TW201140230A - Method of reproducing a substrate, method of manufacturing a mask blank, method of manufacturing a substrate with a multilayer reflective film and method of manufacturing a reflective-type mask blank - Google Patents

Method of reproducing a substrate, method of manufacturing a mask blank, method of manufacturing a substrate with a multilayer reflective film and method of manufacturing a reflective-type mask blank Download PDF

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TW201140230A
TW201140230A TW099138859A TW99138859A TW201140230A TW 201140230 A TW201140230 A TW 201140230A TW 099138859 A TW099138859 A TW 099138859A TW 99138859 A TW99138859 A TW 99138859A TW 201140230 A TW201140230 A TW 201140230A
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Taiwan
Prior art keywords
substrate
film
reproducing
multilayer reflective
gas
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TW099138859A
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Chinese (zh)
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TWI494682B (en
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Masahiro Hashimoto
Osamu Nozawa
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Hoya Corp
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Publication of TWI494682B publication Critical patent/TWI494682B/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
    • 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
    • H01L21/30604—Chemical etching

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Preparing Plates And Mask In Photomechanical Process (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

From a mask blank having a pattern-forming thin film formed on a principal surface of a substrate of glass or from a transfer mask prepared by using the mask blank, the substrate is reproduced by removing the thin film. In a method of reproducing the substrate, the thin film of the mask blank or the transfer mask is removed by bringing the thin film into contact with a material which is in an unexcited state and which contains a compound of fluorine (F) and any element selected from chlorine (Cl), bromine(Br), iodine (I), and xenon (Xe).

