invention.
２．電解エッチング方法
　次に、本件発明に係る電解エッチング方法について説明する。本件発明に係る電解エッチング方法は、卑金属材料からなる基材の表面に貴金属含有金属被膜を備える被処理材をエッチングにより除去するための電解エッチング方法であって、上述した式（１）で表される錯化剤１ｇ／Ｌ～１００ｇ／Ｌを含み、ｐＨが２～７である電解エッチング液に被処理材を浸漬し、当該被処理材を陽極として、他の電極との間で電圧を印加して、当該貴金属含有金属被膜をエッチングしながら、当該基材の表面に陽極酸化被膜を形成させることを特徴とする。 2. Electrolytic etching method Next, the electrolytic etching method according to the present invention will be described. The electrolytic etching method according to the present invention is an electrolytic etching method for removing a material to be processed having a noble metal-containing metal coating on the surface of a base material made of a base metal material, and is represented by the above-described formula (1). A material to be treated is immersed in an electrolytic etching solution containing 1 g / L to 100 g / L of a complexing agent and having a pH of 2 to 7, and a voltage is applied between other electrodes using the material to be treated as an anode. Then, an anodic oxide film is formed on the surface of the base material while etching the noble metal-containing metal film.
　ここで、電解エッチング液については、上述した本件発明に係る電解エッチング液を用いることができるため、ここでは説明を省略する。以下、図１を参照しながら、本件発明に係る電解エッチング方法の手順を説明する。 Here, since the electrolytic etching solution according to the present invention described above can be used for the electrolytic etching solution, the description thereof is omitted here. Hereinafter, the procedure of the electrolytic etching method according to the present invention will be described with reference to FIG.
　図１（ａ）は、被処理材の断面を模式的に示したものである。図１（ａ）に示す被処理材は、上述の卑金属材料からなる基材の表面に、物理蒸着膜である貴金属含有金属被膜を備えたものである。当該実施の形態では、貴金属含有金属被膜はスパッタ法により当該基材の表面に成膜されたＰｔＣｏＣｒ膜とする。この被処理材を、上述した電解エッチング液に浸漬し、当該被処理材を陽極として、他の電極との間で電圧を印加する。 FIG. 1 (a) schematically shows a cross section of a material to be processed. The material to be treated shown in FIG. 1A is provided with a noble metal-containing metal film that is a physical vapor deposition film on the surface of a base material made of the above-mentioned base metal material. In this embodiment, the noble metal-containing metal film is a PtCoCr film formed on the surface of the substrate by sputtering. This material to be treated is immersed in the above-described electrolytic etching solution, and a voltage is applied between the other material with the material to be treated as an anode.
　ここで、電解温度は高い程、電解エッチング速度が速くなるため好ましいが、電解温度が高くなり過ぎると、被処理材の表面に形成された陽極酸化被膜が溶解する場合があり好ましくない。また、浴の分解等が生じ、適切な電解反応を行うことができなくなる場合があり、好ましくない。例えば、３０℃～９０℃とすることが好ましく、５０℃～８０℃とすることがより好ましく、６５℃～７５℃とすることがさらに好ましい。また、その他の電解電流密度等は、基材を構成する材料、例えば、アルミニウム等の具体的な金属材料に応じて、当該金属材料の陽極酸化を行う上で適切な条件とすることが好ましい。 Here, it is preferable that the electrolysis temperature is higher because the electrolytic etching rate becomes faster. However, if the electrolysis temperature is too high, the anodic oxide film formed on the surface of the material to be treated may be dissolved, which is not preferable. In addition, decomposition of the bath may occur, and an appropriate electrolytic reaction may not be performed, which is not preferable. For example, it is preferably 30 ° C. to 90 ° C., more preferably 50 ° C. to 80 ° C., and further preferably 65 ° C. to 75 ° C. In addition, other electrolytic current densities and the like are preferably set to appropriate conditions for anodizing the metal material according to a material constituting the substrate, for example, a specific metal material such as aluminum.
