JP2019054227A - Substrate processing apparatus and substrate processing method - Google Patents

Substrate processing apparatus and substrate processing method Download PDF

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JP2019054227A
JP2019054227A JP2018043388A JP2018043388A JP2019054227A JP 2019054227 A JP2019054227 A JP 2019054227A JP 2018043388 A JP2018043388 A JP 2018043388A JP 2018043388 A JP2018043388 A JP 2018043388A JP 2019054227 A JP2019054227 A JP 2019054227A
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noble metal
metal film
substrate processing
containing member
chemical solution
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JP7020966B2 (en
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康人 吉水
Yasuto Yoshimizu
康人 吉水
裕也 明星
Hironari Akeboshi
裕也 明星
冬馬 伊藤
Fuyuma Ito
冬馬 伊藤
白馬 北川
Hakuba Kitagawa
白馬 北川
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Kioxia Corp
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Toshiba Memory Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/67017—Apparatus for fluid treatment
    • H01L21/67063—Apparatus for fluid treatment for etching
    • H01L21/67075—Apparatus for fluid treatment for etching for wet etching
    • H01L21/6708—Apparatus for fluid treatment for etching for wet etching using mainly spraying means, e.g. nozzles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only

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  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Weting (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

To provide a substrate processing apparatus more suitable for metal film etching.SOLUTION: The substrate processing apparatus includes: a noble-metal-containing member having an uneven portion or a porous portion containing a noble metal; and a chemical solution supply member for supplying a chemical solution. The substrate processing apparatus is configured to supply the chemical solution to etch away the metal while contacting a convex portion of the uneven portion or the porous portion with a predetermined metal surface.SELECTED DRAWING: Figure 1

Description

本発明の実施形態は、基板処理装置および基板処理方法に関する。   Embodiments described herein relate generally to a substrate processing apparatus and a substrate processing method.

基板処理方法の一つに、基板上に形成された金属膜を除去するエッチング工程が知られている。   As one of substrate processing methods, an etching process for removing a metal film formed on a substrate is known.

特開２００８−８１３８９号公報JP 2008-81389 A

本発明が解決しようとする課題は、より金属膜のエッチングに適した基板処理装置、および基板処理方法を提供することである。   The problem to be solved by the present invention is to provide a substrate processing apparatus and a substrate processing method more suitable for etching a metal film.

一実施形態に係る基板処理装置は、貴金属を含む凹凸形状部分または多孔質形状部分を有する貴金属含有部材と、薬液を供給する薬液供給部材と、を備え、所定の金属表面に前記凹凸形状部分の凸部または前記多孔質形状部分を接触させつつ、前記薬液を前記金属表面に供給して前記金属をエッチング除去する。   A substrate processing apparatus according to an embodiment includes a noble metal-containing member having a concavo-convex shape portion or a porous shape portion containing a noble metal, and a chemical solution supply member that supplies a chemical solution, and the concavo-convex shape portion of the concavo-convex shape portion is provided on a predetermined metal surface. The chemical solution is supplied to the metal surface while the convex portion or the porous portion is in contact with the metal surface, and the metal is removed by etching.

第１実施形態に係る基板処理装置の概略的な構成を示す模式図である。It is a schematic diagram which shows schematic structure of the substrate processing apparatus which concerns on 1st Embodiment. 貴金属含有部材の底面の一部を拡大した拡大図である。It is the enlarged view to which a part of bottom face of the noble metal containing member was expanded. （ａ）は、基板のエッチング処理前の状態を示し、（ｂ）は、基板のエッチング処理後の状態を示す。(A) shows the state before the etching process of the substrate, and (b) shows the state after the etching process of the substrate. 第２実施形態に係る基板処理装置の概略的な構成を示す模式図である。It is a schematic diagram which shows schematic structure of the substrate processing apparatus which concerns on 2nd Embodiment. 第２実施形態に係る基板のエッチング工程を説明するための模式図である。It is a schematic diagram for demonstrating the etching process of the board | substrate concerning 2nd Embodiment. 第３実施形態に係る基板処理装置の概略的な構成を示す模式図である。It is a schematic diagram which shows schematic structure of the substrate processing apparatus which concerns on 3rd Embodiment. 基板と貴金属含有部材との接触部分を拡大した拡大図である。It is the enlarged view to which the contact part of a board | substrate and a noble metal containing member was expanded. 第４実施形態に係る基板処理装置の概略的な構成を示す模式図である。It is a schematic diagram which shows schematic structure of the substrate processing apparatus which concerns on 4th Embodiment. 図８に示す基板処理装置の要部を拡大した拡大図である。It is the enlarged view to which the principal part of the substrate processing apparatus shown in FIG. 8 was expanded. （ａ）は第５実施形態に係る基板処理装置の概略的な構成を示す模式図であり、（ｂ）は（ａ）に示す切断線Ａ−Ａに沿った断面図である。(A) is a schematic diagram which shows the schematic structure of the substrate processing apparatus which concerns on 5th Embodiment, (b) is sectional drawing along the cutting line AA shown to (a). （ａ）は第５実施形態の貴金属含有部材１０の拡大図であり、（ｂ）は、（ａ）に示す毛状部材の拡大図である。(A) is an enlarged view of the noble metal containing member 10 of 5th Embodiment, (b) is an enlarged view of the hair-like member shown to (a). （ａ）は第６実施形態に係る基板処理装置の概略的な構成を示す模式図であり、（ｂ）は第１貴金属含有部材の拡大図であり、（ｃ）は第２貴金属含有部材の拡大図である。(A) is a schematic diagram which shows schematic structure of the substrate processing apparatus which concerns on 6th Embodiment, (b) is an enlarged view of a 1st noble metal containing member, (c) is a 2nd noble metal containing member. It is an enlarged view. （ａ）は第１貴金属含有部材の変形例を示す拡大図であり、（ｂ）は第２貴金属含有部材の変形例を示す拡大図である。(A) is an enlarged view which shows the modification of a 1st noble metal containing member, (b) is an enlarged view which shows the modification of a 2nd noble metal containing member. 第７実施形態に係る基板処理装置の概略的な構成を示す模式図である。It is a schematic diagram which shows schematic structure of the substrate processing apparatus which concerns on 7th Embodiment. （ａ）は第７実施形態における基板のエッチング処理前の状態を示し、（ｂ）は基板のエッチング処理後の状態を示す。(A) shows the state before the etching process of the substrate in the seventh embodiment, and (b) shows the state after the etching process of the substrate. 第８実施形態の貴金属含有部材に設けられた毛状部材の拡大図である。It is an enlarged view of the hair-like member provided in the noble metal containing member of 8th Embodiment. （ａ）は、第９実施形態に係る貴金属含有部材の概略的な構成を示す図であり、（ｂ）および（ｃ）は担体の変形例を示す。(A) is a figure which shows the schematic structure of the noble metal containing member which concerns on 9th Embodiment, (b) and (c) show the modification of a support | carrier. （ａ）は第１０実施形態に係る貴金属含有部材の概略的な構成を示す図であり、（ｂ）は網状体の拡大図である。(A) is a figure which shows schematic structure of the noble metal containing member which concerns on 10th Embodiment, (b) is an enlarged view of a net-like body. 第１１実施形態に係る貴金属含有部材の底面の一部を拡大した拡大図である。It is the enlarged view which expanded a part of bottom face of the noble metal containing member which concerns on 11th Embodiment. （ａ）〜（ｃ）は、第１１実施形態に係る貴金属含有部材の変形例を示す図である。(A)-(c) is a figure which shows the modification of the noble metal containing member which concerns on 11th Embodiment. 第１２実施形態に係る貴金属含有部材の底面の一部を拡大した拡大図である。It is the enlarged view to which a part of bottom face of the noble metal containing member which concerns on 12th Embodiment was expanded. 格子積層体の分解斜視図である。It is a disassembled perspective view of a lattice laminated body. 第１２実施形態におけるエッチング処理中の状態を示す。The state in the etching process in 12th Embodiment is shown. 第１３実施形態に係る基板処理装置の概略的な構成を示す模式図である。It is a schematic diagram which shows schematic structure of the substrate processing apparatus which concerns on 13th Embodiment.

以下、図面を参照して本発明の実施形態を説明する。本実施形態は、本発明を限定するものではない。   Hereinafter, embodiments of the present invention will be described with reference to the drawings. This embodiment does not limit the present invention.

（第１実施形態）
図１は、第１実施形態に係る基板処理装置の概略的な構成を示す模式図である。図１に示す基板処理装置１は、基板１００の処理装置であり、貴金属含有部材１０と、薬液供給ノズル２０(薬液供給部材)と、保持部材３０(第１保持部材)と、保持部材３１(第２保持部材)と、を備える。 (First embodiment)
FIG. 1 is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the first embodiment. A substrate processing apparatus 1 shown in FIG. 1 is a processing apparatus for a substrate 100, and includes a noble metal-containing member 10, a chemical solution supply nozzle 20 (chemical solution supply member), a holding member 30 (first holding member), and a holding member 31 ( A second holding member).

図２は、貴金属含有部材１０の底面の一部を拡大した拡大図である。本実施形態では、貴金属含有部材１０は、例えば、ポリビニルアルコール（ＰＶＡ）、ウレタン、テフロン（登録商標）、イオン交換樹脂といった多孔質部材で構成されている。貴金属含有部材１０の底面は、図２に示すように、凹凸面に形成されている。この凹凸面における凸部のピッチｐが狭すぎると、薬液２００が凹凸面内に入り込みにくくなる。その一方で、ピッチｐが広すぎると、貴金属含有部材１０と基板１００との接触が不十分になることが懸念される。そのため、ピッチｐは、数十μｍの範囲内であることが望ましい。また、凹凸面の高さが低すぎると薬液２００が凹凸面内に入り込みにくくなる。そのため、高さは、数十μｍ以上であることが望ましい。   FIG. 2 is an enlarged view in which a part of the bottom surface of the noble metal-containing member 10 is enlarged. In the present embodiment, the noble metal-containing member 10 is composed of a porous member such as polyvinyl alcohol (PVA), urethane, Teflon (registered trademark), or ion exchange resin. As shown in FIG. 2, the bottom surface of the noble metal-containing member 10 is formed in an uneven surface. If the pitch p of the protrusions on the uneven surface is too narrow, the chemical solution 200 is difficult to enter the uneven surface. On the other hand, if the pitch p is too wide, there is a concern that the contact between the noble metal-containing member 10 and the substrate 100 becomes insufficient. For this reason, the pitch p is preferably within a range of several tens of μm. Moreover, when the height of the uneven surface is too low, the chemical solution 200 is difficult to enter the uneven surface. Therefore, the height is desirably several tens of μm or more.

