TWI243860B - Chemical treatment method and chemical treatment apparatus - Google Patents

Chemical treatment method and chemical treatment apparatus Download PDF

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TWI243860B
TWI243860B TW092122808A TW92122808A TWI243860B TW I243860 B TWI243860 B TW I243860B TW 092122808 A TW092122808 A TW 092122808A TW 92122808 A TW92122808 A TW 92122808A TW I243860 B TWI243860 B TW I243860B
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treatment
metal film
chromium
film
processing
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TW092122808A
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Chinese (zh)
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TW200407460A (en
Inventor
Mitsuhiko Yamamoto
Masao Yonemura
Yuka Omodaka
Tomoko Maehara
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Casio Micronics Co Ltd
Murata Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/26—Acidic compositions for etching refractory metals
    • 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
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/07—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process being removed electrolytically
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/07—Electric details
    • H05K2201/0753—Insulation
    • H05K2201/0761—Insulation resistance, e.g. of the surface of the PCB between the conductors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1157—Using means for chemical reduction
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/26—Cleaning or polishing of the conductive pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/388—Improvement of the adhesion between the insulating substrate and the metal by the use of a metallic or inorganic thin film adhesion layer

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • ing And Chemical Polishing (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

A chemical treatment apparatus of this invention is an apparatus by which a chromium film formed on a material to be subjected to film formation is etched into a predetermined pattern. This apparatus includes a cathode electrolysis reduction device for performing an electrolysis reduction treatment for the chromium film as a cathode by using a treatment solution containing chloride ions, and an acid dip device for dipping the chromium film into an acidic treatment solution after the electrolysis reduction treatment is performed by the cathode electrolysis reduction device.

Description

1243860 玖、發明說明： 1明所屬之技術領域 ’ 本發明係關於一種化學處理方法及化學處理裝置，藉 . 其將形成於接受膜形成之材料上之金屬膜蝕刻成預定圖案 〇 先前技術 作爲在長且彈性之載物帶上組合半導體晶片之組合技 術，TAB (帶式自動黏合）技術已長期引起注意。此TAB技 術非常有用，因爲使用載物帶之彈性可實行三維組合，及 馨 可在相同之載物帶上組合多個半導體晶片。 在應用於TAB技術之載物帶上，形成各種由金屬（如 金與銅）製成之線路圖案以電連接半導體晶片。此型載物 帶分爲「二層載物帶」，其上藉濺鍍等直接形成金屬膜而 無需任何黏著劑，及「三層載物帶」，其上藉黏著劑以黏 附金屬箔。比起三層載物帶，二層載物帶具優良之電特徵 且可增加半導體晶片之處理速度，因爲未使用黏著劑。因 此，二層載物帶近來爲最受歡迎之載物帶。 ® 在此二層載物帶中，在帶與金屬膜間形成金屬底漆以 增加其間之黏附性。第1圖顯示經常作爲金屬底漆之金屬 % 及這些金屬底漆之主要特徵。 % 如第1圖所示，例如，在由機械特徵、化學安定性、 與導電性之觀點判斷時，任何作爲金屬底漆之銅、鎳-鉻系 1 金屬、鎳-釩系金屬、及鉻系金屬均具有充分之起初強度。1243860 (1) Description of the invention: 1. The technical field to which the invention belongs' The present invention relates to a chemical processing method and a chemical processing device, by which a metal film formed on a material forming a receiving film is etched into a predetermined pattern. The combination technology of combining semiconductor wafers on a long and flexible carrier tape, TAB (Tape Automatic Bonding) technology has been attracting attention for a long time. This TAB technology is very useful because the elasticity of the carrier tape can be used for three-dimensional combination, and Xin can combine multiple semiconductor wafers on the same carrier tape. On the carrier tape applied to TAB technology, various circuit patterns made of metal (such as gold and copper) are formed to electrically connect the semiconductor wafer. This type of carrier tape is divided into a "two-layer carrier tape" on which a metal film is directly formed without any adhesive by sputtering or the like, and a "three-layer carrier tape" on which an metal foil is attached by an adhesive. Compared with the three-layer carrier tape, the two-layer carrier tape has excellent electrical characteristics and can increase the processing speed of the semiconductor wafer because no adhesive is used. Therefore, the two-layer carrier tape has recently become the most popular carrier tape. ® In this two-layer carrier tape, a metal primer is formed between the tape and the metal film to increase the adhesion between them. Figure 1 shows the metal% often used as metal primers and the main characteristics of these metal primers. % As shown in Figure 1, for example, when judged from the viewpoints of mechanical characteristics, chemical stability, and electrical conductivity, any copper, nickel-chromium series 1 metal, nickel-vanadium series metal, and chromium used as a metal primer All series metals have sufficient initial strength.