　外部電源等から当該被処理材に電流が流れ込むと、電解反応により貴金属含有金属被膜の構成成分であるＰｔ、Ｃｏ、Ｃｒがそれぞれ陽イオンとなり、電解エッチング液中の錯化剤と錯体を形成し、電解エッチング液中に安定に保持される。一方、図１（ｂ）に示すように、電解エッチングにより、基材の表面が露出した部分は陽極酸化されて、陽極酸化被膜が形成される。 When current flows into the material to be treated from an external power source or the like, Pt, Co, and Cr, which are constituent components of the noble metal-containing metal coating, become cations due to the electrolytic reaction, forming a complex with the complexing agent in the electrolytic etching solution. , Stably maintained in the electrolytic etching solution. On the other hand, as shown in FIG. 1B, the portion where the surface of the base material is exposed is anodized by electrolytic etching to form an anodized film.
　電解エッチングが進行するにつれて、図１（ｃ）に示すように、基材の表面から貴金属含有金属被膜が除去されていくと共に、基材の表面の露出部分には陽極酸化被膜が形成されていく。このため、電解エッチング液が基材の表面全面に接触する時点では、基材の表面全面には陽極酸化被膜が全面に形成されている。このため、基材の表面に設けられた貴金属含有金属被膜は、基材と貴金属含有金属被膜との界面に形成される陽極酸化被膜により、基材の表面から物理的に剥離され、これらは金属錯体として電界液中に保持される。 As the electrolytic etching progresses, as shown in FIG. 1C, the noble metal-containing metal film is removed from the surface of the base material, and an anodized film is formed on the exposed portion of the surface of the base material. . For this reason, when the electrolytic etching solution contacts the entire surface of the substrate, an anodized film is formed on the entire surface of the substrate. For this reason, the noble metal-containing metal film provided on the surface of the base material is physically peeled from the surface of the base material by an anodized film formed at the interface between the base material and the noble metal-containing metal film. It is retained in the electrolysis solution as a complex.
　以上の工程により、耐腐食性の低いアルミニウム製の基材の表面に設けられた、耐腐食性の高いＰｔ等の貴金属を含有する貴金属含有金属被膜を基材の表面を浸食することなく、基材の形状を保持した状態で、当該貴金属含有金属被膜のみを選択的にエッチングすることができる。 Through the above steps, the base metal-containing metal film containing noble metal such as Pt having high corrosion resistance provided on the surface of the aluminum base material having low corrosion resistance is eroded without eroding the surface of the base material. Only the noble metal-containing metal film can be selectively etched while maintaining the shape of the material.
　次に、実施例を示して本件発明を具体的に説明する。但し、本件発明は以下の実施例に限定されるものではない。 Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.
　実施例１では、以下の組成の電解エッチング液を１００ｍＬに対して、表面積が０．８８５６ｄｍ２のアルミニウム製基材上に１ｍｍ厚みのＰｔＣｏＣｒスパッタ薄膜（表面積：０．０３２０ｄｍ２）が形成された被処理材を浸漬し、下記の条件で電解エッチングを行った。 In Example 1, the following electrolytic etching solution of the composition with respect to 100 mL, a surface area of 1mm thick on an aluminum substrate 0.8856dm 2 PtCoCr sputtered film (surface area: 0.0320dm 2) to be formed The treatment material was immersed and electrolytic etching was performed under the following conditions.
［電解エッチング液の組成］
ペンタエチレンヘキサミン：５０ｇ／Ｌ
メタンスルホン酸　　　　：４２ｍＬ／Ｌ
硫酸　　　　　　　　　　：１８ｍＬ／Ｌ
硝酸カリウム　　　　　　：２５ｇ／Ｌ
炭酸カリウム　　　　　　：液ｐＨが４になるように添加量を調整した。 [Composition of electrolytic etching solution]
Pentaethylenehexamine: 50 g / L
Methanesulfonic acid: 42 mL / L
Sulfuric acid: 18 mL / L
Potassium nitrate: 25 g / L
Potassium carbonate: The amount added was adjusted so that the solution pH was 4.
［電解条件］
温度　　　　　　　　　　：７０℃
陰極　　　　　　　　　　：Ｔａ／Ｔａ２Ｏ５電極（電極板面積：０．２ｄｍ２）
陽極　　　　　　　　　　：被処理材
電流　　　　　　　　　　：０．３Ａ
時間　　　　　　　　　　：２時間 [Electrolysis conditions]
Temperature: 70 ° C
Cathode: Ta / Ta 2 O 5 electrode (electrode plate area: 0.2 dm 2 )
Anode: Material to be treated Current: 0.3A
Time: 2 hours
　実施例２では、実施例１の電解エッチング液において、ペンタエチレンヘキサミンに代えて、アミノエタンチオールを用いた以外は、実施例１と同様にして、電解エッチングを行った。 In Example 2, electrolytic etching was performed in the same manner as in Example 1 except that aminoethanethiol was used in place of pentaethylenehexamine in the electrolytic etching solution of Example 1.