上記凹凸面には、基板１００と部分的に接触する貴金属膜１１が設けられている。貴金属膜１１は、例えば、白金（Ｐｔ）、金（Ａｕ）、銀（Ａｇ）、およびパラジウム（Ｐｄ）の少なくともいずれかを含んでいることが望ましい。また、貴金属膜１１は、例えば、スパッタ法、無電解めっき法、ＣＶＤ（Chemical Vapor Deposition）法、またはＡＬＤ（Atomic Layer Deposition）法などによって、上記凹凸面に成膜される。無電解めっき法で貴金属膜１１を成膜する場合には、貴金属膜１１との密着性を高めるために貴金属含有部材１０にイオン交換樹脂を用いることが望ましい。また、テフロンを用いた多孔質部材にスパッタ法で貴金属膜１１を成膜する場合には、テフロン表面に予めプラズマ処理を施すことによって、薬液２００に対する耐性を維持しつつ貴金属膜１１との密着性を高めることができる。   A noble metal film 11 that partially contacts the substrate 100 is provided on the uneven surface. The noble metal film 11 desirably includes, for example, at least one of platinum (Pt), gold (Au), silver (Ag), and palladium (Pd). The noble metal film 11 is formed on the uneven surface by, for example, sputtering, electroless plating, CVD (Chemical Vapor Deposition), ALD (Atomic Layer Deposition), or the like. When the noble metal film 11 is formed by the electroless plating method, it is desirable to use an ion exchange resin for the noble metal-containing member 10 in order to improve the adhesion with the noble metal film 11. In addition, when the noble metal film 11 is formed on the porous member using Teflon by the sputtering method, the adhesion to the noble metal film 11 is maintained while maintaining the resistance to the chemical solution 200 by performing plasma treatment on the Teflon surface in advance. Can be increased.

図１に戻って、本実施形態では、薬液供給ノズル２０は、基板１００と上記貴金属膜１１との接触部分に向けてアルカリ性の薬液２００を吐出するノズルを含む。薬液２００は、アルカリ性液と酸化剤との混合液であることが望ましい。アルカリ性液には、例えば、コリン、アンモニア水、および水酸化ナトリウムを用いることができる。一方、酸化剤には、例えば、過酸化水素水およびオゾン水を用いることができる。なお、エッチング効果を高めるために、薬液供給ノズル２０から供給される薬液２００の温度は、８０℃付近であることが望ましい。ただし、薬液２００は、アルカリ性に限定されず、エッチング対象の貴金属膜１１に含まれた成分に応じて酸性であってもよい。   Returning to FIG. 1, in the present embodiment, the chemical liquid supply nozzle 20 includes a nozzle that discharges an alkaline chemical liquid 200 toward a contact portion between the substrate 100 and the noble metal film 11. The chemical solution 200 is desirably a mixed solution of an alkaline solution and an oxidizing agent. For the alkaline liquid, for example, choline, ammonia water, and sodium hydroxide can be used. On the other hand, for example, hydrogen peroxide water and ozone water can be used as the oxidizing agent. In order to enhance the etching effect, the temperature of the chemical solution 200 supplied from the chemical solution supply nozzle 20 is preferably around 80 ° C. However, the chemical solution 200 is not limited to alkaline, and may be acidic depending on the components contained in the noble metal film 11 to be etched.

保持部材３０は、貴金属含有部材１０を昇降可能に保持する。保持部材３０は、例えば、昇降機構に連結されているか、または、当該昇降機構の一部として構成されている。   The holding member 30 holds the noble metal-containing member 10 so as to be movable up and down. The holding member 30 is, for example, connected to the lifting mechanism or configured as a part of the lifting mechanism.

保持部材３１は、基板１００を回転可能に保持する。保持部材３１は、例えば、回転機構に連結されているか、または、当該回転機構の回転軸として構成されている。保持部材３１は、基板１００を載置するステージと連結されていてもよい。   The holding member 31 holds the substrate 100 rotatably. The holding member 31 is, for example, connected to a rotation mechanism or configured as a rotation shaft of the rotation mechanism. The holding member 31 may be connected to a stage on which the substrate 100 is placed.

次に、図３（ａ）および図３（ｂ）を参照して、エッチング処理対象である基板１００の構造について説明する。図３（ａ）は、基板１００のエッチング処理前の状態を示し、図３（ｂ）は、基板１００のエッチング処理後の状態を示す。   Next, with reference to FIG. 3A and FIG. 3B, the structure of the substrate 100 to be etched is described. FIG. 3A shows a state before the etching process of the substrate 100, and FIG. 3B shows a state after the etching process of the substrate 100.

図３（ａ）に示すように、エッチング処理前の基板１００には、金属膜１０１が設けられている。金属膜１０１は積層体１０２上に設けられている。積層体１０２は例えばシリコン等を含有する半導体基板上に設けられている。金属膜１０１は、積層体１０２にパターン（本実施形態では、積層体１０２を貫通するスリット）を形成するために積層体１０２上に形成されたマスクであり、例えば、タングステンを含んでいる。本実施形態において、積層体１０２のパターンは、例えば金属膜１０１に形成されたパターンをマスクにしてエッチングすることにより形成される。この金属膜１０１は、図３（ｂ）に示すように、基板処理装置１のエッチング処理によって除去される。本実施形態において、基板１００は積層体１０２を含むものとして記載し、基板１００は換言するとパターンが形成された積層体１０２を有する半導体装置である。   As shown in FIG. 3A, a metal film 101 is provided on the substrate 100 before the etching process. The metal film 101 is provided on the stacked body 102. The stacked body 102 is provided on a semiconductor substrate containing, for example, silicon. The metal film 101 is a mask formed on the stacked body 102 in order to form a pattern (in this embodiment, a slit penetrating the stacked body 102) in the stacked body 102, and includes, for example, tungsten. In the present embodiment, the pattern of the stacked body 102 is formed, for example, by etching using the pattern formed on the metal film 101 as a mask. The metal film 101 is removed by an etching process of the substrate processing apparatus 1 as shown in FIG. In this embodiment, the substrate 100 is described as including the stacked body 102, and in other words, the substrate 100 is a semiconductor device including the stacked body 102 on which a pattern is formed.

積層体１０２では、絶縁膜１０２ａと導電膜１０２ｂとが交互に設けられている。絶縁膜１０２ａは、例えば、酸化シリコン（ＳｉＯ２）を含んでいる。導電膜１０２ｂは、金属膜１０１と同じくタングステンを含んでいる。導電膜１０２ｂは、例えば、３次元メモリのワードラインに用いることができる。なお、基板１００の構造は、上記構造に限定されず、何かしらのパターンが形成されているものであればよい。 In the stacked body 102, the insulating films 102a and the conductive films 102b are alternately provided. The insulating film 102a includes, for example, silicon oxide (SiO 2 ). The conductive film 102b contains tungsten like the metal film 101. The conductive film 102b can be used for a word line of a three-dimensional memory, for example. Note that the structure of the substrate 100 is not limited to the above structure, and may be any pattern in which some pattern is formed.

以下、本実施形態に係る基板処理装置１を用いた基板処理方法について説明する。ここでは、基板１００のエッチング工程を説明する。   Hereinafter, a substrate processing method using the substrate processing apparatus 1 according to the present embodiment will be described. Here, an etching process of the substrate 100 will be described.

まず、図１に示すように、保持部材３１に保持された基板１００に対して、保持部材３０を用いて貴金属含有部材１０を下降することによって、貴金属含有部材１０の貴金属膜１１を基板１００の金属膜１０１に接触させる。このとき、基板１００の積層体１０２、換言するとパターンの損傷を回避するために、基板１００に加えられる貴金属含有部材１０の圧力は、できるだけ小さいことが望ましい。   First, as shown in FIG. 1, the noble metal-containing member 10 is lowered with respect to the substrate 100 held by the holding member 31 by using the holding member 30, whereby the noble metal film 11 of the noble metal-containing member 10 is formed on the substrate 100. The metal film 101 is brought into contact. At this time, in order to avoid damage to the laminate 102 of the substrate 100, in other words, the pattern, it is desirable that the pressure of the noble metal-containing member 10 applied to the substrate 100 is as small as possible.

次に、薬液供給ノズル２０が、貴金属膜１１と基板１００の金属膜１０１の接触部分に向けて薬液２００を吐出する。このとき、貴金属膜１１は、図３（ａ）に示すように、貴金属含有部材１０の凹凸面に設けられている。そのため、貴金属膜１１の凸部は、パターンの各凸部に設けられた金属膜１０１はそれぞれと接触し、薬液２００は、貴金属膜１１の凹部と金属膜１０１との空隙に入り込み、パターンの各凸部に設けられた金属膜１０１に供給される。これにより、ガルバニック腐食が発生し、金属膜１０１のエッチングが促進される。   Next, the chemical solution supply nozzle 20 discharges the chemical solution 200 toward the contact portion between the noble metal film 11 and the metal film 101 of the substrate 100. At this time, the noble metal film 11 is provided on the uneven surface of the noble metal-containing member 10 as shown in FIG. Therefore, the convex portions of the noble metal film 11 come into contact with the metal films 101 provided on the respective convex portions of the pattern, and the chemical solution 200 enters the gaps between the concave portions of the noble metal film 11 and the metal film 101, and It is supplied to the metal film 101 provided on the convex portion. Thereby, galvanic corrosion occurs and etching of the metal film 101 is promoted.

その後、保持部材３０を用いて貴金属含有部材１０を上昇させると、保持部材３１を用いて基板１００を回転させる。その後、再び、貴金属含有部材１０を下降させ、薬液供給ノズル２０から薬液２００を供給することによって、前回とは異なる位置に形成された金属膜１０１がエッチングされる。このようにして、不要な金属膜１０１が全て除去される。   Thereafter, when the noble metal-containing member 10 is raised using the holding member 30, the substrate 100 is rotated using the holding member 31. Thereafter, the noble metal-containing member 10 is lowered again, and the chemical solution 200 is supplied from the chemical solution supply nozzle 20, whereby the metal film 101 formed at a position different from the previous time is etched. In this way, all unnecessary metal film 101 is removed.

以上説明した本実施形態によれば、基板１００の金属膜１０１に対して貴金属膜１１の凸部を部分的に接触させた状態でアルカリ性の薬液２００でエッチング処理している。そのため、貴金属膜１１と接触している金属膜１０１は、ガルバニック腐食によって高いエッチング速度で除去される一方で、貴金属膜１１と接触していない絶縁膜１０２ａおよび導電膜１０２ｂは除去されない。よって、基板１００のパターンを損傷させることなく金属膜１０１のエッチング速度を高めることができる。特に、本実施形態では、エッチング対象の金属膜１０１と、保護対象の導電膜１０２ｂとが、同じ金属（本実施形態ではタングステン）を含んでいたとしても、金属膜１０１のみを選択的にエッチングすることができ、所望のパターンを有する半導体装置を製造することができる。   According to the present embodiment described above, the etching process is performed with the alkaline chemical solution 200 in a state where the convex portion of the noble metal film 11 is partially in contact with the metal film 101 of the substrate 100. Therefore, the metal film 101 that is in contact with the noble metal film 11 is removed at a high etching rate by galvanic corrosion, while the insulating film 102a and the conductive film 102b that are not in contact with the noble metal film 11 are not removed. Therefore, the etching rate of the metal film 101 can be increased without damaging the pattern of the substrate 100. In particular, in this embodiment, even if the metal film 101 to be etched and the conductive film 102b to be protected contain the same metal (tungsten in this embodiment), only the metal film 101 is selectively etched. And a semiconductor device having a desired pattern can be manufactured.

