TW200928592A - Method for forming patterns and material for coating film - Google Patents

Method for forming patterns and material for coating film Download PDF

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Publication number
TW200928592A
TW200928592A TW097130829A TW97130829A TW200928592A TW 200928592 A TW200928592 A TW 200928592A TW 097130829 A TW097130829 A TW 097130829A TW 97130829 A TW97130829 A TW 97130829A TW 200928592 A TW200928592 A TW 200928592A
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TW
Taiwan
Prior art keywords
pattern
forming
photoresist
film
group
Prior art date
Application number
TW097130829A
Other languages
Chinese (zh)
Inventor
Kiyoshi Ishikawa
Atsushi Sawano
Kazumasa Wakiya
Original Assignee
Tokyo Ohka Kogyo Co Ltd
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Publication date
Priority claimed from JP2007221624A external-priority patent/JP2009053546A/en
Priority claimed from JP2007221629A external-priority patent/JP2009053547A/en
Application filed by Tokyo Ohka Kogyo Co Ltd filed Critical Tokyo Ohka Kogyo Co Ltd
Publication of TW200928592A publication Critical patent/TW200928592A/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

To provide a new pattern forming method in which the number of steps in a double patterning method can be reduced and to provide a material for forming a coating film suitably used for the pattern forming method.The method comprises: applying a first chemically amplified resist composition on a support body 1 to form a first resist film 2; selectively exposing and developing the first resist film 2 to form a plurality of first resist patterns 3; forming a coating film 4 on the surface of each first resist pattern 3 by using a material for forming a coating film containing a polymer containing an oxazoline group to form a plurality of coating patterns 5; applying a second chemically amplified resist composition on the support body 1 where the coating patterns 5 are formed so as to form a second resist film 6; and selectively exposing and developing the second resist film 6 to form a pattern comprising the plurality of coating patterns 5 and a second resist pattern 7 formed in the second resist film 6 on the support body 1.