這些金屬底漆中，銅、鎳-鉻系金屬、及鎳-釩系金屬在高 I -7 - 1243860 溫環境及高濕度環境不安定且易退化，而且亦不適合使用 氰化金電鍍液鍍金。然而，此三種金屬底漆易於鈾刻成預 定圖案。 比起以上三種金屬底漆，鉻系金屬可耐高溫環境及高 濕度環境。此外，鉻系金屬可良好地接受使用氰化金電鍍 液鍍金。 不幸地，此鉻系金屬必須在高溫藉特殊蝕刻法蝕刻， 而且金屬必須以有毒之處理溶液處理，如過錳酸鉀。如此 在實行廢液處置時產生環境負擔，而且製造六價鉻，其處 置在近年來愈趨嚴格地規範。即，發生許多不利之情況。 因而鉻系金屬不適合蝕刻。因此，需要易於蝕刻這些金屬 之化學處理方法及化學處理裝置。 發明內容 本發明之目的爲提供一種可易於蝕刻不適合蝕刻之金 屬（特別是鉻）之化學處理方法，及使用此化學處理方法 之化學處理裝置。 本發明爲將形成於接受膜形成之材料上之金屬膜蝕刻 成預定圖案之化學處理方法及化學處理裝置。依照本發明 之第一態樣，使用含酸基之酸性處理溶液與含鹵素離子之 鹼性處理溶液實行作爲陰極之金屬膜之電解還原處理。然 後將金屬膜浸於另一種酸性處理溶液中。含酸基之酸性處 理溶液之較佳實例爲氫氯酸（HC1)、硫酸（H2S04)、羧酸（RC00H) 、氫氟酸（HF)、與磷酸（Η3Ρ04)。鹵素離子之較佳實例爲氯 化鈉（NaCl )、氯化鉀（KC1 )、與碘化鉀（KI )。較佳爲，另一 1243860 種酸性處理溶液含鹵素離子。 依照本發明之第二態樣，在含氯離子之處理溶液中實 1 行作爲陰極之金屬膜之電解還原處理。然後將此金屬膜浸 · 於酸性處理溶液中。此酸性處理溶液較佳爲含鹵素離子。 _ 在上述之本發明中，可藉簡單之程序將形成接受膜形 成之材料上之金屬膜蝕刻成預定圖案，即，藉電解還原處 理將形成於金屬膜表面上之氧化物還原，然後實行浸酸程 序。 至於形成金屬膜之金屬，使用鉻、鈦、鎢、鈀、與鉬 · 之一。亦可使用含鉻、鈦、鎢、鈀、與鉬至少之一之合金 。至於合金，較佳爲使用鎳鉻合金。特別是在金屬膜含鉻 時，可防止六價鉻之製造。 在電解還原處理中，亦可將金屬膜部份地浸於含氯離 子之處理溶液中。在此情形，金屬膜不必完全地浸於處理 溶液中，例如，僅需將金屬膜部份地浸於處理溶液中。由 於如此減少所使用處理溶液之量，可節省使用之處理溶液 在電解還原處理中，亦可將金屬膜浸於含鹵素離子之 酸性處理溶液中，較佳爲含氯離子之酸性處理溶液，及實 ψ 行作爲陰極之金屬膜之電解還原。由於電解還原係在將金 屬膜浸於含鹵素離子之酸性處理溶液（較佳爲含氯離子之 酸性處理溶液）中時對作爲陰極之金屬膜實行，在將形成 於金屬膜表面上之氧化物還原時，金屬膜可易於蝕刻成預 定圖案。 ’ -9- 1243860 本發明之另外之目的及優點在以下之說明中敘述，而 且部份爲由此說明而顯而易知，或可由本發明之實務得知 。本發明之目的及優點可藉以下特別指出之儀器及組合實 現及得到。 實施方式 以下參考附圖敘述本發明之具體實施例。然而，本發 明之範圍不限於圖式中所示之這些具體實施例。 以下分別地解釋本發明之第一及第二化學處理方法。 第2A至2G圖爲各顯示在各依照本發明具體實施例之化擧 處理方法之程序中，接受膜形成之材料上金屬膜狀態之實 例之切面圖。 [第一化學處理方法] 首先，如第2A圖所示，藉濺鍍等在接受膜形成之材料 110之一個表面上形成具有預定膜厚之鉻膜120。在鉻膜12〇 上，藉濺鍍等形成具預定膜厚之銅膜130。以此方式，得到 欲處理之材料1〇〇。至於材料110，例如，可使用聚醯亞胺 、玻璃環氧基、BT (貳順丁烯二醯亞胺三畊）樹脂、或聚 酯之片狀或載物帶狀彈性基板，或半導體晶圓（例如，由 矽製成）。 如第2B圖所示，然後以光阻劑140塗覆銅膜130。此 外，如第2C圖所示，使光阻劑140經光罩1 50曝光且以預 定之顯影劑顯影。如第2D圖所示，藉此處理在銅膜1 3 〇上 形成預定之光阻劑圖案。 將第2D圖所示之材料1〇〇浸於預定之處理溶液以濕蝕 -10- 1243860 刻銅膜130，及淸洗材料1〇〇。此處理在以 刻處理」，及實行此處理之程序在以下稱 序」。結果，如第2E圖所示，得到其上將 阻劑圖案蝕刻成預定圖案之材料1〇〇。 然後使用第2E圖所示之材料1〇〇作爲 之處理溶液藉初生氫實行鉻膜120之電解 原處理在以下稱爲「陰極電解還原處理」 之程序在以下稱爲「陰極電解還原程序」 原處理之處理溶液爲含酸基之酸性處理溶 之鹼性處理溶液之一。此處理溶液較佳爲 溶液，例如，氫氯酸、硫酸、羧酸、或氟 用含氯離子處理溶液，如K.K. MURATA製建 第3A與3B圖爲顯示陰極電解還原處 圖。如第3A圖所示，在此陰極電解還原處 陰極之材料100及作爲正極之電極板22 — 容器20中之處理溶液24中。如第3B圖所 板22與材料1〇〇部份地浸於處理溶液24 濕蝕刻程序，鉻膜120本身因在其表面上 鈍化。因此，在陰極電解還原程序中，將 成金屬鉻。以去離子水淸洗接受此陰極電 料 100。 然後，藉由將材料100浸於預定處理容 時間而實行鉻膜1 20之浸漬處理。此浸漬 「浸酸處理」，及實行此處理之程序在以 :下稱爲「銅濕蝕 爲「銅濕蝕刻程 銅膜1 3 0依照光 陰極，使用預定 還原。此電解還 ，及實行此處理 。此陰極電解還 液及含鹵素離子 含酸基酸性處理 化氫。例如，使 USAS。 理之原理之略示 理中，可將作爲 起完全浸於含於 示，亦可將電極 中。例如，藉由 形成氧化鉻膜而 此氧化物膜還原 解還原處理之材 容液24中預定之 處理在以下稱爲 下稱爲「浸酸程 -11- 1243860 序」。 用於此浸酸處理之處理溶液爲含鹵素離子之酸性處理 溶液，較佳爲含氯離子之酸性處理溶液。此酸性處理溶液 之實例爲K.K. MURATA製造之SAS。 浸酸處理之處理溶液26之濃度比用於上述陰極電解還 原處理之處理溶液稠密。第3C·圖爲顯示浸酸處理之原理之 略示圖。如第2F圖所示，藉由實行此具有第3C圖所示原 理之浸酸處理，可將材料100之鉻膜120蝕刻成預定圖案 而對材料110之表面不產生任何損壞。 然後以去離子水淸洗第2F圖所示之材料100，及使用 預定之處理溶液去除殘留於材料100上之光阻劑140。將如 此去除光阻劑140之材料100淸洗及乾燥。 如第2G圖所示，經由上述之個別程序，可將在材料1 1 0 上形成之鉻膜120及銅膜130依照光阻劑圖案蝕刻成預定 圖案。 在上述之第一化學處理方法中，可藉由按此順序實行 陰極電解還原程序及浸酸程序，即，藉由組合簡單之程序 ，將在材料110上形成之鉻膜120蝕刻成預定圖案。亦可 防止六價鉻之製造。如此造成易於實行各處理溶液之廢液 處置之優點。 除了防止六價鉻之製造，亦可蝕刻鉻膜120而在各陰 極電解還原程序及浸酸程序中無需使用任何氰化合物作爲 處理溶液。如此比習知方法大爲降低廢液處置之勞力。在 陰極電解還原程序及浸酸程序中亦可使用相當不昂貴之以 -12- 1243860 氯系化學物，如氫氯酸、NaCl溶液、及K.K. MURATA製造 之SAS，作爲處理溶液。由於可使用這些處理溶液鈾刻鉻膜 胃 1 20，鉻蝕刻之成本可大爲降低。 λ [第二化學處理方法] 如第2Ε圖所示而處理之材料100係藉由實行如上述第 一化學處理方法之相同處理而得。然後如第4圖所示，將 材料1〇〇與作爲正極之電極板22浸於含於容器20之預定 處理溶液28中。在此狀態，使用材料100作爲在處理溶液 28中實行鉻膜120之電解還原之陰極。此電解還原處理在 鲁 以下稱爲「酸電解處理」，及實行此處理之程序在以下稱 爲「酸電解程序」。此酸電解處理之處理溶液28爲含鹵素 離子之酸性處理溶液，較佳爲含氯離子酸性處理溶液，如Κ . Κ . MURATA 製造之 SAS 〇 如第2F圖所示，藉此酸電解處理可將鉻膜120蝕刻成 預定圖案，同時將在鉻膜120表面上形成之氧化鉻膜還原 。然後實行如第一化學處理方法之相同處理而得如第2G圖 所示之材料100。 _ 在上述之第二化學處理方法中，可將在接受膜形成之 材料110上形成之鉻膜120經簡單之方法蝕刻成預定圖案 ν ’即，酸電解處理，而且亦可防止六價鉻之製造。此外， , 在第二化學處理方法中，可藉一個酸電解處理程序實行第 〜化學方法中之陰極電解還原處理及浸酸處理兩個程序。 陰極電解還原處理及浸酸處理兩個程序包括這些程序間之 淸洗處理。因此，藉由僅實行一個酸電解處理程序可節省 -13- 1243860 此淸洗處理之勞力。 在第一及第二化學處理方法中，將鉻膜120飩刻。然 1 而，本發明不限於鉻。例如，即使是在使用鈦、鎢、鈀、 . 與鉬時，本發明之化學處理方法可將這些金屬蝕刻成預定 _ 圖案。亦即使是在使用含鉻、鈦、鎢、鈀、與鉬至少之一 之合金時，本發明之化學處理方法仍可將此合金蝕刻成預 定圖案。至於合金，較佳爲使用鎳鉻合金。 其次，[應用例1 ]至[應用例6 ]分別地敘述於下作爲使 用以上第一及第二化學處理方法之各種化學處理裝置之應 φ 用例，即，各種使用依照第一化學處理方法之陰極電解還 原處理與浸酸處理之裝置，及各種使用依照第二化學處理 方法之酸電解處理之裝置。 [應用例1 ]至[應用例4]有關蝕刻形成於載物帶上之金 屬膜之裝置。[應用例5 ]與[應用例6 ]有關蝕刻形成於半導 體晶圓上之金屬膜之裝置。第2E圖所示，假設鉻膜120係 形成於載物帶或半導體晶圓上，及將銅膜1 3 0與光阻劑膜 140在鉻膜120上按此順序蝕刻成預定圖案。 鲁 [應用例1 ] 應用例1有關使用上述第一化學處理方法及其中載物 帶係將其直立而進料之「垂直進料型」裝置之實例，即， 進料使得帶寬度方向垂直。第5圖爲顯示垂直進料型化學 。 處理裝置之實例之略示側切面圖。第6圖爲形成第5圖所 示化學處理裝置之陰極電解還原裝置之略示前切面圖。 _ 如第5圖所不’化學處理裝置30包括實行載物帶ci * -14- 1243860 之陰極電解還原處理用之陰極電解還原裝置31、淸洗載物 帶C1用之淸洗裝置32與34、及實行載物帶C1之浸酸處理 用之浸酸裝置3 3。 在第5圖中，載物帶C1進料用之進料裝置（未示）係 置於陰極電解還原裝置31之左端。亦將捲收載物帶C1用 之捲繞裝置（未示）置於淸洗裝置34之右端。 如第5與6圖所示，陰極電解還原裝置31具有盒狀外 處理浴31a。內處理浴31b係形成於外處理浴31a之實質上 中央位置。外處理浴31a之底部亦作爲內處理浴31b之底 部。內處理浴3 1 b之側壁比外處理浴3 1 a之側壁稍低。 供應管31c之一端連接內處理浴31b之底部。泵31d 、熱交換器3 1 e、及過濾器3 1 f係配置於供應管3 1 c中間。 供應管31c之另一端連接槽31g。槽31g含處理溶液31h。 處理溶液31h爲含酸基之酸性處理溶液與含鹵素離子之鹼 性處理溶液之一。較佳爲，處理溶液31h爲含氯離子處理 溶液，如K.K. MURATA製造之SAS。各排洩管31 i與31 j之 一端連接外處理浴31a與內處理浴31b間之底部。排洩管31i 與31j之另一端連接槽31g。 在操作泵3 1 d時，槽3 1 g中之處理溶液3 1 h經供應 管31c流過熱交換器31e與過濾器31f，而且供應至內處 理浴31b。在將預定量之溶液31h供應至內處理浴31b時 ，處理溶液3 1 h自內處理浴3 1 b超過其側壁流出。即， 處理溶液3 1 h自內處理浴3 1 b溢流至在外處理浴3 1 a側 壁與內處理浴3 1 b側壁間形成之溢流部份3 1 k。流入溢流 1243860 部份3 1 k之處理溶液3 1 h經排洩管3 1 i與3 1 j連接槽3 1 g 。然後處理溶液3 1 h通過上述之個別構件重複地循環。 如第5與6圖所示，在外處理浴31a與內處理浴31b 之側壁中，如垂直長孔之縫31 1與31m形成於載物帶Cl通 過之側壁之預定位置。各縫311與31m具有大於載物帶C1 之寬度及長度。應注意，內處理浴31b中之處理溶液31h 亦經縫3 1 m流出至溢流部份3 1 k中。 電極31η係置於內處理浴31b內部。在內處理浴31b 中，電極31η面對載物帶Cl之一個表面，即，其上形成膜 之表面。電極31η連接電源31x之正極。 在外處理浴3 1 a之側壁中，電極輥3 1 y與3 1 z係配置 於經其裝載載物帶C 1之側壁及經其卸下載物帶C 1之側壁 外部。電極輥3 1 y與3 1 z接觸載物帶C 1之一個表面，即， 形成鉻膜與銅膜之表面。電極輥31y與31z連接電源31x 之負極。 淸洗裝置32與34及浸酸裝置33具有如陰極電解還原 裝置31之實質上相同配置。 淸洗裝置32具有盒狀外處理浴32a，及內處理浴32b 係形成於外處理浴32a之實質上中央位置。供應管32c連 接內處理浴32b之底部。排洩管32i與32 j連接外處理浴32a 之底部。槽32g含淸洗載物帶Cl用之去離子水32h。 在操作泵32d時，槽32g中之去離子水32h經供應管 32c流過熱交換器32e與過濾器32f，而且供應至內處理浴 32b。然後槽32g中之去離子水32h超過內處理浴32b之側 1243860 壁流入溢流部份32k。經排洩管32i與32j將去離子水32h 收集至槽32g，及以如上之相同方式循環。 在外處理浴32a與內處理浴32b之側壁中，如垂直長 孔之縫321與32m形成於載物帶C1通過之側壁之預定位置 。載物帶C1係通過縫3 21與3 2m而進料，而且浸於內處理 浴32b之去離子水32h中。 浸酸裝置33具有盒狀外處理浴33a，及內處理浴33b 係形成於外處理浴33a之實質上中央位置。供應管33c連 接內處理浴33b之底部。排洩管33i與33 j連接外處理浴33a 之底部。槽33g含處理溶液33h。處理溶液33h爲酸性處理 溶液，較佳爲含鹵離子之酸性處理溶液，如K.K. MURATA 製造之SAS。 在操作泵33d時，槽33g中之處理溶液33h經供應管 33c流過熱交換器33e與過濾器33f，而且供應至內處理浴 33b。然後槽33g中之處理溶液33h超過內處理浴33b之側 壁流入溢流部份33k。經排洩管33 i與33j將處理溶液33 h 收集至槽33g，及以如上之相同方式循環。 在外處理浴3 3 a與內處理浴3 3 b之側壁中，如垂直長 孔之縫33 1與33m形成於載物帶C1通過之側壁之預定位置 。載物帶C1係通過縫331與3 3m而進料，而且浸於內處理 浴33b之處理溶液33h中。 淸洗裝置34具有盒狀外處理浴34a，及內處理浴34b 係形成於外處理浴34a之實質上中央位置。供應管34c連 接內處理浴34b之底部。排洩管34i與34 j連接外處理浴34a 1243860 之底部。槽34g含淸洗載物帶Cl用之去離子水34h。 在操作泵34d時，槽34g中之去離子水34h經供應管 34c流過熱交換器34e與過濾器34f，而且供應至內處理浴 3 4b。然後槽34g中之去離子水34h超過內處理浴34b之側 壁流入溢流部份34k。經排洩管34 i與34 j將去離子水34h 收集至槽34g，及以如上之相同方式循環。 在外處理浴34a與內處理浴34b之側壁中，如垂直長 孔之縫341與34πι形成於載物帶C1通過之側壁之預定位置 。載物帶C1係通過縫341與34m而進料，而且浸於內處理 浴34b之去離子水34h中。 進料輥（未示）係配置於各裝置31至34之兩側。這 些進料輥將載物帶C1夾在其間且彼此相鄰以相反方向轉動 。在這些進料輥轉動時，將載物帶C1進料。如上所述，電 極輥31y與31z配置於陰極電解還原裝置31之兩側。進料 輥係與電極輥31y與31z相反，將載物帶C1夾在其間而配 置。 以下解釋化學處理裝置30之操作。 在電極輥31y與31z及進料輥按預定方向轉動時，載 物帶C1以來自進料裝置（未示）之進料方向進料。因而載 物帶C1通過裝置31至34之內處理浴31b至34b，而且由 捲繞裝置（未示）捲收。 以下之處理係在裝置31至34中實行。 即’在陰極電解®原裝置31中’內處理浴31b係以處 理溶液31h充塡，及將電壓施加於電極輥31y與31z及電 1243860 極3 1 η之間。在此狀態，載物帶C1通過縫3 Π與3 1 m且通 過內處理浴31b。在通過內處理浴31b時，載物帶C1接受 陰極電解還原處理。即，在外處理浴31a外部，電極輕31y 與31z接觸其上形成金屬膜之載物帶Cl表面。因此，在內 處理浴31b中，將形成於鉻膜表面上之氧化鉻膜還原。 在淸洗裝置32中，內處理浴32b係以去離子水32h充 塡。載物帶C1通過縫321與3 2m，及在通過內處理浴32b 時以去離子水32h淸洗。 在浸酸裝置33中，內處理浴33b係以處理溶液33h充 塡。載物帶C1通過縫331與33m，及在內處理浴33b中接 受浸酸處理。即，載物帶C1係浸於內處理浴33b之處理溶 液3 3h中而進料，及將形成於載物帶C1上之鉻膜蝕刻成預 定圖案。 在淸洗裝置34中，內處理浴34b係以去離子水34h充 塡。載物帶C1通過縫341與3 4ιώ，及在通過內處理浴34b 時以去離子水34h淸洗。以淸洗裝置34淸洗之載物帶Cl 係經乾燥裝置（未示）乾燥及藉捲繞裝置（未示）捲收。 藉以上之操作，可將形成於載物帶C1上之鉻膜蝕刻成 預定圖案。亦可防止六價鉻之製造。 亦如第5與6圖所示，在陰極電解還原裝置31之陰極 電解還原處理中，可將內處理浴31b完全地以處理溶液31h 充塡，及將載物帶Cl完全浸於處理溶液31h中。亦可將內 處理浴31b不完全地以處理溶液31h充塡，及將其上形成 金屬膜之載物帶C1 一部份表面浸於處理溶液31h中。 一 1 9- 1243860 [應用例2 ] 應用例2使用其中使用上述之第二化學處理方法，及 其爲類似應用例1之垂直進料型化學處理裝置之裝置。第7 圖爲顯示此化學處理裝置之實例之略示切面圖。如第7圖 所示，化學處理裝置40包含實行載物帶C2之酸電解處理 用之電解裝置41，及淸洗載物帶C2用之淸洗裝置42。 在化學處理裝置40中，類似如第5圖所示之化學處理 裝置30，進料裝置及捲繞裝置（均未示）配置於電解裝置 41與淸洗裝置42之兩端。 電解裝置41具有如第5與6圖所示之陰極電解還原裝 置31之實質上相同配置。然而，電極輥41y係置於外處理 浴411之進料裝置側上。電解裝置41亦異於陰極電解還原 裝置3 1在於槽41g含酸性處理溶液，較佳爲含鹵離子（如 氯離子）之酸性處理溶液41h。酸性處理溶液41h之較佳實 例爲K.K. MURATA製造之SAS。 淸洗裝置42具有如第5圖所示之淸洗裝置32與34之 實質上相同配置。因此，在淸洗裝置42中，槽42g中之去 離子水42h藉泵42d之操作經供應管42c流過熱交換器42e 與過濾器42f及至內處理浴42b。去離子水42h自溢流部份 42k循環至排洩管42i與42j。 化學處理裝置40之操作解釋於下。 在電極輥41y及進料輥按預定方向轉動時’載物帶C2 通過電解裝置41與淸洗裝置42中之各內處理浴41b與42b 捲收。 - 2 0 - 1243860 以下之處理係在裝置41及42中實行。 在電解裝置41中，內處理浴41b係以處理溶液41h充 塡。將自內處理浴41b溢流之處理溶液41h由溢流部份41k 經排洩管4 1 i與4 1 j收集至槽4 1 g。藉泵4 1 d之操作，處理 溶液4 1 h自槽4 1 g經熱交換器4 1 e與過濾器4 1 f流至供應 管41c，及循環至內處理浴41b。在電解裝置41中，電源41x 亦將電壓施加於電解輥41y與電極41η之間。 在此狀態，載物帶C2通過縫411與41m且通過內處理 浴41b。在通過內處理浴41b時，載物帶C2接受酸電解處 理。即，在外處理浴41a外部，電極輥41y接觸其上形成 金屬膜之載物帶C2表面。因此，在載物帶C2與電極41η 相對時，將形成於鉻膜表面上之氧化鉻膜還原。然後隨載 物帶C2進料在還原絡膜之區域脫離面對電極41η之區域時 ，在內處理浴41b中藉處理溶液41h將載物帶C2上之鉻膜 蝕刻成預定圖案。 在淸洗裝置42中，外處理浴42a內部之內處理浴42b 係以去離子水42h充塡。載物帶C2通過縫421與42m，及 在通過內處理浴42b時以去離子水42h淸洗。以淸洗裝置42 淸洗之載物帶C2係經乾燥裝置（未示）乾燥，及藉捲繞裝 置（未示）捲收。 藉以上之操作’可將形成於載物帶C2上之鉻膜蝕刻成 預定圖案。亦可防止六價鉻之製造。 [應用例3 ] 應用例3有關使用上述之第一化學處理方法及其中載 - 2 1 - 1243860 物帶係水平地安置而進料之「水平進料型」裝置之實例。 第8圖爲水平進料型化學處理裝置之略示側視圖。 如第8圖所示，化學處理裝置50包括實行載物帶C3 之陰極電解還原處理用之陰極電解還原裝置51、淸洗載物 帶C3用之淸洗裝置52與54、及實行載物帶C3之浸酸處理 用之浸酸裝置5 3。 類似第5至7圖所示之化學處理裝置30與40，在化 學處理裝置50中，在第8圖中載物帶C3進料用之進料裝 置（未示）係置於陰極電解還原裝置51之左端，及在第8 圖中捲收載物帶C3用之捲繞裝置（未示）係置於淸洗裝置 54之右端。 陰極電解還原裝置51具有含處理溶液51b之處理浴51a 。處理溶液51b爲含酸基之酸性處理溶液與含鹵離子之鹼 性處理溶液之一。較佳爲，處理溶液51b爲含氯離子處理 溶液，如K.K. MURATA製造之SAS。流動管51c之兩端連接 處理浴5 1 a底部。泵5 1 d、熱交換器5 1 e、及過濾器5 1 f係 配置於流動管5 1 c中間。在操作泵5 1 d時，處理浴5 1 a中 之處理溶液5 1 b流經流動管5 1 c且經熱交換器5 1 e與過濾 器51f回到處理浴51a。在陰極電解還原裝置51中，形成 此種處理溶液51b循環系統。 兩個電極輥51g與51h係配置於處理浴51a上方，及 連接電源51i之負極。支撐電極輥51g與51h之支持輥51j 與51k各配置於電極輥51g與51h下方。在處理浴51a中 ，安置改變載物帶C3之進料方向用之進料輥511。 -22- 1243860 載物帶C3夾在電極輥51g與支持輥51j之間，在處理 浴51a中捲繞進料輥511，及夾在電極輥51h與支持輥51k 之間。其上形成金屬膜之載物帶C3表面接觸電極輥51g與 51h ° 在處理浴51a中，配置兩個電極51m與51η。電極51m 與51η連接電源51i之正極，及與載物帶C3相對。應注意 ，在處理浴51a中，電極51m與51η與其上形成金屬膜之 載物帶C3表面相對。 淸洗裝置52具有含去離水52b之處理浴52a。流動管 52c之兩端連接處理浴52a底部。泵52d、熱交換器52e、 及過濾器52f係配置於流動管52c中間。在操作泵52d時 ，處理浴52a中之去離水52b流經流動管52c且經熱交換 器52e與過濾器52f回到處理浴52a。在淸洗裝置52中， 形成此種處理溶液52b循環系統。 四個進料輥52g、52h、52i、與52j係配置於處理浴52a 上方。即，進料輥52g與52h在載物帶C3進料方向上游側 成一對，及進料輥52i與52 j在下游側成一對。在處理浴52a 中，安置改變載物帶C3之進料方向用之進料輥521。 載物帶C3夾在進料輥52g與52h之間，及在處理浴52a 中捲繞進料輥521。在淸洗裝置52中，形成此載物帶C3進 料系統。Among these metal primers, copper, nickel-chromium-based metals, and nickel-vanadium-based metals are unstable and easily degraded in high-temperature environments of -7-1243860 and high humidity, and are not suitable for gold plating using a gold cyanide plating solution. However, these three metallic primers are easily engraved into a predetermined pattern. Compared with the above three metal primers, chromium-based metals can withstand high temperature and high humidity environments. In addition, chromium-based metals are well accepted for gold plating using a gold cyanide plating solution. Unfortunately, this chromium-based metal must be etched at high temperatures by special etching methods, and the metal must be treated with a toxic treatment solution, such as potassium permanganate. In this way, the environmental burden is caused when the waste liquid is disposed of, and the production of hexavalent chromium has become more and more strict in recent years. That is, many disadvantageous situations occur. Therefore, chromium-based metals are not suitable for etching. Therefore, there is a need for a chemical processing method and a chemical processing apparatus that can easily etch these metals. SUMMARY OF THE INVENTION The object of the present invention is to provide a chemical treatment method capable of easily etching metal (especially chromium) which is not suitable for etching, and a chemical treatment device using the chemical treatment method. The present invention is a chemical processing method and a chemical processing apparatus for etching a metal film formed on a material forming a receiving film into a predetermined pattern. According to a first aspect of the present invention, an electrolytic reduction treatment of a metal film as a cathode is performed using an acidic treatment solution containing an acid group and an alkaline treatment solution containing a halogen ion. The metal film was then immersed in another acidic treatment solution. Preferred examples of the acidic treatment solution containing an acid group are hydrochloric acid (HC1), sulfuric acid (H2S04), carboxylic acid (RC00H), hydrofluoric acid (HF), and phosphoric acid (3P04). Preferred examples of the halogen ion are sodium chloride (NaCl), potassium chloride (KC1), and potassium iodide (KI). Preferably, another 1243860 kinds of acidic treatment solutions contain halogen ions. According to a second aspect of the present invention, an electrolytic reduction treatment of a metal film as a cathode is performed in a treatment solution containing chloride ions. This metal film was then immersed in an acidic treatment solution. This acidic treatment solution is preferably a halogen ion. _ In the invention described above, the metal film formed on the material forming the receiving film can be etched into a predetermined pattern by a simple procedure, that is, the oxide formed on the surface of the metal film is reduced by electrolytic reduction treatment, and then the dipping is performed. Acid program. As the metal forming the metal film, one of chromium, titanium, tungsten, palladium, and molybdenum is used. Alloys containing at least one of chromium, titanium, tungsten, palladium, and molybdenum can also be used. As for the alloy, a nickel-chromium alloy is preferably used. Especially when the metal film contains chromium, the production of hexavalent chromium can be prevented. In the electrolytic reduction treatment, the metal film may also be partially immersed in a treatment solution containing chlorine ions. In this case, the metal film need not be completely immersed in the processing solution, for example, the metal film only needs to be partially immersed in the processing solution. Since the amount of the treatment solution used is reduced in this way, the treatment solution used can be saved in the electrolytic reduction treatment, and the metal film can also be immersed in an acid treatment solution containing a halogen ion, preferably an acid treatment solution containing a chloride ion, and The electrolytic reduction of the metal film as a cathode is performed. Since electrolytic reduction is performed on a metal film as a cathode when a metal film is immersed in an acidic treatment solution containing a halogen ion (preferably an acidic treatment solution containing a chloride ion), the oxide to be formed on the surface of the metal film During the reduction, the metal film can be easily etched into a predetermined pattern. ′ -9-1243860 The other objects and advantages of the present invention are described in the following description, and part of them are obvious from this description, or can be learned from the practice of the present invention. The objects and advantages of the present invention can be realized and obtained by the instruments and combinations specifically pointed out below. Embodiments Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. However, the scope of the present invention is not limited to the specific embodiments shown in the drawings. The first and second chemical treatment methods of the present invention are explained separately below. Figures 2A to 2G are sectional views each showing an example of a state of a metal film on a film-forming material in a procedure of a chemical treatment method according to a specific embodiment of the present invention. [First chemical treatment method] First, as shown in FIG. 2A, a chromium film 120 having a predetermined film thickness is formed on one surface of a material 110 for receiving a film by sputtering or the like. A copper film 130 having a predetermined film thickness is formed on the chromium film 12 by sputtering or the like. In this way, the material to be processed 100 was obtained. As for the material 110, for example, a polyimide, glass epoxy, BT (isobutylene diimide three farming) resin, or a sheet-like or tape-like elastic substrate of polyester, or a semiconductor crystal can be used. Round (for example, made of silicon). As shown in FIG. 2B, the copper film 130 is then coated with a photoresist 140. In addition, as shown in FIG. 2C, the photoresist 140 is exposed through the photomask 150 and developed with a predetermined developer. As shown in FIG. 2D, a predetermined photoresist pattern is formed on the copper film 13 by this process. The material shown in FIG. 2D is immersed in a predetermined processing solution to wet-etch the copper film 130 by -10- 1243860, and the material is washed. This process is handled immediately ", and the procedure for implementing this process is hereinafter referred to as" order ". As a result, as shown in FIG. 2E, a material 100 on which the resist pattern is etched into a predetermined pattern is obtained. Then, using the material 100 shown in FIG. 2E as the processing solution, the electrolysis process of the chromium film 120 is performed by the primary hydrogen. The process is hereinafter referred to as "cathode electrolytic reduction process". The treatment solution to be treated is one of the alkaline treatment solutions of acid treatment solution containing acid groups. This treatment solution is preferably a solution, for example, hydrochloric acid, sulfuric acid, carboxylic acid, or fluorine. A treatment solution containing a chloride ion, such as manufactured by K.K. Murata. Figures 3A and 3B are diagrams showing a cathode electrolytic reduction place. As shown in Fig. 3A, at this cathode electrolytic reduction place, the material 100 of the cathode and the electrode solution 22 as the positive electrode-the treatment solution 24 in the container 20. As shown in FIG. 3B, the plate 22 and the material 100 are partially immersed in the processing solution 24 in a wet etching process, and the chromium film 120 itself is passivated on its surface. Therefore, in the cathodic electrolytic reduction process, metallic chromium will be formed. Rinse with deionized water to receive this cathode battery 100. Then, the immersion treatment of the chromium film 120 is performed by immersing the material 100 in a predetermined processing capacity time. This immersion "acid treatment" and the procedure for implementing this treatment are referred to as "copper wet etching as" copper wet etching process copper film 130 "according to the photocathode, using a predetermined reduction. Treatment. This cathode electrolysis solution and halogen-containing ions contain acid groups to treat hydrogenated acid. For example, the principle of the principle of USAS can be immersed as shown in the illustration, or it can be used in electrodes. For example, a predetermined treatment in the material storage liquid 24 for the reduction and decompression treatment of the oxide film by forming a chromium oxide film is hereinafter referred to as "the soaking process-11-1243860 sequence". The treatment solution used for this pickling treatment is an acidic treatment solution containing a halogen ion, preferably an acidic treatment solution containing a chloride ion. An example of this acidic treatment solution is SAS manufactured by K.K. Murata. The concentration of the treatment solution 26 for the pickling treatment is denser than that of the treatment solution used for the above-mentioned cathodic electrolysis reduction treatment. Fig. 3C is a schematic diagram showing the principle of the pickling treatment. As shown in FIG. 2F, the chrome film 120 of the material 100 can be etched into a predetermined pattern by performing the acid soaking treatment having the principle shown in FIG. 3C without causing any damage to the surface of the material 110. Then, the material 100 shown in FIG. 2F is rinsed with deionized water, and the photoresist 140 remaining on the material 100 is removed using a predetermined processing solution. The material 100 from which the photoresist 140 has been removed is washed and dried. As shown in FIG. 2G, the chromium film 120 and copper film 130 formed on the material 110 can be etched into a predetermined pattern according to the photoresist pattern through the individual procedures described above. In the above-mentioned first chemical processing method, the chrome film 120 formed on the material 110 can be etched into a predetermined pattern by performing a cathodic electrolytic reduction process and an leaching process in this order, that is, by combining a simple process. It also prevents the production of hexavalent chromium. This has the advantage that the disposal of the waste liquid of each treatment solution is easy. In addition to preventing the production of hexavalent chromium, the chromium film 120 can be etched without using any cyanide compound as a processing solution in each of the cathode electrolytic reduction procedures and the leaching process. This greatly reduces the labor required for waste liquid disposal compared with the conventional method. Quite inexpensive -12-1243860 chlorine-based chemicals, such as hydrochloric acid, NaCl solution, and SAS manufactured by K.K. MURATA, can also be used as the treatment solution in the cathodic electrolytic reduction process and the acid pickling process. Since these treatment solutions can be used to etch a chromium film on the stomach 120, the cost of chromium etching can be greatly reduced. λ [Second chemical treatment method] The material 100 treated as shown in Fig. 2E is obtained by performing the same treatment as the first chemical treatment method described above. Then, as shown in FIG. 4, the material 100 and the electrode plate 22 as a positive electrode are immersed in a predetermined treatment solution 28 contained in a container 20. In this state, the material 100 is used as a cathode for performing electrolytic reduction of the chromium film 120 in the processing solution 28. This electrolytic reduction treatment is hereinafter referred to as "acid electrolytic treatment", and the procedure for carrying out this treatment is hereinafter referred to as "acid electrolytic treatment". This acid electrolytic treatment solution 28 is an acidic treatment solution containing halogen ions, preferably an acidic treatment solution containing chloride ions, such as K.K. Murata's SAS. As shown in FIG. 2F, the acid electrolytic treatment can The chromium film 120 is etched into a predetermined pattern, and at the same time, the chromium oxide film formed on the surface of the chromium film 120 is reduced. Then, the same treatment as in the first chemical treatment method is performed to obtain the material 100 as shown in Fig. 2G. _ In the above-mentioned second chemical processing method, the chromium film 120 formed on the material 110 for receiving the film can be etched into a predetermined pattern by a simple method ν 'that is, acid electrolytic treatment, and the Manufacturing. In addition, in the second chemical treatment method, two procedures of the cathodic electrolytic reduction treatment and the acid dipping treatment in the first to the chemical methods may be implemented by an acid electrolytic treatment program. The two processes of the cathodic electrolytic reduction process and the acid pickling process include a washing process between these processes. Therefore, by implementing only one acid electrolytic treatment program, -13-1243860 labor for this cleaning treatment can be saved. In the first and second chemical processing methods, the chromium film 120 is etched. However, the invention is not limited to chromium. For example, even when using titanium, tungsten, palladium,. And molybdenum, the chemical treatment method of the present invention can etch these metals into a predetermined pattern. Even when an alloy containing at least one of chromium, titanium, tungsten, palladium, and molybdenum is used, the chemical treatment method of the present invention can etch the alloy into a predetermined pattern. As for the alloy, a nickel-chromium alloy is preferably used. Next, [Application Example 1] to [Application Example 6] are described below as application examples of various chemical treatment apparatuses using the above first and second chemical treatment methods, that is, various uses according to the first chemical treatment method. Cathode electrolytic reduction treatment and acid leaching treatment equipment, and various equipment using acid electrolytic treatment according to the second chemical treatment method. [Application Example 1] to [Application Example 4] A device for etching a metal film formed on a carrier tape. [Application Example 5] and [Application Example 6] A device for etching a metal film formed on a semiconductor wafer. As shown in FIG. 2E, it is assumed that the chromium film 120 is formed on a carrier tape or a semiconductor wafer, and a copper film 130 and a photoresist film 140 are etched into a predetermined pattern on the chromium film 120 in this order. Lu [Application Example 1] Application Example 1 relates to an example of a "vertical feeding type" device that uses the above-mentioned first chemical processing method and its carrier tape to feed it upright, that is, feeding the tape so that the width direction of the tape is vertical. Figure 5 shows the vertical feed type chemistry. A schematic side sectional view of an example of a processing device. Fig. 6 is a schematic front sectional view of a cathode electrolytic reduction device forming the chemical treatment device shown in Fig. 5. _ As shown in FIG. 5, the chemical treatment device 30 includes a cathode electrolytic reduction device 31 for performing cathodic electrolytic reduction treatment of the carrier tape ci * -14-1243860, and a washing device 32 and 34 for washing the carrier tape C1. And an acid pickling device 33 for pickling the carrier tape C1. In Fig. 5, a feeding device (not shown) for feeding the carrier tape C1 is placed at the left end of the cathode electrolytic reduction device 31. A winding device (not shown) for winding the carrier tape C1 is also placed at the right end of the cleaning device 34. As shown in Figs. 5 and 6, the cathode electrolytic reduction device 31 includes a box-shaped external treatment bath 31a. The inner processing bath 31b is formed at a substantially central position of the outer processing bath 31a. The bottom of the outer processing bath 31a also serves as the bottom of the inner processing bath 31b. The side wall of the inner processing bath 3 1 b is slightly lower than the side wall of the outer processing bath 3 1 a. One end of the supply pipe 31c is connected to the bottom of the inner processing bath 31b. The pump 31d, the heat exchanger 3 1 e, and the filter 3 1 f are arranged in the middle of the supply pipe 3 1 c. The other end of the supply pipe 31c is connected to a groove 31g. The tank 31g contained the processing solution for 31h. The processing solution 31h is one of an acidic processing solution containing an acid group and an alkaline processing solution containing a halogen ion. Preferably, the treatment solution 31h is a chloride ion treatment solution, such as SAS manufactured by K.K. Murata. One end of each of the drain pipes 31 i and 31 j is connected to the bottom between the outer processing bath 31 a and the inner processing bath 31 b. The other ends of the drain pipes 31i and 31j are connected to the groove 31g. When the pump 3 1 d is operated, the processing solution 31 h in the tank 31 g flows through the heat exchanger 31e and the filter 31f through the supply pipe 31c, and is supplied to the internal processing bath 31b. When a predetermined amount of the solution 31h is supplied to the internal processing bath 31b, the processing solution 31h flows out of the internal processing bath 31b beyond its side wall. That is, the processing solution 3 1 h overflows from the internal processing bath 3 1 b to an overflow portion 31 k formed between the side wall of the external processing bath 3 1 a and the side wall of the internal processing bath 3 1 b. The inflow 1243860 part of the 3 1 k treatment solution 3 1 h passed through the drainage pipes 3 1 i and 3 1 j connected to the tank 3 1 g. The processing solution was then repeatedly circulated through the individual components described above for 3 h. As shown in Figs. 5 and 6, in the side walls of the outer processing bath 31a and the inner processing bath 31b, slits 31 1 and 31 m such as vertical long holes are formed at predetermined positions on the side wall through which the carrier tape Cl passes. Each of the slits 311 and 31m has a width and a length that are larger than the load belt C1. It should be noted that the treatment solution 31h in the internal treatment bath 31b also flows out through the slit 3 1 m into the overflow portion 31 k. The electrode 31η is placed inside the internal processing bath 31b. In the internal processing bath 31b, the electrode 31η faces one surface of the carrier tape Cl, that is, the surface on which the film is formed. The electrode 31n is connected to the positive electrode of the power source 31x. Among the side walls of the outer treatment bath 3 1 a, the electrode rollers 3 1 y and 3 1 z are arranged outside the side wall through which the load belt C 1 is loaded and the side wall through which the load belt C 1 is unloaded. The electrode rollers 3 1 y and 3 1 z are in contact with one surface of the carrier tape C 1, that is, a surface on which a chromium film and a copper film are formed. The electrode rollers 31y and 31z are connected to the negative electrode of the power source 31x. The decanting devices 32 and 34 and the acid pickling device 33 have substantially the same configuration as the cathode electrolytic reduction device 31. The cleaning device 32 has a box-shaped outer processing bath 32a, and an inner processing bath 32b is formed at a substantially central position of the outer processing bath 32a. The supply pipe 32c is connected to the bottom of the inner processing bath 32b. The drain pipes 32i and 32j are connected to the bottom of the external treatment bath 32a. The tank 32g contains the deionized water for the washing of the tritium with Cl for 32h. When the pump 32d is operated, the deionized water 32h in the tank 32g flows through the heat exchanger 32e and the filter 32f through the supply pipe 32c, and is supplied to the internal processing bath 32b. Then, the deionized water 32h in the tank 32g exceeds the side 1243860 of the inner processing bath 32b and flows into the overflow portion 32k. The deionized water 32h was collected to the tank 32g via the drain pipes 32i and 32j, and was circulated in the same manner as above. In the side walls of the outer processing bath 32a and the inner processing bath 32b, slits 321 and 32m such as vertical long holes are formed at predetermined positions of the side walls through which the carrier tape C1 passes. The carrier tape C1 is fed through the slits 3 21 and 32 m, and is immersed in the deionized water 32h of the internal treatment bath 32b. The pickling device 33 has a box-shaped outer processing bath 33a, and an inner processing bath 33b is formed at a substantially central position of the outer processing bath 33a. The supply pipe 33c is connected to the bottom of the inner processing bath 33b. The drain pipes 33i and 33j are connected to the bottom of the external treatment bath 33a. The tank 33g contains the processing solution for 33h. The processing solution 33h is an acidic processing solution, preferably an acidic processing solution containing a halogen ion, such as SAS manufactured by K.K. Murata. When the pump 33d is operated, the processing solution 33h in the tank 33g flows through the heat exchanger 33e and the filter 33f through the supply pipe 33c, and is supplied to the internal processing bath 33b. Then, the processing solution 33h in the tank 33g exceeds the side wall of the internal processing bath 33b and flows into the overflow portion 33k. The treatment solution 33 h was collected into the tank 33 g via the drainage pipes 33 i and 33 j, and was circulated in the same manner as above. In the side walls of the outer processing bath 3 3 a and the inner processing bath 3 3 b, slits 33 1 and 33 m of vertical long holes are formed at predetermined positions of the side walls through which the carrier tape C1 passes. The carrier tape C1 is fed through the slits 331 and 33 m, and is immersed in the processing solution 33h of the internal processing bath 33b. The cleaning device 34 has a box-shaped outer processing bath 34a, and an inner processing bath 34b is formed at a substantially central position of the outer processing bath 34a. The supply pipe 34c is connected to the bottom of the inner processing bath 34b. The drain pipes 34i and 34j are connected to the bottom of the external treatment bath 34a 1243860. The tank 34g contained the deionized water for washing the loaded material with Cl for 34h. When the pump 34d is operated, the deionized water 34h in the tank 34g flows through the heat exchanger 34e and the filter 34f through the supply pipe 34c, and is supplied to the internal processing bath 3 4b. Then, the deionized water 34h in the tank 34g exceeds the side wall of the inner processing bath 34b and flows into the overflow portion 34k. The deionized water 34h was collected to the tank 34g via the drainage pipes 34i and 34j, and was circulated in the same manner as above. In the side walls of the outer processing bath 34a and the inner processing bath 34b, slits 341 and 34m such as vertical long holes are formed at predetermined positions of the side walls through which the carrier tape C1 passes. The carrier tape C1 is fed through the slits 341 and 34m, and is immersed in the deionized water 34h of the internal processing bath 34b. The feeding rollers (not shown) are arranged on both sides of each of the devices 31 to 34. These feed rollers sandwich the carrier tape C1 between them and rotate next to each other in opposite directions. As these feed rollers rotate, the carrier tape C1 is fed. As described above, the electrode rollers 31y and 31z are disposed on both sides of the cathode electrolytic reduction device 31. The feed roller is opposite to the electrode rollers 31y and 31z, and is configured by sandwiching the carrier tape C1 therebetween. The operation of the chemical processing apparatus 30 is explained below. When the electrode rollers 31y and 31z and the feeding roller are rotated in a predetermined direction, the carrier tape C1 is fed in a feeding direction from a feeding device (not shown). Therefore, the carrier tape C1 passes through the processing baths 31b to 34b within the devices 31 to 34 and is taken up by a winding device (not shown). The following processing is performed in the devices 31 to 34. That is, in the "cathode electrolysis® original device 31", the processing bath 31b is charged with the processing solution 31h, and a voltage is applied between the electrode rollers 31y and 31z and the electric 1243860 electrode 3 1 η. In this state, the carrier tape C1 passes through the slits 3 Π and 3 1 m and passes through the inner processing bath 31b. When passing through the inner processing bath 31b, the carrier tape C1 is subjected to a cathodic electrolytic reduction treatment. That is, outside the external processing bath 31a, the electrode light 31y and 31z contact the surface of the carrier tape Cl on which a metal film is formed. Therefore, in the internal processing bath 31b, the chromium oxide film formed on the surface of the chromium film is reduced. In the decanting device 32, the internal treatment bath 32b is filled with deionized water 32h. The carrier tape C1 passes through the slits 321 and 32m, and is washed with deionized water for 32h while passing through the internal treatment bath 32b. In the acid pickling device 33, the internal treatment bath 33b is filled with the treatment solution 33h. The carrier tape C1 is subjected to acid treatment through the slits 331 and 33m, and in the inner processing bath 33b. That is, the carrier tape C1 is immersed in the processing solution 33b of the internal processing bath 33b for feeding, and the chromium film formed on the carrier tape C1 is etched into a predetermined pattern. In the rinsing device 34, the internal treatment bath 34b is filled with deionized water 34h. The carrier tape C1 passes through the slits 341 and 34, and is rinsed with deionized water 34h while passing through the inner processing bath 34b. The carrier tape Cl washed by the washing device 34 is dried by a drying device (not shown) and wound up by a winding device (not shown). By the above operation, the chromium film formed on the carrier tape C1 can be etched into a predetermined pattern. It also prevents the production of hexavalent chromium. As shown in Figures 5 and 6, in the cathodic electrolytic reduction treatment of the cathodic electrolytic reduction device 31, the inner processing bath 31b can be completely filled with the processing solution 31h, and the carrier tape Cl can be completely immersed in the processing solution 31h in. It is also possible to incompletely fill the internal processing bath 31b with the processing solution 31h, and immerse a part of the surface of the carrier tape C1 on which the metal film is formed in the processing solution 31h. 1 1 9-1243860 [Application Example 2] Application Example 2 uses an apparatus in which the above-mentioned second chemical processing method is used, and which is similar to the vertical feed type chemical processing apparatus of Application Example 1. FIG. 7 is a schematic cross-sectional view showing an example of the chemical processing apparatus. As shown in Fig. 7, the chemical processing device 40 includes an electrolytic device 41 for carrying out acid electrolytic treatment of the carrier tape C2, and a washing device 42 for washing the carrier tape C2. In the chemical processing device 40, similar to the chemical processing device 30 shown in FIG. 5, a feeding device and a winding device (none of which are shown) are disposed at both ends of the electrolytic device 41 and the washing device 42. The electrolytic device 41 has substantially the same configuration as the cathode electrolytic reduction device 31 shown in Figs. 5 and 6. However, the electrode roller 41y is placed on the feeding device side of the external processing bath 411. The electrolytic device 41 is also different from the cathode electrolytic reduction device 31. The 41 g of the tank contains an acidic processing solution, preferably an acidic processing solution containing a halogen ion (such as chloride ion) 41h. A preferred example of the acidic treatment solution 41h is SAS manufactured by K.K. Murata. The cleaning device 42 has substantially the same configuration as the cleaning devices 32 and 34 shown in FIG. Therefore, in the decanting device 42, the deionized water 42h in the tank 42g flows through the heat exchanger 42e and the filter 42f and to the inner processing bath 42b through the supply pipe 42c by the operation of the pump 42d. The deionized water 42h is circulated from the overflow part 42k to the drain pipes 42i and 42j. The operation of the chemical processing device 40 is explained below. When the electrode roller 41y and the feed roller are rotated in a predetermined direction, the 'loading belt C2 is wound up by each of the internal processing baths 41b and 42b in the electrolytic device 41 and the cleaning device 42. -2 0-1243860 The following processes are performed in devices 41 and 42. In the electrolytic device 41, the inner processing bath 41b is filled with the processing solution 41h. The treatment solution 41h overflowing from the internal treatment bath 41b was collected from the overflow portion 41k through the drain pipes 4 1 i and 4 1 j to the tank 4 1 g. By the operation of the pump 41d, the treatment solution 41h flows from the tank 41g through the heat exchanger 41e and the filter 41f to the supply pipe 41c, and circulates to the inner processing bath 41b. In the electrolytic device 41, the power source 41x also applies a voltage between the electrolytic roller 41y and the electrode 41n. In this state, the carrier tape C2 passes through the slits 411 and 41m and passes through the inner processing bath 41b. When passing through the inner processing bath 41b, the carrier tape C2 is subjected to acid electrolytic treatment. That is, outside the external treatment bath 41a, the electrode roller 41y contacts the surface of the carrier tape C2 on which the metal film is formed. Therefore, when the carrier tape C2 is opposed to the electrode 41η, the chromium oxide film formed on the surface of the chromium film is reduced. Then, when the material with the carrier tape C2 is fed out of the area facing the electrode 41η in the area of the reduction complex, the chromium film on the carrier tape C2 is etched into a predetermined pattern by the processing solution 41h in the inner processing bath 41b. In the decanting device 42, the inner treatment bath 42b inside the outer treatment bath 42a is filled with deionized water 42h. The carrier tape C2 passed through the slits 421 and 42m, and was washed with deionized water 42h while passing through the inner processing bath 42b. The carrier tape C2 washed by the washing device 42 is dried by a drying device (not shown), and is taken up by a winding device (not shown). By the above operation ', the chromium film formed on the carrier tape C2 can be etched into a predetermined pattern. It also prevents the production of hexavalent chromium. [Application Example 3] Application Example 3 relates to an example of a "horizontal feeding type" device that uses the first chemical treatment method described above and its medium load to be placed horizontally and fed. FIG. 8 is a schematic side view of a horizontal feed type chemical processing apparatus. As shown in FIG. 8, the chemical processing device 50 includes a cathode electrolytic reduction device 51 for carrying out the cathode electrolytic reduction treatment of the carrier tape C3, a washing device 52 and 54 for washing the carrier tape C3, and a carrier tape C3 acid pickling device 53. Similar to the chemical treatment devices 30 and 40 shown in Figs. 5 to 7, in the chemical treatment device 50, the feeding device (not shown) for loading the belt C3 in Fig. 8 is placed in a cathode electrolytic reduction device The left end of 51 and the winding device (not shown) for winding up the carrier tape C3 in FIG. 8 are placed at the right end of the cleaning device 54. The cathode electrolytic reduction device 51 includes a processing bath 51a containing a processing solution 51b. The processing solution 51b is one of an acidic processing solution containing an acid group and a basic processing solution containing a halide ion. Preferably, the treatment solution 51b is a chloride ion-containing treatment solution, such as SAS manufactured by K.K. Murata. The two ends of the flow tube 51c are connected to the bottom of the processing bath 51a. The pump 5 1 d, the heat exchanger 5 1 e, and the filter 5 1 f are arranged in the middle of the flow tube 5 1 c. When the pump 5 1 d is operated, the processing solution 5 1 b in the processing bath 5 1 a flows through the flow tube 5 1 c and returns to the processing bath 51a through the heat exchanger 5 1 e and the filter 51f. In the cathode electrolytic reduction device 51, a circulation system of such a treatment solution 51b is formed. The two electrode rollers 51g and 51h are arranged above the processing bath 51a and connected to the negative electrode of the power source 51i. The support rollers 51j and 51k supporting the electrode rollers 51g and 51h are respectively disposed below the electrode rollers 51g and 51h. In the processing bath 51a, a feeding roller 511 for changing the feeding direction of the carrier tape C3 is set. -22- 1243860 The carrier tape C3 is sandwiched between the electrode roller 51g and the support roller 51j, the feed roller 511 is wound in the processing bath 51a, and it is sandwiched between the electrode roller 51h and the support roller 51k. The surface of the carrier tape C3 on which the metal film is formed contacts the electrode rollers 51g and 51h ° In the processing bath 51a, two electrodes 51m and 51η are arranged. The electrodes 51m and 51η are connected to the positive electrode of the power source 51i, and are opposed to the carrier tape C3. It should be noted that, in the processing bath 51a, the electrodes 51m and 51η are opposed to the surface of the carrier tape C3 on which the metal film is formed. The rinsing device 52 has a treatment bath 52a containing deionized water 52b. Both ends of the flow tube 52c are connected to the bottom of the processing bath 52a. The pump 52d, the heat exchanger 52e, and the filter 52f are arranged in the middle of the flow tube 52c. When the pump 52d is operated, the deionized water 52b in the processing bath 52a flows through the flow pipe 52c and returns to the processing bath 52a through the heat exchanger 52e and the filter 52f. In the decontamination apparatus 52, a circulation system of such a treatment solution 52b is formed. The four feeding rollers 52g, 52h, 52i, and 52j are arranged above the processing bath 52a. That is, the feed rollers 52g and 52h are paired on the upstream side in the feeding direction of the carrier tape C3, and the feed rollers 52i and 52j are paired on the downstream side. In the processing bath 52a, a feeding roller 521 for changing the feeding direction of the carrier tape C3 is set. The carrier tape C3 is sandwiched between the feed rollers 52g and 52h, and the feed roller 521 is wound in the processing bath 52a. In the decanting device 52, this carrier tape C3 feeding system is formed.