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201140230 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種去除光罩基底等之薄膜而再生基板的 I板之再生方法、光罩基底之製造方法、❹層反射膜基 板之製造方法及反射型光罩基底之製造方法。 【先前技術】 -般而言，半導體裝置之製造步驟中，使用光微影法進 行微細圖案之形成。又，該微細圖案之形成中通常使用多 片破稱為光罩之轉印用光罩。該轉印用光罩一般係於透光 性之玻璃基板上設置有包含金屬薄膜等之微細圖案者，且 於該轉印用光罩之製造時亦使用光微影法。 利用光微影法之轉印用光罩之製造中，使用具有用以於 玻璃基板等透光性基板上形成轉印圖案（光罩圖案）之薄膜 (例如遮光膜等）之光罩基底。使用該光罩基底之轉印用光 罩之製造係包括如下步驟而進行：對形成於光罩基底上之 抗餘劑膜實施所期望之圖案描畫之描畫步驟；描畫後，將 上述抗钱劑膜«而形成所期望之抗姓劑圖案之顯影步 驟；將該抗#劑圖案作為光罩而㈣上述薄膜之姓刻步 冑；及將殘餘之抗_圖案剝離去除之H上述顯影步 財，於對形成於光罩基底上之抗蝕劑膜實施所期望之圖 案描畫後供給顯影液’將可溶之抗触劑膜之部位溶解於顯 影液中，從而形成抗姓劑圖案。又，上述姓刻步驟中，將 該抗敍劑圖案作為光罩，藉由乾式兹刻或濕式姓刻，而去 除未形成抗钱劑圖案之薄膜露出之部位，藉此於透光性基 152071.doc 201140230 板上形成所期望之光罩圖案。如此’完成轉印用光罩。 又，作為轉印用光罩之種類，除了先前之於透光性基板 上具有包含鉻系材料之遮光膜圖案之二元型光罩以外，還 眾所周知有半色調型相位偏移光罩。該半色調型相位偏移 光罩係於透光性基板上具有相位偏移膜之結構者，該相位 偏移膜係使實質上不利於曝光之強度之光（例如，相對於 曝光波長為1%〜20%)透射，賦予特定之相位差者，例如使 用含有矽化鉬化合物之材料等。又，趨於使用將含有鉬等 金屬之矽化物之材料用作遮光膜之二元型光罩。 ⑺然而，料來之半導體纟置等電子零件之廉價化競爭變 得激烈，另一方面轉印用光罩之製造成本之抑制亦成為重 要課題。根據如此之背景，要求如下方法：於基板上形成 圖案形成用之薄琪後’不將發現有表面缺陷之光罩基底、 或者發現有於使用光罩基底而製作之轉印用光罩中修正困 難之圖案缺陷之該轉印用光罩作為不良品而直接廢棄，而 自基板上剝離去除薄膜以再生基板。 作為去除玻璃基板上之薄膜之方法，先前―般為使用薄 膜之飯刻劑之方法。例如，於日本專利特開日⑽指585 號公報（專敎獻丨）巾記财使㈣氫氟錄、1錢、石夕氮 氟酸、氟化硼酸中至少任—種與過氧化氫、硝酸中至少任 -種混合Μ之水溶液作為含有魏料金心化物之遮 光性膜之㈣劑，且可使用此種_劑，藉由㈣而將基 板上之含有金心化物之薄膜去I X ’對於含有石夕化翻 等金属石夕化物之薄膜而言，亦可使用氫敦酸而將其去除。 152071.doc •4- 201140230 【發明内容】 [發明所欲解決之問題] 然而’如上述專利文獻丨中所記載之使用蝕刻劑或氫氟 酸將玻璃基板上之含有矽化鉬等金屬矽化物之薄膜去除的 方法中存在如下問題點。 即’由於作為基板之材料之玻璃相對於專利文獻1中所 »己載之触刻劑或氫氟酸為可溶性，因此，不可避免地產生 於去除薄膜後之基板表面形成有白濁所致之變質層，或者 间平滑地研磨之基板表面之表面粗縫度變大等損傷。 為了完全去除如此之損傷而再生基板，必需再研磨，而 且抓取較大研磨量。成膜前之玻璃基板之表面研磨係通常 經過自粗研磨至精密研磨之複數階段之研磨步驟而進行。 於進行再研磨之情形時，如上述般必需採取較大研磨量， 故而必需向複數階段之研磨步驟中之初期階段返回，且再 研磨加工需要長時間，因此再研磨之步驟負荷變大，成本 變高。即，先前之方法中即便進行基板再生，亦未必充分 解決抑制轉印光罩之製造成本之課題。 再者，於日本專利特開2002_4052號公報（專利文獻2)中 ，不有如下方法：II由含有至少C1F3之清洗氣體或該清洗 孔體之電n而將於基板上進行非晶胡等堆積膜之成膜的成 膜裝=中之反應容器内壁所附著的堆積膜去除。然而，於 為了提高清洗速度而使用電漿之情形時，擔心產生電装所 之知傷。業者期望，於光罩基底之基板再生中，抑制去 ”薄膜後之基板表面之變質，及抑制表面粗糙度之惡化， 152071.doc 201140230 因此無法簡單地應用與如上述專利文獻2般可僅去除附著 於反應容器内壁之堆積膜之情形相同之方法。 又’光罩基底之薄膜材料並不限於上料仙等金屬石夕 化物’對應於光罩基底之種類已知有多種薄膜材料，能夠 使用各種薄膜材料所對應之剝離劑（蝕刻劑等）去除基板上 之薄膜而再生基板。然而，即便相對於該等薄膜材料不同 之情形，亦較理想為可儘可能使用相同方法去除薄膜而再 生基板。進而，光罩基底之薄膜亦較多為包括複數層，於 此情形時，即便於各層之材料不同之情形時，亦較理想為 於再生基板時，彳將複數層之薄膜整體一次自I板剝離去 除。 又，近年來，伴隨半導體裝置等中之圖案之高微細化， 要求有高精度、高品質之轉印光罩，於用以製造此種轉印 光罩之光罩基底中，亦趨於較多地使用具有高附加價值之 尚價之基材，實現抑制轉印用光罩之製造成本，並且光罩 基底之基板再生變成亦較先前更重要之課題。 因此本發明之第一目的在於提供一種由於去除薄膜後 之基板之損傷較少、再研磨之步驟負荷亦較少，可降低基 板之再生成本的基板之再生方法。 本發明之第二目的在於提供一種使用藉由該再生方法而 再生之基板之光罩基底之製造方法、附多層反射膜基板之 製造方法及反射型光罩基底之製造方法。 [解決問題之技術手段] 本發明者進行銳意研究，結果發現：使基板上之薄膜與 152071.doc • 6 - 201140230 含有特定之氟系化合物之非激發狀態之物質接觸而將其去 除，藉此可使去除薄膜後之基板之損傷變少。又，發現於 薄膜由例如含有石夕之材料等、能夠由氟系氣體乾式飯刻之 ‘ #料而形成之情形時，上述方法可使去除薄臈後之基板之 損傷特別少，從而適合於基板再生。 本發明者基於以上所說明之事實，進一步繼續銳意研 九’結果完成了本發明。 以下’列舉本發明之各種態樣。 (態樣1) 一種基板之再生方法，其特徵在於：其係將於包含玻璃 之基板之主表面上具備圖案形成用之薄膜之光罩基底或使 用該光罩基底所製作之轉印用光罩之上述薄膜去除而再生 基板之方法，且使上述光罩基底或上述轉印用光罩之上述 薄膜與含有氣（C1)、溴（Br)、碘⑴、及氙（Xe)中之任一元 素與氟（F)之化合物的非激發狀態之物質接觸而將其去 除。 (態樣2) 如態樣1之基板之再生方法’其中上述薄膜包含單層或 複數層，至少接觸於上述基板之層由能夠由氟系氣體乾式 •蝕刻之材料而形成。 (態樣3) 如態樣2之基板之再生方法，其中接觸於上述基板之層 係藉由含有矽（Si)之材料、含有金屬與矽之材料、及含 有组（Ta)之材料中之任—者而形成。 152071.doc 201140230 (態樣4) 如態樣1至3中任一項之基柄之五斗士、+ ** _ι_ 丞板之再生方法，其中上述基板 包含合成石英玻璃。 (態樣5) 一種光罩基底之製造方法，其特徵在於：於藉由態樣i 至4中任-項之基板之再生方法而再生之基板上形成圓 案形成用之薄膜。 (態樣6) 一種基板之再生方法，其特徵在於：其係將附多層反射 膜基板之上述多層反射膜去除而再生基板之方法，該附多 層反射膜基板係於包含玻璃之基板之主表面上具備使低折 射率層與高折射率層交替地積層而成之結構的多層反射 膜’且使上述附多層反射膜基板之上述多層反射膜與含有 氣（C1)、溴（Br)、碘（I)、及氙（Xe)中之任一元素與氟（1?)之 化合物的非激發狀態之物質接觸而將其去除。 (態樣7) 如態樣6之基板之再生方法，其中上述低折射率層包含 矽（Si)，且接觸於上述基板之主表面而形成。 (態樣8) 如態樣6或7之基板之再生方法，其中上述基板包含 Si02-Ti02系低熱膨脹玻璃。 (態樣9) 一種附多層反射膜基板之製造方法，其特徵在於：於藉 由態樣6至8中任一項之基板之再生方法而再生之基板上， 152071.doc 201140230 形成使低折射率層與高折射率層交替地積層而成之結構之 多層反射膜。 (態樣10) 一種基板之再生方法’其特徵在於：其係將於包含玻璃 之基板之主表面上依序具備使低折射率層與高折射率層交 替地積層而成之結構的多層反射膜、與圖案形成用之吸收 體膜的反射型光罩基底或使用該反射型光罩基底所製作之 反射型光罩之上述多層反射膜去除而再生基板之方法，且 使上述反射型光罩基底或上述反射型光罩之上述多詹反射 膜與含有氣（C1)、溴（Br)、碘（I)、及氙（Xe)中之任一元素 與氟（F)之化合物的非激發狀態之物質接觸而將其去除。 (態樣11) 如態樣10之基板之再生方法，其中上述低折射率層包含 矽（Si) ’且接觸於上述基板之主表面而形成。 (態樣12) 如慼樣10或11之基板之再生方法，其中上述基板包含 Si02-Ti〇2系低熱膨脹玻璃。 (態樣13) 一種反射型光罩基底之製造方法，其特徵在於：於藉由 態樣10至12中任一項之基板之再生方法而再生之基板上， 依序形成使低折射率層與高折射率層交替地積層而成之結 構之多層反射膜、與圖案形成用之吸收體膜。 (態樣14) 一種基板之再生方法，其特徵在於··其係將於包含玻璃 152071.doc -9- 201140230 之基板之主表面上具備圖案形成用之薄膜之光罩基底中， 藉由乾式蝕刻處理而對上述薄膜及上述基板進行蝕刻加工 之壓印用模具之製作方法所對應的光罩基底之上述薄膜去 除而再生基板之方法，且使上述光罩基底之上述薄膜與含 有氣（C1)、溴（Br)、碘（I)、及氙（xe)中之任一元素與氟（F) 之化合物的非激發狀態之物質接觸而將其去除。 (態樣15) 如態樣14之基板之再生方法，其中上述薄膜包含單層或 複數層，至少接觸於上述基板之層係藉由以钽（Ta)為主成 分之材料而形成》 (態樣16) 如態樣14或15之基板之再生方法，其中上述基板包含合 成石英玻璃。 (態樣17) 一種光罩基底之製造方法’其特徵在於：於藉由態樣14 至16中任一項之基板之再生方法而再生之基板上，形成圖 案形成用之薄膜。 [發明之效果] 根據本發明’由於作為基板之材料之玻璃係具有如下特 比即，於藉由激發狀態之氟系氣體而進行之乾式飯刻中 易於钮刻’但相對於非激發狀態之氟系化合物之物質則難 以餘刻’故而可減少去除薄膜後之基板之損傷，且再研磨 之步驟負荷亦變少，藉此可降低基板之再生成本。又，根 據本發明，因能夠以低成本再生高品質之基板，故尤其適 152071.doc •10- 201140230 合於使用具有高附加價值之高價之基材之光罩基底的基板 再生。 又，根據本發明，於藉由本發明之再生方法而再生之基 板上形成圖案形成用之薄膜’藉此能夠以低成本製造使用 高品質之再生基板之光罩基底’ χ，於上述基板上形成使 低折射率層與高折射率層交替地積層之結構之多層反射 膜、圖案形成用之吸收體膜等，藉此能夠以低成本製造使 用高品質之再生基板之附多層反射膜基板或反射型光罩基 底。 【實施方式】 以下，對本發明之實施形態進行詳細敍述。 [第1實施形態] 本發明之第1實施形態係一種基板之再生方法，其特徵 在於：其係關於將於包含玻璃之基板之主表面上具備圖案 形成用之薄膜的光罩基底或使用該光罩基底所製作之轉印 用光罩之上述薄膜去除而再生基板之方法’且使上述光罩 基底或上述轉印用光罩之上述薄膜與含有氯（α)、漠 (Br)、峨（I)、及氙（xe)中之任一元素與氟（F)之化合物的非 激發狀態之物質接觸而將其去除。 於本實施形態中所使用之光罩基底係於基板之主表面上 具備圖案形成用之薄膜之光罩基底，具體而言，可列舉於 基板之主表面上具備遮光膜之結構之二元型光罩基底、於 基板之主表面上具備相位偏移膜或相位偏移膜及遮光膜之 結構之相位偏移型光罩基底。又，可列舉具有透射實質上 152071.doc 201140230 不利於曝光之強度之光但不賦予使相位偏移效果產生之相 位差之特性的光半透射膜’或者具備該光半透射膜及遮光 膜之結構之光罩基底。進而，亦可列舉於該等光罩基底之 最上層具備蝕刻光罩膜之結構之光罩基底等。此外，對用 於FPD(flat panel display，平板顯示器）裝置之製造之多灰 階光罩中所使用之光罩基底亦能夠應用。作為該光罩基 底，可列舉於玻璃基板上積層有光半透射膜與遮光膜而成 之結構等。 該遮光膜既可為單層亦可為複數層（例如遮光層與防反 射層之積層結構）。又，於使遮光膜為遮光層與防反射層 之積層結構之情形時，亦可使該遮光層為包含複數層之結 構。又，關於上述相位偏移膜或光半透射膜而言，亦既可 為單層亦可為複數層。 該再生方法係適合於上述薄膜由能夠由氟系氣體（例 如，sf6、cf4、c2f6、chf3 等，或者該等與 He、Ar、 C2H4、〇2專之混合氣體）乾式钮刻之材料而形成之光 罩基底的基板之再生。玻璃基板具有如下特性：容易對乾 式蝕刻所使用之為激發狀態之氟系氣體之電漿進行蝕刻， 仁對非激發狀態之氟系化合物之物質則難以蝕刻。相對於 此，薄膜中所使用之能夠由氟系氣體乾式蝕刻之材料，具 有對非激發狀態之氣系4匕合物之物質亦易於钮刻之特性。 P此夠由氟系氣體乾式蝕刻之材料，對非激發狀態之氟 二化合物之物質易於獲得充分之蝕刻選擇性，尤其易於獲 侍可減少薄膜之剝離所致之對基板之損傷之效果。 152071.doc -12· 201140230 作為能夠由氣系氣趙乾式钱刻之材料，例 r(Si)之材料'含有過渡金屬與綱之材料、含有Γ屬 =之材料、及含有组陳材料等。作為使用如此 盈㈣. ’例如，可列舉具備11由含有過渡金屬 與夕（S1)巧料而形成之遮⑽之：元型光罩基底、具備 藉由含有组(Ta)之材料而形成之遮光膜之二元型光罩基 底”備藉由3有石夕（Sl)之材料或含有過渡金屬與石夕⑼)之 材料而形成之相位偏移膜之相位偏移型光罩基底等。 作為上述含有發⑻之材料，於Μ進而含有氮、氧及 碳之中至少1種元素之材料較佳，具體而言，含有石夕之氮 化物氧化物、碳化物、氮氧化物、碳氧化物、或碳氣氧 化物之材料較佳。 又，作為上述含有過渡金屬與邦i)之材料，除了含有 過度金屬與0之材料以外’可列舉於過渡金屬及石夕中進而 3有氮氧及碳之中至少1種元素之材料，具體而言，含 有過渡金屬石夕化物、或過渡金屬石夕化物之氣化物、氧化 物、碳化物、氣氧化物、碳氧化4勿、或碳氣氧化物之材料 較佳。過渡金屬可應用鉬、组、鎢、鈦、鉻、铪、鎳、 釩、鍅、釕、鍺、銳、釔、鑭、鈀、鐵等。纟中鉬尤其適 合0 又，作為上述含有金屬與矽（Si)之材料，除了含有金屬 與矽之材料以外，可列舉於金屬及矽中進而含有氮、氧及 碳之中至少1種元素之材料。含有金屬與矽（si)之材料包含 上述含有過渡金屬與矽（Si)之材料。金屬除了可應用上述 152071.doc •13- 201140230 過渡金屬以外’還可應用鍺、鎵、鋁、銦、錫等。 又’作為上述含有钽（Ta)之材料，除了钽單體以外，可 列舉组與其他金屬元素（例如Hf、Zr等）之化合物，於钽中 進而含有氮、氧、碳及硼之中至少1種元素之材料，具體 而 s 含有 TaN、TaO、TaC、TaB、TaON、TaCN、TaBN、BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for regenerating an I-plate for removing a film of a photomask substrate or the like, a method for manufacturing a photomask substrate, and a method for producing a palladium reflective film substrate And a method of manufacturing a reflective reticle substrate. [Prior Art] In general, in the manufacturing steps of a semiconductor device, the formation of a fine pattern is performed using a photolithography method. Further, in the formation of the fine pattern, a plurality of transfer masks called broken masks are usually used. The transfer mask is generally provided with a fine pattern including a metal thin film on a light-transmissive glass substrate, and a photolithography method is also used in the production of the transfer mask. In the production of a photomask for transfer by a photolithography method, a photomask substrate having a film (for example, a light-shielding film) for forming a transfer pattern (a mask pattern) on a light-transmissive substrate such as a glass substrate is used. The manufacturing of the transfer reticle using the reticle substrate comprises the steps of: performing a desired pattern drawing step on the anti-surplus film formed on the reticle substrate; after drawing, the above-mentioned anti-money agent a film « to form a desired anti-surname pattern development step; the anti-agent pattern as a mask and (4) the film's last name; and the residual anti-pattern stripped to remove the H development step, After the desired pattern is drawn on the resist film formed on the mask substrate, the developer is supplied with a portion of the soluble anti-contact agent film dissolved in the developer to form an anti-surname pattern. Further, in the above-mentioned surname step, the anti-spy agent pattern is used as a mask, and the exposed portion of the film in which the anti-money agent pattern is not formed is removed by dry etching or wet etching, thereby being transparent to the light-transmitting group. 152071.doc 201140230 The desired reticle pattern is formed on the board. Thus, the transfer photomask is completed. Further, as a type of transfer mask, a halftone type phase shift mask is known in addition to a binary mask having a light-shielding film pattern containing a chromium-based material on a light-transmitting substrate. The halftone phase shift mask is configured to have a phase shift film on a light transmissive substrate, the phase shift film being such that light having a strength that is substantially unfavorable for exposure (for example, with respect to an exposure wavelength of 1) % to 20%) Transmission, for imparting a specific phase difference, for example, a material containing a molybdenum molybdenum compound or the like is used. Further, a binary type mask which uses a material containing a telluride of a metal such as molybdenum as a light-shielding film tends to be used. (7) However, the competition for cheaper electronic components such as semiconductor devices has become fierce, and the suppression of the manufacturing cost of the transfer mask has become an important issue. According to such a background, there is a demand for a method of forming a mask for forming a pattern on a substrate, and not detecting a mask base having a surface defect or detecting a transfer mask produced by using the mask substrate. The transfer mask having a difficult pattern defect is directly discarded as a defective product, and the film is peeled off from the substrate to regenerate the substrate. As a method of removing a film on a glass substrate, a method of using a film of a meal is conventionally used. For example, in Japanese Patent Special Day (10), it refers to the No. 585 bulletin (special offer), the shogunate (4) at least one of hydrogen fluoride recording, 1 money, Shixi nitrofluoric acid, and fluorinated boric acid, and hydrogen peroxide. An aqueous solution of at least one of the mixed niobium in the nitric acid is used as the (four) agent of the light-shielding film containing the ruthenium gold-based compound, and the ruthenium-containing film on the substrate can be used to remove IX by the (4) A film containing a metal ruthenium compound such as Shi Xihua turned can be removed by using hydrogen hydride. 152071.doc • 4-201140230 [Disclosure] [Problems to be Solved by the Invention] However, as described in the above-mentioned patent document, an etchant or hydrofluoric acid is used to contain a metal halide such as molybdenum molybdenum on a glass substrate. The following problems exist in the method of film removal. That is, since the glass as the material of the substrate is soluble relative to the contact agent or hydrofluoric acid contained in Patent Document 1, it is inevitable that the surface of the substrate after the removal of the film is deteriorated by white turbidity. The layer, or the surface of the substrate surface that is smoothly ground between them, has a large degree of roughness and the like. In order to completely remove such damage and regenerate the substrate, it is necessary to re-grind and capture a large amount of grinding. The surface polishing of the glass substrate before film formation is usually carried out by a grinding step in a plurality of stages from coarse grinding to precision grinding. In the case of re-grinding, it is necessary to take a large amount of polishing as described above, so it is necessary to return to the initial stage in the grinding step of the plurality of stages, and the re-polishing process takes a long time, so the step of re-grinding becomes large, and the cost is increased. Becomes high. That is, even in the prior art, even if substrate reproduction is performed, the problem of suppressing the manufacturing cost of the transfer mask is not necessarily solved. Further, in Japanese Laid-Open Patent Publication No. 2002-4052 (Patent Document 2), there is no method in which II is deposited on a substrate by a cleaning gas containing at least C1F3 or an electric n of the cleaning hole body. The deposited film adhered to the inner wall of the reaction container in the film formation of the film formation is removed. However, in the case where plasma is used in order to increase the cleaning speed, there is a fear of causing damage to the electrical equipment. In the substrate reproduction of the reticle base, it is desired to suppress the deterioration of the surface of the substrate after the film is removed, and to suppress the deterioration of the surface roughness, 152071.doc 201140230, therefore, it is not possible to simply apply and remove only as in the above-mentioned Patent Document 2 The method of depositing a film deposited on the inner wall of the reaction container is the same. The film material of the photomask base is not limited to a metal alloy such as a metal material. A variety of film materials are known for the type of the photomask substrate, and can be used. The release agent (etching agent, etc.) corresponding to various film materials removes the film on the substrate to regenerate the substrate. However, even if it is different from the film materials, it is preferable to remove the film by using the same method as much as possible to regenerate the substrate. Further, the film of the mask base is also composed of a plurality of layers. In this case, even when the materials of the layers are different, it is preferable to use the film of the plurality of layers as a whole when the substrate is regenerated. In addition, in recent years, high-precision and high-requirement of patterns in semiconductor devices and the like are required. The quality of the transfer reticle, in the reticle substrate used to manufacture such a transfer reticle, tends to use more expensive substrates with high added value, thereby realizing the manufacture of the reticle for suppressing transfer The cost and the substrate regeneration of the reticle substrate become a more important issue than before. Therefore, the first object of the present invention is to provide a substrate having less damage due to the removal of the film, and less load during the regrind step, which can be reduced. A method for regenerating a substrate for reproducing a substrate. A second object of the present invention is to provide a method of manufacturing a mask base using a substrate regenerated by the reproducing method, a method of manufacturing a multilayer reflective film substrate, and a reflective mask [Technical method for solving the problem] The inventors of the present invention conducted intensive studies and found that the film on the substrate is in contact with a substance containing a specific fluorine-based compound in a non-excited state, 152071.doc • 6 - 201140230 The removal thereof can reduce the damage of the substrate after the film is removed. Further, it can be found that the film can be made of fluorine by, for example, a material containing Shi Xi. In the case where the gas dry rice cooker is formed, the above method can make the damage of the substrate after removing the thin film particularly small, and is suitable for substrate regeneration. The present inventors further proceed to the research based on the facts described above. The present invention has been completed. The following is a description of various aspects of the present invention. (Aspect 1) A method for reproducing a substrate, which is characterized in that a film for pattern formation is provided on a main surface of a substrate including glass. a method of regenerating a substrate by removing the substrate by using the mask substrate or the transfer mask produced by using the mask substrate, and forming the film and the containing film (C1) of the mask base or the transfer mask Any one of bromine (Br), iodine (1), and xenon (Xe) is contacted with a non-excited state of the compound of fluorine (F) to remove it. (Stage 2) The substrate of the aspect 1 In the method of regenerating, the film comprises a single layer or a plurality of layers, and at least the layer contacting the substrate is formed of a material which can be dry-etched by a fluorine-based gas. (Aspect 3) The method for regenerating a substrate according to the aspect 2, wherein the layer contacting the substrate is made of a material containing bismuth (Si), a material containing metal and ruthenium, and a material containing a group (Ta) Formed as a person. 152071.doc 201140230 (Stage 4) The method for regenerating a five-stroke, + ** _ι_ 丞 plate of a shank according to any one of the aspects 1 to 3, wherein the substrate comprises synthetic quartz glass. (Embodiment 5) A method of manufacturing a mask substrate, characterized in that a film for forming a wafer is formed on a substrate which is reproduced by a method for reproducing a substrate of any of the aspects i to 4. (Embodiment 6) A method for reproducing a substrate, characterized in that it is a method of removing a multilayer reflective film having a multilayer reflective film substrate which is attached to a main surface of a substrate including glass a multilayer reflective film having a structure in which a low refractive index layer and a high refractive index layer are alternately laminated, and the multilayer reflective film having the multilayer reflective film substrate and the gas (C1), bromine (Br), and iodine Any one of (I) and 氙 (Xe) is contacted with a non-excited state of a compound of fluorine (1?) to remove it. (Section 7) A method of reproducing a substrate according to Aspect 6, wherein the low refractive index layer comprises bismuth (Si) and is formed in contact with a main surface of the substrate. (Aspect 8) A method of regenerating a substrate according to Aspect 6 or 7, wherein the substrate comprises a SiO 2 -TiO 2 -based low thermal expansion glass. (Surface 9) A method of manufacturing a multilayer reflective film substrate, characterized in that: 153071.doc 201140230 is formed on a substrate regenerated by the substrate regeneration method according to any one of the aspects 6 to 8 A multilayer reflective film of a structure in which a rate layer and a high refractive index layer are alternately laminated. (Surface 10) A method for reproducing a substrate, which is characterized in that a multilayer reflection of a structure in which a low refractive index layer and a high refractive index layer are alternately laminated is sequentially provided on a main surface of a substrate including glass. a method for regenerating a substrate by removing a substrate, a reflective mask substrate for an absorber film for pattern formation, or a multilayer reflective film using a reflective mask made of the reflective mask substrate, and causing the reflective mask The non-excited film of the substrate or the above-mentioned reflective mask and the non-excited compound containing any one of gas (C1), bromine (Br), iodine (I), and xenon (Xe) and fluorine (F) The state of matter contacts and removes it. (Aspect 11) A method of reproducing a substrate according to the aspect 10, wherein the low refractive index layer comprises bismuth (Si)' and is formed in contact with a main surface of the substrate. (Surface 12) A method of regenerating a substrate of the sample 10 or 11, wherein the substrate comprises a SiO 2 -Ti 2 -based low thermal expansion glass. (Aspect 13) A method of manufacturing a reflective reticle substrate, characterized in that a low refractive index layer is sequentially formed on a substrate regenerated by a substrate reproducing method according to any one of the aspects 10 to 12 A multilayer reflective film having a structure in which a high refractive index layer is alternately laminated, and an absorber film for pattern formation. (Section 14) A method for reproducing a substrate, which is characterized in that it is provided in a mask substrate having a film for pattern formation on a main surface of a substrate including glass 152071.doc -9-201140230, by dry type a method of removing a film of the mask base corresponding to the method for producing an imprint mold for etching the film and the substrate by etching, and regenerating the substrate, and the film and the containing gas of the mask base (C1) Any one of bromine (Br), iodine (I), and ruthenium (xe) is contacted with a non-excited state of the compound of fluorine (F) to remove it. (Surface 15) The method for regenerating a substrate according to the aspect 14, wherein the film comprises a single layer or a plurality of layers, and at least the layer contacting the substrate is formed by a material containing tantalum (Ta) as a main component. Sample 16) A method of regenerating a substrate according to aspect 14 or 15, wherein the substrate comprises synthetic quartz glass. (Aspect 17) A method for producing a mask substrate, wherein a film for pattern formation is formed on a substrate which is reproduced by the substrate reproducing method according to any one of the aspects 14 to 16. [Effects of the Invention] According to the present invention, the glass system as the material of the substrate has the following specific ratio, which is easy to be engraved in the dry rice engraving by the fluorine-based gas in the excited state, but is relatively in the non-excited state. The substance of the fluorine-based compound is difficult to be used. Therefore, the damage of the substrate after the removal of the film can be reduced, and the load of the step of re-polishing is also reduced, whereby the regeneration cost of the substrate can be reduced. Further, according to the present invention, since a high-quality substrate can be regenerated at a low cost, it is particularly suitable for substrate reproduction using a reticle substrate having a high-value-added substrate having a high added value, 152071.doc •10-201140230. Moreover, according to the present invention, a film for pattern formation is formed on a substrate reproduced by the reproducing method of the present invention, whereby a mask base ' using a high-quality regenerated substrate can be manufactured at a low cost, and formed on the substrate. A multilayer reflective film having a structure in which a low refractive index layer and a high refractive index layer are alternately laminated, an absorber film for pattern formation, and the like, whereby a multilayer reflective film substrate or reflection using a high quality recycled substrate can be manufactured at low cost. Type reticle base. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. [First Embodiment] A first embodiment of the present invention is a method for reproducing a substrate, which is characterized in that a mask substrate for forming a film for pattern formation on a main surface of a substrate including glass is used. The method of removing the film by the transfer photomask of the photomask base and removing the substrate, and the film of the photomask substrate or the transfer photomask and chlorine (α), desert (Br), and ruthenium Any one of (I) and 氙(xe) is contacted with a non-excited state of the compound of fluorine (F) to remove it. The reticle base used in the present embodiment is a reticle base having a film for pattern formation on the main surface of the substrate, and specifically, a binary type having a structure in which a light shielding film is provided on the main surface of the substrate The mask base has a phase shift type mask base having a phase shift film or a phase shift film and a light shielding film on the main surface of the substrate. Further, a light semi-transmissive film having a property of transmitting substantially no light which is unfavorable to the intensity of exposure but not giving a phase difference due to a phase shift effect, or a light semi-transmissive film and a light-shielding film may be mentioned. Structure of the reticle base. Further, a mask base or the like having a structure in which the mask film is etched on the uppermost layer of the mask base may be used. In addition, a reticle substrate used in a multi-gray reticle for the manufacture of a FPD (flat panel display) device can also be applied. Examples of the reticle base include a structure in which a light semi-transmissive film and a light-shielding film are laminated on a glass substrate. The light shielding film may be a single layer or a plurality of layers (for example, a laminated structure of a light shielding layer and an antireflection layer). Further, when the light shielding film is a laminated structure of a light shielding layer and an antireflection layer, the light shielding layer may have a structure including a plurality of layers. Further, the phase shift film or the light semi-transmissive film may be a single layer or a plurality of layers. The regeneration method is suitable for forming the film from a material which can be dry-engraved by a fluorine-based gas (for example, sf6, cf4, c2f6, chf3, or the like, or a mixed gas of He, Ar, C2H4, or 〇2). Regeneration of the substrate of the reticle substrate. The glass substrate has a characteristic that it is easy to etch a plasma of a fluorine-based gas in an excited state used for dry etching, and it is difficult to etch a substance of a fluorine-based compound in a non-excited state. In contrast to this, a material which can be dry-etched by a fluorine-based gas used in a film, and a substance having a gas-based 4 composition which is in an unexcited state is also easy to be characterized. P is a material which is dry-etched by a fluorine-based gas, and it is easy to obtain sufficient etching selectivity for a non-excited fluorodicarbon compound, and it is particularly easy to obtain an effect of reducing damage to the substrate due to peeling of the film. 152071.doc -12· 201140230 As a material that can be engraved by gas-based gas, the material of r(Si) contains a transition metal and a material, a material containing a genus =, and a material containing a group. For example, it can be exemplified by a mask having a mask (10) formed of a transition metal containing a transition metal (S1), and a meta-type mask base having a material containing a group (Ta). The binary type photomask substrate of the light-shielding film is prepared by a phase shift type photomask substrate of a phase shift film formed of a material having a material of Shi (Sl) or a material containing a transition metal and a stone (9). The material containing the hair (8) is preferably a material containing at least one element selected from the group consisting of nitrogen, oxygen and carbon, and specifically contains a nitride oxide, a carbide, an oxynitride, and a carbon oxide. The material or the material of the carbon gas oxide is preferably used. Further, as the material containing the transition metal and the state i), in addition to the material containing the excessive metal and the 0, it may be exemplified in the transition metal and And a material of at least one element of carbon and, in particular, a vapor, a metal oxide, a carbide, a gas oxide, a carbon oxide, or a carbon gas containing a transition metallite or a transition metal compound. The material of the oxide is preferred. Transition metal It can be applied to molybdenum, group, tungsten, titanium, chromium, niobium, nickel, vanadium, niobium, tantalum, niobium, tantalum, niobium, tantalum, palladium, iron, etc. Molybdenum molybdenum is especially suitable for 0, as the above-mentioned metal and niobium ( The material of Si) may be a material containing at least one of nitrogen, oxygen, and carbon, in addition to a material containing a metal and a ruthenium. The material containing metal and bismuth (si) includes the above transition. Metal and bismuth (Si) materials. In addition to the above-mentioned 152071.doc •13- 201140230 transition metals, metals can also be used for yttrium, gallium, aluminum, indium, tin, etc. In addition to the fluorene monomer, a compound of a group and another metal element (for example, Hf, Zr, etc.) may be mentioned, and further contains at least one element selected from the group consisting of nitrogen, oxygen, carbon, and boron, and s contains TaN. , TaO, TaC, TaB, TaON, TaCN, TaBN,