［評価］
　上記条件で電解エッチングを行った後、被処理材の表面をＥＤＸ（エネルギー分散型Ｘ線分光法）により組成分析を行った。また、電解エッチング液のＩＣＰ発光分析（高周波誘導結合プラズマ発光分光分析）を行った。さらに、実施例１及び実施例２のいずれの場合も、電解エッチング液中に僅かであるが沈殿物が生じたため、沈殿物についてもＩＣＰ発光分析を行った。 [Evaluation]
After performing the electrolytic etching under the above conditions, the composition of the surface of the material to be treated was analyzed by EDX (energy dispersive X-ray spectroscopy). Further, ICP emission analysis (high frequency inductively coupled plasma emission spectroscopy) of the electrolytic etching solution was performed. Furthermore, in both cases of Example 1 and Example 2, a slight amount of precipitate was generated in the electrolytic etching solution. Therefore, ICP emission analysis was also performed on the precipitate.
　実施例１及び実施例２のいずれの電解エッチング液を用いた場合も、電解エッチング後の被処理材の表面の各金属成分の元素比は、Ａｌが１００％であり、Ｐｔ、Ｃｏ、Ｃｒはいずれも０％であった。このことから、本件発明に係る電解エッチング方法によれば、エッチング難物質である貴金属を含有する貴金属含有被膜を被処理材の表面から完全に除去することが可能であることが確認された。 When using any of the electrolytic etching solutions of Example 1 and Example 2, the element ratio of each metal component on the surface of the treated material after electrolytic etching is 100% for Al, and Pt, Co, and Cr are Both were 0%. From this, it was confirmed that according to the electrolytic etching method according to the present invention, it is possible to completely remove the noble metal-containing coating containing the noble metal which is a difficult etching substance from the surface of the material to be treated.
　次に、ＩＣＰ発光分析の結果について説明するＩＣＰ発光分析により、電解エッチング液に含まれるＡｌ、Ｐｔ、Ｃｏ、Ｃｒの各元素比は次のようになった。錯化剤として、ペンタエチレンヘキサミンを含む実施例１の電解エッチング液を用いて電解エッチングを行った場合は、電解エッチング液に含まれるＡｌは２３．０％、Ｐｔは０．５％、Ｃｏは６７．０％、Ｃｒは９．５％であった。一方、錯化剤としてアミノエタンチオールを含む実施例２の電解エッチング液を用いて電解エッチングを行った場合は、電解エッチング液に含まれるＡｌは１．０％、Ｐｔは８１．３％、Ｃｏは８．６％、Ｃｒは９．１％であった。これらのことから、上記式（１）で表される化合物のうち、末端基Ｘがアミノ基の場合は、Ｃｏに対する選択エッチング性を示し、末端基がチオール基の場合はＰｔに対する選択エッチング性を示すことが確認された。 Next, by ICP emission analysis for explaining the results of ICP emission analysis, the element ratios of Al, Pt, Co, and Cr contained in the electrolytic etching solution were as follows. When electrolytic etching was performed using the electrolytic etching solution of Example 1 containing pentaethylenehexamine as a complexing agent, Al contained in the electrolytic etching solution was 23.0%, Pt was 0.5%, and Co was 67.0% and Cr were 9.5%. On the other hand, when electrolytic etching was performed using the electrolytic etching solution of Example 2 containing aminoethanethiol as a complexing agent, Al contained in the electrolytic etching solution was 1.0%, Pt was 81.3%, Co Was 8.6%, and Cr was 9.1%. From these results, among the compounds represented by the above formula (1), when the terminal group X is an amino group, it exhibits selective etching property for Co, and when the terminal group is a thiol group, it exhibits selective etching property for Pt. It was confirmed to show.