また、本実施形態では、貴金属含有部材１０に多孔質部材を用いているので、この多孔質部材に薬液２００を染み込ませることもできる。例えば、薬液供給ノズル２０からこの多孔質部材に薬液２００を直接供給すれば、薬液２００を染み込ませることができる。この場合、新しい(未反応の)薬液２００が、貴金属膜１１と金属膜１０１との接触部分に常時供給されるので、金属膜１０１をより確実に除去することができる。なお、薬液２００を貴金属含有部材１０に直接供給する場合、貴金属含有部材１０の凹凸面からの薬液２００の透過を妨げないようにするため、貴金属膜１１は、凹凸面の全面ではなく部分的に形成されていることが望ましい。ただし、貴金属膜１１自体が多孔質部材の場合、貴金属含有部材１０に凹凸面を形成しなくても薬液２００は貴金属膜１１を透過できる。   Moreover, in this embodiment, since the porous member is used for the noble metal containing member 10, the chemical | medical solution 200 can also be infiltrated into this porous member. For example, if the chemical solution 200 is directly supplied from the chemical solution supply nozzle 20 to the porous member, the chemical solution 200 can be soaked. In this case, since the new (unreacted) chemical solution 200 is constantly supplied to the contact portion between the noble metal film 11 and the metal film 101, the metal film 101 can be more reliably removed. In addition, when supplying the chemical | medical solution 200 directly to the noble metal containing member 10, in order not to prevent permeation | transmission of the chemical | medical solution 200 from the uneven surface of the noble metal containing member 10, the noble metal film 11 is not the whole surface of an uneven surface, but partially. It is desirable that it be formed. However, when the noble metal film 11 itself is a porous member, the chemical solution 200 can permeate the noble metal film 11 without forming an uneven surface on the noble metal-containing member 10.

なお、本実施形態では、薬液を金属膜１０１の表面に供給しやすいように凹凸表面を有する貴金属含有部材１０の凹部を金属膜に接触させず、金属膜１０１と貴金属含有部材１０表面との間に空間を設けている。しかし、貴金属含有部材１０の表面は、必ずしも凹凸でなくともよい。薬液２００を金属膜１０１に供給できるのであれば、平坦な貴金属表面を有する貴金属含有部材１０を金属膜１０１に接触させても十分なエッチング効果が期待できる。例えば図１の基板処理装置１を用いて、薬液２００を基板１００の金属膜１０１のパターン間に直接供給しつつ、基板を回転させ、金属膜１０１を貴金属含有部材１０の貴金属膜１１表面に接触させれば金属膜１０１をエッチング除去できる。   In the present embodiment, the concave portion of the noble metal-containing member 10 having a concavo-convex surface is not brought into contact with the metal film so that the chemical solution can be easily supplied to the surface of the metal film 101, and the gap between the metal film 101 and the surface of the noble metal-containing member 10 is maintained. A space is provided. However, the surface of the noble metal-containing member 10 is not necessarily uneven. If the chemical solution 200 can be supplied to the metal film 101, a sufficient etching effect can be expected even if the noble metal-containing member 10 having a flat noble metal surface is brought into contact with the metal film 101. For example, using the substrate processing apparatus 1 of FIG. 1, while supplying the chemical solution 200 directly between the patterns of the metal film 101 of the substrate 100, the substrate is rotated and the metal film 101 contacts the surface of the noble metal film 11 of the noble metal-containing member 10. Then, the metal film 101 can be removed by etching.

また、本実施形態では、貴金属含有部材１０を、基板１００上における金属膜１０１のパターンに接触させているが、他の金属表面、例えばウェハ状の基板１００のべベル部に設けられた金属膜に接触させてもよい。この場合、基板１００のべベル部に設けられた金属膜を剥離することができる。   In the present embodiment, the noble metal-containing member 10 is brought into contact with the pattern of the metal film 101 on the substrate 100. However, the metal film provided on the other metal surface, for example, the bevel portion of the wafer-like substrate 100. You may make it contact. In this case, the metal film provided on the bevel portion of the substrate 100 can be peeled off.

(第２実施形態)
図４は、第２実施形態に係る基板処理装置の概略的な構成を示す模式図である。図４に示す基板処理装置２は、貴金属含有部材１０と、処理槽４０(薬液供給部材)と、保持部材５０(第１保持部材)と、保持部材５１（第２保持部材）と、を備える。なお、貴金属含有部材１０および基板１００の構造については、第１実施形態と同様であるので、詳細な説明を省略する。 (Second embodiment)
FIG. 4 is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the second embodiment. The substrate processing apparatus 2 shown in FIG. 4 includes a noble metal-containing member 10, a processing tank 40 (chemical solution supply member), a holding member 50 (first holding member), and a holding member 51 (second holding member). . Note that the structures of the noble metal-containing member 10 and the substrate 100 are the same as those in the first embodiment, and a detailed description thereof will be omitted.

処理槽４０の底部には、供給口４１が設けられている。処理槽４０は、供給口４１から供給されたアルカリ性の薬液２００を貯留する。貴金属含有部材１０および基板１００は、この薬液２００に浸漬する。   A supply port 41 is provided at the bottom of the processing tank 40. The processing tank 40 stores the alkaline chemical 200 supplied from the supply port 41. The noble metal-containing member 10 and the substrate 100 are immersed in the chemical solution 200.

保持部材５０は、貴金属含有部材１０を処理槽４０まで搬送可能に保持する。保持部材５０は、例えば、貴金属含有部材１０の搬送機構に連結されているか、または当該搬送機構の一部として構成されている。   The holding member 50 holds the noble metal-containing member 10 so that it can be conveyed to the treatment tank 40. For example, the holding member 50 is connected to the transport mechanism of the noble metal-containing member 10 or is configured as a part of the transport mechanism.

保持部材５１は、基板１００を処理槽４０まで搬送可能に保持する。保持部材５１は、例えば、基板１００の搬送機構に連結されているか、または当該搬送機構の一部として構成されている。   The holding member 51 holds the substrate 100 so that it can be conveyed to the processing bath 40. For example, the holding member 51 is connected to the transport mechanism of the substrate 100 or is configured as a part of the transport mechanism.

以下、本実施形態に係る基板処理装置２を用いた基板処理方法について図５を用いて説明する。ここでも、第１実施形態と同様に、基板１００のエッチング工程を説明する。図５は、第２実施形態に係る基板１００のエッチング工程を説明するための模式図である。   Hereinafter, a substrate processing method using the substrate processing apparatus 2 according to the present embodiment will be described with reference to FIG. Here, as in the first embodiment, the etching process of the substrate 100 will be described. FIG. 5 is a schematic diagram for explaining an etching process of the substrate 100 according to the second embodiment.

まず、保持部材５０を用いて貴金属含有部材１０を処理槽４０へ搬送するとともに、保持部材５１を用いて基板１００を処理槽４０へ搬送する。処理槽４０内では、貴金属含有部材１０と基板１００とを接触させる。具体的には、貴金属含有部材１０の貴金属膜１１と基板１００の金属膜１０１とを部分的に接触させる。このとき、基板１００の積層体１０２の損傷を回避するために、金属膜１０１と貴金属膜１１との接触部分の圧力は、できるだけ小さいことが望ましい。   First, the noble metal-containing member 10 is transferred to the processing tank 40 using the holding member 50, and the substrate 100 is transferred to the processing tank 40 using the holding member 51. In the treatment tank 40, the noble metal-containing member 10 and the substrate 100 are brought into contact with each other. Specifically, the noble metal film 11 of the noble metal-containing member 10 and the metal film 101 of the substrate 100 are partially brought into contact. At this time, in order to avoid damage to the stacked body 102 of the substrate 100, it is desirable that the pressure at the contact portion between the metal film 101 and the noble metal film 11 is as small as possible.

次に、アルカリ性の薬液２００を供給口４１から処理槽４０内に供給する。薬液２００が処理槽４０内に貯留されると、図４に示すように、貴金属含有部材１０および基板１００は、薬液２００に浸漬する。この薬液２００は、貴金属膜１１と金属膜１０１との空隙に入り込む。そのため、第１実施形態と同様に、ガルバニック腐食が発生し、金属膜１０１のエッチングが促進される。その後、貴金属含有部材１０および基板１００は、処理槽４０から搬出され、当該貴金属含有部材１０と別の基板１００が処理槽４０へ搬入される。   Next, the alkaline chemical 200 is supplied from the supply port 41 into the treatment tank 40. When the chemical solution 200 is stored in the treatment tank 40, the noble metal-containing member 10 and the substrate 100 are immersed in the chemical solution 200 as shown in FIG. The chemical solution 200 enters the gap between the noble metal film 11 and the metal film 101. Therefore, as in the first embodiment, galvanic corrosion occurs and the etching of the metal film 101 is promoted. Thereafter, the noble metal-containing member 10 and the substrate 100 are carried out of the processing tank 40, and the noble metal-containing member 10 and another substrate 100 are carried into the processing tank 40.

以上説明した本実施形態によれば、第１実施形態と同様に、金属膜１０１をガルバニック腐食によってエッチングすることによって、基板１００のパターンの損傷を回避しつつ、高いエッチング速度で金属膜１０１を除去できる。   According to the present embodiment described above, the metal film 101 is removed at a high etching rate while avoiding damage to the pattern of the substrate 100 by etching the metal film 101 by galvanic corrosion as in the first embodiment. it can.

また、本実施形態では、処理槽４０内で金属膜１０１を一括して除去している。したがって、第１実施形態に比べて、エッチング処理時間を短縮することができる。   In the present embodiment, the metal film 101 is collectively removed in the processing tank 40. Therefore, the etching processing time can be shortened compared to the first embodiment.

（第３実施形態）
図６は、第３実施形態に係る基板処理装置の概略的な構成を示す模式図である。図６に示す基板処理装置３は、貴金属含有部材１０と、薬液供給ノズル２０と、駆動機構６０と、を備える。なお、薬液供給ノズル２０および基板１００の構造については、第１実施形態と同様であるので、詳細な説明を省略する。 (Third embodiment)
FIG. 6 is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the third embodiment. The substrate processing apparatus 3 shown in FIG. 6 includes a noble metal-containing member 10, a chemical solution supply nozzle 20, and a drive mechanism 60. The structures of the chemical solution supply nozzle 20 and the substrate 100 are the same as those in the first embodiment, and thus detailed description thereof is omitted.

貴金属含有部材１０の形状は、複数枚の基板１００を保持するベルト形状である。ベルトの表面には、貴金属膜１１（図６では不図示）が形成されている。貴金属膜１１は、例えばシリコンゴム等の軟質部材上に堆積されていてもよいし、貴金属含有部材１０自体が、薄い貴金属膜１１のベルトとして成形されていてもよい。   The shape of the noble metal-containing member 10 is a belt shape that holds a plurality of substrates 100. A noble metal film 11 (not shown in FIG. 6) is formed on the surface of the belt. The noble metal film 11 may be deposited on a soft member such as silicon rubber, or the noble metal-containing member 10 itself may be formed as a thin belt of the noble metal film 11.