TaC〇、TaB〇、TaBC、TaCON、TaBON、丁aBCN、 TaBCON之材料等。 該再生方法中，於二元型光罩基底中之遮光膜、相位偏 移型光罩基底中之相位偏移膜等薄膜包含複數層之情形 時，該等複數層之中至少接觸於上述基板之層，適合於藉 由flb夠由敦系氣體乾式飯刻之材料例如上述含有發（$丨）之 材料、含有過渡金屬與矽（Si)之材料、含有金屬與矽（Si)之 材料、及含有鈕（Ta)之材料中的任一者而形成之光罩基底 之基板之再生。 上述光罩基底用之基板只要為相對於所使用之曝光波長 具有透明性者則並無特別限制，可使用合成石英基板、其 他各種玻璃基板（例如，驗石灰玻璃、銘石夕酸鹽玻璃等）， 其中合成石英基板因為於ArF準分子雷射或短於其之波長 之區域中透明性較高，故而尤其可較佳地使用。 忒再生方法係如下之方法：使於如上所述之基板之主表 面上具備圖案形成用之薄膜之光罩基底、或使用該光罩基 底藉由光罩加工技術而製作之轉印用光罩之上述薄膜與含 有氣（C1)、演（Br)、破⑴、及氣（Xe)中之任-元素與氣⑺ 之化合物之非激發狀態之物質接觸而將其去除，藉此再生 152071.doc •14- 201140230 基板。 於玻璃基板與圖案形成用薄膜（尤其係包含能夠由氟系 氣體乾式蝕刻之材料之薄膜）之間，藉由激發狀態之氟系 氣體之電漿而進行之蝕刻、或藉由受到帶電粒子之照射變 為激發狀態之氟系氣體而進行之姓刻，難以獲得钱刻選擇 性。相對於此，對非激發狀態之氟系化合物之物質，可於 玻璃基板與圖案形成用薄膜之間獲得較高之蝕刻選擇性。 再者，使β亥非激發狀態之敦系化合物之物質於流體狀態下 接觸即可’尤佳為於氣體狀態下使其接觸。 另一方面’含有氫離子之氫氟酸溶液或矽氫氟酸溶液 中’氫離子發揮切斷玻璃中之Si-Ο之鍵之作用，易於使氟 與矽結合，因此易於使玻璃熔解，難以獲得本發明之作用 效果。若考慮此方面，則非激發狀態之氟系化合物之物質 中較理想為實質上不含有氫。 作為氯（C1)、溴（Br)、碘（I)、及氙（xe)中之任一元素與 敗（F)之化合物（以下僅稱為「本發明之化合物」），例如， 可較佳地使用 C1F3、C1F、BrF5、BrF、IF3、IF5、XeF2、 XeF4、XeF6、XeOF2、XeOF4、Xe02F2、Xe03F2 或 Xe02F4 等化合物。其中，尤其可較佳地使用cif3。 作為使光罩基底或使用該光罩基底所製作之轉印用光罩 之上述薄膜與含有本發明之化合物之非激發狀態之物質接 觸的方法，例如可較佳地列舉如下方法：於腔室内設置光 罩基底’將含有本發明之化合物之物質以氣體狀態導入至 該腔室内而將腔室内以該氣體置換。 152071.doc -15- 201140230 於以氣體狀態使用含有本發明之化合物之物質之情形 時，可使用本發明之化合物與氮氣、或氬（Ar)、氦（He)、 氖（Ne)、氪（Kr)、氙（Xe)、氡（Rn)等（以下僅稱為氬（Ar)等） 之混合氣體。於以氣體狀態使用含有本發明之化合物之物 質之情形時’可較佳地使用本發明之化合物與氬（Ar)之混 合氣體。 關於使光罩基底或轉印用光罩之上述薄膜與含有本發明 之化合物之非激發的氣體狀態之物質接觸之情形時的處理 條件，例如氣體流量、氣體壓力、溫度、處理時間而言無 需特別限制，但就較佳地獲得本發明之作用之觀點而言， 較理想為根據薄膜之材料或層數（膜厚）而適當選擇。 關於氣體流量而言，例如於使用本發明之化合物與氬之 混合氣體之情形時，較佳為將本發明之化合物以流量比為 1 /〇以上而加以混合。若本發明之化合物之流量少於上述 流量比，則薄膜之剝離之推進變得緩慢，結果為處理時間 變長，剝離變得困難。 又，關於氣體壓力而言，較佳為例如於1〇〇〜76〇 丁〇1^之 範圍中適當選定。若氣體壓力低於上述範圍，則腔室内之 本發明之化合物之氣體量本身過少，薄膜之剝離之推進變 得緩慢，結果為處理時間變長，剝離變得困難。另一方 面，右氣體壓力高於上述範圍（為大氣壓以 ，會流出至腔室之外，且本發明之化合物中亦)含= 面之氣體，故而不佳。 又，關於氣體之溫度而言，較佳為例如於2〇〜5〇〇它之範 152071.doc •16- 201140230 圍中適當選定。若溫度低於上述範圍，則薄膜之剝離之推 進變%•緩慢，結果為處理時間變長，剝離變得困難。另一 方面若/jbl度尚於上述範圍，則剝離迅速推進，雖然可縮 短處理時間’但是有難以獲得薄膜與基板之選擇性，基板 損傷變得稍大之虞。 進而，關於處理時間而言，只要為基本上可自基板剝離 去除薄膜所需之充分之時間即可。由於上述氣體流量、氣 體壓力、溫度，或者由於薄膜之材料、膜厚而處理時間稍 微不同，該處理時間為大約5〜30分鐘之範圍時可較佳地獲 得本發明之作用。 圖1係上述去除薄膜之步驟中所使用之適合之處理裝置 的概略構成圖。 該去除裝置中，由氣體填充容器43、44、流量控制器 …46、嘴出喷嘴47及該等之連接配管而構成有非激發氣 體供給機。光罩基底等之處理基板41係設置於處理裝置之 腔至40内之平台42上。而且，例如2種氣體填充容器43、 44内之氣體分別由流量控制器45、46調節流量後被混合， 自噴出喷嘴47喷出而導入至腔室4〇内。又，腔室4〇内之氣 體通過排氣管48由排氣氣體處理裝置49進行除害處理後， 適當排氣。 於以氣體狀態使用含有氟系化合物之物質之情形時，上 述2種氣料該㈣化合物與氮氣、或氬㈣等稀有氣 體。 上述去除裝置之腔室40為橫置式之u構成，最適合於 152071.doc 201140230 皁片處理。另一方面，作為適合於一次處理多片基板之批 量處理之腔室之構成，例如可考慮以下構成。使腔室為圓 筒形狀之立式’於腔室之外周配置加熱裝置，從而可加熱 腔室内部》進而，於腔室内部配置由合成石英等耐熱性 料而形成之立式之支架，&而可於腔室内縱向地配置複數 個處理基板。 再者，一般而言，作為光罩基底之圖案形成用之薄膜， 亦使用不含有矽之鉻系材料（Cr、Cr〇、CrN、、Materials such as TaC〇, TaB〇, TaBC, TaCON, TaBON, D-ACN, and TaBCON. In the regenerative method, when a film such as a light-shielding film in a binary photomask substrate or a phase shift film in a phase-shifting photomask substrate includes a plurality of layers, at least the plurality of the plurality of layers are in contact with the substrate. The layer is suitable for materials which are dry-burned by the Dun-type gas by flb, such as the above-mentioned material containing hair ($丨), the material containing transition metal and bismuth (Si), the material containing metal and bismuth (Si), And regeneration of the substrate of the reticle base formed by any of the materials containing the button (Ta). The substrate for the mask base is not particularly limited as long as it has transparency with respect to the exposure wavelength to be used, and a synthetic quartz substrate or various other glass substrates (for example, limestone glass, etched lime oxide glass, etc.) can be used. Among them, the synthetic quartz substrate is particularly preferably used because it has high transparency in an ArF excimer laser or a region shorter than the wavelength thereof. The 忒 regeneration method is a method of providing a reticle substrate having a film for pattern formation on a main surface of the substrate as described above, or a transfer reticle formed by a reticle processing technique using the reticle substrate The film is contacted with a substance containing a non-excited state of a compound of any one of the gas (C1), the (Br), the broken (1), and the gas (Xe) and the gas (7), thereby removing 152071. Doc •14- 201140230 Substrate. The glass substrate and the pattern forming film (especially including a film of a material which can be dry-etched by a fluorine-based gas) are etched by a plasma of a fluorine-based gas in an excited state, or by being subjected to charged particles. When the fluorine-based gas that has become an excited state is irradiated, it is difficult to obtain the selectivity of the money. On the other hand, in the non-excited fluorine-based compound, a high etching selectivity can be obtained between the glass substrate and the pattern-forming film. Further, it is preferable to bring the substance of the compound which is in the non-excited state of the β-helic state into contact with the fluid state, and it is preferable to contact it with a gas state. On the other hand, in the hydrofluoric acid solution or the hydrofluoric acid solution containing hydrogen ions, the hydrogen ion acts to cut the bond of Si-Ο in the glass, and it is easy to combine fluorine and ruthenium, so that it is easy to melt the glass and it is difficult to melt the glass. The effects of the present invention are obtained. In consideration of this aspect, it is preferred that the fluorine-based compound in a non-excited state contains substantially no hydrogen. As a compound of any one of chlorine (C1), bromine (Br), iodine (I), and xenon (xe) and a compound of the formula (F) (hereinafter simply referred to as "the compound of the present invention"), for example, Preferably, a compound such as C1F3, C1F, BrF5, BrF, IF3, IF5, XeF2, XeF4, XeF6, XeOF2, XeOF4, Xe02F2, Xe03F2 or Xe02F4 is used. Among them, cif3 is particularly preferably used. As a method of bringing the film of the photomask base or the transfer photomask produced using the photomask base into contact with the non-excited state of the compound of the present invention, for example, the following method can be preferably used: in the chamber Providing a reticle base' introduces a substance containing the compound of the present invention into the chamber in a gaseous state to replace the chamber with the gas. 152071.doc -15- 201140230 When the substance containing the compound of the present invention is used in a gaseous state, the compound of the present invention can be used with nitrogen, or argon (Ar), strontium (He), cerium (Ne), cerium ( A mixed gas of Kr), xenon (Xe), rhodium (Rn), or the like (hereinafter simply referred to as argon (Ar) or the like). When a substance containing the compound of the present invention is used in a gaseous state, a mixed gas of the compound of the present invention and argon (Ar) can be preferably used. It is not necessary to treat the conditions of the film of the reticle base or the transfer reticle in contact with the substance containing the non-excited gaseous state of the compound of the present invention, such as gas flow rate, gas pressure, temperature, and treatment time. It is particularly limited, but from the viewpoint of preferably obtaining the action of the present invention, it is preferably selected as appropriate depending on the material or the number of layers (film thickness) of the film. Regarding the gas flow rate, for example, in the case of using a mixed gas of the compound of the present invention and argon, it is preferred to mix the compound of the present invention at a flow ratio of 1 /〇 or more. When the flow rate of the compound of the present invention is less than the above flow ratio, the progress of peeling of the film becomes slow, and as a result, the treatment time becomes long and peeling becomes difficult. Further, the gas pressure is preferably selected as appropriate, for example, in the range of 1 〇〇 to 76 〇 〇 ^. When the gas pressure is less than the above range, the gas amount of the compound of the present invention in the chamber itself is too small, and the progress of peeling of the film becomes slow. As a result, the treatment time becomes long and peeling becomes difficult. On the other hand, if the right gas pressure is higher than the above range (at atmospheric pressure, it will flow out of the chamber, and the compound of the present invention also contains a gas of the surface), it is not preferable. Further, as for the temperature of the gas, it is preferably selected, for example, in the range of 2 〇 5 5 152 152071.doc • 16 - 201140230. When the temperature is lower than the above range, the peeling of the film becomes slower and slower, and as a result, the treatment time becomes longer and peeling becomes difficult. On the other hand, if the /jbl degree is still in the above range, the peeling proceeds rapidly, and although the treatment time can be shortened, it is difficult to obtain the selectivity of the film and the substrate, and the substrate damage becomes slightly larger. Further, the treatment time may be a sufficient time required to substantially remove the film from the substrate. The effect of the present invention can be preferably obtained by the above gas flow rate, gas pressure, temperature, or treatment time due to the material and film thickness of the film being slightly different, and the treatment time is in the range of about 5 to 30 minutes. Fig. 1 is a schematic block diagram showing a suitable processing apparatus used in the above step of removing a film. In the removing device, the gas-filled containers 43, 44, the flow rate controller ... 46, the nozzle-out nozzle 47, and the connecting pipes are configured to constitute a non-excited gas supply device. The processing substrate 41 of the mask substrate or the like is disposed on the stage 42 in the cavity 40 of the processing apparatus. Further, for example, the gases in the two kinds of gas-filled containers 43, 44 are adjusted by the flow rate controllers 45 and 46, and are mixed, and are ejected from the discharge nozzles 47 to be introduced into the chambers 4A. Further, the gas in the chamber 4 is evacuated by the exhaust gas treatment device 49 through the exhaust pipe 48, and then appropriately exhausted. In the case where a substance containing a fluorine-based compound is used in a gaseous state, the above-mentioned two kinds of gas materials are a compound of the above (4), a rare gas such as nitrogen or argon (tetra). The chamber 40 of the above removal device is constructed as a horizontally disposed u, and is most suitable for the treatment of soap tablets by 152071.doc 201140230. On the other hand, as a configuration of a chamber suitable for batch processing of a plurality of substrates at a time, for example, the following configuration can be considered. The vertical chamber in which the chamber is cylindrical, the heating device is disposed outside the chamber, and the inside of the chamber can be heated. Further, a vertical bracket formed of a heat-resistant material such as synthetic quartz is disposed inside the chamber, & And a plurality of processing substrates may be disposed longitudinally in the chamber. Further, in general, as a film for pattern formation of a mask base, a chromium-based material (Cr, Cr〇, CrN, or