 また、実施例１の電解エッチング液を用いた場合、沈殿物量は０．３８７ｇであった。この沈殿物に含まれるＡｌは１０．５％、Ｐｔは７７．４％、Ｃｏは９．０％、Ｃｒは３．１％であった。一方、実施例２の電解エッチング液を用いた場合、沈殿物量は１．８７ｇであった。この沈殿物に含まれるＡｌは４５．８％、Ｐｔは３．６％、Ｃｏは４５．６％、Ｃｒは５．０％であった。すなわち、電解エッチング液中には僅かに沈殿物が生じるが、実施例１の電解エッチング液を用いた場合には沈殿物中のＰｔ検出量が多く、実施例２の電解エッチング液を用いた場合には沈殿物中のＣｏ検出量が多くなる。この結果からも上述のとおり、各電解エッチング液中の式（１）で表される化合物の末端基Ｘに応じて、各貴金属成分に対する選択エッチング性がみられることが確認された。従って、貴金属含有被膜を構成する貴金属成分が一種類の場合は、より適切な化合物を用いることにより、その貴金属成分を選択的にエッチングすることが可能になる。また、貴金属含有被膜を構成する貴金属成分が２種類である場合、いずれかの成分を電解エッチング液側に、他の成分を沈殿物側に多く回収することができるため、それぞれの貴金属成分の再生が容易になる。 In addition, when the electrolytic etching solution of Example 1 was used, the amount of precipitate was 0.387 g. Al contained in the precipitate was 10.5%, Pt was 77.4%, Co was 9.0%, and Cr was 3.1%. On the other hand, when the electrolytic etching solution of Example 2 was used, the amount of precipitate was 1.87 g. Al contained in the precipitate was 45.8%, Pt was 3.6%, Co was 45.6%, and Cr was 5.0%. That is, a slight precipitate is generated in the electrolytic etching solution, but when the electrolytic etching solution of Example 1 is used, the amount of Pt detected in the precipitate is large, and the electrolytic etching solution of Example 2 is used. Increases the amount of Co detected in the precipitate. From this result, as described above, it was confirmed that the selective etching property for each noble metal component was observed according to the terminal group X of the compound represented by the formula (1) in each electrolytic etching solution. Therefore, when the precious metal component constituting the precious metal-containing film is one type, it is possible to selectively etch the precious metal component by using a more appropriate compound. In addition, when there are two types of noble metal components constituting the noble metal-containing coating, it is possible to recover a large amount of either component on the electrolytic etching solution side and other components on the precipitate side. Becomes easier.
　なお、各実施例においてそれぞれ電解エッチング液にはＡｌも検出された。また、微量であるが沈殿物も確認され、沈殿物からもＡｌが検出された。しかしながら、Ａｌはイオン化傾向が高く、Ｐｔ、Ｃｏ等の貴金属成分と比較すると極めてエッチングされやすい物質であることを考慮すると、本件発明によれば被処理部材の表面が溶出するのを有効に抑制することができたと結論付けることができる。また、目視により電解エッチングの前後における基材の形状を観察したところ、基材の形状は電解エッチング前後において変化がなく、基材の形状を保持することが可能であることが確認された。 In each example, Al was also detected in the electrolytic etching solution. Moreover, although it was trace amount, the deposit was also confirmed and Al was detected also from the deposit. However, considering that Al has a high ionization tendency and is a material that is extremely easily etched compared with noble metal components such as Pt and Co, according to the present invention, the surface of the member to be treated is effectively suppressed from being eluted. We can conclude that we were able to. Further, when the shape of the base material before and after the electrolytic etching was visually observed, it was confirmed that the shape of the base material did not change before and after the electrolytic etching, and the shape of the base material could be maintained.
　本件発明によれば、式（１）で表される錯化剤を含むｐＨが２～６の電解エッチング液を用いて、当該被処理材を陽極として、他の電極との間で電圧を印加して、貴金属含有金属被膜をエッチングしながら、貴金属含有金属被膜を構成する金属成分を電解エッチング液中で錯体として安定に保持することができる。これと同時に、基材の表面が露出した場合、基材の表面に陽極酸化被膜が形成されるため、卑金属材料からなる基材の表面が電解エッチング液に溶出するのを防止することができる。また、基材の表面に陽極酸化被膜を形成することにより、基材の表面から貴金属含有金属被膜を物理的に剥離することができる。すなわち、本件発明によれば、基材の形状を保持した状態で、被処理材の表面から貴金属含有金属被膜のみを選択的にエッチングすることができる。従って、物理蒸着成膜装置のチャンバ内に設けられるシールド板の再生等に好適に本件発明を適用することができる。 According to the present invention, using an electrolytic etching solution having a pH of 2 to 6 containing the complexing agent represented by the formula (1), a voltage is applied between the treated material as an anode and another electrode. Thus, while etching the noble metal-containing metal film, the metal components constituting the noble metal-containing metal film can be stably held as a complex in the electrolytic etching solution. At the same time, when the surface of the base material is exposed, an anodized film is formed on the surface of the base material, so that it is possible to prevent the surface of the base material made of a base metal material from eluting into the electrolytic etching solution. Moreover, a noble metal containing metal film can be physically peeled from the surface of a base material by forming an anodic oxide film on the surface of a base material. That is, according to the present invention, it is possible to selectively etch only the noble metal-containing metal film from the surface of the material to be processed while maintaining the shape of the base material. Therefore, the present invention can be suitably applied to the regeneration of the shield plate provided in the chamber of the physical vapor deposition apparatus.