駆動機構６０は、貴金属含有部材１０に取り付けられている。駆動機構６０が回転することによって、貴金属含有部材１０は薬液供給ノズル２０の下方で一方向Ｘに移動する。つまり、駆動機構６０は、ベルトコンベア方式で複数枚の基板１００を搬送する。   The drive mechanism 60 is attached to the noble metal-containing member 10. As the drive mechanism 60 rotates, the noble metal-containing member 10 moves in one direction X below the chemical solution supply nozzle 20. That is, the drive mechanism 60 conveys a plurality of substrates 100 by a belt conveyor method.

以下、本実施形態に係る基板処理装置３を用いた基板処理方法について説明する。ここでも、第１実施形態と同様に、基板１００のエッチング工程を説明する。   Hereinafter, a substrate processing method using the substrate processing apparatus 3 according to the present embodiment will be described. Here, as in the first embodiment, the etching process of the substrate 100 will be described.

まず、基板１００を反転して貴金属含有部材１０上に載置する。そのため、図７に示すように、基板１００の金属膜１０１が貴金属含有部材１０の貴金属膜１１に接触する。続いて、駆動機構６０が貴金属含有部材１０を駆動して基板１００を搬送する。基板１００が薬液供給ノズル２０の直下に到達すると、薬液供給ノズル２０は、薬液２００を吐出する。   First, the substrate 100 is inverted and placed on the noble metal-containing member 10. Therefore, as shown in FIG. 7, the metal film 101 of the substrate 100 contacts the noble metal film 11 of the noble metal-containing member 10. Subsequently, the driving mechanism 60 drives the noble metal-containing member 10 to convey the substrate 100. When the substrate 100 reaches just below the chemical solution supply nozzle 20, the chemical solution supply nozzle 20 discharges the chemical solution 200.

吐出された薬液２００は、基板１００から貴金属膜１１へ拡散する。このとき、薬液２００は、金属膜１０１と貴金属膜１１との空隙にも入り込む。そのため、上述した他の実施形態と同様に、ガルバニック腐食が発生し、金属膜１０１のエッチングが促進される。   The discharged chemical 200 is diffused from the substrate 100 to the noble metal film 11. At this time, the chemical solution 200 also enters the gap between the metal film 101 and the noble metal film 11. Therefore, galvanic corrosion occurs and etching of the metal film 101 is promoted as in the other embodiments described above.

その後、駆動機構６０が貴金属含有部材１０を駆動すると、次の基板１００が薬液供給ノズル２０の直下に到達し、当該基板１００に設けられた金属膜１０１が同様に除去される。このようにして、貴金属含有部材１０に載置された複数の基板１００にそれぞれ設けられた金属膜１０１が、連続的に除去される。   Thereafter, when the driving mechanism 60 drives the noble metal-containing member 10, the next substrate 100 reaches just below the chemical solution supply nozzle 20, and the metal film 101 provided on the substrate 100 is similarly removed. In this way, the metal films 101 respectively provided on the plurality of substrates 100 placed on the noble metal-containing member 10 are continuously removed.

以上説明した本実施形態においても、金属膜１０１をガルバニック腐食によってエッチングすることによって、基板１００のパターンの損傷を回避しつつ、高いエッチング速度で金属膜１０１を除去できる。   Also in this embodiment described above, the metal film 101 can be removed at a high etching rate while avoiding damage to the pattern of the substrate 100 by etching the metal film 101 by galvanic corrosion.

また、本実施形態では、複数の基板１００を連続的にエッチング処理できる。したがって、装置の稼働率を向上させることが可能となる。   In the present embodiment, the plurality of substrates 100 can be continuously etched. Therefore, it is possible to improve the operating rate of the apparatus.

（第４実施形態）
図８は、第４実施形態に係る基板処理装置の概略的な構成を示す模式図である。また、図９は、図８に示す基板処理装置４の要部を拡大した拡大図である。 (Fourth embodiment)
FIG. 8 is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the fourth embodiment. FIG. 9 is an enlarged view of the main part of the substrate processing apparatus 4 shown in FIG.

図８および図９に示すように、本実施形態に係る基板処理装置４は、貴金属含有部材１０と、薬液供給ノズル２０と、保持部材７０（第１保持部材）と、保持部材７１（第２保持部材）と、を備える。なお、薬液供給ノズル２０および基板１００の構造については、第１実施形態と同様であるので、詳細な説明を省略する。   As shown in FIGS. 8 and 9, the substrate processing apparatus 4 according to this embodiment includes a noble metal-containing member 10, a chemical solution supply nozzle 20, a holding member 70 (first holding member), and a holding member 71 (second holding member). Holding member). The structures of the chemical solution supply nozzle 20 and the substrate 100 are the same as those in the first embodiment, and thus detailed description thereof is omitted.

貴金属含有部材１０は、複数の基板１００を保持する円板状に形成されている。貴金属含有部材１０の上面は、凹凸面である。この凹凸面には、図９に示すように、貴金属膜１１が設けられている。なお、貴金属含有部材１０は、第３実施形態と同様に、シリコンゴム等の軟質部材上に堆積されていてもよいし、貴金属含有部材１０自体が、薄い円板として成形されていてもよい。   The noble metal-containing member 10 is formed in a disk shape that holds the plurality of substrates 100. The upper surface of the noble metal-containing member 10 is an uneven surface. As shown in FIG. 9, a noble metal film 11 is provided on the uneven surface. As in the third embodiment, the noble metal-containing member 10 may be deposited on a soft member such as silicon rubber, or the noble metal-containing member 10 itself may be formed as a thin disk.

保持部材７０は、貴金属含有部材１０を回転可能に保持する。保持部材７０は、例えば、回転機構に連結されているか、または、当該回転機構の一部として構成されている。   The holding member 70 holds the noble metal-containing member 10 rotatably. The holding member 70 is connected to, for example, a rotation mechanism or configured as a part of the rotation mechanism.

保持部材７１は、複数の基板１００を、貴金属含有部材１０と同時に同じ方向に回転可能に保持する。保持部材７１は、例えば、保持部材７０と同じ回転機構に連結されているか、当該回転機構の一部として構成される。   The holding member 71 holds the plurality of substrates 100 so as to be rotatable in the same direction simultaneously with the noble metal-containing member 10. For example, the holding member 71 is connected to the same rotation mechanism as the holding member 70 or is configured as a part of the rotation mechanism.

以下、本実施形態に係る基板処理装置４を用いた基板処理方法について説明する。ここでも、第１実施形態と同様に、基板１００のエッチング工程を説明する。   Hereinafter, a substrate processing method using the substrate processing apparatus 4 according to the present embodiment will be described. Here, as in the first embodiment, the etching process of the substrate 100 will be described.

まず、保持部材７１に保持された複数の基板１００を、貴金属含有部材１０の上に載置する。このとき、金属膜１０１が貴金属膜１１に接触するように、各基板１００は反転して保持部材７１に保持されている。   First, the plurality of substrates 100 held by the holding member 71 are placed on the noble metal-containing member 10. At this time, each substrate 100 is inverted and held by the holding member 71 so that the metal film 101 contacts the noble metal film 11.

続いて、保持部材７０を用いて貴金属含有部材１０を回転させる。貴金属含有部材１０の回転と同時に、基板１００も同じ方向に回転する。そのため、貴金属含有部材１０と基板１００との間にはせん断応力がほぼかからない。   Subsequently, the noble metal-containing member 10 is rotated using the holding member 70. Simultaneously with the rotation of the noble metal-containing member 10, the substrate 100 also rotates in the same direction. Therefore, almost no shear stress is applied between the noble metal-containing member 10 and the substrate 100.

次に、薬液供給ノズル２０がアルカリ性の薬液２００を貴金属含有部材１０の中心に向けて吐出する。吐出された薬液２００は、貴金属含有部材１０の回転で発生する遠心力によって、貴金属含有部材１０の外周に向かって拡散する。このとき、薬液２００は、金属膜１０１と貴金属膜１１との空隙にも入り込む。そのため、上述した他の実施形態と同様に、ガルバニック腐食が発生し、金属膜１０１のエッチングが促進される。   Next, the chemical solution supply nozzle 20 discharges the alkaline chemical solution 200 toward the center of the noble metal-containing member 10. The discharged chemical 200 is diffused toward the outer periphery of the noble metal-containing member 10 due to the centrifugal force generated by the rotation of the noble metal-containing member 10. At this time, the chemical solution 200 also enters the gap between the metal film 101 and the noble metal film 11. Therefore, galvanic corrosion occurs and etching of the metal film 101 is promoted as in the other embodiments described above.

以上説明した本実施形態においても、金属膜１０１を貴金属膜１１と接触させることによって、エッチング速度を高めている。また、本実施形態では、基板１００は、貴金属含有部材１０と同時に同じ方向に回転するので、これらの間にせん断応力はほぼかからない。よって、基板１００のパターンの損傷を回避することができる。   Also in the present embodiment described above, the etching rate is increased by bringing the metal film 101 into contact with the noble metal film 11. Moreover, in this embodiment, since the board | substrate 100 rotates in the same direction simultaneously with the noble metal containing member 10, a shear stress is not substantially applied between these. Therefore, damage to the pattern of the substrate 100 can be avoided.

（第５実施形態）
図１０（ａ）は、第５実施形態に係る基板処理装置の概略的な構成を示す模式図である。図１０（ａ）に示すように、本実施形態の基板処理装置５は、薬液２００を貴金属含有部材１０へ直接供給する通液ノズル８０（薬液供給部材）を備える。 (Fifth embodiment)
FIG. 10A is a schematic diagram showing a schematic configuration of a substrate processing apparatus according to the fifth embodiment. As shown in FIG. 10A, the substrate processing apparatus 5 of this embodiment includes a liquid passing nozzle 80 (chemical solution supply member) that directly supplies the chemical solution 200 to the noble metal-containing member 10.

図１０（ｂ）は、図１０（ａ）に示す切断線Ａ−Ａに沿った断面図である。図１０（ｂ）に示すように、本実施形態の貴金属含有部材１０は、複数の通液孔１０５を有する。各通液孔１０５は、通液ノズル８０と連通している。   FIG. 10B is a cross-sectional view along the cutting line AA shown in FIG. As shown in FIG. 10B, the noble metal-containing member 10 of the present embodiment has a plurality of liquid passage holes 105. Each liquid passage hole 105 communicates with the liquid passage nozzle 80.

図１１（ａ）は、貴金属含有部材１０の拡大図である。図１１（ａ）に示すように、本実施形態の貴金属含有部材１０の底面には、ブラシのように束ねられた柔軟な複数の毛状部材１２が設けられている。これらの毛状部材１２は、貴金属含有部材１０の凹凸形状部分を構成する。   FIG. 11A is an enlarged view of the noble metal-containing member 10. As shown to Fig.11 (a), the flexible several bristle member 12 bundled like the brush is provided in the bottom face of the noble metal containing member 10 of this embodiment. These bristle members 12 constitute an uneven portion of the noble metal-containing member 10.