浸酸裝置53具有含處理溶液53b之處理浴53a。處理· 溶液53b爲酸性處理溶液，較佳爲含鹵素離子（如氯離子 )之酸性處理溶液。此酸性處理溶液之實例爲K.K. MURAT A -23- 1243860 製造之SAS。流動管53c之兩端連接處理浴53a底部。泵53d 、熱交換器5 3 e、及過濾器5 3 f係配置於流動管5 3 c中間。 在操作泵5 3 d時，處理浴5 3 a中之處理溶液5 3 b流經流動 管53c且經熱交換器53e與過濾器53f回到處理浴53a。在 浸酸裝置53中，形成此種處理溶液53b循環系統。 四個進料輥532、5311、53卜與53」係配置於處理浴53& 上方。即，進料輥53g與53h在載物帶C3進料方向上游側 成一對，及進料輥5 3 i與5 3 j在下游側成一對。在處理浴5 3 a 中，安置改變載物帶C3之進料方向用之進料輥531。 馨 載物帶C3夾在進料輥53g與53h之間，在處理浴53a 中捲繞進料輥531，及夾在進料輥53i與53j之間。 淸洗裝置54具有如淸洗裝置52之相同配置。即，含 去離水54b之處理浴54a。由流動管54c、泵54d、熱交換 器54e、過濾器54f、及處理浴54a組成之循環系統具有如 淸洗裝置52之相同配置。由處理浴54a上方之四個進料輥 54g、54h、54i、與54j及處理浴54a中之進料輥541組成 之進料系統具有如淸洗裝置52之相同配置。 ® 在裝置51、52、53、與54之處理浴51a、52a、53a、 與54a中，溶液51b、52b、53b、與54b係藉攪動器（未示 . )等攪動。 化學處理裝置50之操作解釋於下。 在包括電極輥51g與51h之進料輥按預定方向轉動時 ，載物帶C3以來自進料裝置（未示）之進料方向進料，及 通過裝置51至54之處理浴51a至54a由捲繞裝置捲收。 _ 2 4 - 1243860 如第8圖所示，在側面觀看時，載物帶c 3係Z形地進料。 以下之處理係在裝置5 1至5 4中實行。 在陰極電解還原裝置51中，處理浴51a係以處理溶液 51b充塡，及將電壓施加於電極輥51g與51h及電極51m與 5 1 η之間。在此狀態，載物帶C3在通過處理浴5 1 a時接受 陰極電解還原處理。即，在處理浴51a外部，電極輥51g 與51h接觸其上形成金屬膜之載物帶C3表面。因此，在電 極51m與51η之影響下，將形成於鉻膜表面上之氧化鉻膜 還原。 在淸洗裝置52中，處理浴52a係以去離子水52b充塡 ，及載物帶C3在通過處理浴52a時以去離子水52b淸洗。 在浸酸裝置5 3中，處理浴5.3 a係以處理溶液5 3 b，及 載物帶C3在通過處理浴53a時接受浸酸處理。即，載物帶 C3係浸於處理浴53a之處理溶液53b中而進料，及將鉻膜 蝕刻成預定圖案。 在淸洗裝置54中，處理浴54a係以去離子水54b充塡 ，及載物帶C3在通過處理浴54a時以去離子水54b淸洗。 以淸洗裝置54淸洗之載物帶C3係經乾燥裝置（未示）乾 燥及藉捲繞裝置（未示）捲收。 藉以上之操作，可將形成於載物帶C3上之鉻膜蝕刻成 預定圖案。亦可防止六價鉻之製造。 [應用例4 ] 應用例4使用其中使用上述之第二化學處理方法，及 其爲類似應用例3之水平進料型化學處理裝置之裝置。第9 -25- 1243860 圖爲顯示此化學處理裝置之實例之略示側切面圖。如第9 圖所示，化學處理裝置60包含實行載物帶C4之酸電解處 理用之電解裝置61，及淸洗載物帶C4用之淸洗裝置62。 在化學處理裝置60中，類似如第8圖所示之化學處理 裝置50，進料裝置及捲繞裝置（均未示）係配置於第9圖 所示之電解裝置61與淸洗裝置62之兩端。 電解裝置61具有含處理溶液61b之處理浴61a。處理 溶液61b爲含鹵離子之酸性處理溶液，較佳爲含氯離子處 理溶液，如K.K. MURAT A製造之SAS。電解裝置61具有類 似第8圖所示之陰極電解還原裝置51之循環系統。即，處 理溶液61b藉供應管61c、泵61d、熱交換器61e、過濾器 6 1 f、及處理浴6 1 a組成之循環系統在個別構件間循環。 電極輥61g係置於處理浴61a上方，及連接電源61 i 之負極。支撐電極輥61g之支持輥61h係置於電極輥61g 下方。電極輥61g及支持輥61h配係置於載物帶C4進料方 向之上游側。兩個彼此相鄰之進料輥6 1 j與6 1 k係配置於 載物帶C4進料方向之下游側。在處理浴61a中，安置改變 載物帶C4之進料方向用之進料輥611。 載物帶C4夾在電極輥61g與支持輥61h之間，在處理 浴61a中捲繞進料輥611，及夾在電極輥61 j與支持輥61k 之間。其上形成金屬膜之載物帶C4表面接觸電極輥61g。 電極61m係置於處理浴61a中及連接電源61i之正極 。應注意，在處理浴61a中，在載物帶C4到達進料輥611 之前，電極61m與其上形成金屬膜之載物帶C4表面相對。 -26- 1243860 淸洗裝置62具有如第8圖所示之淸洗裝置52之相同 配置。即，處理浴62a含去離水62b。由流動管62c、泵62d 、熱交換器62e、過濾器62f、與處理浴62a組成之循環系 統，及由處理浴62a上方之四個進料輥62g、62h、62i、與 62j、及處理浴62a內部之進料輥621組成之進料系統，具 有如前述淸洗裝置52之相同配置。 化學處理裝置60之操作解釋於下。 在包括電極輥61g之進料輥按預定方向轉動時，載物 帶C4以來自進料裝置之進料方向進料，及通過裝置61與62 之處理浴61a與62a由捲繞裝置捲收。如第9圖所示，在 側面觀看時，載物帶C4係Z形地進料。 以下之處理係在裝置61與62中實行。 在電解裝置61中，處理浴61a係以處理溶液61b充塡 ，及將電壓施加於電極輥61g與電極61m之間。在此狀態 ，載物帶C4在通過處理浴61a時接受酸電解處理。 即，在處理浴61a外部，電極輥61g接觸其上形成金 屬膜之載物帶C4表面。因此，在電極61m之影響下，在與 電極61m相對時，將形成於鉻膜表面上之氧化鉻膜還原。 由於鉻膜浸於處理溶液61b中，以處理溶液61b將此鉻膜 蝕刻成預定圖形。 在淸洗裝置62中，處理浴62a係以去離子水62b充塡 ，及載物帶C4在通過處理浴62a時以去離子水62b淸洗。 以淸洗裝置62淸洗之載物帶C4係經乾燥裝置（未示）乾 燥及藉捲繞裝置（未示）捲收。 1243860 藉以上之操作，可將形成於載物帶C4上之鉻膜蝕 預定圖案。亦可防止六價鉻之製造。 [應用例1 ]至[應用例4 ]揭示各具有金屬膜形成於 表面上之載物帶Cl、C2、C3、與C4之處理。然而，兩 面上均具金屬膜之載物帶亦可以如上之相同方式處理 此情形，在以處理溶液充塡之處理浴中電極與載物帶 表面相對，而且連接電之正極。 在[應用例1]之陰極電解還原裝置31中，陰極電 原處理係以充塡處理溶液31h之內處理浴31b實行。 ，除了此配置，內處理浴31b中亦可裝設連接供應管 之淋浴噴嘴，使得此淋浴噴嘴面對載物帶C1形成金屬 表面，及將處理溶液31h自淋浴噴嘴噴向載物帶C1。 類似陰極電解遼原裝置31，浸酸裝置33中亦可在 理浴33b中裝設淋浴噴嘴，及將處理溶液33h自淋浴 噴向載物帶C1。 如果金屬膜係形成於載物帶C1之兩個表面上，則 浴噴嘴裝設在陰極電解還原裝置31與浸酸裝置33之 理浴31b與33b而面對載物帶C1之兩個表面，及將處 液31h與33h自這些淋浴噴嘴噴向載物帶C1。 此外，在[應用例3]之陰極電解還原裝置51中， 電解還原處理係以充塡處理溶液51b之內處理浴51a 。然而，除了此配置，內處理浴51a中亦可裝設連接 管51c之淋浴噴嘴，使得此淋浴噴嘴面對載物帶C3形 屬膜之表面，及將處理溶液51b自淋浴噴嘴噴向載物^ 刻成 一個 個表 。在 兩個 解還 然而 31c 膜之 內處 噴嘴 將淋 內處 理溶 陰極 實行 供應 成金 ψ C3 -28- 1243860 類似陰極電解還原裝置5 1，浸酸裝置5 3中亦可在處理 浴53a中裝設淋浴噴嘴，及將處理溶液53b自淋浴噴嘴噴 向載物帶C3。 如果金屬膜係形成於載物帶C3之兩個表面上，則將淋 浴噴嘴裝設在陰極電解還原裝置51與浸酸裝置53之處理 浴51a與53a而面對載物帶C3之兩個表面，及將處理溶液 51b與53b自這些淋浴噴嘴噴向載物帶C3。 [應用例5 ] 應用例5有關使用上述之第一化學處理方法，及其係 在將形成於半導體晶圓上之金屬膜蝕刻成預定圖案時使用 之化學處理裝置。此化學處理裝置包括實行半導體晶圓上 之金屬膜之陰極電解還原處理用之陰極電解還原裝置、及 在陰極電解還原裝置後實行半導體晶圓上之金屬膜之浸酸 處理用之浸酸裝置。 首先，陰極電解還原裝置解釋於下。 第10圖爲顯示陰極電解還原裝置71之實例之縱側切 面圖。如第10圖所示，杯2係置於支撐台1上。杯2之下 部開放，及杯2係以此開放表面向下而安裝於支撐台丨上 。支撐台1爲可垂直移動，及杯2係固定於裝置主體。因 而支撐台1上下移動而杯2固定於裝置主體。 吸入路徑3係形成於支撐台1中。吸入路徑3經吸入 路徑3下方之導管3a連接吸入工具，如真空泵（未示）。 在支撐台1之上部中，形成大量朝上之吸入孔3b。圍繞吸 - 29- 1243860 入孔3 b之表面由上向外傾斜，因而在支撐台1上形成傾斜 連接表面la。在結合杯2時，傾斜連接表面la連接引導環 9之傾斜連接表面9b (後述），因而有效地使支撐台丨與 杯2對齊。 網狀陽極電極4係形成於杯2內部之上部中。陽極電 極4連接電源19之陽極5。在杯2之下部中，形成塑膠氟 化橡膠製之圓形板狀封鎖片6以圍繞杯2之開放表面。在 封鎖片6之下表面上，形成三個板狀陰極電極7。陰極電極 7相等地間隔，即，以120。之中心角分隔，而且連接電源 19之陰極。 引導環9係重疊且整合於封鎖片6之下側。在杯2之 下部中，對齊突起2 a係以三個相等地間隔之部份形成，即 ，以120°之中心角分隔。對齊穿孔6a以與對齊突起2a爲 一對一對應而形成於封鎖片6中，對齊穿孔7 a係形成於陰 極電極7中，及對齊凹口 9a係形成於引導環9之上部。 對齊突起2a延伸通過對齊穿孔6a與7a且連接對齊凹 口 9a，因而將封鎖片6及陰極7固定於杯2。由上向外傾 斜之傾斜連接表面9b係形成於引導環9之內緣上。傾斜連 接表面9b連接支撐台1之傾斜連接表面la。 在上述之杯2、封鎖片6、陰極電極7、及引導環9整 合時，陰極電極7在引導環9內部暴露約3至4毫米，及 其餘被封鎖片6與引導環9完全地覆蓋。因此，僅各陰極 電極7之末端部份接觸處理溶液12，及其餘完全不接觸處 理溶液12。0-環10係插入引導環9之下表面與支撐台1之 -30- 1243860 間。 半導體晶圓W1係支撐於支撐台1上，而半導體晶圓W1 之邊緣鉗夾於封鎖片6與支撐台1之間。此外，半導體晶 圓W1經連接端子（未示）連接各陰極電極7之末端部份。 槽13含流入杯2中之處理溶液12。處理溶液12爲含 酸基之酸性處理溶液與含鹵素離子之鹼性處理溶液之一。 較佳爲，處理溶液12爲含氯離子處理溶液，如K.K. MURATA 製造之S AS。用於將處理溶液12自槽13上泵之泵14位於 槽1 3上方。供應路徑1 5係形成於泵1 4與杯2之下部之間 。藉泵1 4自槽1 3上泵之處理溶液1 2經供應路徑1 5流入 杯2中。 排洩路徑1 6係形成於杯2上部之實質上中央部份中。 在杯2外部，放洩閥17連接排洩路徑16。回位路徑1 8係 自排洩路徑16與放洩閥17間之通路分出，及連接槽13。 浸酸裝置敘述於下。 第11圖爲顯示浸酸裝置72之實例之縱向側切面圖。 如第1 1圖所示，杯82係形成於支撐台81上。杯82之下 部開放，及杯82係以此開放表面向下而安裝於支撐台8 1 上。在杯82之下部中，形成塑膠氟化橡膠製之圓形板狀封 鎖片6 (未不）以圍繞杯82之開放表面。支撐台81爲可垂 直移動，及杯82係固定於裝置主體。因而支撐台81上下 移動而杯82固定於裝置主體。 吸入路徑83係形成於支撐台81中。吸入路徑83經吸 入路徑83下方之導管83a連接吸入工具，如真空泵（未示 -31- 1243860 )。在支撐台81之上部中，形成大量朝上之吸入孔83b。 所有吸入孔83b均被杯82覆蓋。0-環84係插入杯82之下 部與支撐台8 1之間。 半導體晶圓W1係鉗夾於杯82之下部與支撐台81之間 〇 槽85位於杯82下方。槽85含流入杯82中之處理溶 液86。處理溶液86爲酸性處理溶液，例如，含鹵素離子之 酸性處理溶液，較佳爲氯離子。此酸性處理溶液之較佳實 例爲K.K. MURATA製造之SAS。用於將處理溶液86自槽85 上泵之泵87位於槽85上方。供應路徑88係形成於泵87 與杯82之間。藉泵87自槽85上泵之處理溶液86經供應 路徑8 8流入杯8 2中。 排洩路徑89係形成於杯82上部之實質上中央部份中 。在杯82外部，放洩閥90連接排洩路徑89。回位路徑91 係自排洩路徑89與放洩閥89間之通路分出，及連接槽85 〇 第10與11圖所示之陰極電解還原裝置71與浸酸裝置 72之操作並解釋於下。 首先，在陰極電解還原裝置71中，支撐台1與杯2係 藉由將支撐台1自杯2下移而分離。然後將半導體晶圓wi 固定於支撐台1之支撐表面上’使得形成於半導體晶圓W1 上之金屬膜朝上。操作連接導管3a之吸入工具以將吸力施 加於吸入孔3b，因而藉吸入將半導體晶圓W1固定於支撐台 1上。 -32 - 1243860 繼而在半導體晶圓wi如此固定時’將提供〇 -環i〇 支撐台1上移以連接支撐台1之傾斜連接表面la與引導 9之傾斜連接表面9b，因而使支撐台1與杯2對齊。以 方式，杯2之內部被封鎖片6之下表面及〇-環10完全封 。在此狀態，半導體晶圓W1之邊緣緊密接觸封鎖片6之 表面，及半導體晶圓W1上之金屬膜連接陰極電極7。 然後驅動泵1 4以將來自槽1 3之處理溶液1 2經供應 徑1 5供應至杯2中。結果，處理溶液1 2自半導體晶圓 上方流入杯2中，及隨時間在杯2中累積。在此階段’ 洩閥17仍關閉，及將杯2中之空氣排入槽13中然後經 洩路徑16及回位路徑18至外部，所以無空氣殘留於管 系統中。類似杯2之內部空氣，亦將在半導體晶圓W1表 上產生之氣體排至外部。 在陽極電極4完全浸於流入杯2中之處理溶液12且 理溶液1 2經排洩路徑1 6到達回位路徑1 8時，實行半導 晶圓W1之陰極電解還原處理。即，藉電源19在陽極電棰 與各陰極電極7之間供應電流預定之時間，因而使半導 晶圓W1上之鉻膜變成陰極。結果，鉻膜在處理溶液12 接受電解還原，所以將在鉻膜表面上形成之氧化鉻膜還 〇 在將電流施加預定之時間而完成陰極電解還原處理 ，打開放洩閥1 7以使排洩路徑1 6及回位路徑1 8暴露於 氣。結果，將回位路徑18中之處理溶液12經回位路徑 收集至槽1 3。由於槽1 3位於杯2下方，經供應路徑1 5 之 rm 此 鎖 下 路 W1 放 排 路 面 處 體 4 體 中 原 時 大 18 與 -33 - 1243860 泵1 4亦將杯2中之處理溶液1 2收集至槽1 3。然後將支撐 台1下移而將藉吸力固定於支撐表面之半導體晶圓W1釋放 。以此方式完成陰極電解還原裝置71之陰極電解還原處理 〇 然後藉如轉移機械人之轉移工具（未示）將半導體晶 圓W1轉移至淸洗裝置（未示），及以淸洗裝置淸洗。在淸 洗處理完成時，將半導體晶圓W1轉移至第11圖所示之浸 酸裝置72。 在浸酸裝置72中，支撐台81與杯82係藉由將支撐台 81自杯82下移而分離。將半導體晶圓W1固定於支撐台81 之支撐表面上，使得形成於半導體晶圓W1上之金屬膜朝上 。操作連接導管83a之吸入工具以將吸力施加於吸入孔83b ，因而藉吸入將半導體晶圓W1固定於支撐台81上。 繼而在半導體晶圓W1如此固定時，將提供0-環84之 支撐台81上移以使支撐台81與杯82對齊。以此方式，杯 82之內部被完全封鎖。 然後驅動泵87以將來自槽85之處理溶液86經供應路 徑88供應至杯82中。結果，處理溶液86自半導體晶圓W1 上方流入杯82中，及隨诗間在杯82中累積。在此階段， 放洩閥90仍關閉，及將杯82中之空氣排入槽85中然後經 排洩路徑89及回位路徑9 1至外部，所以無空氣殘留於管 路系統中。類似杯82之內部空氣，亦將在半導體晶圓W1 表面上產生之氣體排至外部。 在杯82中累積預定量之處理溶液86時，停止自槽85 1243860 供應處理溶液86，及實行半導體晶圓W1之浸酸處理。即， 將半導體晶圓W1浸於杯82中之處理溶液86預定之時間。 結果，將半導體晶圓W1上之鉻膜蝕刻成預定圖案。 然後打開放洩閥90以使排洩路徑89及回位路徑91暴 露於大氣。結果，將回位路徑91中之處理溶液86經回位 路徑91收集至槽85。由於槽85位於杯82下方，經供應路 徑88與泵87亦將杯82中之處理溶液86收集至槽85。然 後將支撐台81下移而將藉吸力固定於支撐表面之半導體晶 圓W1釋放。以此方式完成浸酸裝置72之浸酸處理。 藉以上之操作，可將形成於半導體晶圓W1上之鉻膜蝕 刻成預定圖案。亦可防止六價鉻之製造。 [應用例6 ] 應用例6有關使用前述之第二化學處理方法，及其中 如應用例5將半導體晶圓上之金屬膜蝕刻成預定圖案之化 學處理裝置之實例。第12圖爲顯示此化學處理裝置之電解 裝置80之實例之略示切面圖。電解裝置80具有如第10圖 所示之陰極電解還原裝置71之實質上相同配置及功能。因 此，如第10圖所示之陰極電解還原裝置71之相同參考號 碼表示電解裝置80中之相同零件，而且省略其解釋。電解 裝置80之操作在以下亦僅簡要地敘述。在第1 2圖所示之 電解裝置80中，槽13含處理溶液95，其爲含鹵素離子之 酸性處理溶液，較佳爲含氯離子處理溶液，如K . K . MURAT A 製造之SAS。 電解裝置80之操作敘述於下。 -35 - 1243860 即，類似第10圖所示之陰極電解還原裝置71’在電 解裝置80中將半導體晶圓W2固定於預定位置’整合支撐 台1與杯2，及將處理溶液95供應至杯2中。在杯2中累 積預定量之處理溶液95時，實行半導體晶圓W2之酸電解 處理。 更特別地，藉電源19在陽極電極4與各陰極電極7之 間供應電流預定之時間，因而在處理溶液95中實行半導體 晶圓W2之鉻膜（陰極）之電解還原。即，將在鉻膜表面上 形成之氧化鉻膜還原。然後停止來自電源19之電力。藉由 維持此狀態而將半導體晶圓W2保持浸於酸性處理溶液95 中。結果將半導體晶圓W2上之鉻膜蝕刻成預定圖案。 然後將處理溶液95收集至槽85,及將藉吸力固定於 支撐台81之半導體晶圓W2釋放，因而完成電解裝置80之 酸電解處理。 藉以上之操作，可將形成於半導體晶圓W2上之鉻膜蝕 刻成預定圖案。亦可防止六價鉻之製造。 在上述[應用例1]至[應用例6]中解釋之第一及第二化 學處理方法及裝置中，可將載物帶上或半導體晶圓上之鉻 膜蝕刻成預定圖案。這些化學處理方法及化學處理裝置類 似地可應用於在各種基板（如載物帶與彈性基板）上形成 電線圖案、凸塊等。此方法及裝置亦可應用於在半導體晶 圓（例如，由矽製成）上形成電路圖案，例如，IC與LSI 。此方法及裝置可特別地應用於其中將形成於材料上之鉻 膜蝕刻成預定圖案之技術領域。 1243860 在[應用例1 ]至[應用例6 ]所述之裝置中係蝕刻鉻膜。 然而，即使是在使用鈦、鎢、鈀、鉬、及含鉻、鈦、鎢、 鈀、與鉬至少之一之合金時，亦可藉[應用例1]至[應用例 6]之裝置將這些金屬蝕刻成預定圖案。至於合金，較佳爲 使用鎳鉻合金。第一及第二化學處理方法亦不僅可應用於 形成於帶（如載物帶）上之金屬膜，亦可應用於形成於片 上之金屬膜。在此情形，各處理僅需以[應用例5 ]與[應用 例6 ]解釋之分批方式實行。 此外，在[應用例1 ]至[應用例6 ]所述之裝置中，亦可 在處理溶液循環系統與供應系統中間形成分離薄膜。在此 情形，即使在蝕刻鉻膜時製造六價鉻，分離薄膜亦在收集 處理溶液時防止此六價鉻隨廢液流出。 其次，將本發明人進行之各種關於上述第一及第二化 學處理方法之測試解釋於[實驗1 ]至[實驗4 ],及說明各測 試之結果與考量。 [實驗1 ] 在實驗1中，藉由在依照上述化學處理方法之銅濕蝕 刻處理、陰極電解還原處理、與浸酸處理中進行變化，及 藉由改變這些處理之各種條件，而測試銅膜與鉻膜之蝕刻 狀態。第1 3圖顯示實驗1之結果。 參考第13圖，使用藉由在一片聚醯亞胺帶上按此順序 形成鉻膜與銅膜而得之材料作爲1與2號實驗之測試材料 。亦使用在一片聚醯亞胺帶上形成鉻膜及在此鉻膜上將銅 膜齡刻成預定圖案而得之材料作爲3至8號實驗之測試材 -37 - 1243860 料。在第13圖中，「同時（A)」表示銅濕蝕刻處理與浸酸 處理係使用相同之處理溶液實行而不實行任何陰極電解還 原處理。「個別（B )」表示個別地實行銅濕蝕刻處理與陰極 電解還原處理及/或浸酸處理，即，表示陰極電解還原處理 及/或浸酸處理係在銅濕蝕刻處理後實行。「陽極電解氧化 (C)」表示藉由使用欲處理之材料作爲陽極因而將鉻膜氧化 ，而在預定之處理溶液中實行電解氧化代替陰極電解還原 處理。在第13圖右上角之「Cu剝落」及「Cr剝落」行中 ，銅膜與鉻膜之蝕刻狀態以「〇」或「X」表示。「〇」或「 X」係基於在各處理後是否可目視地證實聚醯亞胺片而決定 〇 在1與2號實驗中，將銅膜蝕刻成預定圖案，但是鉻 膜則否。其表示即使是在藉由使用相同之處理溶液同時實 行銅濕蝕刻處理與浸酸處理時，仍無法隨銅膜同時將鉻膜 蝕刻成預定圖案。 在3至6號實驗中，在獨立地實行浸酸、陽極電解氧 化、及陰極電解還原處理時，未鈾刻鉻膜。 在7號實驗中，在對測試材料實行陰極電解還原處理 與浸酸處理時蝕刻鉻膜。更特別地，在作爲含氯離子處理 溶液之K · K · MURATA製造之SAS中使用測試材料作爲陰極 而實行電解還原時’將鉻膜蝕刻成預定圖案，及將此材料 浸於相同之處理溶液中。應注意，7號實驗之條件「處理溶 液濃度（體積％ ) 5 0 / 5 0」、「電流密度（安培/ d m 2 ) 5 /」 、「溫度（°C) 3 0 / 3 0」、及「時間（秒）2/8及5/8」 -38 - 1243860 表示在陰極電解還原程序中處理溶液濃度爲50體積％，電 流密度爲5安培/ dm2，處理溶液溫度爲30°C，及處理時間 爲2與5秒，及在浸酸程序中處理溶液濃度爲50體積％， 處理溶液溫度爲30°C，及處理時間爲8秒。 在8號實驗中，在加入亞硫酸氫鈉作爲處理溶液之還 原劑時未蝕刻鉻膜。即，即使是在浸漬係藉由加入還原劑 以將形成於鉻膜表面上之氧化鉻膜還原而簡單地實行，不 實行任何還原氧化物膜之陰極電解還原程序時，仍無法蝕 刻鉻膜。 [實驗2 ] 在實驗2中，藉由改變實驗1之7號實驗之各種條件 而測試鉻膜之蝕刻狀態，更特別地證驗實驗1之7號實驗 之結果。第14圖顯示實驗2之結果。至於欲處理之材料， 使用藉由在一片聚醯亞胺帶上形成鉻膜及在此鉻膜上將銅 膜蝕刻成預定圖案而得之材料。 在第14圖右上角之「Cr剝落」行中，「0」表示將鉻 膜蝕刻。其係基於在各處理後是否可目視地證實聚醯亞胺 片而決定。 在1號實驗中，即使是在以1安培/ dm2之相當低電流 密度實行陰極電解還原處理時，亦將鉻膜蝕刻成預定圖案 。在2號實驗中，在將電流密度增至5安培/ dm2時，即， 在使電流密度比1號實驗高時，處理時間縮短。 在3至6號實驗中，即使是在以5體積％之相當低處理 溶液濃度實行浸酸處理及陰極電解還原處理時，亦將鉻膜 -39- 1243860 蝕刻成預定圖案。 在3至8號實驗中，在浸酸處理及陰極電解還原處理 中將處理溶液濃度增加時，處理時間縮短。其表示處理溶 液濃度與處理速度有關。 [實驗3] 在實驗3中，基於實驗1與實驗2之1號實驗，證驗 在陰極電解還原程序中含氯離子酸性處理溶液之影響下， 是否發生鉻膜表面上之鉻還原。更特別地，在陰極電解還 原程序中，陰極電解還原處理係藉由使用NaCl溶液作爲含 · 氯離子中性處理溶液代替含氯離子酸性處理溶液而實行。 然後藉由省略浸酸程序或藉由實行浸酸程序而測試鉻膜之 蝕刻狀態。第1 5圖顯示實驗3之結果。至於欲處理之材料 ，使用藉由在一片聚醯亞胺帶上形成鉻膜及在此鉻膜上將 銅膜蝕刻成預定圖案而得之材料。 在第15圖右上角之「Cr剝落」行中，鉻膜之蝕刻狀 態以「0」或「X」表示。「0」或「X」係基於在各處理後 是否可目視地證實聚醯亞胺片而決定。 ® 在1號實驗，鉻膜僅在實行使用NaCl溶液作爲含氯離 子中性處理溶液之陰極電解還原處理時未蝕刻。在2號實 . 驗中，比較作爲對照之1號實驗，在按此順序實行使用NaC 1 ^ 溶液作爲含氯離子中性處理溶液之陰極電解還原處理、及 使用K.K. MURATA製造之SAS之浸漬處理時，將鉻膜蝕刻 成預定圖案。 2號實驗顯示，即使是在實行使用含氯離子中性處理 一40- 1243860 m: ’ 理 時處 mil .111 理性 處酸 原子 還離 解氯 電含 極 僅 陰不 之， 液即 溶 。 理案 處圖 性定 酸預 子成 離刻 氯触 含膜 替絡 代將 液可 溶仍 溶液，含氯離子中性處理溶液亦可應用於陰極電解還原程 序。其大槪地表示，在處理溶液中鉻膜表面上之氧化鉻不 在含氯離子酸性處理溶液之影響下，而是在處理溶液中之 氫之影響下還原。 [實驗4 ] 在實驗4中，證驗陰極電解還原程序中處理溶液之pH 依附性。更特別地，在陰極電解還原程序中，陰極電解還 原處理係使用藉由將NaOH加入NaCl溶液作爲含氯離子中 性處理溶液代替酸性處理溶液，因而將此NaCl溶液之pH 變成5、7、9、與10而得之處理溶液實行。然後藉由實行 浸酸程序而測試鉻膜之蝕刻狀態。第1 6圖顯示實驗之結果 〇 至於欲處理之材料，使用藉由在一片聚醯亞胺帶上形 成鉻膜而得之材料。在第16圖右上角之「Cr剝落」行中， 鉻膜之蝕刻狀態以「0」或「X」表示。「〇」或「X」係基 於在各處理後是否可目視地證實聚醯亞胺片而決定。1至4 號實驗之結果顯示，不論pH爲中性或鹼性，均可以可靠地 蝕刻鉻膜。 [實驗5 ] 在實驗5中，藉由使用氫氯酸、硫酸、與中性NaCl溶 液作爲處理，偵測六價鉻是否存在於本發明化學處理方法 之處理溶液中。應注意，一般之火燄原子吸收光譜測定術 -41- 1243860 偵測包括三價鉻與六價鉻之鉻，及六價鉻係使用一般之二 (苯胺）脲偵測。至於欲處理之材料，使用藉由在一片聚 醯亞胺膜上形成鉻膜及在此鉻膜上將銅膜蝕刻成預定圖案 而得之材料。第17圖顯示實驗5之結果^ 參考第17圖，「鉻（D)」表示各處理溶液中之三價鉻 與六價鉻。 第17圖顯示’在氫氯酸、硫酸、與中性NaCl溶液中 均偵測到鉻。然而，雖然在硫酸中偵測到六價鉻，在氫氯 酸與N aC 1溶液中幾乎未或完全未偵測到六價鉻。在浸酸程 序中使用中性NaCl溶液作爲處理溶液時，鉻膜未蝕刻成預 定圖案。基於這些結果，實驗5顯示，在浸酸程序中使用 含氯離子酸性處理溶液作爲處理溶液時，幾乎未或完全未 製造六價鉻。 實例1與2現在解釋於下作爲上述化學處理方法之實 用例。 (實例1 ) 藉濺鑛將25微米厚聚醯亞胺膜之一個表面塗覆500埃 厚金屬鉻膜，然後以相同之方法塗覆1微米厚銅膜。然後 將塗覆這些鉻膜與銅膜之聚醯亞胺膜表面進一步塗覆7微 米厚銅膜，因而製備具8微米厚銅膜之膜載物帶。在此膜 載物帶上使用光阻劑乾膜因而形成鈾刻光阻劑膜，而藉預 定之方法形成預定之電路圖案。 繼而在下示條件（1 )下浸漬而蝕刻銅膜，因而得到具預 定電路圖案之膜載物帶。鉻膜之鉻未蝕刻而是保留成爲聚 -42- 1243860 醯亞胺膜表面上之殘渣。 (1 )蝕刻條件 飩刻溶液 ...A - p r 〇 c 浴溫 …50士 1 〇C pH • ••8 · 1 士8 銅濃度 …140土5 處理時間 …30秒 在鈾刻處理時 ，攪動鈾 然後在下示條件（2 )下 鉻膜表面還原。 (2)陰極電解還原處理條件 處理溶液 • ••SAS ( E 處理溶液濃度 …5 0毫5Ί 浴溫 ··· 30士 1 〇C 極性 …欲處理 電流密度 ...2安培 電解時間 …3秒 繼而在下示條件（3 )下 鉻。 (3 )浸酸處理條件 處理溶液 • ••SAS ( f 浴溫 • ••30 士 1°C 處理溶液濃度 ··· 5 0 0 毫 處理時間 …1 5秒 【·K. MURATA 製造） 升/公升 :ess(MeltexK.K·製造） _ ,5 克/公升 刻溶液同時搖動欲處理之材料。 ，藉鉻膜之陰極電解還原處理將 Φ :·Κ. MURATA 製造） 卜，公升 之材料爲陰極 /dm2 ，藉由實行浸酸處理蝕刻鉻膜之 -43- 1243860 (實例2 ) 依照如實例1之相同步驟實行處理，直到類似實例1 蝕刻聚醯亞胺膜之一個表面上之銅膜。如同實例1，在蝕刻 銅膜後，鉻膜之鉻未蝕刻而是保留成爲聚醯亞胺膜表面上 之殘渣。 其次，在下示條件（4)下，同時實行鉻膜之陰極電解還 原處理與浸酸處理。即，將陰極電解還原處理實行預定之 時間，同時將欲處理之材料浸於處理溶液中。結果，將鉻 膜表面還原，及鉻立即溶於處理溶液中且自聚醯亞胺膜去 除。即，在相同之程序中於處理溶液中將鉻膜表面還原及 蝕刻鉻膜。 (4)陰極電解還原處理與浸酸處理之條件 處理溶液 ."SAS ( K . K . MURATA製造） 處理溶液濃度…500毫升/公升 浴溫 ..·3 0±1°〇 處理時間 …1 5秒 極性 …欲處理之材料爲陰極 電流密度 ...2安培/ dm2 另外之優點及修改對熟悉此技藝者爲易知的。因此， 本發明在其廣義態樣中不受在此所示及所述之指定細節及 代表性具體實施例限制。因而可進行各種修改而不背離所 附·申請專利範圍及其等致物界定之一般發明槪念之精神及 範圍。 圖式簡單說明 一 4 4 一 1243860 加入且組成此說明書之一部份之附圖描述本發明現有 之較佳具體實施例，而且與上示之製造說明及下示之較佳 具體例之詳細說明一起用以解釋本發明之原理。 - 第1圖爲顯示經常作爲金屬底漆之金屬及這些金屬底 . 漆之特徵之列表； 第2A圖爲顯示以依照本發明具體實施例之化學處理方 法接受膜形成之材料之實例之切面圖； 第2B圖爲顯示以光阻劑塗覆之第2A圖所示材料之實 例之切面圖； · 第2C圖爲顯示第2B圖所示材料經光罩曝光之狀態之 實例之切面圖； 第2D圖爲顯示其上形成光阻劑圖案之材料之實例之切 面圖； 第2E圖爲顯示其上依照光阻劑圖案鈾刻銅膜之材料之 實例之切面圖； 第2F圖爲顯示其上由第2E圖所示狀態蝕刻鉻膜之材 料之實例之切面Η; ® 第2G圖爲顯示其上由第2F圖所示狀態去除光阻劑之 材料之實例之切面圖； . 第3A圖爲顯示陰極電解還原處理之原理之略示圖； 4 第3B圖爲顯示陰極電解還原處理之原理之略示圖； 第3C圖爲顯示浸酸處理之原理之略示圖； 第4圖爲顯示酸電解處理之原理之略示圖； 第5圖爲顯示垂直進料型化學處理裝置之實例之略示 -45- 1243860 側切面圖； 第6圖爲顯示形成第5圖所示化學處理裝置之陰極電 解還原裝置之略示前切面圖； 第7圖爲顯示化學處理裝置之實例之略示側切面圖； 第8圖爲顯示水平進料型化學處理裝置之實例之略示 側切面圖； 第9圖爲顯示化學處理裝置之實例之略示側切面圖； 第10圖爲顯示陰極電解還原裝置之實例之縱向側切面 圖； 第1 1圖爲顯示浸酸裝置之實例之縱向側切面圖； 第12圖爲顯示化學處理裝置之電解裝置之實例之縱向 側切面圖； 第13圖爲顯示在依照此化學處理方法之各處理中改變 處理條件時，銅膜與鉻膜蝕刻狀態之測試結果之列表； 第14圖爲顯示在改變第13圖所示之實驗7之各條件 時，鉻膜蝕刻狀態之測試結果之列表； 第15圖爲顯示進行以檢查在陰極電解還原程序時，在 含氯離子之酸性處理溶液影響下，在鉻膜表面上是否發生 鉻還原之測試之結果之列表； 第16圖爲顯示進行以檢查在陰極電解還原程序時，鉻 膜是否被處理溶液蝕刻之pH依附測試之結果之列表；及 第17圖爲顯示進行以檢查在使用氫氯酸、硫酸、與NaCl 溶液作爲處理溶液時，在浸酸程序中六價鉻是否存在於處 理溶液中之測試之結果之列表。 -46- 1243860 元件符號說明 1 支撐台 2 杯 2a 對齊突起 3 吸入路徑 3a 導管 3b 吸入孔 4 陽極電極 5 陽極 6 封鎖片 7 陰極電極 8 陰極 9 引導環 9a 對齊凹口 9b 傾斜連接表面 10 0-環 12 處理溶液 13 槽 14 泵 15 供應路徑 16 排洩路徑 17 放拽閥 18 回位路徑 19 電源The acid pickling device 53 has a processing bath 53a containing a processing solution 53b. The treatment and solution 53b is an acidic treatment solution, and is preferably an acidic treatment solution containing a halogen ion (such as chloride ion). An example of this acidic treatment solution is K. K.  MURAT A -23- 1243860 SAS. Both ends of the flow tube 53c are connected to the bottom of the processing bath 53a. The pump 53d, the heat exchanger 5 3e, and the filter 5 3 f are arranged in the middle of the flow tube 5 3 c. When the pump 5 3 d is operated, the processing solution 5 3 b in the processing bath 5 3 a flows through the flow tube 53c and returns to the processing bath 53a through the heat exchanger 53e and the filter 53f. In the acid pickling device 53, a circulation system of such a treatment solution 53b is formed. The four feeding rollers 532, 5311, 53b, and 53 "are arranged above the processing bath 53 &. That is, the feed rollers 53g and 53h are paired on the upstream side in the feeding direction of the carrier tape C3, and the feed rollers 5 3i and 5 3j are paired on the downstream side. In the processing bath 5 3 a, a feeding roller 531 for changing the feeding direction of the carrier tape C3 is set. The carrier tape C3 is sandwiched between the feed rollers 53g and 53h, wound around the feed roller 531 in the processing bath 53a, and sandwiched between the feed rollers 53i and 53j. The rinsing device 54 has the same configuration as the rinsing device 52. That is, the treatment bath 54a containing the deionized water 54b. The circulation system composed of the flow tube 54c, the pump 54d, the heat exchanger 54e, the filter 54f, and the processing bath 54a has the same configuration as the decanting device 52. The feeding system consisting of the four feeding rollers 54g, 54h, 54i above the processing bath 54a, and 54j and the feeding roller 541 in the processing bath 54a has the same configuration as the cleaning device 52. ® In the treatment baths 51a, 52a, 53a, and 54a of the devices 51, 52, 53, and 54, the solutions 51b, 52b, 53b, and 54b are borrowed by agitators (not shown.  ) And so on. The operation of the chemical processing device 50 is explained below. When the feeding roller including the electrode rollers 51g and 51h is rotated in a predetermined direction, the carrier tape C3 is fed in a feeding direction from a feeding device (not shown), and the processing baths 51a to 54a passing through the devices 51 to 54 The winding device winds up. _ 2 4-1243860 As shown in Figure 8, when viewed from the side, the carrier tape c 3 is fed in a zigzag pattern. The following processing is performed in the devices 51 to 54. In the cathode electrolytic reduction device 51, the processing bath 51a is filled with a processing solution 51b, and a voltage is applied between the electrode rolls 51g and 51h and between the electrodes 51m and 5 1 η. In this state, the carrier tape C3 is subjected to a cathodic electrolytic reduction treatment while passing through the processing bath 5 1 a. That is, outside the processing bath 51a, the electrode rollers 51g and 51h contact the surface of the carrier tape C3 on which a metal film is formed. Therefore, under the influence of the electrodes 51m and 51η, the chromium oxide film formed on the surface of the chromium film is reduced. In the cleaning device 52, the processing bath 52a is filled with deionized water 52b, and the carrier tape C3 is rinsed with deionized water 52b when passing through the processing bath 52a. In the acid pickling device 5 3, the treatment bath 5. 3 a is the treatment solution 5 3 b, and the carrier tape C3 is subjected to the pickling treatment while passing through the treatment bath 53a. That is, the carrier tape C3 is fed by immersing in the processing solution 53b of the processing bath 53a, and the chromium film is etched into a predetermined pattern. In the rinsing device 54, the treatment bath 54a is filled with deionized water 54b, and the carrier tape C3 is rinsed with deionized water 54b when passing through the treatment bath 54a. The carrier tape C3 washed by the washing device 54 is dried by a drying device (not shown) and wound up by a winding device (not shown). By the above operation, the chromium film formed on the carrier tape C3 can be etched into a predetermined pattern. It also prevents the production of hexavalent chromium. [Application Example 4] Application Example 4 uses an apparatus in which the above-mentioned second chemical processing method is used, and it is a horizontal feed type chemical processing apparatus similar to Application Example 3. Page 9 -25- 1243860 The figure is a schematic side sectional view showing an example of this chemical treatment device. As shown in Fig. 9, the chemical processing device 60 includes an electrolytic device 61 for performing acid electrolysis treatment of the carrier tape C4, and a washing device 62 for washing the carrier tape C4. In the chemical processing device 60, similar to the chemical processing device 50 shown in FIG. 8, the feeding device and the winding device (neither shown) are arranged in the electrolytic device 61 and the washing device 62 shown in FIG. Both ends. The electrolytic device 61 includes a processing bath 61a containing a processing solution 61b. The treatment solution 61b is an acidic treatment solution containing a halide ion, and preferably a treatment solution containing a chloride ion, such as K. K.  SAS manufactured by MURAT A. The electrolytic device 61 has a circulation system similar to the cathode electrolytic reduction device 51 shown in FIG. That is, the processing solution 61b is circulated among the individual components by a circulation system composed of the supply pipe 61c, the pump 61d, the heat exchanger 61e, the filter 6 1 f, and the processing bath 6 1 a. The electrode roller 61g is placed above the processing bath 61a and connected to the negative electrode of the power source 61i. A support roller 61h supporting the electrode roller 61g is placed below the electrode roller 61g. The electrode roller 61g and the support roller 61h are arranged on the upstream side of the carrier tape C4 in the feeding direction. Two adjacent feed rollers 6 1 j and 6 1 k are arranged on the downstream side in the feeding direction of the carrier tape C4. In the processing bath 61a, a feeding roller 611 for changing the feeding direction of the carrier tape C4 is set. The carrier tape C4 is sandwiched between the electrode roller 61g and the support roller 61h, and the feed roller 611 is wound in the processing bath 61a, and is sandwiched between the electrode roller 61j and the support roller 61k. The surface of the carrier tape C4 on which the metal film was formed contacted the electrode roller 61 g. The electrode 61m is a positive electrode placed in the processing bath 61a and connected to a power source 61i. It should be noted that, in the processing bath 61a, before the carrier tape C4 reaches the feed roller 611, the electrode 61m is opposed to the surface of the carrier tape C4 on which a metal film is formed. -26- 1243860 The cleaning device 62 has the same configuration as the cleaning device 52 shown in FIG. That is, the processing bath 62a contains deionized water 62b. A circulation system composed of a flow tube 62c, a pump 62d, a heat exchanger 62e, a filter 62f, and a processing bath 62a, and four feed rollers 62g, 62h, 62i, and 62j, and a processing bath above the processing bath 62a The feeding system composed of the feeding roller 621 inside 62a has the same configuration as the aforementioned washing device 52. The operation of the chemical processing device 60 is explained below. When the feeding roller including the electrode roller 61g is rotated in a predetermined direction, the carrier tape C4 is fed in the feeding direction from the feeding device, and the processing baths 61a and 62a passing through the devices 61 and 62 are taken up by the winding device. As shown in Fig. 9, when viewed from the side, the carrier tape C4 is fed in a zigzag manner. The following processing is performed in the devices 61 and 62. In the electrolytic device 61, the processing bath 61a is filled with a processing solution 61b, and a voltage is applied between the electrode roller 61g and the electrode 61m. In this state, the carrier tape C4 is subjected to an acid electrolytic treatment when passing through the processing bath 61a. That is, outside the processing bath 61a, the electrode roller 61g contacts the surface of the carrier tape C4 on which a metal film is formed. Therefore, under the influence of the electrode 61m, the chromium oxide film formed on the surface of the chromium film is reduced when it faces the electrode 61m. Since the chromium film is immersed in the processing solution 61b, the chromium film is etched into a predetermined pattern with the processing solution 61b. In the decontamination apparatus 62, the treatment bath 62a is filled with deionized water 62b, and the carrier tape C4 is decontaminated with deionized water 62b when passing through the treatment bath 62a. The carrier tape C4 washed with the washing device 62 is dried by a drying device (not shown) and wound up by a winding device (not shown). 1243860 By the above operation, a predetermined pattern of the chromium film formed on the carrier tape C4 can be etched. It also prevents the production of hexavalent chromium. [Application Example 1] to [Application Example 4] The treatments of the carrier tapes Cl, C2, C3, and C4 each having a metal film formed on the surface are disclosed. However, a carrier tape with a metal film on both sides can also be treated in the same way as above. In a treatment bath filled with a treatment solution, the electrode is opposite the surface of the carrier tape and is connected to the positive electrode of electricity. In the cathode electrolytic reduction device 31 of [Application Example 1], the cathode electrolysis treatment is performed in a treatment bath 31b filled with a treatment solution 31h. In addition to this configuration, a shower nozzle connected to the supply pipe can also be installed in the internal processing bath 31b, so that the shower nozzle faces the carrier tape C1 to form a metal surface, and the treatment solution 31h is sprayed from the shower nozzle to the carrier tape C1. Similar to the cathode electrolysis Liaoyuan device 31, the acid immersion device 33 can also be equipped with a shower nozzle in the bath 33b, and spray the treatment solution 33h from the shower to the carrier belt C1. If the metal film is formed on both surfaces of the carrier tape C1, the bath nozzles are installed on the physical baths 31b and 33b of the cathode electrolytic reduction device 31 and the acid pickling device 33 and face the two surfaces of the carrier tape C1. And spray the liquid 31h and 33h from these shower nozzles to the carrier tape C1. Further, in the cathode electrolytic reduction device 51 of [Application Example 3], the electrolytic reduction treatment is performed by treating the bath 51a with the treatment solution 51b filled therein. However, in addition to this configuration, a shower nozzle of the connecting pipe 51c can also be installed in the internal processing bath 51a, so that the shower nozzle faces the surface of the carrier tape with the C3-shaped film, and the treatment solution 51b is sprayed from the shower nozzle to the carrier ^ Carved into tables. The nozzles inside the 31c membrane will supply the solution processing cathode into gold ψ C3 -28-1243860 similar to the cathode electrolytic reduction device 51, and the acid immersion device 51 can also be installed in the treatment bath 53a. The shower nozzle, and the treatment solution 53b is sprayed from the shower nozzle toward the carrier tape C3. If the metal film is formed on the two surfaces of the carrier tape C3, the shower nozzles are installed on the processing baths 51a and 53a of the cathode electrolytic reduction device 51 and the acid pickling device 53 and face the two surfaces of the carrier tape C3. And spray the treatment solutions 51b and 53b from these shower nozzles to the carrier tape C3. [Application Example 5] Application Example 5 relates to the use of the first chemical processing method described above, and a chemical processing apparatus used when a metal film formed on a semiconductor wafer is etched into a predetermined pattern. This chemical processing device includes a cathode electrolytic reduction device for performing cathodic electrolytic reduction treatment of a metal film on a semiconductor wafer, and an acid pickling device for performing pickling treatment of a metal film on a semiconductor wafer after the cathodic electrolytic reduction device. First, the cathode electrolytic reduction device is explained below. Fig. 10 is a longitudinal sectional view showing an example of the cathode electrolytic reduction device 71. As shown in FIG. 10, the cup 2 is placed on the supporting table 1. The lower part of the cup 2 is opened, and the cup 2 is mounted on the supporting table 丨 with the open surface facing downward. The support table 1 is vertically movable, and the cup 2 is fixed to the device body. Therefore, the support table 1 moves up and down and the cup 2 is fixed to the apparatus main body. The suction path 3 is formed in the support table 1. The suction path 3 is connected to a suction tool such as a vacuum pump (not shown) through a conduit 3a below the suction path 3. In the upper portion of the support table 1, a large number of suction holes 3b facing upward are formed. The surface surrounding the suction hole 3 b is inclined from the top to the outside, thereby forming an inclined connection surface la on the supporting table 1. When the cup 2 is joined, the inclined connection surface la connects the inclined connection surface 9b (described later) of the guide ring 9, thereby effectively aligning the support table 丨 with the cup 2. The mesh anode electrode 4 is formed in the upper portion inside the cup 2. The anode electrode 4 is connected to the anode 5 of the power source 19. In the lower part of the cup 2, a circular plate-shaped blocking piece 6 made of plastic fluorinated rubber is formed to surround the open surface of the cup 2. On the lower surface of the blocking sheet 6, three plate-like cathode electrodes 7 are formed. The cathode electrodes 7 are equally spaced, that is, at 120. The center angle is separated, and the cathode of the power source 19 is connected. The guide ring 9 is overlapped and integrated under the blocking piece 6. In the lower part of the cup 2, the alignment protrusions 2a are formed at three equally spaced portions, that is, separated by a central angle of 120 °. The alignment holes 6a are formed in the blocking piece 6 in a one-to-one correspondence with the alignment protrusions 2a, the alignment holes 7a are formed in the cathode electrode 7, and the alignment notches 9a are formed on the upper portion of the guide ring 9. The alignment protrusions 2a extend through the alignment holes 6a and 7a and connect the alignment notches 9a, thereby fixing the blocking piece 6 and the cathode 7 to the cup 2. An inclined connection surface 9b inclined from the top to the outside is formed on the inner edge of the guide ring 9. The inclined connection surface 9b is connected to the inclined connection surface 1a of the support table 1. When the cup 2, the blocking sheet 6, the cathode electrode 7, and the guide ring 9 are integrated, the cathode electrode 7 is exposed within the guide ring 9 for about 3 to 4 mm, and the rest is completely covered by the blocking sheet 6 and the guide ring 9. Therefore, only the end portion of each cathode electrode 7 contacts the treatment solution 12 and the rest does not contact the treatment solution 12 at all. The 0-ring 10 is inserted between the lower surface of the guide ring 9 and the -30-1243860 of the support table 1. The semiconductor wafer W1 is supported on the support table 1, and the edge of the semiconductor wafer W1 is clamped between the blocking piece 6 and the support table 1. In addition, the semiconductor wafer W1 is connected to a terminal portion of each cathode electrode 7 via a connection terminal (not shown). The tank 13 contains the processing solution 12 flowing into the cup 2. The treatment solution 12 is one of an acidic treatment solution containing an acid group and a basic treatment solution containing a halogen ion. Preferably, the treatment solution 12 is a chloride-containing treatment solution, such as K. K.  S AS manufactured by MURATA. A pump 14 for pumping the treatment solution 12 from the tank 13 is located above the tank 13. The supply path 15 is formed between the pump 14 and the lower part of the cup 2. The processing solution 12 pumped from the tank 1 3 by the pump 14 flows into the cup 2 through the supply path 15. The excretion path 16 is formed in a substantially central portion of the upper portion of the cup 2. Outside the cup 2, a drain valve 17 is connected to the drain path 16. The return path 18 is branched from the path between the drain path 16 and the drain valve 17 and the connection groove 13. The pickling device is described below. FIG. 11 is a longitudinal side sectional view showing an example of the acid pickling device 72. FIG. As shown in FIG. 11, the cup 82 is formed on the support stand 81. The lower part of the cup 82 is opened, and the cup 82 is mounted on the supporting table 8 1 with this open surface downward. In the lower part of the cup 82, a circular plate-shaped locking piece 6 (not shown) made of plastic fluorinated rubber is formed to surround the open surface of the cup 82. The support table 81 is vertically movable, and the cup 82 is fixed to the apparatus main body. Therefore, the support table 81 moves up and down and the cup 82 is fixed to the apparatus main body. The suction path 83 is formed in the support stand 81. The suction path 83 is connected to a suction tool, such as a vacuum pump (not shown -31-1243860) via a conduit 83a below the suction path 83. In the upper portion of the support table 81, a large number of upwardly directed suction holes 83b are formed. All the suction holes 83 b are covered by the cup 82. The 0-ring 84 is inserted between the lower part of the cup 82 and the supporting table 81. The semiconductor wafer W1 is clamped between the lower part of the cup 82 and the support table 81. The groove 85 is located below the cup 82. The tank 85 contains the processing solution 86 flowing into the cup 82. The processing solution 86 is an acidic processing solution, for example, an acidic processing solution containing a halogen ion, and preferably a chloride ion. A preferred example of this acidic treatment solution is K. K.  