CiON CrCN、CrOC、CrOCN等）。於為該等薄膜之情形 時，既可使用I前之鉻系材料之去除方法，亦彳使用以高 溫供給本發明之化合物之方法、或使本發明之化合物為氣 體狀L，以其與氧（〇2)氣之混合氣體供給之方法。於以高 溫供給上述化合物之方法之情形時，作為鉻系材料之供給 條件，例如，將供給氣體中之本發明之化合物之濃度設為 90/。以上，更佳為1〇〇% ,處理對象物之表面溫度成為 280°C〜35〇t即可。又，較理想為將處理時間設為5分鐘以 上’更佳為6分鐘以上，將腔室内之壓力設為1 kpa左右， 將供給氣體流量設為3〇〇 sccm左右。 有於將包括含有過渡金屬與矽之材料之薄膜作為遮光膜 之二疋型光罩基底中，於遮光膜之上使用鉻系材料之薄膜 作為蝕刻光罩膜之情形。又，有於將包括含有過渡金屬與 石夕之材料之薄膜作為相位偏移膜之相位偏移型光罩基底 中’於相位偏移膜之上使用鉻系材料之薄膜作為用以形成 遮光帶之遮光膜的情形。又，有於將包括含有過渡金屬與 152071.doc •18· 201140230 矽之材料之薄膜作為光半透射膜之光罩基底中，於光半透 射膜之上使用鉻系材料之薄膜作為用以形成遮光帶之遮光 膜的情形。進而’亦有於鉻系材料之遮光膜之上，積層包 含能夠由氟系氣體乾式蝕刻之材料之薄膜作為蝕刻光罩膜 之構成的光罩基底。於該等情形時，去除鉻系材料之薄膜 之階段可使用上述方法或先前之鉻系材料之去除方法。 根據該再生方法，藉由使光罩基底等之薄膜與含有本發 明之化合物之非激發狀態（較佳為非激發且氣耀狀態）之物 質接觸，而於與包含玻璃之基板（尤其係合成石英基板）之 間獲得較高之蝕刻選擇性，因此可使去除薄膜後之基板之 損傷減少。 如此，於自光罩基底去除薄膜之後，對基板之表面進行 短時間精密研磨，藉此可恢復為去除薄膜前之高平滑之基 板之表面粗糙度《該再生方法係因薄膜之去除所致之基板 表面之損傷較少，故而再研磨之情形之研磨量亦較少即 可，從而能夠回到自粗研磨至精密研磨之複數階段之研磨 步驟中之最終階段（精密研磨）。因此，由於再研磨之步驟 負荷亦變少，故可降低基板之再生成本’並且可再生高品 質之基板。如此，該再生方法係因能夠以低成本再生高品 質之基板，故而尤其適合於使用具有高附加價值之高價之 基材的光罩基底之基板再生。 又，亦可提供一種使用藉由該再生方法而再生之基板之 光罩基底之製造方法。即，於藉由該再生方法而再生之基 板上，使用例如濺鍍成膜法，再次形成圖案形成用之薄 152071.doc •19- 201140230 膜’藉此能夠以低成本製造使用高品質之再生基板之光罩 基底。 [第2實施形態] 本發明之第2實施形態係一種基板之再生方法，其特徵 在於：其係關於將於包含玻璃之基板之主表面上具備使低 折射率層與高折射率層交替地積層而成之結構之多層反射 膜的附多層反射膜基板之上述多層反射膜去除而再生基板 之方法，且使上述附多層反射膜基板之上述多層反射膜與 含有氣（C1)、溴（Br)、碘（I)、及氙（Xe)中之任一元素與氟 (F)之化合物的非激發狀態之物質接觸而將其去除。 近年來’於半導體產業中，伴隨半導體裝置之微細化， 使用極紫外（Extreme Ultra Violet，以下稱為EUV)光之曝 光技術即EUV微影被視為有希望。此處，所謂EUV光，係 指軟X射線區域或真空紫外線區域之波長帶之光，具體而 言係波長為0.2〜100 nm左右之光。作為於該EUV微影中所 使用之光罩提出有反射型光罩》如此之反射型光罩係如下 者：於基板上形成有反射曝光之光之多層反射膜，於該多 層反射膜上將吸收曝光之光之吸收體膜形成為圖案狀。 上述附多層反射膜基板可用作用以製造上述反射型光罩 之反射型光罩基底，即於基板上依序具備反射曝光之光之 多層反射膜、與吸收曝光之光之圖案形成用之吸收體膜的 反射型光罩基底用之基板。而且，於基板上形成有多層反 射膜之後，藉由表面缺陷檢查而發現有膜下缺陷等之附多 層反射膜基板無法用作反射型光罩基底用之基板，因此業 152071.doc • 20· 201140230 者期望暫時去除上述多層反射膜而再生基板。 上述多層反射膜係使低折射率層與高折射率層交替地積 層而成之多層膜，一般而言，使用使重元素或其化合物之 薄膜、與輕元素或其化合物之薄膜交替地積層〜的週期 左右而成之多層膜。 例如作為相對於波長13〜14 nm之EUV光之多層反射 膜，可較佳地使用將Mo膜與Si膜交替地積層40週期左右而 成之Mo/Si週期積層膜。除此以外，作為於EUV光之區域 所使用之多層反射膜’存在Ru/Si週期多層膜、^〇/;^週期 夕層膜、Mo化合物/si化合物週期多層膜、Si/Nb週期多層 膜、Si/M〇/Ru週期多層膜、Si/M〇/Ru/M〇週期多層膜、CiON CrCN, CrOC, CrOCN, etc.). In the case of such films, it is possible to use a method of removing a chromium-based material before I, a method of supplying a compound of the present invention at a high temperature, or a compound of the present invention as a gas L, and oxygen. (〇2) A method of supplying a mixed gas of gas. In the case of a method of supplying the above compound at a high temperature, as a supply condition of the chromium-based material, for example, the concentration of the compound of the present invention in the supplied gas is set to 90/. The above is more preferably 1% by weight, and the surface temperature of the object to be treated is 280 ° C to 35 ° t. Further, it is preferable to set the treatment time to 5 minutes or more to more preferably 6 minutes or more, to set the pressure in the chamber to about 1 kpa, and to set the supply gas flow rate to about 3 〇〇 sccm. In the case of a bismuth-type reticle substrate comprising a film containing a material of a transition metal and ruthenium as a light-shielding film, a film of a chrome-based material is used as an etched photomask film on the light-shielding film. Further, in a phase shift type reticle substrate including a film containing a transition metal and a stone material as a phase shift film, a film using a chrome-based material on the phase shift film is used as a light shielding band. The case of the light shielding film. Further, in a reticle substrate comprising a film comprising a transition metal and a material of 152071.doc • 18· 201140230 作为 as a light semi-transmissive film, a film of a chrome-based material is used as a film on the semi-transmissive film for forming The case of the light shielding film of the light shielding tape. Further, on the light-shielding film of the chromium-based material, a film comprising a film of a material which can be dry-etched by a fluorine-based gas as a film of the etching mask is laminated. In such cases, the above method or the removal method of the prior chromium-based material may be used at the stage of removing the film of the chromium-based material. According to the regeneration method, by contacting a film such as a mask base with a substance containing a non-excited state (preferably a non-excited and flammable state) of the compound of the present invention, it is combined with a substrate containing glass (especially A higher etching selectivity is obtained between the quartz substrates), so that damage to the substrate after film removal can be reduced. In this way, after the film is removed from the mask substrate, the surface of the substrate is precisely ground for a short time, thereby recovering the surface roughness of the substrate after the film is removed. The regeneration method is caused by the removal of the film. The surface of the substrate is less damaged, so that the amount of polishing in the case of regrind is small, so that it can be returned to the final stage (precision grinding) in the grinding step from the coarse grinding to the precise grinding. Therefore, since the load is less in the step of re-polishing, the regeneration cost of the substrate can be reduced' and the substrate of high quality can be regenerated. As described above, this regeneration method is particularly suitable for substrate reproduction using a mask base having a high added value of a high-priced substrate because it can reproduce a substrate of high quality at a low cost. Further, a method of manufacturing a mask base using a substrate regenerated by the reproducing method can be provided. In other words, on the substrate regenerated by the regenerating method, for example, a thin film forming method is used, and a thin film for forming a pattern 152071.doc • 19-201140230 film is formed again, whereby high-quality recycling can be manufactured at low cost. The reticle base of the substrate. [Second Embodiment] A second embodiment of the present invention is a method for reproducing a substrate, which is characterized in that a main surface of a substrate containing glass is provided with a low refractive index layer and a high refractive index layer alternately a method of removing a substrate by removing the multilayer reflective film of the multilayer reflective film of the multilayer reflective film having a laminated structure, and the above-mentioned multilayer reflective film with the multilayer reflective substrate and the gas (C1) and bromine (Br) Any one of iodine (I) and ruthenium (Xe) is contacted with a non-excited state of the compound of fluorine (F) to remove it. In recent years, in the semiconductor industry, EUV lithography, which is an exposure technique using Extreme Ultra Violet (hereinafter referred to as EUV) light, has been considered to be promising with the miniaturization of semiconductor devices. Here, the term "EUV light" refers to light in a wavelength band of a soft X-ray region or a vacuum ultraviolet region, and specifically, light having a wavelength of about 0.2 to 100 nm. As a photomask used in the EUV lithography, a reflective reticle is proposed. The reflective reticle is such that a multilayer reflective film having reflected light is formed on the substrate, and the multilayer reflective film is formed on the substrate. The absorber film that absorbs the exposed light is formed into a pattern. The multilayer reflective film substrate can be used as a reflective reticle substrate for manufacturing the reflective reticle, that is, a multilayer reflective film having a light for reflecting exposure on a substrate, and an absorber for forming a pattern for absorbing exposure light. A substrate for a reflective mask substrate of a film. Further, after the multilayer reflective film is formed on the substrate, the multilayer reflective film substrate which is found to have a sub-film defect or the like by surface defect inspection cannot be used as a substrate for a reflective mask base, and therefore 152071.doc • 20· 201140230 It is desirable to temporarily remove the multilayer reflective film and regenerate the substrate. The multilayer reflective film is a multilayer film in which a low refractive index layer and a high refractive index layer are alternately laminated. Generally, a film of a heavy element or a compound thereof, and a film of a light element or a compound thereof are alternately laminated. The multilayer film formed by the cycle. For example, as the multilayer reflective film of EUV light having a wavelength of 13 to 14 nm, a Mo/Si periodic laminated film formed by alternately stacking a Mo film and a Si film for about 40 cycles can be preferably used. In addition, as a multilayer reflective film used in the region of EUV light, there are a Ru/Si periodic multilayer film, a periodic film, a Mo compound/si compound periodic multilayer film, and a Si/Nb periodic multilayer film. , Si/M〇/Ru periodic multilayer film, Si/M〇/Ru/M〇 periodic multilayer film,

Si/Ru/Mo/Ru週期多層膜等。只要根據曝光波長適當選擇 材質即可。 又，作為上述玻璃基板，為了防止曝光時之熱所致之圖 案之變形’宜使用具有㈣·〇χ1()·7/χ^範圍内、更佳為 0±0.3xl(TVC之範圍内之低熱膨脹係數者，作為具有該範 圍之低熱膨脹係數之素材，例如可使用若為非晶玻璃，則 只要為Si〇2_Ti〇j玻璃、石英玻璃、結晶化玻璃即可析出 β:英固溶體之結晶化玻璃等。χ，為了獲得高反射率及 高轉印精纟’較m有較高之平滑性與平土旦度之基板。 尤佳為具有〇·15 nmRq以下之平滑之表面⑽㈣見方區域 中之平滑性)與50 nm以下之平坦度(142 _見方區域中之 平坦度）。再者，表示平滑性之單位Rq為均方根粗糙度， 可利用原子力顯微鏡敎。又，平坦度係由TIR(T〇tai 152071.doc 21 201140230Si/Ru/Mo/Ru periodic multilayer film and the like. Simply select the material according to the exposure wavelength. Further, as the glass substrate, in order to prevent deformation of the pattern due to heat during exposure, it is preferable to use a range of (4)·〇χ1()·7/χ^, more preferably 0±0.3xl (within the range of TVC). In the case of a low thermal expansion coefficient, as a material having a low thermal expansion coefficient in this range, for example, if amorphous glass is used, β: in solid solution can be precipitated as long as Si〇2_Ti〇j glass, quartz glass, or crystallized glass. Crystallized glass, etc.. In order to obtain high reflectivity and high transfer precision, a substrate with higher smoothness and flatness than m. Especially a smooth surface with 〇15 nmRq or less (10) (4) See the smoothness in the square area) and the flatness below 50 nm (142 _ _ flatness in the square area). Further, the unit Rq indicating the smoothness is a root mean square roughness, and can be obtained by an atomic force microscope. Also, the flatness is determined by TIR (T〇tai 152071.doc 21 201140230

Indicated Reading，量錶讀數差）所示之表示表面之翹曲 (變形量）之值，且係將以基板表面為基準利用最小平方法 而決定之平面作為焦平面，較該焦平面處於更上方之基板 表面之最高位置、與較焦平面處於更下方之基板表面之最 低位置的高低差之絕對值。 該再生方法適合再生例如如上述M〇/Si週期積層膜般之 上述低折射率層包含矽（Si)、且接觸於上述基板之主表面 而形成之附多層反射膜基板的基板。又，該再生方法適合 再生例如如上述Si〇2_Ti〇2系玻璃般之基板包含低熱膨脹玻 璃之附多層反射膜基板之基板。尤其，於Si〇2_Ti〇2系低熱 膨脹玻璃之情形時’若欲利用氫氟酸溶液或矽氫氟酸溶液 將基板主表面上之多層反射膜剝離，則存在由於Ti自基板 脫落’而導致表面粗縫度大幅惡化之較大問題，因此該再 生方法尤其有效。 即便於附多層反射膜基板中，亦可藉由使附多層反射膜 基板之多層反射膜與含有本發明之化合物之非激發狀態之 物質接觸將其去除而再生基板。 於本實施形態中，作為化合物，即氯（C1)、溴（Br)、破 ⑴、及氙（Xe)中之任一元素與氟（F)之化合物，與上述第1 實施形態之情形相同’例如，可較佳地使用C1F3、C1F、Indicated Reading, the difference in the reading of the gauge) indicates the value of the warpage (deformation amount) of the surface, and the plane determined by the least square method based on the surface of the substrate is used as the focal plane, which is higher than the focal plane. The absolute value of the height difference between the highest position of the substrate surface and the lowest position of the substrate surface located below the focal plane. This reproducing method is suitable for reproducing a substrate having a multilayer reflective film substrate formed by contacting the main surface of the substrate with the low refractive index layer containing bismuth (Si) as in the above-described M〇/Si periodic laminated film. Further, the reproducing method is suitable for regenerating a substrate including a multilayer reflective film substrate having a low thermal expansion glass, such as the above-mentioned Si〇2_Ti〇2 glass. In particular, in the case of Si〇2_Ti〇2 based low thermal expansion glass, if the multilayer reflective film on the main surface of the substrate is to be peeled off by using a hydrofluoric acid solution or a hydrofluoric acid solution, there is a case where Ti is detached from the substrate. This method of regeneration is particularly effective because the surface roughness is greatly deteriorated. That is, in the multilayer reflective film substrate, the substrate can be regenerated by contacting the multilayer reflective film with the multilayer reflective film substrate in contact with the non-excited state of the compound of the present invention. In the present embodiment, the compound, that is, the compound of any one of chlorine (C1), bromine (Br), broken (1), and xenon (Xe) and fluorine (F) is the same as in the first embodiment. 'For example, C1F3, C1F, etc. can be preferably used.