図１１（ｂ）は、毛状部材１２の拡大図である。図１１（ｂ）に示すように、毛状部材１２では、絶縁体１２１が芯部を構成している。この絶縁体１２１は、貴金属膜１２２で覆われている。絶縁体１２１は、例えばポリプロピレンを含み、貴金属膜１２２は例えば白金を含んでいる。貴金属膜１２２は、絶縁体１２１を部分的に覆っていてもよいし、絶縁体１２１全体を覆っていてもよい。また、絶縁体１２１は、貴金属のナノ粒子で覆われていてもよい。   FIG. 11B is an enlarged view of the hair-like member 12. As shown in FIG. 11B, in the hairy member 12, the insulator 121 constitutes a core part. The insulator 121 is covered with a noble metal film 122. The insulator 121 includes, for example, polypropylene, and the noble metal film 122 includes, for example, platinum. The noble metal film 122 may partially cover the insulator 121 or may cover the entire insulator 121. The insulator 121 may be covered with noble metal nanoparticles.

基板処理装置５では、通液ノズル８０が薬液２００を貴金属含有部材１０へ供給すると、この薬液２００は、通液孔１０５を通過して毛状部材１２の側面に沿って流れる。これにより、例えば金属膜１０１（図３参照）のような被加工物をエッチングする際に、図１１（ｂ）に示すように、毛状部材１２と金属膜１０１との接触箇所（エッチング箇所）が薬液２００で満たされる。   In the substrate processing apparatus 5, when the liquid passing nozzle 80 supplies the chemical liquid 200 to the noble metal-containing member 10, the chemical liquid 200 flows along the side surface of the hair-like member 12 through the liquid passing hole 105. Thereby, when etching a workpiece such as the metal film 101 (see FIG. 3), for example, as shown in FIG. 11B, the contact portion (etching portion) between the hair-like member 12 and the metal film 101. Is filled with the chemical solution 200.

金属膜１０１と毛状部材１２の先端部とが接触すると、金属膜１０１が高電位のアノード領域となり、毛状部材１２が低電位のカソード領域となる。この電位差によって、ガルバニック腐食が発生する。このとき、腐食電流Ｉcorrは、下記の式（１）に基づいて算出できる。 When the metal film 101 and the tip of the hairy member 12 come into contact, the metal film 101 becomes a high potential anode region, and the hairy member 12 becomes a low potential cathode region. This potential difference causes galvanic corrosion. At this time, the corrosion current I corr can be calculated based on the following equation (1).

Ｉcorr＝(Ｅcathode−Ｅanode)/(Ｒelectrolyte+Ｒanode+Ｒcathode+Ｒa/e+Ｒc/e) （１）
式（１）において、起電力Ｅanodeおよび抵抗Ｒanodeは、アノード領域の起電力および抵抗をそれぞれ示す。起電力Ｅcathodeおよび抵抗Ｒcathodeは、カソード領域の起電力および抵抗をそれぞれ示す。抵抗Ｒelectrolyteは、薬液２００の抵抗を示す。接触抵抗Ｒa/eは、アノード領域と薬液２００の接触抵抗、すなわち、金属膜１０１と薬液２００との接触抵抗を示す。接触抵抗Ｒc/eは、カソード領域と薬液２００との接触抵抗、すなわち、毛状部材１２と薬液２００との接触抵抗を示す。 I corr = (E cathode −E anode ) / (R electrolyte + R anode + R cathode + R a / e + R c / e ) (1)
In the formula (1), an electromotive force E anode and a resistance R anode indicate an electromotive force and a resistance in the anode region, respectively. An electromotive force E cathode and a resistance R cathode indicate an electromotive force and resistance in the cathode region, respectively. The resistance R electrolyte indicates the resistance of the chemical solution 200. The contact resistance R a / e indicates the contact resistance between the anode region and the chemical solution 200, that is, the contact resistance between the metal film 101 and the chemical solution 200. The contact resistance R c / e indicates the contact resistance between the cathode region and the chemical solution 200, that is, the contact resistance between the hairy member 12 and the chemical solution 200.

本実施形態では、毛状部材１２の先端部が、エッチング時に撓るので、金属膜１０１と貴金属膜１２２との接触面積が大きくなる。そのため、アノード領域とカソード領域の接触抵抗Ｒa/ｃは、小さくなる。これにより、エッチング速度を効率的に高めることが可能になる。 In the present embodiment, the tip of the bristle member 12 bends during etching, so that the contact area between the metal film 101 and the noble metal film 122 increases. For this reason, the contact resistance Ra / c between the anode region and the cathode region becomes small. This makes it possible to increase the etching rate efficiently.

なお、本実施形態では、薬液２００は、例えば、導電性の高い強アルカリ液であってもよい。この場合、抵抗Ｒelectrolyte、接触抵抗Ｒa/e、および接触抵抗Ｒc/eが小さくなる。そのため、上記の式（１）によれば、腐食電流Ｉcorrが増加するので、エッチング速度を高めることが可能になる。 In the present embodiment, the chemical solution 200 may be, for example, a strong alkaline solution with high conductivity. In this case, the resistance R electrolyte , the contact resistance R a / e , and the contact resistance R c / e are reduced. Therefore, according to the above equation (1), since the corrosion current I corr increases, the etching rate can be increased.

（第６実施形態）
図１２（ａ）は、第６実施形態に係る基板処理装置６の概略的な構成を示す模式図である。図１２（ａ）に示すように、本実施形態の基板処理装置６は、貴金属含有部材１０の代わりに、第１貴金属含有部材１０ａおよび第２貴金属含有部材１０ｂを備える点で、第１実施形態の基板処理装置１と異なる。 (Sixth embodiment)
FIG. 12A is a schematic diagram showing a schematic configuration of the substrate processing apparatus 6 according to the sixth embodiment. As shown in FIG. 12A, the substrate processing apparatus 6 according to the present embodiment includes the first noble metal-containing member 10 a and the second noble metal-containing member 10 b instead of the noble metal-containing member 10. Different from the substrate processing apparatus 1 of FIG.

図１２（ｂ）は、第１貴金属含有部材１０ａの拡大図である。図１２（ｂ）に示すように、第１貴金属含有部材１０ａの底面には、ブラシのように束ねられた柔軟な複数の毛状部材１３が設けられている。これらの毛状部材１３は、第１貴金属含有部材１０ａの凹凸形状部分を構成する。毛状部材１３の表面には、第５実施形態で説明した毛状部材１２と同様に、貴金属膜が形成されている。   FIG. 12B is an enlarged view of the first noble metal-containing member 10a. As shown in FIG. 12B, a plurality of flexible bristle members 13 bundled like a brush are provided on the bottom surface of the first noble metal-containing member 10a. These bristle members 13 constitute an uneven portion of the first noble metal-containing member 10a. A noble metal film is formed on the surface of the hair-like member 13 in the same manner as the hair-like member 12 described in the fifth embodiment.

図１２（ｃ）は、第２貴金属含有部材１０ｂの拡大図である。図１２（ｃ）に示すように、第２貴金属含有部材１０ｂの底面には、凹凸形状を有するスポンジ１４が設けられている。スポンジ１４の表面にも、貴金属膜が形成されている。スポンジ１４の凸部間のピッチｐ２（第２ピッチ）は、毛状部材１３の先端間のピッチｐ１（第１ピッチ）よりも小さい。なお、第１貴金属含有部材１０ａおよび第２貴金属含有部材１０ｂの構造は、上記の構造に限定されない。   FIG. 12C is an enlarged view of the second noble metal-containing member 10b. As shown in FIG. 12C, a sponge 14 having an uneven shape is provided on the bottom surface of the second noble metal-containing member 10b. A noble metal film is also formed on the surface of the sponge 14. The pitch p <b> 2 (second pitch) between the convex portions of the sponge 14 is smaller than the pitch p <b> 1 (first pitch) between the tips of the hair-like members 13. In addition, the structure of the 1st noble metal containing member 10a and the 2nd noble metal containing member 10b is not limited to said structure.

図１３（ａ）は、第１貴金属含有部材１０ａの変形例を示す拡大図である。図１３（ａ）に示すように、第１貴金属含有部材１０ａは、例えば、第１実施形態の貴金属含有部材１０と同様に、第１貴金属膜１１ａで覆われた凹凸形状を有していてもよい。   Fig.13 (a) is an enlarged view which shows the modification of the 1st noble metal containing member 10a. As shown in FIG. 13A, the first noble metal-containing member 10a may have an uneven shape covered with the first noble metal film 11a, for example, similarly to the noble metal-containing member 10 of the first embodiment. Good.

図１３（ｂ）は、第２貴金属含有部材１０ｂの変形例を示す拡大図である。図１３（ｂ）に示すように、第２貴金属含有部材１０ｂには、第１貴金属膜１１ａの表面に、第２貴金属膜１１ｂが形成されていてもよい。第２貴金属膜１１ｂのピッチｐ２（第２ピッチ）は、第１貴金属膜１１ａのピッチｐ１（第１ピッチ）よりも小さい。   FIG.13 (b) is an enlarged view which shows the modification of the 2nd noble metal containing member 10b. As shown in FIG. 13 (b), the second noble metal film 11b may be formed on the surface of the first noble metal film 11a in the second noble metal-containing member 10b. The pitch p2 (second pitch) of the second noble metal film 11b is smaller than the pitch p1 (first pitch) of the first noble metal film 11a.

以下、本実施形態に係る基板処理装置６を用いた半導体装置の製造方法について説明する。基板処理装置６は、例えば、図３に示す積層体１０２上に形成された金属膜１０１の除去に用いられる。   Hereinafter, a method for manufacturing a semiconductor device using the substrate processing apparatus 6 according to the present embodiment will be described. The substrate processing apparatus 6 is used, for example, for removing the metal film 101 formed on the stacked body 102 shown in FIG.

まず、保持部材３０で第１貴金属含有部材１０ａを下降することによって、毛状部材１３または第１貴金属膜１１ａを基板１００の金属膜１０１に接触させる。   First, the bristle member 13 or the first noble metal film 11 a is brought into contact with the metal film 101 of the substrate 100 by lowering the first noble metal-containing member 10 a by the holding member 30.

次に、薬液供給ノズル２０が、薬液２００を吐出する。その結果、薬液２００は、毛状部材１２の隙間または貴金属膜１１ａの凹部に入り込んで金属膜１０１に供給される。これにより、ガルバニック腐食が発生し、金属膜１０１のエッチングが促進される。   Next, the chemical solution supply nozzle 20 discharges the chemical solution 200. As a result, the chemical solution 200 enters the gap between the hair-like members 12 or the recesses of the noble metal film 11 a and is supplied to the metal film 101. Thereby, galvanic corrosion occurs and etching of the metal film 101 is promoted.