Murata's SAS. A pump 87 for pumping the processing solution 86 from the tank 85 is located above the tank 85. The supply path 88 is formed between the pump 87 and the cup 82. The processing solution 86 pumped from the tank 85 by the pump 87 flows into the cup 8 2 through the supply path 8 8. An excretion path 89 is formed in a substantially central portion of the upper portion of the cup 82. Outside the cup 82, a drain valve 90 is connected to the drain path 89. The return path 91 is separated from the path between the drain path 89 and the drain valve 89, and the connection tank 85. The operation of the cathode electrolytic reduction device 71 and the acid leaching device 72 shown in Figs. 10 and 11 is explained below. First, in the cathode electrolytic reduction device 71, the support table 1 and the cup 2 are separated by moving the support table 1 down from the cup 2. The semiconductor wafer wi is then fixed on the support surface of the support table 1 'so that the metal film formed on the semiconductor wafer W1 faces upward. The suction tool of the connection duct 3a is operated to apply suction to the suction hole 3b, and the semiconductor wafer W1 is fixed on the support table 1 by suction. -32-1243860 Then when the semiconductor wafer wi is so fixed, the '-ring i0' support table 1 is moved up to connect the inclined connection surface la of the support table 1 and the inclined connection surface 9b of the guide 9, thereby making the support table 1 Align with cup 2. In this way, the inside of the cup 2 is completely sealed by the lower surface of the blocking piece 6 and the O-ring 10. In this state, the edge of the semiconductor wafer W1 is in close contact with the surface of the blocking piece 6, and the metal film on the semiconductor wafer W1 is connected to the cathode electrode 7. The pump 14 is then driven to supply the treatment solution 12 from the tank 13 to the cup 2 via the supply path 15. As a result, the processing solution 12 flows into the cup 2 from above the semiconductor wafer, and accumulates in the cup 2 over time. At this stage ', the drain valve 17 is still closed, and the air in the cup 2 is discharged into the tank 13 and then to the outside through the drain path 16 and the return path 18, so no air remains in the pipe system. Similar to the internal air of Cup 2, the gas generated on the surface of the semiconductor wafer W1 is also exhausted to the outside. When the anode electrode 4 is completely immersed in the processing solution 12 flowing into the cup 2, and the processing solution 12 reaches the return path 18 through the drain path 16, the cathode electrolytic reduction treatment of the semiconductor wafer W1 is performed. That is, a current is supplied between the anode electrode and each cathode electrode 7 by a power source 19 for a predetermined time, so that the chromium film on the semiconductor wafer W1 becomes a cathode. As a result, the chromium film undergoes electrolytic reduction in the processing solution 12. Therefore, the chromium oxide film formed on the surface of the chromium film is restored. The cathode electrolytic reduction process is completed after a predetermined time is applied to the current. 16 and 18 of the return path were exposed to gas. As a result, the treatment solution 12 in the return path 18 is collected to the tank 13 through the return path. Since the tank 1 3 is located below the cup 2, via the rm of the supply path 1 5 this lock way W1 discharges the road surface body 4 in the body. The original size is 18 and -33-1243860. The pump 1 4 also puts the processing solution in the cup 2 1 2 Collect to tank 1 3. Then, the supporting table 1 is moved down to release the semiconductor wafer W1 fixed to the supporting surface by suction. In this way, the cathodic electrolytic reduction treatment of the cathodic electrolytic reduction device 71 is completed. Then, the semiconductor wafer W1 is transferred to a cleaning device (not shown) by a transfer tool (not shown) such as a transfer robot, and is cleaned by the cleaning device . When the rinsing process is completed, the semiconductor wafer W1 is transferred to the acid pickling device 72 shown in FIG. In the acid pickling device 72, the support table 81 and the cup 82 are separated by moving the support table 81 down from the cup 82. The semiconductor wafer W1 is fixed on the supporting surface of the support table 81 so that the metal film formed on the semiconductor wafer W1 faces upward. The suction tool of the connection duct 83a is operated to apply suction to the suction hole 83b, so that the semiconductor wafer W1 is fixed on the support table 81 by suction. Then, when the semiconductor wafer W1 is so fixed, the support table 81 provided with the 0-ring 84 is moved up to align the support table 81 with the cup 82. In this way, the inside of the cup 82 is completely blocked. The pump 87 is then driven to supply the processing solution 86 from the tank 85 into the cup 82 via the supply path 88. As a result, the processing solution 86 flows into the cup 82 from above the semiconductor wafer W1 and accumulates in the cup 82 with Shijian. At this stage, the bleed valve 90 is still closed, and the air in the cup 82 is discharged into the tank 85 and then to the outside through the bleed path 89 and the return path 91, so no air remains in the piping system. Like the internal air of the cup 82, the gas generated on the surface of the semiconductor wafer W1 is also exhausted to the outside. When a predetermined amount of the processing solution 86 is accumulated in the cup 82, the supply of the processing solution 86 from the tank 85 1243860 is stopped, and the pickling treatment of the semiconductor wafer W1 is performed. That is, the semiconductor wafer W1 is immersed in the processing solution 86 in the cup 82 for a predetermined time. As a result, the chromium film on the semiconductor wafer W1 is etched into a predetermined pattern. Then, the drain valve 90 is opened so that the drain path 89 and the return path 91 are exposed to the atmosphere. As a result, the processing solution 86 in the return path 91 is collected to the tank 85 through the return path 91. Since the tank 85 is located below the cup 82, the processing solution 86 in the cup 82 is also collected to the tank 85 via the supply path 88 and the pump 87. Then, the supporting table 81 is moved down to release the semiconductor wafer W1 fixed to the supporting surface by suction. In this way, the acid pickling treatment of the acid pickling device 72 is completed. With the above operations, the chromium film formed on the semiconductor wafer W1 can be etched into a predetermined pattern. It also prevents the production of hexavalent chromium. [Application Example 6] Application Example 6 relates to an example of a chemical processing device using the aforementioned second chemical processing method, and a chemical processing device such as Application Example 5 for etching a metal film on a semiconductor wafer into a predetermined pattern. Fig. 12 is a schematic cross-sectional view showing an example of the electrolytic device 80 of the chemical processing device. The electrolytic device 80 has substantially the same configuration and function of the cathode electrolytic reduction device 71 as shown in FIG. Therefore, the same reference numerals of the cathode electrolytic reduction device 71 as shown in Fig. 10 indicate the same parts in the electrolytic device 80, and the explanation thereof is omitted. The operation of the electrolytic device 80 is also described briefly below. In the electrolytic device 80 shown in FIG. 12, the tank 13 contains a treatment solution 95, which is an acidic treatment solution containing a halogen ion, preferably a chlorine ion-containing treatment solution, such as K.  K.  SAS manufactured by MURAT A. The operation of the electrolytic device 80 is described below. -35-1243860 That is, similarly to the cathode electrolytic reduction device 71 shown in FIG. 10, the semiconductor wafer W2 is fixed at a predetermined position in the electrolytic device 80, the supporting table 1 and the cup 2 are integrated, and the processing solution 95 is supplied to the cup. 2 in. When a predetermined amount of the processing solution 95 is accumulated in the cup 2, the acid electrolytic treatment of the semiconductor wafer W2 is performed. More specifically, an electric current is supplied between the anode electrode 4 and each cathode electrode 7 by a power source 19 for a predetermined time, so that electrolytic reduction of the chromium film (cathode) of the semiconductor wafer W2 is performed in the processing solution 95. That is, the chromium oxide film formed on the surface of the chromium film is reduced. Then the power from the power source 19 is stopped. The semiconductor wafer W2 is kept immersed in the acidic processing solution 95 by maintaining this state. As a result, the chromium film on the semiconductor wafer W2 is etched into a predetermined pattern. Then, the processing solution 95 is collected to the tank 85, and the semiconductor wafer W2 fixed to the support table 81 by suction is released, thereby completing the acid electrolytic treatment of the electrolytic device 80. By the above operations, the chromium film formed on the semiconductor wafer W2 can be etched into a predetermined pattern. It also prevents the production of hexavalent chromium. In the first and second chemical processing methods and apparatus explained in the above [Application Example 1] to [Application Example 6], the chromium film on the carrier tape or the semiconductor wafer can be etched into a predetermined pattern. These chemical processing methods and chemical processing devices are similarly applicable to the formation of wire patterns, bumps, etc. on various substrates (such as carrier tapes and elastic substrates). This method and device can also be applied to the formation of circuit patterns on semiconductor wafers (for example, made of silicon), such as ICs and LSIs. This method and apparatus are particularly applicable to the technical field in which a chromium film formed on a material is etched into a predetermined pattern. 1243860 In the device described in [Application Example 1] to [Application Example 6], the chromium film is etched. However, even when using titanium, tungsten, palladium, molybdenum, and alloys containing at least one of chromium, titanium, tungsten, palladium, and molybdenum, the devices of [Application Example 1] to [Application Example 6] can be used These metals are etched into a predetermined pattern. As for the alloy, nickel-chromium alloy is preferably used. The first and second chemical processing methods are also applicable not only to metal films formed on a tape (such as a carrier tape), but also to metal films formed on a sheet. In this case, each process need only be performed in a batch manner as explained in [Application Example 5] and [Application Example 6]. In addition, in the devices described in [Application Example 1] to [Application Example 6], a separation film may be formed between the processing solution circulation system and the supply system. In this case, even if hexavalent chromium is produced when the chromium film is etched, the separation film prevents this hexavalent chromium from flowing out with the waste liquid when collecting the processing solution. Next, the various tests performed by the present inventors on the above-mentioned first and second chemical treatment methods are explained in [Experiment 1] to [Experiment 4], and the results and considerations of each test are explained. [Experiment 1] In Experiment 1, the copper film was tested by changing the copper wet etching treatment, the cathodic electrolytic reduction treatment, and the acid dipping treatment according to the above-mentioned chemical treatment method, and by changing various conditions of these treatments. Etching state with chromium film. Figure 13 shows the results of Experiment 1. Referring to Fig. 13, a material obtained by forming a chromium film and a copper film on a polyimide tape in this order was used as a test material for Experiments 1 and 2. A material obtained by forming a chromium film on a piece of polyimide tape and engraving the copper film age into a predetermined pattern on this chromium film was also used as the test material for Nos. 3 to 8-1243860. In Fig. 13, "simultaneous (A)" indicates that the copper wet etching treatment and the acid immersion treatment are performed using the same treatment solution without performing any cathode electrolytic reduction treatment. "Individual (B)" means that the copper wet etching treatment and the cathodic electrolytic reduction treatment and / or the pickling treatment are performed individually, that is, the cathodic electrolytic reduction treatment and / or the pickling treatment are performed after the copper wet etching treatment. "Anodic electrolytic oxidation (C)" means that the chromium film is oxidized by using the material to be treated as an anode, and electrolytic oxidation is performed in a predetermined processing solution instead of the cathodic electrolytic reduction treatment. In the rows of "Cu peeling" and "Cr peeling" in the upper right corner of Fig. 13, the etching state of the copper film and the chromium film is indicated by "0" or "X". "〇" or "X" is determined based on whether the polyimide sheet can be visually confirmed after each treatment. ○ In experiments 1 and 2, the copper film was etched into a predetermined pattern, but the chromium film was not. This means that even when the copper wet etching treatment and the acid leaching treatment are performed simultaneously by using the same processing solution, the chromium film cannot be etched into a predetermined pattern simultaneously with the copper film. In experiments Nos. 3 to 6, when leaching, anodic electrolytic oxidation, and cathodic electrolytic reduction were performed independently, the chrome film was not etched by uranium. In the experiment No. 7, the chromium film was etched when the test material was subjected to a cathodic electrolytic reduction treatment and an acid pickling treatment. More specifically, when electrolytic reduction is performed using a test material as a cathode in a SAS manufactured by K · K · MURATA as a chloride-containing treatment solution, the chromium film is etched into a predetermined pattern, and the material is immersed in the same treatment solution. in. It should be noted that the conditions of Experiment No. 7 "Processing solution concentration (vol%) 50/50", "Current density (Amp / dm2) 5 /", "Temperature (° C) 3 0/30", and "Time (seconds) 2/8 and 5/8" -38-1243860 means that the concentration of the processing solution is 50% by volume, the current density is 5 amps / dm2, the temperature of the processing solution is 30 ° C, and The time was 2 and 5 seconds, and the concentration of the treatment solution in the pickling process was 50% by volume, the temperature of the treatment solution was 30 ° C, and the treatment time was 8 seconds. In experiment No. 8, the chromium film was not etched when sodium bisulfite was added as a reducing agent for the treatment solution. That is, even if the immersion system is simply implemented by adding a reducing agent to reduce the chromium oxide film formed on the surface of the chromium film, the chromium film cannot be etched without performing a cathodic electrolytic reduction procedure of a reduced oxide film. [Experiment 2] In Experiment 2, the etching state of the chromium film was tested by changing various conditions of Experiment No. 7 in Experiment No. 1, and the results of Experiment No. 7 in Experiment No. 1 were more specifically verified. Figure 14 shows the results of Experiment 2. As a material to be processed, a material obtained by forming a chromium film on a piece of polyimide tape and etching a copper film into a predetermined pattern on the chromium film is used. In the "Cr peeling" line in the upper right corner of Fig. 14, "0" indicates that the chromium film is etched. It is determined based on whether or not the polyimide tablet can be visually confirmed after each treatment. In Experiment No. 1, the chrome film was etched into a predetermined pattern even when the cathode electrolytic reduction treatment was performed at a relatively low current density of 1 amp / dm2. In the experiment No. 2, when the current density was increased to 5 amps / dm2, that is, when the current density was made higher than the experiment No. 1, the processing time was shortened. In experiments Nos. 3 to 6, the chrome film -39-1243860 was etched into a predetermined pattern even when the leaching treatment and the cathodic electrolytic reduction treatment were performed at a concentration of a relatively low processing solution of 5 vol%. In experiments Nos. 3 to 8, when the concentration of the treatment solution was increased in the soaking treatment and the cathodic electrolytic reduction treatment, the treatment time was shortened. It indicates that the processing solution concentration is related to the processing speed. [Experiment 3] In Experiment 3, based on Experiment No. 1 and Experiment No. 1, it was verified whether the reduction of chromium on the surface of the chromium film occurred under the influence of the acid treatment solution containing chloride ions in the cathodic electrolytic reduction procedure. More specifically, in the cathodic electrolytic reduction process, cathodic electrolytic reduction treatment is performed by using a NaCl solution as a chloride ion-containing neutral treatment solution instead of a chloride ion-containing acidic treatment solution. The etching state of the chromium film is then tested by omitting the pickling process or by performing the pickling process. Figure 15 shows the results of Experiment 3. As for the material to be processed, a material obtained by forming a chromium film on a piece of polyimide tape and etching the copper film into a predetermined pattern on the chromium film is used. In the "Cr peeling" line in the upper right corner of Fig. 15, the etching state of the chromium film is indicated by "0" or "X". "0" or "X" is determined based on whether the polyimide tablet can be visually confirmed after each treatment. ® In Experiment No. 1, the chromium film was not etched only during the cathodic electrolytic reduction treatment using a NaCl solution as a neutral ion-containing treatment solution. On the 2nd.  In the test, the experiment No. 1 as a control was compared, and in this order, a cathodic electrolytic reduction treatment using a NaC 1 ^ solution as a neutral treatment solution containing chloride ions was performed, and K was used. K.  In the immersion treatment of SAS manufactured by Murata, a chromium film is etched into a predetermined pattern. Experiment No. 2 shows that even in the implementation of neutral treatment using chloride ions, a 40- 1243860 m: ’time mil. 111 Reasonably, the acid atom also dissociates the chlorine, and the electrode contains only yin, but the liquid dissolves. The solution of the plan is to determine the acid preion formation and ionization. Chlorine contact with the membrane, replace the solution with soluble solution, and the chloride-containing neutral treatment solution can also be used in the cathodic electrolytic reduction process. It states that the chromium oxide on the surface of the chromium film in the treatment solution is not reduced under the influence of the chloride ion-containing acidic treatment solution, but is reduced under the influence of hydrogen in the treatment solution. [Experiment 4] In Experiment 4, the pH dependence of the treatment solution in the cathodic electrolytic reduction procedure was verified. More specifically, in the cathodic electrolytic reduction process, the cathodic electrolytic reduction treatment uses the addition of NaOH to the NaCl solution as a neutral treatment solution containing chloride ions instead of the acidic treatment solution, so the pH of this NaCl solution becomes 5, 7, 9 The treatment solution obtained with 10 was carried out. The etch state of the chromium film was then tested by performing an immersion acid procedure. Figure 16 shows the results of the experiment. As for the material to be treated, a material obtained by forming a chromium film on a polyimide tape was used. In the "Cr peeling" line in the upper right corner of Fig. 16, the etching state of the chromium film is indicated by "0" or "X". "0" or "X" is determined based on whether or not the polyimide tablet can be visually confirmed after each treatment. The results of experiments Nos. 1 to 4 show that the chromium film can be reliably etched regardless of whether the pH is neutral or alkaline. [Experiment 5] In Experiment 5, by using hydrochloric acid, sulfuric acid, and a neutral NaCl solution as treatments, it was detected whether hexavalent chromium was present in the treatment solution of the chemical treatment method of the present invention. It should be noted that the general flame atomic absorption spectrometry -41-1243860 detection includes chromium of trivalent and hexavalent chromium, and hexavalent chromium is generally detected using aniline (aniline) urea. As a material to be processed, a material obtained by forming a chromium film on a polyimide film and etching a copper film into a predetermined pattern on the chromium film is used. Fig. 17 shows the results of Experiment 5. Referring to Fig. 17, "Cr (D)" indicates trivalent chromium and hexavalent chromium in each treatment solution. Figure 17 shows that chromium was detected in hydrochloric acid, sulfuric acid, and neutral NaCl solutions. However, although hexavalent chromium was detected in sulfuric acid, almost no or no hexavalent chromium was detected in the solution of hydrochloric acid and NaCl. When a neutral NaCl solution was used as the treatment solution in the acid leaching process, the chromium film was not etched into a predetermined pattern. Based on these results, Experiment 5 showed that almost no or no hexavalent chromium was produced when using a chloride ion-containing acidic treatment solution as the treatment solution in the pickling process. Examples 1 and 2 are now explained as practical examples of the above-mentioned chemical treatment method. (Example 1) One surface of a 25 micron thick polyimide film was coated with a 500 angstrom metal chromium film by sputtering, and then a 1 micron copper film was coated in the same manner. Then, the surface of the polyimide film coated with these chromium and copper films was further coated with a copper film of 7 micrometers thick, thereby preparing a film carrier tape with a copper film of 8 micrometers thick. A photoresist dry film is used on this film carrier tape to form a uranium-etched photoresist film, and a predetermined circuit pattern is formed by a predetermined method. Then, the copper film was immersed and etched under the condition (1) shown below to obtain a film carrier tape having a predetermined circuit pattern. The chromium of the chromium film is not etched but remains as a residue on the surface of the poly-42-1243860 sulfonimide film. (1) Etching conditions Etching solution. . . A-pr 〇c bath temperature… 50 ± 10 ° C pH • •• 8 · 1 ± 8 copper concentration… 140 ± 5 processing time… 30 seconds during the uranium etching process, stir the uranium and then chromium under the conditions shown below (2) The membrane surface is reduced. (2) Cathodic electrolytic reduction treatment conditions Treatment solution • •• SAS (E Treatment solution concentration… 50 0 5 5 Ί Bath temperature… 30 ± 10 ℃ Polarity… Current density to be processed. . . 2 amps Electrolysis time… 3 seconds. Chromium under the conditions (3) below. (3) Pickling treatment conditions Treatment solution • •• SAS (f bath temperature • •• 30 ± 1 ° C concentration of the treatment solution ··· 5 0 0 mM Treatment time… 1 5 seconds [· K.  Made by MURATA) liter / litre: ess (MeltexK. K · manufactured) _, 5 g / L engraving solution while shaking the material to be treated. , By the cathode electrolytic reduction treatment of chromium film will be Φ: · Κ.  (Made by Murata). The material in litres is cathode / dm2, and the chrome film is etched by -43-1243860 (Example 2). Follow the same steps as in Example 1 until the polyimide is etched. A copper film on one surface of the film. As in Example 1, after the copper film was etched, the chromium of the chromium film was not etched but remained as a residue on the surface of the polyimide film. Secondly, under the condition (4) shown below, the cathode electrolytic reduction treatment and the acid leaching treatment of the chromium film are simultaneously performed. That is, the cathode electrolytic reduction treatment is performed for a predetermined time, and the material to be treated is immersed in the treatment solution. As a result, the surface of the chromium film was reduced, and chromium was immediately dissolved in the treatment solution and removed from the polyimide film. That is, the chromium film surface is reduced and etched in the treatment solution in the same procedure. (4) Conditions for cathodic electrolytic reduction treatment and pickling treatment treatment solution. " SAS (K.  K.  MURATA) Treatment solution concentration ... 500ml / liter bath temperature. . · 3 0 ± 1 ° 〇 Processing time… 15 seconds Polarity… The material to be processed is cathode current density. . . 2 amps / dm2 Additional advantages and modifications are readily apparent to those skilled in the art. Therefore, the invention in its broader aspects is not limited by the specific details and representative embodiments shown and described herein. Therefore, various modifications can be made without departing from the spirit and scope of the general invention concept as defined by the scope of the attached patent application and its inventions. The drawings briefly explain a 4 4-1243860. The drawings added and constituting a part of this specification describe the existing preferred specific embodiments of the present invention, and the detailed description with the manufacturing instructions shown above and the preferred specific examples shown below Together to explain the principles of the invention. -Figure 1 shows the metals often used as metal primers and these metal primers.  List of characteristics of lacquer; Figure 2A is a cross-sectional view showing an example of a film-forming material that is received by a chemical treatment method according to a specific embodiment of the present invention; Figure 2B is a view showing Figure 2A coated with a photoresist Sectional view of an example of a material; Fig. 2C is a cross-sectional view showing an example of a state where the material shown in Fig. 2B is exposed through a photomask; Fig. 2D is a cross-sectional view showing an example of a material on which a photoresist pattern is formed Figure 2E is a cross-sectional view showing an example of a material on which a copper film is etched in accordance with a photoresist pattern; Figure 2F is a cross-sectional view showing an example of a material on which a chromium film is etched by the state shown in Figure 2E; Figure 2G is a cross-sectional view showing an example of the material on which the photoresist is removed from the state shown in Figure 2F;.  Fig. 3A is a schematic diagram showing the principle of the cathodic electrolytic reduction treatment; 4 Fig. 3B is a schematic diagram showing the principle of the cathodic electrolytic reduction treatment; Fig. 3C is a schematic diagram showing the principle of the acid pickling treatment; The figure is a schematic diagram showing the principle of acid electrolytic treatment; Fig. 5 is a schematic diagram showing an example of a vertical feed type chemical treatment device -45-1243860; Fig. 6 is a diagram showing the formation of the chemistry shown in Fig. 5 A schematic front sectional view of a cathode electrolytic reduction device of a processing device; FIG. 7 is a schematic side sectional view showing an example of a chemical processing device; and FIG. 8 is a schematic side sectional view showing an example of a horizontal feed type chemical processing device Fig. 9 is a schematic side sectional view showing an example of a chemical treatment device; Fig. 10 is a longitudinal side sectional view showing an example of a cathode electrolytic reduction device; Fig. 11 is a longitudinal side view showing an example of an acid leaching device Sectional view; FIG. 12 is a longitudinal side sectional view showing an example of an electrolytic device of a chemical treatment device; FIG. 13 is a view showing the etching of a copper film and a chromium film when the processing conditions are changed in each treatment according to this chemical treatment method List of test results of the state; Figure 14 is a list showing the test results of the chromium film etching state when the conditions of Experiment 7 shown in Figure 13 are changed; Figure 15 is a display showing the progress of the electrolytic reduction process at the cathode List of results of tests on whether chromium reduction occurred on the surface of the chromium film under the influence of an acidic treatment solution containing chloride ions; Figure 16 is a diagram showing how the chromium film was treated by the solution during the cathodic electrolytic reduction process A list of the results of the pH dependency test for etching; and FIG. 17 is a diagram showing the results of checking to see if hexavalent chromium is present in the treatment solution during the leaching process when using hydrochloric acid, sulfuric acid, and NaCl solutions as the treatment solution. List of test results. -46- 1243860 Description of component symbols 1 Support table 2 Cup 2a Alignment protrusion 3 Suction path 3a Catheter 3b Suction hole 4 Anode electrode 5 Anode 6 Blocking plate 7 Cathode electrode 8 Cathode 9 Guide ring 9a Alignment notch 9b Inclined connection surface 10 0- Ring 12 Process solution 13 Tank 14 Pump 15 Supply path 16 Drain path 17 Pull valve 18 Return path 19 Power supply