BrF5、BrF、IF3、IF5、XeF2、XeF4、XeF6、XeOF2、 XeOF4、Xe02F2、Xe03F2或Xe02F4等化合物，可尤佳地使 用 C1F3 。 作為使多層反射膜與含有本發明之化合物之非激發狀態 152071.doc -22- 201140230 之物質接觸的方法，與上述第1實施形態相同，可列舉如 下方法：於腔室内設置光罩基底，將含有本發明之化合物 之物質以氣體狀態導入至該腔室内，而將腔室内以該氣體 置換。又’與上述第i實施形態相同，亦可使用圖1所示之 處理裝置’將玻璃基板上之多層反射膜去除。於以氣體狀 態使用含有本發明之化合物之物質之情形時，可使用本發 明之化合物與氮氣、或氬（Ar)等之混合氣體。於此情形 時’且使用本發明之化合物與氬（Ar)之混合氣體。 關於使多層反射膜與含有本發明之化合物之非激發之氣 體狀態的物質接觸之情形之較佳的處理條件，例如氣體流 里、氣體壓力、溫度、處理時間之較佳之條件而言，與上 述第1實施形態之情形大致相同，較理想為根據多層反射 膜之材料或層數（膜厚）而適當選定。 根據該再生方法，由於藉由使上述附多層反射膜基板之 多層反射膜與含有上述化合物之非激發狀態之物質接觸， 而於與包含玻璃之基板（尤其係低熱膨脹性玻璃基板）之間 可獲得較高之姓刻選擇性，因此可使多層反射膜之去除後 之基板之損傷減少。 如此，於自附多層反射膜基板去除多層反射膜之後，對 基板之表面進行再研磨，藉此可恢復為多層反射膜去除前 之高平滑之基板之表面粗糙度。該再生方法因多層反射膜 之去除所致之基板表面之損傷較少，故而再研磨之情形之 研磨直亦較少即可’從而能夠回到自粗研磨至精密研磨之 複數階段之研磨步驟中之最終階段（精密研磨）。因此，由 152071.doc -23- 201140230 於再研磨之步驟負荷亦變少，故而可降低基板之再生成 本，並且可再生高品質之基板。又，該再生方法因能夠以 低成本再生高品質之基板，故尤其適合於使用具有高附加 價值之高價之基材之附多層反射膜基板之基板再生。 又’亦可提供使用藉由該再生方法而再生之基板之附多 層反射膜基板之製造方法。使用例如DC(Direct Current， 直流）磁控濺鍍法或離子束濺鍍法，於藉由該再生方法而 再生之基板上，再次形成使低折射率層與高折射率層交替 地積層而成之結構之多層反射膜，藉此能夠以低成本製造 使用高品質之再生基板之附多層反射膜基板。 又’該再生方法不僅使上述附多層反射膜基板之基板再 生’亦適合於反射型光罩基底之基板之再生。即，可於基 板之主表面上’使反射型光罩基底或使用該反射型光罩基 底所製作之反射型光罩之上述多層反射膜、與含有上述化 合物之非激發狀態之物質接觸而將其去除，藉此再生基 板，上述反射型光罩基底係依序具備使低折射率層與高折 射率層交替地積層而成之結構之多層反射膜、與圖案形成 用之吸收體膜。 再者，上述吸收體膜係具有吸收作為曝光之光之例如 EUV光之功能者，且可較佳地使用例如钽單體或以 為成刀之材料。作為以Ta為主成分之材料，可使用含有 Ta與B之材料，含有^與^^之材料，含有Ta#B、進而含有 〇與N之至少任一者之材料，含有^與“之材料，含有仏、 Si與N之材料，含有Ta#Ge之材料，含有η、^與N之材 152071.doc -24 - 201140230 料，含有Ta與Hf之材料，含有Ta、H^N之材料，含有 h、财與〇之材料，含有Ta與Zr之材料，含有Ta、Zr^N 之材料，及含有Ta、Zr與〇之材料等。 又，通常，為了保護多層反射膜，而於多層反射膜與吸 收體膜之間設置保護膜或緩衝膜。作為保護膜之材料，除 了夕以外，還可使用釕或於釘令含有銳、錯、姥之中1種 以上之元素之釕化合物，作為緩衝膜之材料，主要使用上 述絡系材料。 根據忒再生方法，於此種反射型光罩基底或反射型光罩 之It形時，能夠將上述多層反射膜與積層於其上之吸收體 膜（具有保護膜之情形時為保護膜及吸收體膜）一併去除。 亦於再生反射型光罩基底或反射型光罩之基板之情形 時，以氣體狀態使用含有本發明之化合物之物質之情形 時，亦可使用本發明之化合物與氮氣、或氬（Ar)等之混合 氣體。於再生反射型光罩基底或反射型光罩之基板之情形 時’亦可較佳地使用上述本發明之化合物與氬（Ar)之混合 氣體°關於使反射型光罩基底等之多層反射膜與含有本發 明之化合物之非激發之氣體狀態的物質接觸之情形時之較 佳的處理條件’例如氣體流量、氣體壓力、溫度、處理時 間之較佳之條件而言，與上述附多層反射膜基板之情形大 致相同。 再者’關於吸收體膜使用鉻系材料之構成、或設置有鉻 系材料之緩衝膜之構成之反射型光罩基底或反射型光罩而 吕’絡系材料之吸收體膜或緩衝膜之去除可使用上述方法 152071.doc •25· 201140230 或先前之鉻系材料之去除方法。 根據該再生方法’藉由使上述反射型光罩基底等之多層 反射膜與含有本發明之化合物之非激發狀態之物質接觸， 而於與玻璃基板（尤其係低熱膨脹性玻璃基板）之間獲得較 尚之姓刻選擇性，因此可使多層反射膜與其上之積層膜 (吸收體膜，或者保護膜及吸收體膜）之去除後之基板的損 傷變少。該再生方法因如此般多層反射膜等之去除所致之 基板表面之損傷較少，故而再研磨之步驟負荷亦變少，從 而可降低基板之再生成本，並且可再生高品質之基板。 又’亦可提供一種使用藉由該再生方法而再生之基板之 反射型光罩基底之製造方法。即，使用例如DC磁控濺鍍 法或離子束錢鐘法’於藉由該再生方法而再生之基板上形 成使低折射率層與高折射率層交替地積層而成之結構多層 反射膜，於其上，藉由磁控濺鍍法等，而形成保護膜或圖 案形成用之吸收體膜（或者緩衝膜及吸收體膜），藉此以低 成本製造使用高品質之再生基板之反射型光罩基底。 又’於處理對象之反射型光罩基底或反射型光罩之構成 為多層反射膜上之保護膜使用有鉻系材料，且吸收體膜使 用鉻系以外之材料（鈕單體或以钽為主成分之材料等）之情 形時，亦此夠僅去除吸收體膜。於此情形時，將供給氣體 中之本發明之化合物之濃度（以氣體流量比表示之濃度）設 為80 /〇以上，更佳為9〇%以上，使吸收體膜之表面溫度自 180 c變為220 c即可。又，較理想為將處理時間設為5分 名里以上，更佳為7分鐘以上，將腔室内之壓力設為〜“Ο 152071.doc -26 - 201140230Compounds such as BrF5, BrF, IF3, IF5, XeF2, XeF4, XeF6, XeOF2, XeOF4, Xe02F2, Xe03F2 or Xe02F4 may preferably use C1F3. As a method of bringing the multilayer reflective film into contact with a substance containing the non-excited state of 152071.doc -22- 201140230 of the compound of the present invention, as in the first embodiment, a method of providing a mask base in a chamber will be described. The substance containing the compound of the present invention is introduced into the chamber in a gaseous state, and the chamber is replaced with the gas. Further, similarly to the above-described first embodiment, the multilayer reflective film on the glass substrate can be removed by using the processing apparatus shown in Fig. 1. When a substance containing the compound of the present invention is used in a gaseous state, a mixed gas of a compound of the present invention and nitrogen or argon (Ar) may be used. In this case, a mixed gas of the compound of the present invention and argon (Ar) is used. Preferred processing conditions for contacting the multilayer reflective film with a substance containing a non-excited gaseous state of the compound of the present invention, for example, a gas stream, a gas pressure, a temperature, a treatment time, and the like The case of the first embodiment is substantially the same, and is preferably selected as appropriate depending on the material or the number of layers (film thickness) of the multilayer reflective film. According to the regeneration method, the multilayer reflective film with the multilayer reflective film substrate can be brought into contact with a substrate containing a glass (especially a low thermal expansion glass substrate) by contacting the multi-reflective film containing the compound in a non-excited state. A higher selectivity of the surname is obtained, so that the damage of the substrate after removal of the multilayer reflective film can be reduced. In this manner, after the multilayer reflective film is removed from the multilayer reflective film substrate, the surface of the substrate is repolished, whereby the surface roughness of the highly smooth substrate before the multilayer reflective film is removed can be restored. The regeneration method has less damage to the surface of the substrate due to the removal of the multilayer reflective film, so that the grinding in the case of re-grinding is less straightened, so that it can be returned to the grinding step from the coarse grinding to the precision grinding. The final stage (precision grinding). Therefore, the load is reduced in the regrind step by 152071.doc -23- 201140230, so that the reconstitution of the substrate can be reduced and the high quality substrate can be regenerated. Further, since this reproducing method can reproduce a high-quality substrate at a low cost, it is particularly suitable for substrate regeneration using a multilayer reflective film substrate having a high-value-added substrate. Further, a method of manufacturing a multi-layer reflective film substrate using a substrate regenerated by the reproducing method can be provided. By using, for example, DC (Direct Current) magnetron sputtering or ion beam sputtering, the low refractive index layer and the high refractive index layer are alternately laminated on the substrate regenerated by the regeneration method. The multilayer reflective film having the structure can thereby manufacture a multilayer reflective film substrate using a high-quality recycled substrate at low cost. Further, the reproducing method not only regenerates the substrate on which the multilayer reflective film substrate is attached, but is also suitable for the reproduction of the substrate of the reflective mask substrate. That is, the multilayer reflective film of the reflective mask base or the reflective mask produced using the reflective mask base can be brought into contact with the non-excited state containing the compound on the main surface of the substrate. The substrate is removed, and the reflective mask substrate is provided with a multilayer reflective film having a structure in which a low refractive index layer and a high refractive index layer are alternately laminated, and an absorber film for pattern formation. Further, the above absorber film has a function of absorbing, for example, EUV light as light for exposure, and a material such as a ruthenium monomer or a knife can be preferably used. As a material containing Ta as a main component, a material containing Ta and B, a material containing ^ and ^^, a material containing at least one of Ta#B and further containing yttrium and N, and a material containing "and" may be used. a material containing ruthenium, Si and N, a material containing Ta#Ge, a material containing η, ^ and N 152071.doc -24 - 201140230 material, a material containing Ta and Hf, a material containing Ta, H^N, A material containing h, money, and bismuth, a material containing Ta and Zr, a material containing Ta, Zr^N, a material containing Ta, Zr, and bismuth, etc. Further, in order to protect the multilayer reflective film, it is reflected in multiple layers. A protective film or a buffer film is provided between the film and the absorber film. As a material of the protective film, a ruthenium compound containing one or more elements including sharp, wrong or ruthenium may be used as a material for the protective film. The material of the buffer film mainly uses the above-mentioned composite material. According to the 忒 regeneration method, when the reflective reticle base or the reflective reticle is formed in an It shape, the multilayer reflective film and the absorber film laminated thereon can be laminated. (When there is a protective film, it is a protective film and an absorber film) Also, in the case of regenerating a reflective reticle base or a substrate of a reflective reticle, when a substance containing the compound of the present invention is used in a gaseous state, the compound of the present invention may be used with nitrogen or argon (Ar). Mixture gas, etc. When regenerating the reflective reticle base or the substrate of the reflective reticle, it is also preferable to use the above-mentioned compound of the present invention and argon (Ar) mixed gas. Preferred processing conditions for a multilayer reflective film of a substrate or the like in contact with a substance containing a non-excited gaseous state of the compound of the present invention, such as a preferred condition of gas flow rate, gas pressure, temperature, and treatment time, The above-mentioned multilayer reflective film substrate is substantially the same. Further, a reflective reticle base or a reflective reticle is used in which a chrome-based material is used as the absorber film or a buffer film of a chrome-based material is provided. The removal of the absorber film or buffer film of the matrix material may be carried out using the above method 152071.doc • 25· 201140230 or the previous method of removing the chromium material. The regeneration method is obtained by bringing a multilayer reflective film such as the reflective mask base or the like into contact with a substance containing a non-excited state of the compound of the present invention to obtain a comparison with a glass substrate (especially a low thermal expansion glass substrate). Since the surname is selective, the damage of the substrate after removal of the multilayer reflective film and the laminated film (absorber film or protective film and absorber film) thereon is reduced. The regeneration method is such a multilayer reflective film. Since the damage of the substrate surface caused by the removal is small, the load of the regrind step is also reduced, so that the regeneration cost of the substrate can be reduced, and a high-quality substrate can be regenerated. Further, a regeneration method can be provided. A method of manufacturing a reflective reticle substrate of a regenerated substrate. That is, a structural multilayer reflective film in which a low refractive index layer and a high refractive index layer are alternately laminated is formed on a substrate reproduced by the regeneration method using, for example, a DC magnetron sputtering method or an ion beam clock method. On the other hand, an absorber film (or a buffer film and an absorber film) for forming a protective film or a pattern is formed by a magnetron sputtering method or the like, thereby producing a reflective type using a high-quality regenerated substrate at low cost. Photomask base. Further, the reflective mask base or the reflective mask of the processing target is formed of a chrome-based material for the protective film on the multilayer reflective film, and the absorbing material is made of a material other than the chrome-based material. In the case of a material of the main component, etc., it is also sufficient to remove only the absorber film. In this case, the concentration of the compound of the present invention (concentration expressed by the gas flow ratio) in the supply gas is set to 80 / 〇 or more, more preferably 9 % by weight or more, so that the surface temperature of the absorber film is from 180 c. It becomes 220 c. Further, it is preferable to set the processing time to 5 or more, more preferably 7 minutes or more, and set the pressure in the chamber to ~ "Ο 152071.doc -26 - 201140230