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200928592 九、發明說明 【發明所屬之技術領域】 本發明係關於一種圖型形成方法及被覆膜形成用材 料，更詳細言之，係關於一種以雙重曝影（double patterning )法形成圖型之圖型形成方法、及該圖型形成 . 方法上所適用之被覆膜形成用材料。 — 此外，本發明係關於一種圖型形成方法及被覆膜形成 〇 用材料，更詳細言之，係關於—種使用由水溶性樹脂組成 物所成之被覆膜形成用材料的形成微細圖型之圖型形成方 法、及該圖型形成方法上所適用之被覆膜形成用材料者。 【先前技術】 在基板上形成微細圖型’並藉由將其作爲光罩進行飩 刻而將該圖型之下層加工之技術（圖型形成技術），已於 半導體產業之1C製作等上被廣泛地採用，而受到相當大 Φ 的矚目。 微細圖型一般係由有機材料所構成，並以微影法或奈 米壓印法等技術而形成。例如微影法中，在基板等之支持 體之上’形成由含有樹脂等基材成分之光阻組成物所成之 " 光阻膜’再對於該光阻膜，介由所定圖型形成之光罩（光 罩圖型）’利用光、電子射線等放射線進行選擇性曝光， 施加顯像處理，可在上述光阻膜上形成所定形狀之光阻圖 型的步驟。經曝光之部分在顯像液中變化成具有溶解之特 性的光阻組成物稱爲正型，而曝光之部分在顯像液中變化 -5- 200928592 成具有不溶解之特性的光阻組成物則稱爲負型。再者，可 將上述光阻圖型作爲光罩，而將基板以蝕刻進行加工之步 驟，製造序導體元件等。 近年，由於微影技術之進歩，圖型之微細化正急速地 進行著。微細化之手法，一般而言，係以曝光光源之短波 . 長化爲目標。具體而言，傳統上係使用g線、i線所代表 之紫外線，惟現在使用KrF準分子雷射或ArF準分子雷射 φ 之半導體元件已開始量產，例如藉由使用ArF準分子雷射 之微影，可在45nm左右之解像性形成圖型。此外，爲進 一步提升解像性起見，較此等準分子雷射爲更短波長之F2 準分子雷射、電子線、EUV (極紫外線）或X線等，亦正 進行檢討中。 在光阻組成物中，係追求對於此等曝光光源之感度、 可再現微細尺寸之圖型的解像性等微影特性。可滿足此種 要求之光阻組成物，有使用含有：因爲酸之作用其鹼溶解 ❿ 性會變化之基材成分、及因爲曝光而發生酸之酸發生劑， 其化學增幅型光阻組成物（專利文獻1參照）。例如，正 型之化學增幅型光阻，一般而言，其基材成分，係含有可 * 因酸之作用而使鹼溶解性增大之樹脂，在光阻圖型形成 " 時，由於曝光，其酸發生劑會發生酸，而曝光部則成爲鹼 可溶性。 用以進一步提升解像性之手法，已知其一者係：在曝 光機之對物透鏡及樣品之間’使其夾著較空氣爲更高折射 率之液體（浸液媒介）而進行曝光（浸漬曝光）之微影 -6 - 200928592 法，即所謂浸液微影（Liquid Immersion Lithography，以 下亦稱爲「浸液曝光」）（非專利文獻1參照）。 利用浸赞曝光，即使使用相同之曝光波長之光源，亦 可達成與使用更短波長之光源或更高NA透鏡之情形爲相 同之高解像性，而且其焦點深度範圍亦不會降低。此外， 浸液曝光，並可應用現存之曝光装置而進行。因此，浸液 曝光係可預期能以低成本、高解像性、且焦點深度範圍亦 優良之情形下，形成光阻圖型；且在需要高額設備投資之 半導體元件之製造中，其不論成本或解像度等微影特性 上，皆能賦予半導體產業相當大之效果而受到極大之注 @。 浸液曝光，在全部之圖型形狀之形成上皆爲有效，進 而，並可與現在檢討中之位相移動法、變形照明法等超解 像技術加以組合。目前，浸液曝光技術，主要係以ArF準 分子雷射爲光源之技術被活潑地硏究著。此外，現在，浸 液媒介，主要則以水爲硏究對象。 最近，最新被提案之微影技術之一者，係進行2次以 上圖型化而形成圖型之雙重曝影法（非專利文獻2、3參 照）。根據此種雙重曝影法，可較1次之圖型化所形成之 圖型而形成更微細圖型。例如非專利文獻2中，係記載圖 3所示之方法。 亦即’首先，如圖3(a)所示者，準備一個由基板 101、下層膜102、及硬光罩103所層合而成之層合體。接 著，在硬光罩1〇3上設置光阻膜，再將該光阻膜如圖3 200928592 (b)所示者’介由光罩l〇5進行選擇性曝光而顯像，而 形成間隔寬度爲d/ 4所成多數之溝渠圖型，且以間距d 配置之光阻圖翠104。然後，將光阻圖型104作爲光罩而 進行硬光罩103之蝕刻後，再除去殘餘之光阻圖型1〇4。 藉此’如圖3(c)所示者，可製得複印有光阻圖型之硬光 • 罩103’。