- 47- 1243860 20 容器 22 電極板 24 處理溶液 26 處理溶液 28 處理溶液 30 化學處理裝置 3 1 陰極電解還原裝置 31a 外處理浴 31b 內處理浴 31c 供應管 31d 泵 31e 熱交換器 31 f 過濾器 31g 槽 31h 處理溶液 3 1 i 排洩管 31 j 排洩管 31k 溢流部份 3 11 縫 3 1m 縫 31n 電極 3 1 x 電源 31y 電極輥 31z 電極輥 -4 8 _ 1243860 32 淸 洗 裝 置 32a 外 處 理 浴 32b 內 處 理 浴 32c 供 應 管 32d 泵 32e 熱 交 換 器 32f 過 濾 器 32g 槽 32h 去 離 子 水 32i 排 洩 管 32j 排 洩 管 32k 溢 流 部 份 321 縫 32m 縫 33 浸 酸 裝 置 33a 外 處 理 浴 33b 內 處 理 浴 33c 供 應 管 33d 泵 33e 熱 交 換 器 33f 過 濾 器 33g 槽 33h 處 理 溶 液 33 i 排 洩 管 -49- 1243860 33j 排洩管 33k 溢流部份 33 1 縫 3 3m 縫 34 淸洗裝置 34a 外處理浴 34b 內處理浴 34c 供應管 34d 泵 3 4 e 熱交換器 34f 過濾器 34g 槽 34h 去離子水 34i 排洩管 34j 排洩管 34k 溢流部份 341 縫 3 4m 縫 40 化學處理裝置 41 電解裝置 41a 外處理浴 41b 內處理浴 41c 供應管 41 d 泵-47- 1243860 20 container 22 electrode plate 24 processing solution 26 processing solution 28 processing solution 30 chemical processing device 3 1 cathode electrolytic reduction device 31a external processing bath 31b internal processing bath 31c supply pipe 31d pump 31e heat exchanger 31 f filter 31g Tank 31h Treatment solution 3 1 i Drain pipe 31 j Drain pipe 31k Overflow section 3 11 Slot 3 1m Slot 31n Electrode 3 1 x Power source 31y Electrode roller 31z Electrode roller-4 8 _ 1243860 32 Detergent device 32a External treatment bath 32b Internal treatment bath 32c supply pipe 32d pump 32e heat exchanger 32f filter 32g tank 32h deionized water 32i drain pipe 32j drain pipe 32k overflow section 321 slit 32m slit 33 acid pickling device 33a outer treatment bath 33b inner treatment bath 33c supply Pipe 33d Pump 33e Heat exchanger 33f Filter 33g Tank 33h Process solution 33 i Drain pipe -49- 1243860 33j Drain pipe 33k Overflow part 33 1 seam 3 3m seam 34 Detergent device 34a Outer treatment bath 34b Inner treatment bath 34c Supply pipe 34d Pump 3 4 e Heat exchanger 34f Filters groove 34g 34h 34i deionized water draining pipe 34j 34k overflow drain tube 41 slit portion 341 electrolytic chemical treatment apparatus 40 apparatus 3 4m outer slit 41a 41b within the treatment bath treatment bath supply pipe 41c pump 41 D