Ton*。藉此，可自反射型光罩基底或反射型光罩再生附多 層反射膜基板。進而，可藉由在該經再生之附多層反射膜 基板上再次形成吸收體膜，而製造反射型光罩基底。 [第3實施形態] 本發明之第3實施形態係一種基板之再生方法，其特徵 在於：其係關於將於包含玻璃之基板之主表面上具備圖案 形成用之薄膜之光罩基底中，藉由乾式姓刻處理而對上述 薄膜及上述基板進行蝕刻加工之壓印用模具之製作方法所 對應的光罩基底之上述薄膜去除而再生基板之方法，且使 上述光罩基底之上述薄膜與含有氯、溴（Br)、碘G)、 及氙（Xe)中之任一元素與氟（F)之化合物的非激發狀態之物 質接觸而將其去除。 於藉由半導體裝置之微細電路圖案、微細圖案而附加有 光學功能之光學零件製作、使用於硬磁碟驅動機等之磁性 記錄媒體中之磁性層之微細圖案形成所使用的壓印用模具 (壓模）之製作中，使用在合成石英玻璃等玻璃基板上具備 圖案形成用之薄膜之光罩基底。於該光罩基底上形成所期 望之抗蝕劑圖案，將該抗蝕劑圖案作為光罩而對上述薄膜 進行蝕刻加工，藉此形成薄膜圖案（光罩圖案），進而將該 薄膜圖案作為光罩，對上述基板進行蝕刻加工，從而於透 光性基板形成階梯圖案，藉此製作壓印用模具。 該再生方法亦適合於此種壓印用模具之製作方法所對應 之光罩基底之基板之再生。 該再生方法尤其適合於如下基板之再生：上述光罩基底 152071 .doc •27· 201140230 中之薄膜包含單層或複數層，至少接觸於上述基板之層係 藉由以纽㈣為主成分之材料而形成之光罩基底。作為此 種光罩基底，例如’可列舉如下光罩基底等作為—例：上 述4膜至包含上層與下層之積層膜，上層係由以&為主 成分之㈣形成’下層係由以钽⑽為主成分之材料形 成且月b夠藉由使用氣系氣體之乾式姓刻處理而對該等薄 膜進行姓刻加 JL 〇 以1_為主成分之材料，有例如等丁压 化合物，或者以該等Ta化合物作為基礎材料並添加有例如 B、Ge ' Nb ' Si、C、N等副材料而成之材料等。然而，以 Ta為主成分之材料具有與含有氧之氣體接觸時易於被氧化 之特性。除了以TaHf、TaZr、TaHfZr為主成分之材料以外 以Ta為主成分之材料，能夠由激發狀態之氣系氣體與激發 狀態之氟系氣體之兩者而触刻，但以經氧化之Ta為主成分 之材料則難以由使用有激發狀態之氣系氣體之乾式蝕刻而 蝕刻，變成僅能夠由激發狀態之氟系氣體而蝕刻。於此情 形時’敗系氣體變得難以獲得與玻璃基板之蝕刻選擇性， 剝離後之玻璃基板之損傷變大，因此本發明之效果非常明 顯。 又’以TaHf、TaZr、TaHfZr為主成分之材料能夠由激發 狀態之氯系氣體而蝕刻，但難以由激發狀態之氟系氣體而 蝕刻。該等材料亦易於氧化，若氧化則變得由激發狀態之 氣糸氣體亦難以钱刻。於此情形時，於與玻璃基板之間， 變得難以獲得由氣系氣體而進行之蝕刻選擇性，剝離後之 152071.doc •28- 201140230 玻璃基板之損傷變大，因此本發明之效果非常明顯。 上述光罩基底用之基板可使用合成石英基板、其他各種 玻璃基板（例如驗石灰玻璃、鋁矽酸鹽玻璃等），其中尤佳 為使用合成石英基板。 於本實施形態之壓印用模具之製作方法所對應之光罩基 底中，亦可藉由使光罩基底之薄膜與含有本發明之化合物 之非激發狀態之物質接觸而將其去除從而再生基板。 關於本實施形態中所使用之本發明之化合物，即氣 (C1)、溴（Br)、蛾（I)、及氙（Xe)之中之任一元素與氟（F)之 化合物而言，亦與上述第1實施形態之情形相同，例如， 可較佳地使用 C1F3、C1F、BrF5、BrF、IF3、IF5、XeF2、 XeF4、XeF6、XeOF2、XeOF4、Xe02F2、Xe03F2 或 Xe02F4 等化合物，可尤佳地使用C1F3。 於本實施形態中，作為使光罩基底之薄膜與含有本發明 之化合物之非激發狀態之物質接觸之方法，亦與上述第1 實施形態相同，可較佳地列舉如下方法：於腔室内設置光 罩基底，將含有本發明之化合物之物質以氣體狀態導入至 該腔室内，而將腔室内以該氣體置換。又，與上述第1實 施形態相同，亦可使用圖1所示之處理裝置，將光罩基底 薄膜去除。於以氣體狀態使用含有本發明之化合物之物質 之情形時，可使用本發明之化合物與氮氣或氬（Ar)等之混 合氣體。又，於該情形時，可較好地使用本發明之化合物 與氬（Ar)之混合氣體。關於使光罩基底之薄膜與含有本發 明之化合物之非激發之氣體狀態之物質接觸之情形之較佳 152071.doc -29- 201140230 的處理條件’例如氣體流量、氣體壓力、溫度、處理時間 ，較佳之條件而言，與上述第！實施形態之情形大致相 5 理心為根據薄膜之材料或層數（膜厚）而適當選定。 "據該再生方法，使上述壓印用模具之製作方法所對應 之光罩基底之薄膜與含有本發明之化合物的非激發狀態之 質接觸而將其去除’藉此於與包含玻璃之基板（尤其係 〇成石英玻璃基板）之間可獲得較高之蝕刻選擇性，因此 可使去除薄膜後之基板之損傷變少。 如此，於本實施形態中，亦由於因薄膜之去除所致之基 板表面之損傷較少，故再研磨之步驟負荷亦變少，藉此可 降低基板之再生成本，並且可再生高品質之基板。 又’亦可提供一種使用藉由該再生方法而再生之基板之 壓印用模具之製作方法所對應的光罩基底之製造方法。 即，使用例如DC磁控濺鍍法等，而於藉由該再生方法而 再生之基板上再次形成圖案形成用之薄膜，藉此能夠以低 成本製造使用高品質之再生基板之光罩基底。 [實施例] 以下’藉由實施例’而更具體地對本發明之實施形態進 行說明。並且，亦對相對於實施例之比較例進行說明。 (實施例1) 於包含合成石英玻璃之透光性基板上，使用單片式濺渡 裝置’對濺渡靶材使用鉬（Mo)與矽（Si)之混合靶材（原子％ 比Mo:Si=12:88)，於氬（Ar)、氮（N2)及氦（He)之混合氣體環 境（氣體壓力0.3 Pa，氣體流量比Ar:N2:He=8:72:100)中， 152071.doc •30· 201140230 將DC電源之電力設為3.0 kW，藉由反應性濺鍍（DC濺 鍍），而形成膜厚70 nm之由以鉬、矽、及氮為主要構成要 素之單層所構成之ArF準分子雷射（波長193 nm)用相位偏 移膜，從而製作相位偏移光罩基底。再者，該相位偏移膜 於ArF準分子雷射（波長193 nm)中，透射率變為4.52%，相 位差變為182.5度。 其次，若假設以上述方式而製作之相位偏移光罩基底中 存在有不能容許之表面缺陷，則將該相位偏移光罩基底之 相位偏移膜去除而進行基板之再生。 即，於腔室内設置上述相位偏移光罩基底，向該腔室内 導入C1F3與Ar之混合氣體（流量比ClF3:Ar=0.2:1.8(SLM (Standard Liter per Minute，每分鐘標準升）)），而將腔室 内以該氣體置換，藉此使上述相位偏移光罩基底之相位偏 移膜接觸於非激發狀態之上述混合氣體。將此時之氣體壓 力調節為488〜502 Torr，將溫度調節為195〜202°C，將處理 時間設為10分鐘。 利用電子顯微鏡對如此去除包含MoSiN之相位偏移膜之 基板的表面進行觀察後，未確認到相位偏移膜之殘渣或白 濁等之變質層之產生。又，測定相位偏移膜去除後之基板 之表面反射率（200〜700 nm)，與成膜前之基板沒有變化。 進而，利用原子力顯微鏡（AFM，Atomic Force Microscopy) 測定將相位偏移膜去除之基板之表面粗糙度之結果為 Ra=0.32 nm，Rmax=6.27 nm，與相位偏移膜之剝離前之基 板之表面粗链度（Ra=0.11 nm、Rmax=l .26 nm)相比則變得 152071.doc -31 - 201140230 稍微粗糙，但是藉由對基板表面進行再精密研磨（通常之 研磨步驟中之最終階段）而可容易地恢復表面粗糙度。 即’根據該再生方法，可確認到去除薄膜後之基板之損 傷較少^ 又’藉由在以上述方式所再生之基板上再次形成上述相 位偏移膜’可製造使用可高品質之再生基板之相位偏移型 光罩基底。 (實施例2) 於包含合成石英玻璃之透光性基板上，使用單片式濺渡 裝置’對濺渡靶材使用鉬（Mo)與矽（Si)之混合靶材（原子％ 比Mo:Si=21:79)，於氬（Ar)與氮（N2)之混合氣體環境（氣體 壓力0.07 Pa’氣體流量比Ar:N2=25:28)中，將DC電源之電 力設為2.1 kW，藉由反應性濺鍍（DC濺鍍），以膜厚5〇 nm 形成M0S1N膜（遮光層），繼而’使用M〇/Si靶材（原子％比 Mo:Si=4:96)，於氬（Ar)、氧（〇2)、氮（n2)及氦（He)之混合 氣體環境（氣體壓力0.1 Pa，氣體流量比Ar:〇2:N2:He= 6:3:11:17)中，將1)(：電源之電力設為3()1{^，以膜厚1〇1^ 形成MoSiON膜（防表面反射層），藉此形成包含M〇SiN膜與 MoSiON膜之積層之ArF準分子雷射（波長193 nm)用遮光 . 膜，從而製作二元型光罩基底。再者，相對於ArF準分子 雷射之遮光膜之光學濃度為3.0。 其-人，右假設以上述方式而製作之二元型光罩基底中存 在有不能容許之表面缺陷’則將該二元型光罩基底之遮光 膜去除而進行基板之再生。 152071.doc •32- 201140230 即，於腔室内設置上述二元型光罩基底，向該腔室内導 入C1F3與Ar之混合氣體（流量比ClF3:Ar=0.2:1.8(SLM))，而 將腔室内以該氣體置換，藉此使上述二元型光罩基底之遮 光膜與非激發狀態之上述混合氣體接觸。將此時之氣體壓 力調節為495〜5〇2 Torr ’將溫度調節為195〜201。(：，將處理 時間設為10分鐘。 利用電子顯微鏡對如此去除包含MoSiN膜與MoSiON膜 之積層之遮光膜之基板的表面進行觀察後，未確認到遮光 膜之殘渣或白濁等之變質層之產生。又，測定遮光膜去除 後之基板之表面反射率（200〜700 nm)，與成膜前之基板沒 有變化。進而，利用原子力顯微鏡（AFM)測定將遮光膜去 除之基板之表面粗糙度之結果為Ra=〇 22 nm，Rmax=3 ()6 nm ’與遮光膜之剝離前之基板之表面粗縫度 nm、Rmax=1.20 nm)相比變得稍微粗糙，但是藉由對基板 表面進行再精密研磨（通常之研磨步驟中之最終階段）而可 容易地恢復表面粗糙度。 即，根據該再生方法，可確認到去除薄膜後之基板之損 傷較少。 又，藉由在以上述方式所再生之基板上再次形成上述遮 光膜可製造使用向品質之再生基板之二元型光罩基底。 (實施例3) 於包含合成石英玻璃之透光性基板上，使用單片式濺渡 裝置，對濺渡靶材使用钽（Ta)靶材，於氙（Xe)與氮（NO之 混合氣體環境（氣體壓力〇 〇76 pa，氣體流量比Xe : 152071.doc •33· 201140230 乂=71:29)中，將DC電源之電力設為i 5 kw ’藉由反應性 濺鍍（DC濺鍍）’以膜厚42 nm形成TaN膜，繼而，使用化靶 材，於氬（Ar)與氧（〇2)之混合氣體環境（氣體壓力〇 3 pa， 氣體流量比Αι···〇2=58··32·5)中，將Dc電源之電力設為2 〇 kW，以膜厚9 nm形成TaO膜，藉此形成包含TaN膜與Ta〇 膜之積層之ArF準分子雷射（波長193 nm)用遮光膜，從而 製作二元型光罩基底。再者，相對於ArF準分子雷射之遮 光膜之光學濃度為3.1。 其-人，若假设以上述方式而製作之二元型光罩基底中存 在有不能容許之表面缺陷，則將該二元型光罩基底之遮光 膜去除而進行基板之再生。 即，於腔至内设置上述二元型光罩基底，向該腔室内導 入C1F3與Ar之混合氣體（流量比ciF3:Ar=0.2:1.8(SLM))，而 將腔室内以該氣體置換，藉此使上述二元型光罩基底之遮 光膜與非激發狀態之上述混合氣體接觸。將此時之氣體壓 力調節為496〜504 Torr，將溫度調節為198〜wye，將處理 時間設為10分鐘。 利用電子顯微鏡對如此去除包含TaN膜與Ta〇膜之積層 之遮光膜之基板的表面進行觀察後，未確認到遮光膜之殘 渣或白濁等之變質層之產生。又，測定遮光膜去除後之基 板之表面反射率（2〇〇〜7〇〇 nm)，與成膜前之基板沒有變 化。進而，利用原子力顯微鏡（AFM)測定去除遮光膜之基 板之表面粗链度之結果為Ra=l .57 nm，Rmax=21.4 nm，與 遮光臈之剝離前之基板之表面粗糙度（Ra=〇丨丨nm， 152071.doc -34- 201140230Ton*. Thereby, the multi-layer reflective film substrate can be regenerated from the reflective reticle base or the reflective reticle. Further, a reflective mask substrate can be manufactured by forming an absorber film again on the regenerated multilayer reflective film substrate. [Third Embodiment] A third embodiment of the present invention is a method for reproducing a substrate, which is characterized in that a mask substrate having a film for pattern formation on a main surface of a substrate including glass is used. a method of removing a film on a mask base corresponding to a method for producing an imprint mold by etching a film and a substrate by a dry type, and regenerating the substrate, and the film and the film on the mask base Any one of chlorine, bromine (Br), iodine G), and xenon (Xe) is contacted with a non-excited state of the compound of fluorine (F) to remove it. The embossing mold used for forming a fine pattern of a magnetic layer used in a magnetic recording medium such as a hard disk drive or the like, and an optical component to which an optical function is added by a fine circuit pattern or a fine pattern of a semiconductor device ( In the production of a stamper, a mask base having a film for pattern formation on a glass substrate such as synthetic quartz glass is used. Forming a desired resist pattern on the mask substrate, etching the film by using the resist pattern as a mask, thereby forming a thin film pattern (a mask pattern), and further using the film pattern as light In the cover, the substrate is etched to form a step pattern on the light-transmitting substrate, thereby preparing a stamping die. This regeneration method is also suitable for the regeneration of the substrate of the reticle base corresponding to the method of manufacturing the embossing mold. The regeneration method is particularly suitable for the regeneration of a substrate in which the film of the reticle substrate 152071.doc • 27· 201140230 comprises a single layer or a plurality of layers, and at least the layer contacting the substrate is made of a material mainly composed of New Zealand (4). The reticle base is formed. As such a mask base, for example, a mask base or the like can be exemplified as the above-mentioned 4 film to a laminate film including an upper layer and a lower layer, and the upper layer is formed by (4) which is a main component of & (10) The material of the main component is formed and the month b is sufficient for the film to be subjected to a dry-type treatment using a gas-based gas, and the film is subjected to a material of a JL 11_ as a main component, for example, an isobutyl compound, or A material obtained by adding a sub-material such as B, Ge 'Nb 'Si, C, N or the like to the above-mentioned Ta compound as a base material. However, a material containing Ta as a main component has a property of being easily oxidized when it comes into contact with a gas containing oxygen. A material containing Ta as a main component other than TaHf, TaZr, and TaHfZr as a main component can be inscribed by both the gas gas in an excited state and the fluorine-based gas in an excited state, but the oxidized Ta is The material of the main component is hardly etched by dry etching using a gas-based gas having an excited state, and can be etched only by the fluorine-based gas in an excited state. In this case, it is difficult to obtain the etching selectivity with the glass substrate, and the damage of the glass substrate after the peeling becomes large. Therefore, the effects of the present invention are remarkable. Further, a material containing TaHf, TaZr, and TaHfZr as a main component can be etched by a chlorine-based gas in an excited state, but it is difficult to etch by a fluorine-based gas in an excited state. These materials are also prone to oxidation, and if oxidized, the gas is excited by the excited state. In this case, it is difficult to obtain the etching selectivity by the gas-based gas between the glass substrate and the glass substrate, and the damage of the glass substrate after the peeling is 152071.doc • 28-201140230 becomes large, so the effect of the present invention is very obvious. As the substrate for the mask base, a synthetic quartz substrate or various other glass substrates (e.g., limpid glass, aluminosilicate glass, etc.) can be used, and among them, a synthetic quartz substrate is particularly preferably used. In the mask base corresponding to the method for producing an imprint mold of the present embodiment, the film of the photomask base may be removed by contacting the film containing the non-excited state of the compound of the present invention to regenerate the substrate. . The compound of the present invention used in the present embodiment, that is, a compound of any one of gas (C1), bromine (Br), moth (I), and xenon (Xe) and fluorine (F), Also in the same manner as in the first embodiment, for example, a compound such as C1F3, C1F, BrF5, BrF, IF3, IF5, XeF2, XeF4, XeF6, XeOF2, XeOF4, Xe02F2, Xe03F2 or Xe02F4 can be preferably used. Good to use C1F3. In the present embodiment, as a method of bringing the film of the mask base into contact with the substance in the non-excited state of the compound of the present invention, as in the first embodiment, the following method can be preferably used: In the mask substrate, a substance containing the compound of the present invention is introduced into the chamber in a gaseous state, and the chamber is replaced with the gas. Further, similarly to the above-described first embodiment, the mask base film can be removed by using the processing apparatus shown in Fig. 1. When a substance containing the compound of the present invention is used in a gaseous state, a mixed gas of a compound of the present invention and nitrogen or argon (Ar) or the like can be used. Further, in this case, a mixed gas of the compound of the present invention and argon (Ar) can be preferably used. The processing conditions of the preferred 152071.doc -29- 201140230 for the case of contacting the film of the reticle substrate with the substance containing the non-excited gas state of the compound of the present invention, such as gas flow rate, gas pressure, temperature, treatment time, In terms of better conditions, with the above! In the case of the embodiment, it is roughly selected according to the material or the number of layers (film thickness) of the film. According to the regeneration method, the film of the reticle base corresponding to the method for producing the embossing die is brought into contact with the non-excited state of the compound of the present invention to remove the film from the substrate containing the glass. A high etching selectivity can be obtained between (especially, a quartz glass substrate), so that damage to the substrate after film removal can be reduced. As described above, in the present embodiment, since the surface of the substrate is less damaged by the removal of the film, the step load for re-polishing is also reduced, whereby the regeneration cost of the substrate can be reduced, and the high-quality substrate can be regenerated. . Further, a method of manufacturing a mask base corresponding to a method of producing an imprint mold using a substrate reproduced by the reproducing method can be provided. In other words, by using, for example, a DC magnetron sputtering method, a film for pattern formation is formed again on the substrate regenerated by the reproducing method, whereby the mask substrate using the high-quality regenerated substrate can be manufactured at a low cost. [Embodiment] Hereinafter, embodiments of the present invention will be described more specifically by way of the embodiments. Further, a comparative example with respect to the embodiment will be described. (Example 1) On a light-transmissive substrate containing synthetic quartz glass, a monolithic splash device was used to use a mixed target of molybdenum (Mo) and bismuth (Si) for a splash target (atomic % ratio Mo: Si=12:88), in a mixed gas atmosphere of argon (Ar), nitrogen (N2) and helium (He) (gas pressure 0.3 Pa, gas flow ratio Ar: N2: He = 8:72:100), 152071 .doc •30· 201140230 The power of the DC power supply is set to 3.0 kW, and by reactive sputtering (DC sputtering), a single layer with a thickness of 70 nm and containing molybdenum, niobium, and nitrogen as main components is formed. The ArF excimer laser (wavelength 193 nm) was constructed using a phase shift film to fabricate a phase shift mask substrate. Further, in the phase shift film of the ArF excimer laser (wavelength 193 nm), the transmittance became 4.52%, and the phase difference became 182.5 degrees. Next, if it is assumed that there is an unacceptable surface defect in the phase shift mask substrate produced as described above, the phase shift film of the phase shift mask base is removed to regenerate the substrate. That is, the phase shift mask base is disposed in the chamber, and a mixed gas of C1F3 and Ar is introduced into the chamber (flow ratio ClF3: Ar=0.2:1.8 (SLM (Standard Liter per Minute)) The chamber is replaced with the gas, whereby the phase shifting film of the phase shift mask base is brought into contact with the mixed gas in a non-excited state. The gas pressure at this time was adjusted to 488 to 502 Torr, the temperature was adjusted to 195 to 202 ° C, and the treatment time was set to 10 minutes. When the surface of the substrate on which the phase shift film containing MoSiN was removed was observed by an electron microscope, the occurrence of a deteriorated layer such as a residue or a cloud of the phase shift film was not confirmed. Further, the surface reflectance (200 to 700 nm) of the substrate after the phase shift film removal was measured, and the substrate before the film formation was not changed. Further, the surface roughness of the substrate from which the phase shift film was removed was measured by an atomic force microscope (AFM, Atomic Force Microscopy), and the result was Ra = 0.32 nm, Rmax = 6.27 nm, and the surface of the substrate before peeling from the phase shift film. The coarse chain (Ra=0.11 nm, Rmax=l.26 nm) is slightly rougher than 152071.doc -31 - 201140230, but by re-precision grinding the surface of the substrate (usually the final stage in the grinding step) ) The surface roughness can be easily restored. That is, according to the regeneration method, it is confirmed that the damage of the substrate after the removal of the film is small. Further, the high-quality regenerated substrate can be manufactured by forming the phase-shift film again on the substrate reproduced in the above manner. Phase shift type reticle substrate. (Example 2) A mixed target of molybdenum (Mo) and bismuth (Si) was used for a splash target on a light-transmissive substrate containing synthetic quartz glass using a monolithic splash device (atomic % ratio Mo: Si=21:79), in a mixed gas atmosphere of argon (Ar) and nitrogen (N2) (gas pressure 0.07 Pa' gas flow ratio Ar: N2 = 25: 28), the power of the DC power source was set to 2.1 kW, The MOS1N film (light-shielding layer) was formed by reactive sputtering (DC sputtering) at a film thickness of 5 〇 nm, and then 'M〇/Si target (atomic % ratio Mo: Si=4:96) was used in argon. (A), oxygen (〇2), nitrogen (n2) and helium (He) mixed gas environment (gas pressure 0.1 Pa, gas flow ratio Ar: 〇 2: N2: He = 6: 3: 11: 17) , 1) (: power supply power is set to 3 () 1 {^, a film thickness of 1 〇 1 ^ is formed to form a MoSiON film (anti-surface reflection layer), thereby forming an ArF comprising a laminate of an M 〇 SiN film and a MoSiON film. The excimer laser (wavelength 193 nm) uses a light-shielding film to fabricate a binary mask substrate. Furthermore, the optical density of the light-shielding film relative to the ArF excimer laser is 3.0. Formed in a binary reticle substrate The surface defect of the binary mask is removed, and the light-shielding film of the binary mask base is removed to regenerate the substrate. 152071.doc •32- 201140230 That is, the above-mentioned binary mask base is placed in the chamber, and the chamber is placed inside the chamber. Introducing a mixed gas of C1F3 and Ar (flow ratio ClF3: Ar=0.2:1.8 (SLM)), and replacing the gas in the chamber with the gas, thereby making the light-shielding film of the binary type mask base and the non-excited state described above The gas is contacted. The gas pressure at this time is adjusted to 495 to 5 〇 2 Torr 'The temperature is adjusted to 195 to 201. (:, the treatment time is set to 10 minutes. The removal of the MoSiN film and the MoSiON film by the electron microscope is thus performed. After observing the surface of the substrate of the light-shielding film of the laminate, no deterioration of the light-shielding film or the occurrence of a deteriorated layer such as white turbidity was observed. Further, the surface reflectance (200 to 700 nm) of the substrate after the removal of the light-shielding film was measured. The substrate before the film did not change. Further, the surface roughness of the substrate from which the light-shielding film was removed was measured by atomic force microscopy (AFM), and the result was Ra = 〇 22 nm, Rmax = 3 () 6 nm ' and before the peeling of the light-shielding film base The surface roughness nm, Rmax=1.20 nm) is slightly rougher than that, but the surface roughness can be easily restored by re-precision polishing the substrate surface (usually the final stage in the grinding step). According to this regeneration method, it was confirmed that the substrate after the film removal was less damaged. Further, by forming the light-shielding film again on the substrate reproduced as described above, a binary mask using a quality-reproduced substrate can be manufactured. Substrate. (Example 3) Using a monolithic splash device on a light-transmissive substrate containing synthetic quartz glass, a tantalum (Ta) target was used for the splash target, and a mixed gas of xenon (Xe) and nitrogen (NO) was used. In the environment (gas pressure 〇〇76 pa, gas flow ratio Xe: 152071.doc •33· 201140230 乂=71:29), the power of the DC power supply is set to i 5 kw 'by reactive sputtering (DC sputtering) ) 'TaN film is formed at a film thickness of 42 nm, and then a target gas is used in a mixed gas atmosphere of argon (Ar) and oxygen (〇2) (gas pressure 〇3 pa, gas flow ratio Αι···〇2= In 58.·32·5), the power of the Dc power source is set to 2 〇 kW, and a TaO film is formed at a film thickness of 9 nm, thereby forming an ArF excimer laser including a laminate of a TaN film and a Ta 〇 film (wavelength 193). Nm) using a light-shielding film to fabricate a binary photomask substrate. Further, the optical density of the light-shielding film with respect to the ArF excimer laser is 3.1. It is assumed that the binary light produced in the above manner is assumed If there is an unacceptable surface defect in the cover substrate, the light shielding film of the binary mask base is removed to regenerate the substrate. The binary type mask substrate is disposed inwardly, and a mixed gas of C1F3 and Ar is introduced into the chamber (flow ratio ciF3: Ar=0.2:1.8 (SLM)), and the chamber is replaced with the gas, thereby making the above The light-shielding film of the binary reticle base is brought into contact with the mixed gas in the non-excited state, and the gas pressure at this time is adjusted to 496 to 504 Torr, the temperature is adjusted to 198 to wye, and the processing time is set to 10 minutes. When the surface of the substrate including the light-shielding film of the TaN film and the Ta 〇 film was removed by the microscope, the deterioration of the light-shielding film or the deterioration layer such as white turbidity was not observed. Further, the surface of the substrate after the light-shielding film removal was measured. The reflectance (2 〇〇 to 7 〇〇 nm) did not change from the substrate before film formation. Further, the surface roughness of the substrate on which the light-shielding film was removed by atomic force microscopy (AFM) was Ra = 1.57 nm. , Rmax=21.4 nm, surface roughness of the substrate before peeling off with shading Ra (Ra=〇丨丨nm, 152071.doc -34- 201140230