続いて、保持部材３０を用いて第１貴金属含有部材１０ａを上昇させ、保持部材３２（第３保持部材）を用いて第２貴金属含有部材１０ｂを下降させる。その後、再び、薬液供給ノズル２０から薬液２００を供給することによって、金属膜１０１がエッチングされる。このとき、第２貴金属含有部材１０ｂのピッチｐ２は第１貴金属含有部材１０ａのピッチｐ１よりも小さいので、表面積が大きい。そのため、金属膜１０１との接触面積が大きくなる。これにより、第１貴金属含有部材１０ａのエッチング時に残った金属膜１０１を除去することが可能となる。   Subsequently, the first noble metal-containing member 10a is raised using the holding member 30, and the second noble metal-containing member 10b is lowered using the holding member 32 (third holding member). Thereafter, the metal film 101 is etched again by supplying the chemical solution 200 from the chemical solution supply nozzle 20. At this time, since the pitch p2 of the second noble metal-containing member 10b is smaller than the pitch p1 of the first noble metal-containing member 10a, the surface area is large. Therefore, the contact area with the metal film 101 is increased. Thereby, it becomes possible to remove the metal film 101 remaining during the etching of the first noble metal-containing member 10a.

なお、第１貴金属含有部材１０ａおよび第２貴金属含有部材１０ｂを組み合わせることは、被加工物の残渣を除去する目的以外にも適用できる。また、上述した方法の他に、第１貴金属含有部材１０ａおよび第２貴金属含有部材１０ｂで交互にエッチングしてもよい。   In addition, combining the first noble metal-containing member 10a and the second noble metal-containing member 10b can be applied for purposes other than the purpose of removing the residue of the workpiece. In addition to the method described above, the first noble metal-containing member 10a and the second noble metal-containing member 10b may be alternately etched.

本実施形態に係る基板処理装置６によれば、ピッチの異なる貴金属含有部材を備えることによって、より確実に金属膜をエッチングすることができる。   According to the substrate processing apparatus 6 according to the present embodiment, the metal film can be more reliably etched by providing the noble metal-containing members having different pitches.

（第７実施形態）
図１４は、第７実施形態に係る基板処理装置の概略的な構成を示す模式図である。図１４に示すように、本実施形態に係る基板処理装置７は、第１実施形態の基板処理装置１の構成要素に加えて、冷却機構９０を備える。冷却機構９０は、例えば薬液供給ノズル２０の端部に設置され、薬液２００を冷却する。冷却機構９０は、例えば冷却ガスを用いて、薬液２００を冷却する。 (Seventh embodiment)
FIG. 14 is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the seventh embodiment. As shown in FIG. 14, the substrate processing apparatus 7 according to this embodiment includes a cooling mechanism 90 in addition to the components of the substrate processing apparatus 1 of the first embodiment. The cooling mechanism 90 is installed, for example, at the end of the chemical solution supply nozzle 20 and cools the chemical solution 200. The cooling mechanism 90 cools the chemical | medical solution 200, for example using cooling gas.

図１５（ａ）は、本実施形態における基板１００のエッチング処理前の状態を示し、図１５（ｂ）は、本実施形態における基板１００のエッチング処理後の状態を示す。本実施形態では、基板１００の上に膜１０３が設けられ、この膜１０３の上に金属膜１０１が設けられている。膜１０３は、金属膜であってもよいし、絶縁膜であってもよい   FIG. 15A shows a state before the etching process of the substrate 100 in the present embodiment, and FIG. 15B shows a state after the etching process of the substrate 100 in the present embodiment. In this embodiment, a film 103 is provided on the substrate 100, and a metal film 101 is provided on the film 103. The film 103 may be a metal film or an insulating film.

貴金属含有部材１０を用いて金属膜１０１をエッチングする場合、高温および高濃度の薬液２００を用いるとエッチング速度は高くなる。エッチング速度が必要以上に高くなると、金属膜１０１だけでなく膜１０３の一部もエッチングされることが懸念される。   When the metal film 101 is etched using the noble metal-containing member 10, the etching rate is increased when the high temperature and high concentration chemical 200 is used. If the etching rate becomes higher than necessary, there is a concern that not only the metal film 101 but also a part of the film 103 is etched.

そこで、本実施形態では、冷却機構９０で薬液２００を冷却することによって、過剰なエッチングを回避できる。これにより、金属膜１０１のエッチング精度を向上させることが可能となる。   Therefore, in this embodiment, excessive etching can be avoided by cooling the chemical solution 200 with the cooling mechanism 90. Thereby, the etching accuracy of the metal film 101 can be improved.

なお、上記のような過剰なエッチングを回避するために、薬液２００を希釈してもよい。この場合、薬液２００の濃度が低下するので、膜１０３のエッチングを回避できる。よって、金属膜１０１のエッチング精度を向上させることが可能となる。   In order to avoid excessive etching as described above, the chemical solution 200 may be diluted. In this case, since the concentration of the chemical solution 200 decreases, etching of the film 103 can be avoided. Therefore, the etching accuracy of the metal film 101 can be improved.

また、冷却機構９０は、基板１００の下部に設置されてもよい。この場合、基板１００が低温状態になるので、金属膜１０１のエッチング時に基板１００を介して薬液２００を冷却できる。   In addition, the cooling mechanism 90 may be installed in the lower part of the substrate 100. In this case, since the substrate 100 is in a low temperature state, the chemical solution 200 can be cooled through the substrate 100 when the metal film 101 is etched.

さらに、本実施形態では、膜１０３の表面に、表面保護剤１０４を添加してもよい。表面保護剤１０４として、例えば防腐剤または被膜形成剤を用いることができる。表面保護剤１０４が防腐剤であり、膜１０３が金属膜である場合、膜１０３の腐食を抑制することができる。一方、表面保護剤１０４が被膜形成剤であり、膜１０３が絶縁膜である場合、膜１０３の溶解を抑制することができる。   Furthermore, in this embodiment, a surface protective agent 104 may be added to the surface of the film 103. As the surface protective agent 104, for example, a preservative or a film forming agent can be used. When the surface protective agent 104 is a preservative and the film 103 is a metal film, corrosion of the film 103 can be suppressed. On the other hand, when the surface protective agent 104 is a film forming agent and the film 103 is an insulating film, dissolution of the film 103 can be suppressed.

（第８実施形態）
図１６は、第８実施形態の貴金属含有部材１０に設けられた毛状部材１５の拡大図である。本実施形態では、毛状部材１５は、図１１（ａ）に示す第５実施形態に係る貴金属含有部材１０の毛状部材１２の代わりに設けられている。 (Eighth embodiment)
FIG. 16 is an enlarged view of the hair-like member 15 provided in the noble metal-containing member 10 of the eighth embodiment. In this embodiment, the hair-like member 15 is provided instead of the hair-like member 12 of the noble metal-containing member 10 according to the fifth embodiment shown in FIG.

毛状部材１５では、導電体１５１が金属膜１５３で覆われ、金属膜１５３は、貴金属膜１５２で覆われている。導電体１５１は、例えば導電性カーボンを含み、貴金属膜１５２は例えば白金を含んでいる。金属膜１５３は、例えば銅のような貴金属よりも比抵抗の小さい金属を含んでいる。   In the hairy member 15, the conductor 151 is covered with a metal film 153, and the metal film 153 is covered with a noble metal film 152. The conductor 151 includes, for example, conductive carbon, and the noble metal film 152 includes, for example, platinum. The metal film 153 includes a metal having a specific resistance smaller than that of a noble metal such as copper.

以上説明した本実施形態によれば、毛状部材１５の芯部は、導電体１５１で構成されている。そのため、カソード領域の抵抗Ｒcathodeは、第５実施形態の毛状部材１２よりも小さくなる。これにより、腐食電流Ｉcorrが増加するので、エッチング速度を高めることが可能になる。 According to the present embodiment described above, the core portion of the hair-like member 15 is composed of the conductor 151. Therefore, the resistance R cathode of the cathode region is smaller than that of the hair-like member 12 of the fifth embodiment. Thereby, since the corrosion current I corr increases, the etching rate can be increased.

さらに、本実施形態では、導電体１５１と貴金属膜１５２との間に、貴金属膜１５２よりも比抵抗の小さな金属膜１５３が形成されている。そのため、上記抵抗Ｒcathodeをさらに低減することができ、その結果、エッチング速度をより一層高めることが可能になる。 Further, in the present embodiment, a metal film 153 having a specific resistance smaller than that of the noble metal film 152 is formed between the conductor 151 and the noble metal film 152. Therefore, the resistance R cathode can be further reduced, and as a result, the etching rate can be further increased.

（第９実施形態）
図１７（ａ）は、第９実施形態に係る貴金属含有部材１０の概略的な構成を示す図である。本実施形態では、貴金属を含んだ導電性の担体１６が、図１１（ａ）に示す第５実施形態に係る毛状部材１５の代わりに貴金属含有部材１０の底面に設けられている。担体１６は、イオン交換樹脂等の多孔質材で構成される。担体１６内には、例えば白金等のナノ粒子が含まれている。 (Ninth embodiment)
FIG. 17A is a diagram illustrating a schematic configuration of the noble metal-containing member 10 according to the ninth embodiment. In this embodiment, the electroconductive support | carrier 16 containing a noble metal is provided in the bottom face of the noble metal containing member 10 instead of the bristle member 15 which concerns on 5th Embodiment shown to Fig.11 (a). The carrier 16 is made of a porous material such as an ion exchange resin. The carrier 16 contains nanoparticles such as platinum.

本実施形態では、通液ノズル８０が薬液２００を貴金属含有部材１０へ供給すると、この薬液２００は、貴金属含有部材１０に形成された通液孔１０５を通過する。その後、薬液２００は、担体１６の内部を通過して担体１６と被加工物との接触箇所に流出する。その後、担体１６に含まれた貴金属および薬液２００によって、被加工物はエッチングされる。   In the present embodiment, when the liquid nozzle 80 supplies the chemical liquid 200 to the noble metal-containing member 10, the chemical liquid 200 passes through the liquid passage hole 105 formed in the noble metal-containing member 10. Thereafter, the chemical solution 200 passes through the inside of the carrier 16 and flows out to a contact portion between the carrier 16 and the workpiece. Thereafter, the workpiece is etched by the noble metal and chemical 200 contained in the carrier 16.

以上説明した本実施形態によれば、担体１６によって薬液２００の通液性を確保しつつ、担体１６に含まれた貴金属によってエッチングを促進することができる。   According to the present embodiment described above, etching can be promoted by the noble metal contained in the carrier 16 while ensuring the liquid permeability of the chemical solution 200 by the carrier 16.

なお、本実施形態では、担体１６を例えば図１７（ｂ）に示す担体１６ａのように毛状に加工してもよい。または、担体１６を例えば図１７（ｂ）に示す担体１６ｂのような櫛形状に加工してもよい。この場合、薬液２００の流路が拡大するので、エッチング箇所への薬液２００の通液性を向上させることができる。   In the present embodiment, the carrier 16 may be processed into a hair like a carrier 16a shown in FIG. Or you may process the support | carrier 16 into the comb shape like the support | carrier 16b shown, for example in FIG.17 (b). In this case, since the flow path of the chemical solution 200 is enlarged, the liquid permeability of the chemical solution 200 to the etching site can be improved.