　　１０・・・被処理材
　　１１・・・基材
　　１２・・・貴金属含有金属被膜
　　１３・・・陽極酸化被膜 DESCRIPTION OF SYMBOLS 10 ... To-be-processed material 11 ... Base material 12 ... Noble metal containing metal film 13 ... Anodized film

Claims (4)

  1. 　卑金属材料からなる基材の表面に貴金属含有金属被膜を備える被処理材をエッチングにより除去するための電解エッチング方法であって、
    　下記式（１）で表される錯化剤１ｇ／Ｌ～１００ｇ／Ｌを含み、ｐＨが２～７である電解エッチング液に前記被処理材を浸漬し、
    　当該被処理材を陽極として、他の電極との間で電圧を印加して、当該貴金属含有金属被膜をエッチングしながら、当該基材の表面に陽極酸化被膜を形成させること、
    　を特徴とする電解エッチング方法。
    Figure JPOXMLDOC01-appb-C000001
    　但し、上記式（１）において、１≦ｎ≦７であり、Ｘはアミノ基又はチオール基である。     An electrolytic etching method for removing, by etching, a material having a noble metal-containing metal coating on the surface of a base material made of a base metal material,
    The material to be treated is immersed in an electrolytic etching solution containing 1 g / L to 100 g / L of a complexing agent represented by the following formula (1) and having a pH of 2 to 7,
    Forming a anodic oxide coating on the surface of the base material while etching the noble metal-containing metal coating by applying a voltage between the electrode to be treated and another electrode,
    An electrolytic etching method characterized by the above.
    Figure JPOXMLDOC01-appb-C000001
    However, in said formula (1), it is 1 <= n <= 7 and X is an amino group or a thiol group.
  2. 　前記電解エッチング液の組成成分には、塩化物イオン源として作用する物質は含まれない請求項１に記載の電解エッチング方法。 2. The electrolytic etching method according to claim 1, wherein the composition component of the electrolytic etching solution does not include a substance acting as a chloride ion source.
  3. 　前記電解エッチング液の組成成分には、カリウムイオン源として作用する物質が含まれる請求項１又は請求項２に記載の電解エッチング方法。 3. The electrolytic etching method according to claim 1, wherein the composition component of the electrolytic etching solution contains a substance that acts as a potassium ion source.
  4. 　卑金属材料からなる基材の表面に貴金属含有金属被膜を備える被処理材をエッチングにより除去するための電解エッチング液であって、
    　下記式（１）で表される錯化剤１ｇ／Ｌ～１００ｇ／Ｌを含み、ｐＨが２～７であることを特徴とする電解エッチング液。
    Figure JPOXMLDOC01-appb-C000002
    　但し、上記式（１）において、１≦ｎ≦７であり、Ｘはアミノ基又はチオール基である。     An electrolytic etching solution for removing, by etching, a material to be processed having a noble metal-containing metal coating on the surface of a base material made of a base metal material,
    An electrolytic etching solution comprising 1 to 100 g / L of a complexing agent represented by the following formula (1) and having a pH of 2 to 7.
    Figure JPOXMLDOC01-appb-C000002
    However, in said formula (1), it is 1 <= n <= 7 and X is an amino group or a thiol group.
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JP2007063652A (en) * 2005-09-02 2007-03-15 Kanto Gakuin Univ Surface Engineering Research Institute Method for forming copper electroless plated film
JP2012049386A (en) * 2010-08-27 2012-03-08 Osaka Univ Electrolytic etching apparatus and method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023217411A3 (en) * 2022-05-09 2024-03-14 Oerlikon Surface Solutions Ag, Pfäffikon Use of sulfonic acids in dry electrolytes to remove vapor deposited and/or thermally sprayed coatings on metal surfaces

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