-50- 1243860 41 e 熱交換器 41 f 過濾器 41g 槽 41h 處理溶液 41 i 排洩管 41 j 排洩管 41k 溢流部份 41 1 縫 41m 縫 41n 電極 41x 電源 41y 電極輥 41 z 竃極輥 42 淸洗裝置 42a 外處理浴 42b 內處理浴 42c 供應管 42d 泵 42e 熱交換器 42f 過濾器 42g 槽 42h 去離子水 42 i 排洩管 42j 排洩管 1243860 42k 溢流部份 421 縫 42m 縫 50 化學處理裝置 51 陰極電解還原裝置 51a 處理浴 5 1b 處理溶液 51c 流動管-50- 1243860 41 e heat exchanger 41 f filter 41g tank 41h treatment solution 41 i drain pipe 41 j drain pipe 41k overflow 41 1 slit 41m slit 41n electrode 41x power supply 41y electrode roller 41 z 竃 pole roller 42 淸Washing device 42a External treatment bath 42b Internal treatment bath 42c Supply pipe 42d Pump 42e Heat exchanger 42f Filter 42g Tank 42h Deionized water 42 i Drain pipe 42j Drain pipe 1243860 42k Overflow part 421 Seam 42m Seam 50 Chemical treatment device 51 Cathode electrolytic reduction device 51a Process bath 5 1b Process solution 51c Flow tube