（第１０実施形態）
図１８（ａ）は、第１０実施形態に係る貴金属含有部材１０の概略的な構成を示す図である。本実施形態では、貴金属を含んだ網状体１７が、図１１（ａ）に示す第５実施形態に係る毛状部材１５の代わりに貴金属含有部材１０の底面に設けられている。 (10th Embodiment)
FIG. 18A is a diagram illustrating a schematic configuration of the noble metal-containing member 10 according to the tenth embodiment. In the present embodiment, a net-like body 17 containing a noble metal is provided on the bottom surface of the noble metal-containing member 10 instead of the bristle member 15 according to the fifth embodiment shown in FIG.

図１８（ｂ）は、網状体１７の拡大図である。網状体１７では、紐状の導電性カーボン１７１が網状に加工されている。導電性カーボン１７１には、貴金属のナノ粒子１７２が付着されている。   FIG. 18B is an enlarged view of the mesh body 17. In the net 17, string-like conductive carbon 171 is processed into a net. Noble metal nanoparticles 172 are attached to the conductive carbon 171.

本実施形態では、通液ノズル８０が薬液２００を貴金属含有部材１０へ供給すると、この薬液２００は、貴金属含有部材１０に形成された通液孔１０５を通過する。その後、薬液２００は、網状体１７の隙間を通って網状体１７と被加工物との接触箇所に流出する。その後、網状体１７に含まれた貴金属のナノ粒子１７２および薬液２００によって、被加工物はエッチングされる。   In the present embodiment, when the liquid nozzle 80 supplies the chemical liquid 200 to the noble metal-containing member 10, the chemical liquid 200 passes through the liquid passage hole 105 formed in the noble metal-containing member 10. Thereafter, the chemical 200 flows out through the gap between the mesh body 17 to the contact portion between the mesh body 17 and the workpiece. Thereafter, the workpiece is etched by the noble metal nanoparticles 172 and the chemical solution 200 contained in the network 17.

以上説明した本実施形態によれば、網状体１７によって、薬液２００の通液性を確保しつつ、網状体１７に含まれたナノ粒子１７２によってエッチングを促進することができる。   According to the present embodiment described above, etching can be promoted by the nanoparticles 172 contained in the mesh body 17 while ensuring the liquid permeability of the chemical solution 200 by the mesh body 17.

（第１１実施形態）
図１９は、第１１実施形態に係る貴金属含有部材の底面の一部を拡大した拡大図である。図１９に示すように、中間部材１８が貴金属膜１１の凸部に形成されている。中間部材１８は例えば導電性の金属、炭素を含む単体または化合物、またはポリマー等が考えられる。中間部材１８は導電体であるので、金属膜１０１と貴金属含有部材１０との電気的な接続は確保される。すなわち、金属膜１０１の腐食回路は成立する。より好ましくは、中間部材１８は、炭素を含む単体または化合物である。炭素を含むことで還元電位が高くなり、腐食速度、すなわちエッチング速度を向上させることができる。 (Eleventh embodiment)
FIG. 19 is an enlarged view of a part of the bottom surface of the noble metal-containing member according to the eleventh embodiment. As shown in FIG. 19, the intermediate member 18 is formed on the convex portion of the noble metal film 11. The intermediate member 18 may be, for example, a conductive metal, a simple substance or compound containing carbon, or a polymer. Since the intermediate member 18 is a conductor, electrical connection between the metal film 101 and the noble metal-containing member 10 is ensured. That is, the corrosion circuit of the metal film 101 is established. More preferably, the intermediate member 18 is a simple substance or a compound containing carbon. By containing carbon, the reduction potential is increased, and the corrosion rate, that is, the etching rate can be improved.

本実施形態でも、薬液２００を供給している間、貴金属膜１１が金属膜１０１と直接的に接触していなくても、中間部材１８を介して金属膜１０１をエッチングできる。   Also in this embodiment, the metal film 101 can be etched through the intermediate member 18 even when the noble metal film 11 is not in direct contact with the metal film 101 while the chemical solution 200 is being supplied.

さらに、本実施形態では、貴金属膜１１が被加工物である金属膜１０１に直接的に接触しないので、貴金属膜１１を構成する貴金属の摩耗による脱離を防止することができる。貴金属の脱離を防止することによって、貴金属による被加工物の汚染も防止することができる。   Furthermore, in this embodiment, since the noble metal film 11 does not directly contact the metal film 101 that is the workpiece, detachment due to wear of the noble metal constituting the noble metal film 11 can be prevented. By preventing the detachment of the noble metal, contamination of the workpiece by the noble metal can also be prevented.

なお、図１９において、中間部材１８は第１実施形態で示した貴金属含有部材１０の凸部に設けられるように示したが、第１実施形態に限定されず、例えば第５実施形態および第８実施形態で示した毛状部材１２、１５の金属膜１０１との接触部分に設けられていてもよい。また、凸部のみに限定されず、貴金属含有部材１０の凹部にも中間部材１８が形成されていてもよい。   In FIG. 19, the intermediate member 18 is shown to be provided on the convex portion of the noble metal-containing member 10 shown in the first embodiment. However, the intermediate member 18 is not limited to the first embodiment, and for example, the fifth embodiment and the eighth embodiment. You may provide in the contact part with the metal film 101 of the hair-like members 12 and 15 shown by embodiment. Moreover, the intermediate member 18 may be formed also in the recessed part of the noble metal containing member 10 without being limited only to the convex part.

上記毛状部材１２、１５に本実施形態の中間部材１８を適用する場合、腐食速度をより向上させるために、薬液２００の抵抗を下げることも考えられる。または、中間部材１８の抵抗を下げることも考えられる。   When the intermediate member 18 of the present embodiment is applied to the hair-like members 12 and 15, it is conceivable to reduce the resistance of the chemical solution 200 in order to further improve the corrosion rate. Alternatively, the resistance of the intermediate member 18 can be lowered.

薬液２００の抵抗を下げるために、例えば薬液２００に塩を添加してもよいし、カソード領域となる毛状部材１２、１５とアノード領域となる金属膜１０１との距離を短くしてもよい。中間部材１８の抵抗を下げるために、中間部材１８の体積を大きくしてもよい。なお、中間部材１８は、膜状でもよいし、繊維状の材料が複数積み重なったメッシュ状であってもよい。   In order to reduce the resistance of the chemical solution 200, for example, a salt may be added to the chemical solution 200, or the distance between the hair members 12 and 15 serving as the cathode region and the metal film 101 serving as the anode region may be shortened. In order to reduce the resistance of the intermediate member 18, the volume of the intermediate member 18 may be increased. The intermediate member 18 may be in the form of a film or a mesh in which a plurality of fibrous materials are stacked.

例えば、図２０（ａ）に示すように、上記毛状部材１２、１５と被加工膜である金属膜１０１との間に、メッシュ状の中間部材１８を設けることが考えられる。また、別の変形例として、図２０（ｂ）に示すように、白金粒子等の貴金属粒子を貴金属含有部材１０とし、当該貴金属粒子を囲うようにメッシュ状の中間部材１８を設けてもよい。この場合、メッシュ状の中間部材１８は通液性を有するため、本実施形態の効果を有しつつ、金属膜１０１をエッチングすることが可能となる。さらに別の変形例として、図２０（ｃ）に示すように、板状の貴金属含有部材１０の底面（下端）に、中間部材１８を部分的に設けてもよい。この場合も、中間部材１８を金属膜１０１に接触させながら金属膜１０１をエッチングすることが可能である。   For example, as shown in FIG. 20A, it is conceivable to provide a mesh-like intermediate member 18 between the bristle members 12 and 15 and the metal film 101 which is a film to be processed. As another modified example, as shown in FIG. 20B, noble metal particles such as platinum particles may be used as the noble metal-containing member 10 and a mesh-like intermediate member 18 may be provided so as to surround the noble metal particles. In this case, since the mesh-shaped intermediate member 18 has liquid permeability, the metal film 101 can be etched while having the effects of the present embodiment. As yet another modification, as shown in FIG. 20C, an intermediate member 18 may be partially provided on the bottom surface (lower end) of the plate-like noble metal-containing member 10. Also in this case, the metal film 101 can be etched while the intermediate member 18 is in contact with the metal film 101.

（第１２実施形態）
図２１は、第１２実施形態に係る貴金属含有部材の底面の一部を拡大した拡大図である。図２１に示すように、本実施形態に係る貴金属含有部材１０は、複数の格子積層体１９で構成される。複数の格子積層体１９は、互いに直交する２方向（Ｘ方向およびＹ方向）に間隔をとって配列されている。格子積層体１９間には、内部空間が設けられている。この内部空間は、薬液２００の流路として機能する。 (Twelfth embodiment)
FIG. 21 is an enlarged view of a part of the bottom surface of the noble metal-containing member according to the twelfth embodiment. As shown in FIG. 21, the noble metal-containing member 10 according to this embodiment includes a plurality of lattice laminates 19. The plurality of lattice laminates 19 are arranged at intervals in two directions (X direction and Y direction) orthogonal to each other. An internal space is provided between the lattice laminates 19. This internal space functions as a flow path for the chemical solution 200.

図２２は、格子積層体１９の分解斜視図である。格子積層体１９では、複数の格子体１９ａ〜１９ｃが積層されている。なお、格子体の積層数および格子の数は、特に制限されない。格子体１９ａ〜１９ｃは、貴金属を予め担持した細線を格子状に組むことによって形成できる。または、細線を格子状に組んだ後、その格子体に貴金属を担持することによっても形成できる。その後、これらの格子体を積層することによって格子積層体１９を形成できる。   FIG. 22 is an exploded perspective view of the lattice laminate 19. In the lattice laminate 19, a plurality of lattice bodies 19 a to 19 c are laminated. It should be noted that the number of laminated lattice bodies and the number of lattices are not particularly limited. The lattice bodies 19a to 19c can be formed by assembling thin wires carrying precious metals in advance in a lattice shape. Alternatively, it can be formed by assembling thin wires in a lattice and then supporting a noble metal on the lattice. Thereafter, the lattice laminate 19 can be formed by laminating these lattices.

図２３は、本実施形態におけるエッチング処理中の状態を示す。図２３に示すように、各格子体１９ａ〜１９ｃを積層した格子積層体１９によって、貴金属と金属膜１０１との接触面積が増加する。また、各格子体１９ａ〜１９ｃの段差によって、薬液２００の通液性が確保される。これにより、金属膜１０１のエッチング速度を高めることが可能となる。   FIG. 23 shows a state during the etching process in the present embodiment. As shown in FIG. 23, the contact area between the noble metal and the metal film 101 is increased by the lattice laminate 19 in which the lattices 19a to 19c are laminated. Moreover, the liquid permeability of the chemical | medical solution 200 is ensured by the level | step difference of each grid | lattice body 19a-19c. Thereby, the etching rate of the metal film 101 can be increased.