其次’如圖3 ( d)所示者，將光罩105之位置 加以移動，再於硬光罩103’上塗佈光阻材料，以形成塡充 φ 於硬光罩103’内之空隙，且較硬光罩103’之厚度更厚之膜 厚度的光阻膜。再者，將該光阻膜，介由移動之光罩105 而進行選擇性曝光，顯像、並形成光阻圖型1 06。然後， 將光阻圖型106作爲光罩而進行硬光罩1〇3,之鈾刻後，除 去殘餘之光阻圖型106。藉此，如圖3(e)所示者，可製 得間隔寬度爲d / 4所成多數之溝渠圖型，且以間距d / 2 配置之圖型所複印之硬光罩103”。最後，藉由將硬光罩 1〇3”作爲光罩進行蝕刻，可於下層膜1〇2上複印硬光罩 ❹ 103”之圖型，而形成所使用光罩1〇5之i/2之間距之圖 型 102’ 。 如此地，根據雙重曝影法，即可在使用相同曝光波長 之光源，且使用相同之光阻組成物下，形成更高解像性之 " 光阻圖型。此外，雙重曝影法，係可使用現存之曝光装置 而進行者。 [專利文獻1]特開2003 — 241385號公報 [非專利文獻 l]OPTRONICS N0.4 ( 2003 年）。 [非專利文獻 2]Proceedings of SPIE 第 525 6 卷、第 200928592 985 〜994 頁（2003 年）» [非專利文獻 3]Proceedings of SPIE 第 6153 卷、第 615301— 1 〜19 頁（2006 年）。 【發明內容】 . [發明之揭示] 然而，在傳統之雙重曝影法中，一般必須於基板上設 φ 置下層膜，此外，爲在基板上形成圖型起見，必須將光阻 膜之圖型化進行至少2次，並於其下層之硬光罩之蝕刻亦 進行至少2次。 此外，如使用上述雙重曝影法時，雖可形成高解像性 之光阻圖型，惟由於近年追求電子機器之進一步小型化， 而需求能以更高解像度進行之微細光阻圖型形成技術。 本發明係有鑑於上述情事所完成者，其目的係提供一 種可減低雙重曝影法中之步驟數目的新穎圖型形成方法、 〇 及在該圖型形成方法中適用之被覆膜形成用材料。 此外’本發明之目的，係提供一種用以形成更微細圖 型之新穎圖型形成方法、及該圖型形成方法中適用之被覆 膜形成用材料。 本發明者們，爲達成上述之目的而進行了銳意之檢 討。其結果，發現了在第一之光阻圖型之表面上，藉由使 用水溶性樹脂組成物所成之被覆膜形成用材料而形成被覆 膜’可減低雙重曝影法中之步驟數目，從而完成了本發 明。 -9 - 200928592 此外，本發明者們並發現：藉由在光阻圖型之表面， 使用水溶性樹脂組成物所成之被覆膜形成用材料而形成被 覆膜，再將由被覆膜所被覆之光阻圖型進行曝光•顯像. 除去，形成由前述被覆膜成分所成之圖型，可形成更微細 圖型，從而完成了本發明。更具體而言，本發明係包含以 ^ 下之發明。 亦即，本發明爲一種圖型形成方法，其特徵係含有： Φ 在支持體上塗佈光阻組成物而形成光阻膜之步驟、及將該 光阻膜介由光罩圖型進行選擇性曝光、顯像而形成光阻圖 型之步驟、及在該光阻圖型之表面上使用被覆膜形成用材 料而形成被覆膜之步驟，以及，進而，以下之（i)或 (Π)之步驟； (i) 在以該被覆膜所被覆之該光阻圖型形成之該支 持體上’塗佈第二之光阻組成物而形成第二之光阻膜之步 驟、及將該第二之光阻膜介由第二之光罩圖型進行選擇性 φ 曝光、顯像而形成第二之光阻圖型之步驟 (ii) 將以該被覆膜所被覆之該光阻圖型進行曝光、 顯像，而形成由該被覆膜成分所成之圖型之步驟。 瓤 本發明之第一之態樣，係一種圖型形成方法，其特徵 * 係包含：在支持體上’塗佈第一之光阻組成物而形成第一 之光阻膜之步驟、及將該第一之光阻膜介由第一之光罩圖 型進行選擇性曝光、顯像而形成第一之光阻圖型之步驟、 及在該第一之光阻圖型之表面上，使用水溶性樹脂組成物 所成之被覆膜形成用材料形成被覆膜、並形成被覆圖型之 -10- 200928592 步驟、及在該被覆圖型形成之該支持體上塗佈第二之光阻 組成物並形成第二之光阻膜之步驟、及將該第二之光阻膜 介由第二之光罩圖型進^行選擇性曝光、顯像而形成第二之 光阻圖型之步驟。 本發明之第二之態樣，係一種圖型形成方法，其特徵 . 係包含：在支持體上，塗佈正型光阻組成物而形成光阻膜 之步驟、將該光阻膜介由光罩圖型進行選擇性曝光、顯像 0 而形成光阻圖型之步驟、在該光阻圖型之表面上，使用水 溶性樹脂組成物所成之被覆膜形成用材料而形成被覆膜之 步驟、將以該被覆膜所被覆之該光阻圖型進行曝光、顯像 而形成由該被覆膜成分所成之圖型之步驟。 本發明之第三之態樣’係一種被覆膜形成用材料，其 係由第一之態樣及第二之態樣之圖型形成方法上使用之水 溶性樹脂物所成之被覆膜形成材料，其特徵係由包含含有 噁唑啉基之聚合物之被覆膜形成用材料，或含有水溶性樹 ❹ 脂及水溶性交聯劑所成之水溶液構成者。 如依據本發明之上述桌一之態樣及第三之態樣，可提 供一種可減低雙重曝影法中之步驟數目之新穎之圖型形成 方法、及該圖型形成方法上所適用之被覆膜形成用材料。 