51d 泵 51e 熱交換器 5 1 f 過濾器 5 1 g 電極輥 5 1 h 電極輥 51 i' 電源 51 j 支持輥 51k 支持輥51d pump 51e heat exchanger 5 1 f filter 5 1 g electrode roller 5 1 h electrode roller 51 i 'power supply 51 j support roller 51k support roller

511 進料輥 5 1m 電極 51η 電極 52 淸洗裝置 52a 處理浴 52b 去離子水 52c 流動管 52d 泵 - 52- 1243860 52e 熱 交 換 器 52f 過 濾 器 52g 進 料 輥 52h 進 料 輥 52i 進 料 輥 52j 進 料 車昆 521 進 料 輥 53 浸 酸 裝 置 53a 處 理 浴 53b 處 理 溶 液 53c 流 動 管 53d 泵 53e 熱 交 換 器 53 f 過 濾 器 53g 進 料 輥 53h 進 料 輥 53i 進 料 輥 53j 進 料 輥 53 1 進 料 輥 54 淸 洗 裝 置 54a 處 理 浴 54b 去 離 子 水 5 4c 流 動 管 54d 泵 1243860 54e 熱交換器 54f 過濾器 54g 進料輥 54h 進料輥 54i 進料輥 54j 進料輥 541 進料輥 60 化學處理裝置 61 電解裝置 61a 處理浴 61b 處理溶液 61c 供應管 6 Id 泵 61 e 熱交換器 61 f 過濾器 6 1 g 電極輥 61h 支持輥 6 1 i 電源 61 j 支持輥 61k 支持輥 61 1 進料輥 61m 電極 62 淸洗裝置 62a 處理浴511 Feed roller 5 1m Electrode 51η Electrode 52 Detergent device 52a Processing bath 52b Deionized water 52c Flow tube 52d Pump-52- 1243860 52e Heat exchanger 52f Filter 52g Feed roller 52h Feed roller 52i Feed roller 52j Feed Feeder car 521 Feed roller 53 Pickling device 53a Treatment bath 53b Process solution 53c Flow tube 53d Pump 53e Heat exchanger 53 f Filter 53g Feed roller 53h Feed roller 53i Feed roller 53j Feed roller 53 1 Feed Roller 54 Cleaning device 54a Processing bath 54b Deionized water 5 4c Flow tube 54d Pump 1243860 54e Heat exchanger 54f Filter 54g Feed roller 54h Feed roller 54i Feed roller 54j Feed roller 541 Feed roller 60 Chemical treatment device 61 Electrolytic device 61a Process bath 61b Process solution 61c Supply pipe 6 Id pump 61 e Heat exchanger 61 f Filter 6 1 g Electrode roller 61h Support roller 6 1 i Power supply 61 j Support roller 61k Support roller 61 1 Feed roller 61m electrode 62 decanter 62a treatment bath