（第１３実施形態）
図２４は、第１３実施形態に係る基板処理装置の概略的な構成を示す模式図である。本実施形態に係る貴金属含有部材１０は、例えば、上述した毛状部材１２、１５のようなブラシ形状である。この貴金属含有部材１０は、基板１００の周りを回転できる。 (13th Embodiment)
FIG. 24 is a schematic diagram showing a schematic configuration of the substrate processing apparatus according to the thirteenth embodiment. The noble metal-containing member 10 according to the present embodiment has a brush shape such as the bristle members 12 and 15 described above, for example. The noble metal-containing member 10 can rotate around the substrate 100.

本実施形態の貴金属含有部材１０を用いて基板１００のベベル部１００ｃ（側面）を加工する場合、図２４に示すように、薬液供給ノズル２０からだけなく、通液ノズル８０を通じて貴金属含有部材１０からも薬液２００をベベル部１００ｃに供給する。このとき、基板１００の表面１００ａ（デバイス面）は下向きになっているので、薬液２００が表面１００ａに流れ込むおそれがある。   When the bevel portion 100c (side surface) of the substrate 100 is processed using the noble metal-containing member 10 of the present embodiment, as shown in FIG. 24, not only from the chemical solution supply nozzle 20 but also from the noble metal-containing member 10 through the liquid passing nozzle 80. The chemical solution 200 is supplied to the bevel portion 100c. At this time, since the surface 100a (device surface) of the substrate 100 faces downward, the chemical solution 200 may flow into the surface 100a.

そこで、本実施形態では、基板１００の下側から例えば窒素（Ｎ２）ガス３００を吹きかけることによって、薬液２００を飛ばしている。さらに、表面１００ａを保護するために、板状のシールド２２が基板１００の下側に設置されている。 Therefore, in the present embodiment, the chemical solution 200 is blown by blowing, for example, nitrogen (N 2 ) gas 300 from the lower side of the substrate 100. Furthermore, a plate-like shield 22 is installed on the lower side of the substrate 100 in order to protect the surface 100a.

以上説明した本実施形態によれば、基板１００の表面１００ａだけでなく、裏面１００ｂおよびベベル部１００ｃも加工することができる。   According to the present embodiment described above, not only the front surface 100a of the substrate 100 but also the back surface 100b and the bevel portion 100c can be processed.

本発明のいくつかの実施形態を説明したが、これらの実施形態は、例として提示したものであり、発明の範囲を限定することは意図していない。これら実施形態は、その他の様々な形態で実施されることが可能であり、発明の要旨を逸脱しない範囲で、種々の省略、置き換え、変更を行うことができる。これら実施形態やその変形は、発明の範囲や要旨に含まれると同様に、特許請求の範囲に記載された発明とその均等の範囲に含まれるものである。   Although several embodiments of the present invention have been described, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the spirit of the invention. These embodiments and their modifications are included in the scope and gist of the invention, and are also included in the invention described in the claims and the equivalents thereof.

１０ 貴金属含有部材、１０ａ 第１貴金属含有部材、１０ｂ 第２貴金属含有部材、１２，１３，１５ 毛状部材、１６ 担体、１７ 網状体、１８ 中間部材、１９ 格子積層体、１９ａ〜１９ｃ 格子体、２０ 薬液供給ノズル（薬液供給部材）、３０，５０，７０ 第１保持部材、３１，５１，７１ 第２保持部材、４０ 処理槽（薬液供給部材）、６０ 駆動機構、８０ 通液ノズル（薬液供給部材）、９０ 冷却機構、１０５ 通液孔、１５１ 導電体、１５２ 貴金属膜、１５３ 金属膜 DESCRIPTION OF SYMBOLS 10 Noble metal containing member, 10a 1st noble metal containing member, 10b 2nd noble metal containing member, 12, 13, 15 Hairy member, 16 Carrier, 17 Net body, 18 Intermediate member, 19 Lattice laminated body, 19a-19c Grid body, 20 chemical liquid supply nozzle (chemical liquid supply member), 30, 50, 70 first holding member, 31, 51, 71 second holding member, 40 treatment tank (chemical liquid supply member), 60 drive mechanism, 80 liquid passing nozzle (chemical liquid supply) Member), 90 cooling mechanism, 105 liquid passage hole, 151 conductor, 152 noble metal film, 153 metal film

Claims (20)

貴金属を含む凹凸形状部分または多孔質形状部分を有する貴金属含有部材と、
薬液を供給する薬液供給部材と、を備え、
所定の金属表面に前記凹凸形状部分の凸部または前記多孔質形状部分を接触させつつ、前記薬液を前記金属表面に供給して前記金属をエッチング除去する、基板処理装置。 A noble metal-containing member having an uneven shape portion or a porous shape portion containing a noble metal;
A chemical solution supply member for supplying the chemical solution,
The substrate processing apparatus which supplies the said chemical | medical solution to the said metal surface, and etches and removes the said metal, making the convex part of the said uneven | corrugated shaped part, or the said porous shape part contact the predetermined | prescribed metal surface. 前記凹凸形状部分は、多孔質材を表面に有する凹凸面である、請求項１に記載の基板処理装置。   The substrate processing apparatus according to claim 1, wherein the uneven portion is an uneven surface having a porous material on a surface. 前記貴金属含有部材を昇降可能に保持する第１保持部材と、前記所定の金属表面を回転可能に保持する第２保持部材と、をさらに備える、請求項１または２に記載の基板処理装置。   The substrate processing apparatus of Claim 1 or 2 further provided with the 1st holding member which hold | maintains the said noble metal containing member so that raising / lowering is possible, and the 2nd holding member which hold | maintains the said predetermined metal surface rotatably. 前記貴金属は、白金（Ｐｔ）、金（Ａｕ）、銀（Ａｇ）、およびパラジウム（Ｐｄ）の少なくともいずれかを含む、請求項１から３のいずれかに記載の基板処理装置。   The substrate processing apparatus according to claim 1, wherein the noble metal includes at least one of platinum (Pt), gold (Au), silver (Ag), and palladium (Pd). 前記貴金属含有部材は、前記薬液供給部材と連通する複数の通液孔を有する、
請求項１から４のいずれかに記載の基板処理装置。 The noble metal-containing member has a plurality of liquid passage holes communicating with the chemical liquid supply member.
The substrate processing apparatus according to claim 1. 前記貴金属含有部材は、第１貴金属含有部材と、前記第１貴金属含有部材よりも凸部のピッチが小さい第２貴金属含有部材と、を有する、請求項１から５のいずれかに記載の基板処理装置。   The substrate processing according to claim 1, wherein the noble metal-containing member includes a first noble metal-containing member and a second noble metal-containing member having a convex pitch smaller than that of the first noble metal-containing member. apparatus. 前記薬液を冷却する冷却機構をさらに備える、請求項１から６のいずれかに記載の基板処理装置。   The substrate processing apparatus according to claim 1, further comprising a cooling mechanism that cools the chemical solution. 前記貴金属含有部材は、前記複数の通液孔を通過した薬液とともに前記金属をエッチング除去する複数の毛状部材を有し、各毛状部材は、導電体と、前記貴金属を含む貴金属膜と、前記導電体と前記貴金属膜との間に設けられ、前記貴金属よりも比抵抗の小さい金属膜と、を有する、請求項５に記載の基板処理装置。   The noble metal-containing member has a plurality of hairy members that etch away the metal together with the chemical solution that has passed through the plurality of liquid passage holes, and each hairy member includes a conductor, a noble metal film containing the noble metal, The substrate processing apparatus according to claim 5, further comprising: a metal film that is provided between the conductor and the noble metal film and has a smaller specific resistance than the noble metal. 前記貴金属含有部材は、前記貴金属のナノ粒子を含んだ担体または網状体を有する、請求項５に記載の基板処理装置。   The substrate processing apparatus according to claim 5, wherein the noble metal-containing member has a carrier or a network including the noble metal nanoparticles. 前記凸部に導電体が設けられている、請求項１に記載の基板処理装置。   The substrate processing apparatus of Claim 1 with which the conductor is provided in the said convex part. 前記貴金属含有部材は、前記貴金属を含んだ複数の格子体を積層した格子積層体を有する、請求項１に記載の基板処理装置。   The substrate processing apparatus according to claim 1, wherein the noble metal-containing member has a lattice laminate in which a plurality of lattice bodies containing the noble metal are laminated. 基板上に金属膜を形成し、
貴金属を前記金属膜に接触させた状態で、薬液を前記金属膜に供給することによって、前記金属膜をエッチング除去する、基板処理方法。 Form a metal film on the substrate,
A substrate processing method for etching and removing the metal film by supplying a chemical solution to the metal film in a state where the noble metal is in contact with the metal film. 前記金属膜をエッチング除去することで、前記パターン表面を露出する、請求項１２に記載の基板処理方法。   The substrate processing method according to claim 12, wherein the pattern surface is exposed by etching and removing the metal film. 前記薬液は、アルカリ性である、請求項１２または１３に記載の基板処理方法。   The substrate processing method according to claim 12 or 13, wherein the chemical solution is alkaline. 前記貴金属は凹凸状の表面を有し、前記凹凸表面を前記金属膜に接触させた状態で、前記薬液を前記金属膜に供給する、請求項１２から１４のいずれかに記載の基板処理方法。   The substrate processing method according to claim 12, wherein the noble metal has an uneven surface, and the chemical solution is supplied to the metal film in a state where the uneven surface is in contact with the metal film. 前記貴金属は多孔質状であり、前記多孔質状の貴金属を前記金属膜に接触させた状態で、前記薬液を前記金属膜に供給する、請求項１２から１５のいずれかに記載の基板処理方法。   The substrate processing method according to claim 12, wherein the noble metal is porous, and the chemical solution is supplied to the metal film in a state where the porous noble metal is in contact with the metal film. . 前記貴金属を含む第１貴金属含有部材で前記金属膜をエッチングした後、前記第１貴金属含有部材よりも凸部のピッチが小さい第２貴金属含有部材で前記金属膜をエッチングする、請求項１２から１６のいずれかに記載の基板処理方法。   17. The metal film is etched with a second noble metal-containing member having a convex pitch smaller than that of the first noble metal-containing member after the metal film is etched with the first noble metal-containing member containing the noble metal. The substrate processing method according to any one of the above. 前記薬液を冷却して前記金属膜をエッチングする、請求項１２から１７のいずれかに記載の基板処理方法。   The substrate processing method according to claim 12, wherein the chemical solution is cooled to etch the metal film. 前記貴金属を含む毛状部材を前記金属膜に接触させながら、前記金属膜をエッチングする、請求項１２から１８のいずれかに記載の基板処理方法。   19. The substrate processing method according to claim 12, wherein the metal film is etched while contacting the hair-like member containing the noble metal with the metal film. 前記貴金属のナノ粒子を含んだ担体または網状体を前記金属膜に接触させながら、前記金属膜をエッチングする、請求項１２から１８のいずれかに記載の基板処理方法。   19. The substrate processing method according to claim 12, wherein the metal film is etched while contacting the metal film with a carrier or network containing the noble metal nanoparticles.
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