Rmax=1·26 nm)相比變得稍微祕’但是藉由對基板表面 進行再精密研磨（通常之研磨步驟中之最終階段）而可容易 地恢復表面粗糙度。 即，根據該再生方法，可確認去除薄膜後之基板之損傷 較少。 又，藉由在以上述方式所再生之基板上再次形成上述遮 光膜，可製造使用向品質之再生基板之二元型光罩基底。 (實施例4) 於包含Si〇2_Ti〇2系玻璃（熱膨脹係數〇 2χ1〇-7/β(：)之基板 (平滑性0.15 rnnRq以下，平坦度5〇 nm以下）上，形成適合 於13〜14 nm之EUV光波長區域之M〇/si週期多層反射膜。 即’多層反射膜係使用Mo靶材與Si靶材，藉由離子束濺鍍 而於基板上交替地積層而形成。首先，形成4 2 nm之Si 膜、2.8 nm之Mo膜，將其作為一週期，積層4〇週期之後， 形成4.2 nm之Si膜’最後，使用RuNb靶材形成2.5 nm之 RuNb膜作為保護膜。 如此製作附多層反射膜基板。對該多層反射膜以入射角 6·0度入射13.5 nm之EUV光而測定反射率，結果為65.9%。 其次’若假設以上述方式而製作之附多層反射膜基板中 存在有不能容許之表面缺陷，則將該附多層反射膜基板之 多層反射膜去除而進行基板之再生。 即’於腔室内設置上述附多層反射膜基板，向該腔室内 導入ClF^Ar之混合氣體（流量比clF3:Ar=〇 2:1 8(SLm))， 而將腔室内以該氣體置換，藉此使上述附多層反射膜基板 152071.doc -35- 201140230 之多層反射膜與非激發狀態之上述混合氣體接觸。將此時 之氣體壓力調節為495〜502 Torr，將溫度調節為 195~2〇l°C，將處理時間設為1〇分鐘。 利用電子顯微鏡對如此去除包含M〇膜與Si膜之交替積層 膜之EUV多層反射膜之基板的表面進行觀察後，未確認到 多層反射膜之殘渣或白濁等之變質層之產生。又，測定多 層反射膜去除後之基板之表面反射率（2〇〇〜7〇〇 ，與成 膜前之基板沒有變化。進而，利用原子力顯微鏡（AFM)測 定將多層反射膜去除之基板之表面粗糙度之結果為 Ra=1.09 nm，Rmax=13_8 nm,與多層反射膜之剝離前之基 板之表面粗縫度（Ra=〇. 11 nm，Rmax=1 26 nm)相比變得粗 縫，但是藉由對基板表面進行再精密研磨（通常之研磨步 驟中之最終階段）而可容易地恢復表面粗糙度。 即，根據該再生方法，可確認到將附多層反射膜基板之 多層反射膜去除後之基板之損傷較少。 又，藉由在以上述方式所再生之基板上再次形成上述多 層反射膜，可製造使用高品質之再生基板之附多層反射膜 基板。 (實施例5) 首先，以與實施例4相同之順序而製作附多層反射膜基 板。 其-入，於RuNb保護膜上，使用單片式濺渡裝置，對濺 渡靶材使用钽（Ta)與硼（B)之混合靶材（原子％比Ta:B = 8〇: 2〇) ’於氙（Xe)與氮（N2)之混合氣體環境（氣體流量比Xe: 152071.doc -36 - 201140230 N2=13:6)中，將DC電源之電力設為1.5 kW，藉由反應性濺 鍵（DC減鍍），以膜厚50 nm形成TaBN膜，繼而，同樣使用 TaB混合乾材’於氬（Ar)與氧（〇2)之混合氣體環境（氣體流 量比Αγ:〇2=5 8:32.5)中，將DC電源之電力設為0.7 kW，以 膜厚15 nm形成TaBO膜，藉此形成包含TaBN膜與TaBO膜 之積層之吸收體膜，從而製作應用有EUV曝光之光之反射 型光罩基底。 其次’若假設以上述方式而製作之反射型光罩基底中存 在不能容許之表面缺陷，則將該反射型光罩基底之吸收體 膜等薄膜及多層反射膜全部去除而進行基板之再生。 即’於腔室内設置上述反射型光罩基底，向該腔室内導 入〇1?3與八1*之混合氣體（流量比(：吓3:八1=0.2:1.8(81^))，而 將腔室内以該氣體置換，藉此使非激發狀態之上述混合氣 體接觸於上述反射型光罩基底之吸收體膜之表面。將此時 之氣體壓力調節為495〜502 Torr，將溫度調節為 195〜201°C，將處理時間設為1〇分鐘。 利用電子顯微鏡對如此將包含TaBN與TaBO之積層結構 之吸收體膜、RuNb保護膜、包含M〇膜與si膜之交替積層 膜之EUV多層反射膜全部去除之基板的表面進行觀察後， 未確認到多層反射膜等之殘渣或白濁等之變質層之產生。 又，測疋去除後之基板之表面反射率（2〇〇〜7〇〇 nm)，與成 膜前之基板沒有變化。進而，利用原子力顯微鏡（AFM)測 定經去除之基板之表面粗糙度之結果為Ra=丨丨2 nm， Rmax=14.3 nm ’與剝離前之基板之表面粗糙度（Ra=〇 u 152071.doc •37· 201140230 nm，Rmax=1.26 nm)相比變得粗糙，但是藉由對基板表面 進行再精密研磨（通常之研磨步驟中之最終階段）而可容易 地恢復表面粗糙度。 即’根據該再生方法’可確認到將反射型光罩基底之吸 收體膜、保護膜、及多層反射膜全部去除後之基板之損傷 較少。 又’藉由在以上述方式所再生之基板上再次形成上述多 層反射膜、保護膜及吸收體膜，可製造使用高品質之再生 基板之應用有EUV曝光之光之反射型光罩基底。 (實施例6) 於包含合成石英玻璃之透光性基板上，使用單片式濺渡 裝置，對濺渡靶材使用钽（Ta)與铪（Hf)之合金靶材（原子％Rmax = 1·26 nm) is slightly more delicate than that, but the surface roughness can be easily restored by re-precision polishing the surface of the substrate (usually the final stage in the grinding step). That is, according to this regeneration method, it was confirmed that the damage of the substrate after the removal of the film was small. Further, by forming the above-mentioned light shielding film again on the substrate reproduced as described above, it is possible to manufacture a binary type mask substrate using a quality-reproducing substrate. (Example 4) It is suitable for 13 on a substrate containing Si〇2_Ti〇2-based glass (thermal expansion coefficient 〇2χ1〇-7/β(:) (smoothness 0.15 rnnRq or less, flatness 5 〇 nm or less) M〇/si periodic multilayer reflective film of ~14 nm EUV light wavelength region. That is, the 'multilayer reflective film system is formed by alternately laminating on the substrate by ion beam sputtering using a Mo target and a Si target. A 42 nm Si film and a 2.8 nm Mo film were formed as one cycle, and a 4.2 nm Si film was formed after 4 cycles of stacking. Finally, a RuNb film of 2.5 nm was formed as a protective film using a RuNb target. The multilayer reflective film substrate was produced in this manner, and the reflectance was measured by injecting E3.5 light of 13.5 nm at an incident angle of 6·0 degrees, and found to be 65.9%. Next, it is assumed that a multilayer reflective film is produced in the above manner. When there is an unacceptable surface defect in the substrate, the multilayer reflective film with the multilayer reflective film substrate is removed to regenerate the substrate. That is, the multilayer reflective film substrate is placed in the chamber, and ClF^Ar is introduced into the chamber. Mixed gas (flow ratio clF3: Ar = 〇2:1 8 (SLm)), and the gas is replaced in the chamber, whereby the multilayer reflective film with the multilayer reflective film substrate 152071.doc -35 - 201140230 is brought into contact with the mixed gas in a non-excited state. At this time, the gas pressure was adjusted to 495 to 502 Torr, the temperature was adjusted to 195 to 2 〇 l ° C, and the treatment time was set to 1 〇 minutes. The alternating laminated film including the M 〇 film and the Si film was removed by an electron microscope. After observing the surface of the substrate of the EUV multilayer reflective film, the occurrence of the deterioration layer of the multilayer reflective film or the turbid layer such as white turbidity was not confirmed. Further, the surface reflectance of the substrate after the removal of the multilayer reflective film was measured (2 〇〇 7 7 〇). 〇, the substrate before the film formation did not change. Further, the surface roughness of the substrate from which the multilayer reflective film was removed was measured by atomic force microscopy (AFM), and the result was Ra=1.09 nm, Rmax=13_8 nm, and peeling from the multilayer reflective film. The surface roughness of the front substrate (Ra=〇.11 nm, Rmax=1 26 nm) becomes coarser than that of the substrate, but by re-precision grinding the surface of the substrate (usually the final stage in the grinding step) Easy to recover In the regenerative method, it was confirmed that the substrate having the multilayer reflective film with the multilayer reflective film substrate removed was less damaged. Further, the multilayer was formed again on the substrate reproduced in the above manner. The reflective film can be used to manufacture a multilayer reflective film substrate using a high-quality recycled substrate. (Example 5) First, a multilayer reflective film substrate was produced in the same manner as in Example 4. The film was formed on a RuNb protective film. Using a monolithic splash device, a mixed target of tantalum (Ta) and boron (B) is used for the splash target (atomic% ratio Ta: B = 8〇: 2〇) '氙(Xe) with nitrogen In the mixed gas environment of (N2) (gas flow ratio Xe: 152071.doc -36 - 201140230 N2=13:6), the power of the DC power source is set to 1.5 kW, by reactive sputtering (DC plating). Forming a TaBN film at a film thickness of 50 nm, and then using a TaB mixed dry material in a mixed gas atmosphere of argon (Ar) and oxygen (〇2) (gas flow ratio Αγ: 〇2 = 5 8:32.5), The power of the DC power source is set to 0.7 kW, and a TaBO film is formed at a film thickness of 15 nm, thereby forming a TaBN film and a TaBO film. The laminated body film is laminated to produce a reflective reticle substrate to which EUV-exposed light is applied. Next, if there is an unacceptable surface defect in the reflective reticle base produced as described above, the film such as the absorber film of the reflective reticle base and the multilayer reflection film are all removed to regenerate the substrate. That is, the reflective mask base is provided in the chamber, and a mixed gas of 〇1?3 and 八1* is introduced into the chamber (flow ratio (: scare 3: eight 1 = 0.2: 1.8 (81^)), and The chamber is replaced with the gas, whereby the mixed gas in a non-excited state is brought into contact with the surface of the absorber film of the reflective mask base. The gas pressure at this time is adjusted to 495 to 502 Torr, and the temperature is adjusted to 195 to 201 ° C, the treatment time was set to 1 〇 minutes. The EUV of the absorber film including the laminated structure of TaBN and TaBO, the RuNb protective film, and the alternate laminated film including the M 〇 film and the SiO film were subjected to an electron microscope. When the surface of the substrate on which the multilayer reflective film was completely removed was observed, no deterioration of the multilayer reflective film or the like, or the occurrence of a deteriorated layer such as white turbidity was observed. Further, the surface reflectance of the substrate after the removal of the ruthenium was measured (2 〇〇 to 7 〇〇). Nm), there is no change from the substrate before film formation. Further, the surface roughness of the removed substrate is measured by atomic force microscopy (AFM), and the result is Ra=丨丨2 nm, Rmax=14.3 nm' and the substrate before peeling. Surface roughness (Ra=〇u 152071.doc • 37·201140230 nm, Rmax=1.26 nm) is rougher than the surface, but the surface roughness can be easily restored by re-precision polishing the substrate surface (usually the final stage in the grinding step). In the "reproduction method", it was confirmed that the substrate after removing the absorber film, the protective film, and the multilayer reflective film of the reflective reticle base was less damaged. Further, the above-mentioned formation was performed again on the substrate reproduced in the above manner. The multilayer reflective film, the protective film, and the absorber film can be used to manufacture a reflective mask substrate using EUV-exposed light using a high-quality recycled substrate. (Example 6) On a light-transmissive substrate containing synthetic quartz glass, Using a monolithic splash device, alloy targets of tantalum (Ta) and hafnium (Hf) are used for the splash target (atomic %)