-54- 1243860 62b 去離子水 62c 流動管 62d 泵 62e 熱交換器 62f 過濾器 62g 進料輥 62h 進料輥 62i 進料輥 62j 進料輥 621 進料輥 71 陰極電解還原裝置 72 浸酸裝置 80 電解裝置 81 支撐台 82 杯 83 吸入路徑 83a 導管 83b 吸入孔 84 0 -環 85 槽 86 處理溶液 87 泵 88 供應路徑 89 排洩路徑-54- 1243860 62b Deionized water 62c Flow tube 62d Pump 62e Heat exchanger 62f Filter 62g Feed roller 62h Feed roller 62i Feed roller 62j Feed roller 621 Feed roller 71 Cathode electrolytic reduction device 72 Acid pickling device 80 Electrolysis unit 81 Support stage 82 Cup 83 Suction path 83a Duct 83b Suction hole 84 0-ring 85 Tank 86 Process solution 87 Pump 88 Supply path 89 Drain path

-55- 放浅閥 回位路徑 處理溶液 材料 材料 鉻膜 銅膜 光阻劑 光罩 載物帶 載物帶 載物帶 載物帶 半導體晶圓 半導體晶圓 -56 --55- Shallow valve Return path Process solution Material Material Chromium film Copper film Photoresist Photomask Carrier tape Carrier tape Carrier tape Carrier tape Semiconductor wafer Semiconductor wafer -56-

Claims (1)

1243860 拾、申請專利範圍： 1· 一種化學處理方法，藉其將形成於接受膜形成之材料上 之金屬膜蝕刻成預定圖案，其包括·· 藉由使用含酸基之第一酸性處理溶液及含鹵素離子之鹼 性處理溶液之一，實行作爲陰極之金屬膜之電解還原之 陰極電解還原步驟；及 在陰極電解還原步驟後將金屬膜浸於第二酸性處理溶液 中之浸酸步驟。 2 ·如申請專利範圍第1項之方法，其中第一酸性處理溶液 爲選自氫氯酸、硫酸、竣酸、氟化氫、與磷酸之一員。 3·如申請專利範圍第1項之方法，其中鹵素離子爲選自氯 化鈉、氯化鉀、與碘化鉀之一員。 4·如申請專利範圍第i項之方法，其中第二酸性處理溶液 含鹵素離子。 5· —種化學處理方法，藉其將形成於接受膜形成之材料上 之金屬膜蝕刻成預定圖案，其包括： 藉由使用含鹵素離子之處理溶液，實行作爲陰極之金屬 膜之電解還原之陰極電解還原步驟；及 在陰極電解還原步驟後將金屬膜浸於酸性處理溶液中之 浸酸步驟。 6 ·如申請專利範圍第5項之方法，其中酸性處理溶液含鹵 素離子。 7·如申請專利範圍第4至6項中任一項之方法，其中鹵素 離子爲氯離子。 - 57- 1243860 8 ·如申請專利範圍第1至6項中任一項之方法，其中陰極 電解還原步驟包括將金屬膜之一部份浸於含鹵素離子之 處理溶液。 9·如申請專利範圍第8項之方法，其中形成金屬膜之金屬 爲一種選自鉻、鈦、鎢、钯、與鉬之金屬。 10·如申請專利範圍第8項之方法，其中形成金屬膜之金屬 爲一種含選自鉻、鈦、鎢、鈀、與鉬至少之一之合金。 11· 一種化學處理方法，藉其將形成於接受膜形成之材料上 之金屬膜蝕刻成預定圖案， · 其中將金屬膜浸於含鹵素離子之酸性處理溶液，及實 行作爲陰極之金屬膜之電解還原。 1 2 ·如申請專利範圍第1至5項及第丨i項中任一項之方法， 其中形成金屬膜之金屬爲一種選自鉻、鈦、鎢、鈀、與 鉬之金屬。 1 3 ·如申請專利範圍第丨至5項及第1 1項中任一項之方法， 其中形成金屬膜之金屬爲一種含選自鉻、鈦、鎢、鈀、 與鉬至少之一之合金。 春 I4·如申請專利範圍第11項之方法，其中鹵素離子爲氯離子 〇 15.—種化學處理裝置，藉其將形成於接受膜形成之材料上 _ 之金屬膜蝕刻成預定圖案，其包括 陰極電解還原裝置，其藉由使用含酸基之第一酸性處 理溶液及含鹵素離子之鹼性處理溶液之一，實行作爲陰 極之金屬膜之電解還原處理；及 -58- 1243860 浸酸裝置，其在藉陰極電解還原裝置實行陰極電解還 原處理後，將金屬膜浸於第二酸性處理溶液中。 16·—種化學處理裝置，藉其將形成於接受膜形成之材料上 之金屬膜蝕刻成預定圖案，其包括電解裝置，其將金屬 膜浸於含鹵素離子之酸性處理溶液中，及實行作爲陰極 之金屬膜之電解還原處理。 17.如申請專利範圍第15或16項之裝置，其中鹵素離子爲 氯離子。 18·如申請專利範圍第15或16項之裝置，其中在電解還原 φ 處理中，將金屬膜之一部份浸於含鹵素離子與酸基之一 之處理溶液。 19. 如申請專利範圍第18項之裝置，其中鹵素離子爲氯離子 〇 20. 如申請專利範圍第18項之裝置，其中形成金屬膜之金屬 爲一種選自鉻、鈦、鎢、鈀、與鉬之金屬。 21·如申請專利範圍第18項之裝置，其中形成金屬膜之金屬 爲一種含選自鉻、鈦、鎢、鈀、與鉬至少之一之合金。 馨 22.如申請專利範圍第15或16項之裝置，其中形成金屬膜 之金屬爲一種選自鉻、鈦、鎢、鈀、與鉬之金屬。 · 23·如申請專利範圍第15或16項之裝置，其中形成金屬膜 之金屬爲一種含選自鉻、鈦、鎢、鈀、與鉬至少之一之 合金。 - 59 -1243860 Patent application scope: 1. A chemical treatment method by which a metal film formed on a material forming a receiving film is etched into a predetermined pattern, which includes ... by using a first acidic treatment solution containing an acid group and One of the alkaline treatment solutions containing halogen ions, a cathodic electrolytic reduction step of electrolytic reduction of a metal film as a cathode; and an acid leaching step of immersing the metal film in a second acidic processing solution after the cathodic electrolytic reduction step. 2. The method according to item 1 of the scope of patent application, wherein the first acidic treatment solution is a member selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, hydrogen fluoride, and phosphoric acid. 3. The method of claim 1 in which the halogen ion is a member selected from the group consisting of sodium chloride, potassium chloride, and potassium iodide. 4. The method according to item i of the patent application scope, wherein the second acidic treatment solution contains a halogen ion. 5. · A chemical treatment method by which a metal film formed on a material forming a receiving film is etched into a predetermined pattern, which includes: performing an electrolytic reduction of a metal film as a cathode by using a processing solution containing a halogen ion A cathodic electrolytic reduction step; and an leaching step of immersing the metal film in an acidic treatment solution after the cathodic electrolytic reduction step. 6. The method of claim 5 in which the acidic treatment solution contains halogen ions. 7. The method according to any one of claims 4 to 6, wherein the halogen ion is a chloride ion. -57- 1243860 8-The method according to any one of claims 1 to 6, wherein the cathodic electrolytic reduction step includes immersing a part of the metal film in a treatment solution containing a halogen ion. 9. The method according to item 8 of the application, wherein the metal forming the metal film is a metal selected from chromium, titanium, tungsten, palladium, and molybdenum. 10. The method according to item 8 of the application, wherein the metal forming the metal film is an alloy containing at least one selected from the group consisting of chromium, titanium, tungsten, palladium, and molybdenum. 11. A chemical treatment method by which a metal film formed on a material forming a receiving film is etched into a predetermined pattern, in which a metal film is immersed in an acidic treatment solution containing a halogen ion, and electrolysis of a metal film as a cathode is performed reduction. 1 2. The method according to any one of claims 1 to 5 and i, wherein the metal forming the metal film is a metal selected from chromium, titanium, tungsten, palladium, and molybdenum. 1 3 · The method according to any one of claims 1-5 to 11 and 11, wherein the metal forming the metal film is an alloy containing at least one selected from chromium, titanium, tungsten, palladium, and molybdenum . Spring I4. The method according to item 11 of the scope of patent application, in which the halogen ion is chloride ion. 15. A chemical processing device by which a metal film formed on a material forming a receiving film is etched into a predetermined pattern, which includes Cathode electrolytic reduction device, which uses one of the first acidic treatment solution containing an acid group and the alkaline treatment solution containing a halogen ion to perform electrolytic reduction treatment as a metal film of the cathode; and -58-1243860 acid immersion device, After performing a cathodic electrolytic reduction treatment by a cathodic electrolytic reduction device, the metal film is immersed in a second acidic processing solution. 16. · A chemical processing device by which a metal film formed on a material forming a receiving film is etched into a predetermined pattern, and includes an electrolysis device which immerses the metal film in an acidic processing solution containing a halogen ion, and performs as Electrolytic reduction of the metal film of the cathode. 17. The device according to claim 15 or 16, wherein the halogen ion is a chloride ion. 18. The device according to item 15 or 16 of the patent application scope, wherein in the electrolytic reduction φ treatment, a part of the metal film is immersed in a treatment solution containing one of a halogen ion and an acid group. 19. If the device in the scope of the patent application is under item 18, wherein the halogen ion is chloride ion. 20. In the device in the scope of the patent application under item 18, wherein the metal forming the metal film is a member selected from chromium, titanium, tungsten, palladium, Metal of molybdenum. 21. The device of claim 18, wherein the metal forming the metal film is an alloy containing at least one selected from the group consisting of chromium, titanium, tungsten, palladium, and molybdenum. Xin 22. The device of claim 15 or 16, wherein the metal forming the metal film is a metal selected from chromium, titanium, tungsten, palladium, and molybdenum. · 23. The device of claim 15 or 16, wherein the metal forming the metal film is an alloy containing at least one selected from the group consisting of chromium, titanium, tungsten, palladium, and molybdenum. -59-
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