比Ta:Hf=80:20)，於氬氣體環境（氣體壓力〇·3 pa)中，將DC 電源之電力設為2.0 kW，藉由反應性濺鍍（DC濺鍍），以膜 厚7 nm形成TaHf膜（導電性膜），繼而，使用鉻靶材，於氬 (Ar)與氮（NO之混合氣體環境中，以膜厚2.5 nm形成CrN膜 (Cr:N=80:2(^子％比），藉此形成TaHf膜與CrN膜之積層薄 膜’從而製作壓印用模具之製作所使用之光罩基底。 其次，若假設以上述方式而製作之光罩基底中存在不能 容許之表面缺陷’則將該光罩基底之上述積層薄膜去除而 進行基板之再生。 即’首先，利用噴嘴對CrN膜表面喷塗硝酸鈽銨、過氣 酸及純水之混合液，從而去除CrN膜。 其次’於腔室内設置去除上述CrN膜之光罩基底，向該 152071.doc •38- 201140230 腔室内導入C1F3與Ar之混合氣體（流量比ciF3:Ar=0.2:1.8 (SLM))，而將腔室内以該氣體置換，藉此使上述光罩基底 之TaHf膜與非激發狀態之上述混合氣體接觸。將此時之氣 體壓力調節為495〜502 Torr，將溫度調節為195〜2〇1。〇’將 處理時間設為10分鐘。 利用電子顯微鏡對如此去除TaHf膜與CrN膜之積層薄膜 之基板的表面進行觀察後，未確認到積層薄膜之殘渣或白 濁等之變質層之產生。又，測定積層薄膜去除後之基板之 表面反射率（200〜700 nm)，與成膜前之初始之基板沒有變 化。進而，利用原子力顯微鏡（AFM)測定去除積層薄膜後 之基板之表面粗糙度之結果為Ra=1 4〇 nm，Rmax=18 〇 nm’與積層薄膜之剝離前之基板之表面粗縫度 nm，Rmax=1.20 nm)相比變得粗糙，但是藉由對基板表面 進行再精密研磨（通常之研磨步驟中之最終階段）而可容易 地恢復表面粗糙度。 即，根據該再生方法，可確認到上述光罩基底之積層薄 膜去除後之基板之損傷較少。 又’藉由在以上述方式所再生之基板上再次形成上述 TaHf膜與CrN膜之積層薄膜，可製造使用高品質之再生基 板之壓印用模具製作用之光罩基底。 (比較例1) 藉由先前之方法而將實施例丨中所製作之相位偏移光罩 基底之相位偏移膜去除而進行基板之再生。 即，將上述相位偏移光罩基底浸潰於收納於處理槽中之 15207I.doc •39- 201140230 氨氣酸溶液（濃度0,2%)。冑&時之氨氣酸溶液之溫度設為 贼’將處理時間設為30分鐘。再者，處理過程中一面適 當搖動光罩基底一面進行處理。 利用電子顯微鏡對如此去除包含河“…之相位偏移膜之 基板之表面進行觀察後，雖未特別觀察到相位偏移膜之殘 渣，但是可確認到於基板表面產生白濁等所引起之變質 層。又，測定相位偏移膜去除後之基板之表面反射率 (200〜700 nm)，由於該變質層所產生之影響與成膜前之基 板相比反射率整體性地下降。進而，可確認到：利用原子 力顯微鏡（AFM)測定將相位偏移膜去除後之基板之表面粗 糙度之結果為Ra=15.1 nm，Rmax=150 nm，與相位偏移膜 之剝離前之基板之表面粗糙度（Ra=〇 U nrn，Rmax=i.26 nm)相比粗链非常大，膜去除所致之基板損傷較大。因 此’為了藉由對基板表面進行再研磨而恢復良好之表面粗 縫度’必須自通常之成膜前之基板研磨步驟之中的最初階 段起進行再研磨，再研磨之步驟負荷變大。 【圖式簡單說明】 圖1係去除薄膜之步驟中所使用之處理裝置之概略構成 圖。 【主要元件符號說明】 40 腔室 41 處理基板 42 平台 43 ' 44 氣體填充容器 152071.doc 40· 201140230 45 ' 46 流量控制器 47 喷出喷嘴 48 排氣管 49 排氣體處理裝置 152071.doc •41 -Ratio Ta:Hf=80:20), in an argon gas environment (gas pressure 〇·3 pa), the power of the DC power source is set to 2.0 kW, and by reactive sputtering (DC sputtering), the film thickness is 7 Nm forms a TaHf film (conductive film), and then, using a chromium target, a CrN film is formed at a film thickness of 2.5 nm in a mixed gas atmosphere of argon (Ar) and nitrogen (Cr: N=80:2 (^ By the sub-% ratio), a laminated film of the TaHf film and the CrN film is formed to form a photomask substrate used for the production of the imprint mold. Next, it is assumed that there is an unacceptable surface in the photomask substrate produced in the above manner. In the defect, the laminated film of the mask base is removed to regenerate the substrate. That is, first, a surface of the CrN film is sprayed with a mixture of cerium ammonium nitrate, peroxy acid and pure water by a nozzle to remove the CrN film. Secondly, a reticle substrate for removing the above CrN film is disposed in the chamber, and a mixed gas of C1F3 and Ar is introduced into the chamber of 152071.doc •38-201140230 (flow ratio ciF3: Ar=0.2:1.8 (SLM)), and Replacing the gas with the gas, thereby making the TaHf film of the mask base and the non-excited state described above The gas is contacted. The gas pressure at this time is adjusted to 495 to 502 Torr, and the temperature is adjusted to 195 to 2 〇 1. The treatment time is set to 10 minutes. The layer of the TaHf film and the CrN film is removed by an electron microscope. After the surface of the substrate of the film was observed, no deterioration of the laminated film or the occurrence of a deteriorated layer such as white turbidity was observed. Further, the surface reflectance (200 to 700 nm) of the substrate after the laminated film removal was measured, and the initial before film formation. The substrate has no change. Further, the surface roughness of the substrate after removing the laminated film by atomic force microscopy (AFM) is Ra = 14 〇 nm, Rmax = 18 〇 nm' and the surface of the substrate before peeling of the laminated film. The roughness nm, Rmax=1.20 nm) is rougher than that, but the surface roughness can be easily restored by re-precision polishing the substrate surface (usually the final stage in the grinding step). According to the method, it is confirmed that the substrate after the removal of the laminated film of the mask base is less damaged. Further, the TaHf is formed again by the substrate regenerated in the above manner. A laminated film for a stamping mold using a high-quality recycled substrate can be produced by laminating a film with a CrN film. (Comparative Example 1) The phase-shifted light produced in Example 藉 by the prior method was used. The phase shift film of the cover base is removed to regenerate the substrate. That is, the phase shift mask base is immersed in the 15207I.doc •39-201140230 ammonia acid solution (concentration 0, 2%) accommodated in the treatment tank. The temperature of the ammonia acid solution at the time of 胄 & is set to thief 'set the treatment time to 30 minutes. Furthermore, one side of the reticle base is appropriately shaken during processing. When the surface of the substrate including the phase shift film of the river was removed by an electron microscope, the residue of the phase shift film was not particularly observed, but it was confirmed that the surface of the substrate was white turbid or the like. Further, the surface reflectance (200 to 700 nm) of the substrate after the phase-shift film removal is measured, and the influence of the altered layer is lower than that of the substrate before the film formation. Further, it can be confirmed. The result of measuring the surface roughness of the substrate after removing the phase shift film by atomic force microscopy (AFM) is Ra = 15.1 nm, Rmax = 150 nm, and the surface roughness of the substrate before peeling of the phase shift film ( Ra=〇U nrn, Rmax=i.26 nm) is much larger than the thick chain, and the substrate damage caused by the film removal is large. Therefore, 'the surface roughness is restored to re-grind the surface of the substrate' It is necessary to re-grind from the initial stage of the substrate polishing step before the film formation, and the load of the step of polishing is increased. [Simplified illustration] Fig. 1 is the treatment used in the step of removing the film. [Main component symbol description] 40 Chamber 41 Processing substrate 42 Platform 43 ' 44 Gas filled container 152071.doc 40· 201140230 45 ' 46 Flow controller 47 Spray nozzle 48 Exhaust pipe 49 Exhaust body treatment Device 152071.doc •41 -

Claims (1)

201140230 七、申請專利範圍： 1· 一種基板之再生方法，其特徵在於：其係將於包含玻璃 之基板之主表面上具備圖案形成用之薄膜的光罩基底或 使用該光罩基底所製作之轉印用光罩之上述薄膜去除而 再生基板的方法，且 使上述光罩基底或上述轉印用光罩之上述薄膜與含有 氣（C1)、溴（Br)、碘（I)、及氙（Xe)中之任一元素與氟 之化合物的非激發狀態之物質接觸而將其去除。 2. 如請求項1之基板之再生方法，其中上述薄膜包含單層 或複數層，至少接觸於上述基板之層係由能夠由氟系氣 體乾式钱刻之材料而形成。 3. 如請求項2之基板之再生方法，其中接觸於上述基板之 層係藉由含有矽（si)之材料、含有金屬與矽（Si)之材料、 及含有组（Ta)之材料中之任一者而形成。 4. 如請求項1之基板之再生方法，其中上述基板包含合成 石英玻璃。 5. —種光罩基底之製造方法，其特徵在於：於藉由如請求 項1之基板之再生方法而再生之基板上，形成圖案形成 用之薄膜。 6· —種基板之再生方法，其特徵在於：其係將附多層反射 膜基板之多層反射膜去除而再生基板之方法，該附多層 反射膜基板係於包含玻璃之基板之主表面上具備使低折 射率層與高折射率層交替地積層而成之結構之多層反射 膜，且 152071.doc 201140230 使上述附多層反射膜基板之上述多層反射膜與含有氣 (C1)、溴（Br)、碘（I)、及氙（Xe)中之任一元素與敗（F)之 化合物的非激發狀態之物質接觸而將其去除。 7. 如請求項6之基板之再生方法’其中上述低折射率層包 含石夕（Si)，且接觸於上述基板之主表面而形成。 8. 如請求項6之基板之再生方法，其中上述基板包含Si〇2_ Ti02系低熱膨脹玻璃。 9. 一種附多層反射膜基板之製造方法，其特徵在於：於藉 由如請求項6之基板之再生方法而再生之基板上，形成 使低折射率層與高折射率層交替地積層而成之結構之多 層反射膜。 10. —種基板之再生方法’其特徵在於：係係將於包含玻璃 之基板之主表面上依序具備使低折射率層與高折射率層 交替地積層而成之結構的多層反射膜、與圖案形成用之 吸收體膜的反射型光罩基底或使用該反射型光罩基底所 製作之反射型光罩之上述多層反射膜去除而再生基板之 方法，且 使上述反射型光罩基底或上述反射型光罩之上述多層 反射膜與包含氣（C1)、溴（Br)、碘（I)、及氙（Xe)中之任一 元素與氟（F)之化合物之非激發狀態之物質接觸而將其去 除。 11·如請求項10之基板之再生方法，其中上述低折射率層包 含石夕（Si) ’且接觸於上述基板之主表面而形成。 12.如請求項1〇之基板之再生方法，其中上述基板包含Si〇2_ 152071.doc 201140230 Ti〇2系低熱膨脹玻璃。 13. —種反射型光罩基底之製造方法，其特徵在於：於藉由 如請求項10之基板之再生方法而再生之基板上，依序形 • 成使低折射率層與咼折射率層交替地積層而成之結構之 多層反射膜與圖案形成用之吸收體膜。 14. 一種基板之再生方法，其特徵在於：其係將於包含玻璃 之基板之主表面上具備圖案形成用之薄膜之光罩基底 中，藉由乾式蝕刻處理而對上述薄膜及上述基板進行蝕 刻加工之壓印用模具之製作方法所對應的光罩基底之上 述薄膜去除而再生基板之方法，且 使上述光罩基底之上述薄膜與含有氣、溴（Br)、 碘（I)、及氙（Xe)中之任一元素與氟（F)之化合物之非激發 狀態之物質接觸而將其去除。 15. 如請求項14之基板之再生方法，其中上述薄膜包含單層 或複數層，至少接觸於上述基板之層係藉由以组（丁勾為 主成分之材料而形成。 16·如凊求項14之基板之再生方法，其中上述基板包含合成 石英玻璃。 17. —種光罩基底之製造方法，其特徵在於··於藉由如請求 ^ 項14之基板之再生方法而再生之基板上，形成圖案形成 用之薄膜。 152071.doc201140230 VII. Patent application scope: 1. A method for reproducing a substrate, which is characterized in that it is provided on a main surface of a substrate including glass, and a photomask substrate having a film for pattern formation or a photomask substrate is used. a method of removing the film by the transfer photomask and regenerating the substrate, and the film of the photomask substrate or the transfer photomask and the gas (C1), bromine (Br), iodine (I), and ruthenium Any element of (Xe) is contacted with a non-excited state of the fluorine compound to remove it. 2. The method of reproducing a substrate according to claim 1, wherein the film comprises a single layer or a plurality of layers, and at least the layer contacting the substrate is formed of a material which can be dry-burned by a fluorine-based gas. 3. The method of reproducing a substrate according to claim 2, wherein the layer contacting the substrate is made of a material containing bismuth (si), a material containing metal and bismuth (Si), and a material containing a group (Ta). Formed by either. 4. The method of reproducing a substrate according to claim 1, wherein the substrate comprises synthetic quartz glass. A method of producing a reticle substrate, characterized in that a film for pattern formation is formed on a substrate which is reproduced by the substrate reproducing method of claim 1. A method for reproducing a substrate, which is characterized in that a multilayer reflective film having a plurality of layers of a reflective film substrate is removed to regenerate a substrate, and the multilayer reflective film substrate is provided on a main surface of a substrate including glass. a multilayer reflective film having a structure in which a low refractive index layer and a high refractive index layer are alternately laminated, and 152071.doc 201140230 causes the above multilayer reflective film with a multilayer reflective film substrate to contain gas (C1), bromine (Br), Any one of iodine (I) and ruthenium (Xe) is removed by contact with a non-excited state of the compound of the defeat (F). 7. The method of reproducing a substrate according to claim 6, wherein the low refractive index layer contains Si (Si) and is formed in contact with a main surface of the substrate. 8. The method of reproducing a substrate according to claim 6, wherein the substrate comprises Si〇2_Ti02 based low thermal expansion glass. 9. A method of producing a multilayer reflective film substrate, comprising: forming a low refractive index layer and a high refractive index layer alternately on a substrate reproduced by a substrate reproducing method according to claim 6; A multilayer reflective film of the structure. 10. A method for reproducing a substrate, characterized in that a multilayer reflective film having a structure in which a low refractive index layer and a high refractive index layer are alternately laminated is provided on a main surface of a substrate including glass, a method of regenerating a substrate by removing the substrate by using a reflective mask substrate for patterning the absorber film or a reflective mask of the reflective mask produced using the reflective mask substrate, and using the reflective mask substrate or The above-mentioned multilayer reflective film of the reflective reticle and a substance containing a non-excited state of a compound of any one of gas (C1), bromine (Br), iodine (I), and xenon (Xe) and fluorine (F) Remove it by contact. The method of reproducing a substrate according to claim 10, wherein the low refractive index layer comprises a stone (Si)' and is formed in contact with a main surface of the substrate. 12. The method of claim 1, wherein the substrate comprises Si〇2_152071.doc 201140230 Ti〇2 low thermal expansion glass. A method of manufacturing a reflective reticle substrate, characterized by: sequentially forming a low refractive index layer and a ruthenium refractive index layer on a substrate regenerated by a substrate reproducing method according to claim 10 A multilayer reflective film of a structure which is alternately laminated and an absorber film for pattern formation. A method for reproducing a substrate, characterized in that the film and the substrate are etched by a dry etching process in a mask substrate having a film for pattern formation on a main surface of a substrate including glass. a method of removing a film of the mask base corresponding to the method for producing a stamping die, and regenerating the substrate, and the film and the gas containing the bromo (Br), iodine (I), and ruthenium Any element of (Xe) is removed by contact with a non-excited state of the compound of fluorine (F). 15. The method for reproducing a substrate according to claim 14, wherein the film comprises a single layer or a plurality of layers, and at least the layer contacting the substrate is formed by a group (a material having a main component). The method for reproducing a substrate according to Item 14, wherein the substrate comprises synthetic quartz glass. 17. A method of manufacturing a reticle substrate, characterized in that it is regenerated on a substrate by a method for reproducing a substrate according to claim 14. Forming a film for pattern formation. 152071.doc
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