如依據本發明之上述第二之態樣及第三之態樣，可提 供一種可形成更微細圖型之新穎之圖型形成方法、及該圖 型形成方法上所適用之被覆膜形成用材料。 本發明之進一步其他之目的、特徵、及優點，應可根 據以下記載而被充分地理解。此外，本發明之利益，應可 -11 - 200928592 以參照附件圖示之以下說明而成爲明確者。 【實施方式】 u [實施發明之最佳型態] [實施之型態1] _ 關於本發明之一實施型態，係說明如下所示。此外， 本發明之實施型態並不限於以下所述，合先敘明。 Ο 《第一之態樣之圖型形成方法》 本發明之圖型形成方法，係使用光阻組成物之圖型形 成方法。此種光阻組成物，係於本發明之實施時點爲習於 此技藝之業者所可利用，而可使用之習知光阻組成物，惟 並非限定於此範圍。其中，又以使用化學增幅型光阻組成 物爲較佳。 化學增幅型光阻組成物，其並無限制，可由被提案作 Φ 爲化學增幅型光阻組成物的許多化學增幅型光阻組成物之 中，根據所使用之曝光光源、微影特性等而適當地選擇。 化學增幅型光阻組成物可爲負型光阻組成物，亦可爲正型 光阻組成物，較佳者則爲正型光阻組成物。 '化學增幅型光阻組成物，其一般係將：會因酸之作用 而發生鹼溶解性變化之基材成分（A)(以下稱爲（A) 成分）以及因曝光而發生酸之酸發生劑成分（B)(以下 稱爲（B)成分），溶解於有機溶劑（S)(以下稱爲 (S )成分）中所成者。 -12- 200928592 在此，所謂的「基材成分」’係指具有膜形成能之有 機化合物，其較佳者係使用分子量500以上之有機化合 物。藉由該有機化合物之分于量在500以上，可提升膜形 成能，並容易形成奈米程度之圖型。 前述分子量在500以上之有機化合物，主要可分別爲 _ 分子量500以上2000以下之低分子量之有機化合物（以 下，稱爲低分子化合物）、以及分子量較2000更大之高 φ 分子量之樹脂（聚合物）。前述低分子化合物，一般係使 用非聚合物。如係樹脂（聚合物）時，係使用其「分子 量」以GPC (凝膠滲透色層分析法）進行聚苯乙烯換算之 質量平均分子量者。以下，如僅稱「樹脂」時，係分子量 較2000更大之樹脂。 (A)成分，可爲藉酸之作用其鹼溶解性會發生變化 之低分子化合物，亦可爲藉酸之作用其鹼溶解性會發生變 化之樹脂，或亦可爲此等之混合物者。 φ (A)成分，一般而言，其作爲化學增幅型光阻用之 基材成分之有機化合物，可以1種單獨、或2種以上混合 加以使用。 * 化學增幅型光阻組成物如係負型光阻組成物時， 、 (A)成分除了可使用：藉酸之作用其鹼溶解性會減少之 基材成分外，該負型光阻組成物亦可進而配合使用交聯 劑。此種負型光阻組成物中，如因曝光而使（B)成分發 生酸時，藉由該酸之作用在（A)成分與交聯劑之間會產 生交聯，（A)成分則會由鹼可溶性變成鹼不溶性。因 -13- 200928592 此’在光阻圖型之形成中，如對於在基板上塗佈該負型光 阻組成物所得之光阻膜進行選擇性曝光時，曝光部會變成 鹼不溶性’而相對地，未曝光部則保持鹼可溶性而不改 變，因此可進行鹼顯像。 負型光阻組成物之（A)成分，一般可使用鹼可溶性 . 樹脂，該鹼可溶性樹脂，例如有具有選自α_ (羥基烷 基）丙烯酸及α -（羥基烷基）丙烯酸之低級烷基酯之中 0 之1種以上衍生單位之樹脂，其可形成膨潤少之良好光阻 圖型而較佳。再者，α-（羥基烷基）丙烯酸係：在羧基 結合之0：位之碳原子上結合有氫原子之丙烯酸，或在該《 位之碳原子上結合有羥基烷基（較佳者爲碳數1〜5之羥 基烷基）之〇：—羥基烷基丙烯酸，其一者或二者。 交聯劑，舉例而言，一般如使用具有羥甲基或烷氧基 甲基之甘脲等胺系交聯劑時，可形成膨潤少之良好光阻圖 型而較佳。交聯劑之配合量，相對於鹼可溶性樹脂100質 φ 量份，係以1〜50質量份爲較佳。 化學增幅型光阻組成物如係正型光阻組成物時， (Α)成分可使用具有酸解離性溶解抑制基，且因酸之作 用而其鹼溶解性會增大之基材成分。此種正型光阻組成 ' 物，在曝光前係鹼不溶性，而在光阻圖型形成時，藉由曝 光而由（Β)成分發生酸時，因該酸之作用，酸解離性溶 解抑制基會解離，且（A )成分會變成鹼可溶性。因此， 在光阻圖型之形成中，如對於在基板上塗佈該正型光阻組 成物所得到之光阻膜進行選擇性曝光時，曝光部會變成鹼 -14- 200928592 可溶性，而另一方面，未曝光部則保持鹼不溶性而無變 化，可進行鹼性顯像。 正型光阻組成物之（A )成分，只要係具有酸解離性 溶解抑制基者即可，並以下述（A — 1)成分及/或（A-2)成分爲更佳。 _ · (A— 1)成分：具有酸解離性溶解抑制基之樹脂。 • ( A — 2 )成分：具有酸解離性溶解抑制基之低分子 φ 化合物。 以下，茲更具體地說明（A— 1)成分及（A — 2)成 分之較佳態樣。 [(A— 1 )成分] (A-1)成分，係以含有具有酸解離性溶解抑制基之 構成單位之樹脂爲較佳。 該樹脂中，具有前述酸解離性溶解抑制基之構成單位 φ 之比例，相對於構成該樹脂之全構成單位之總計量，係以 20〜80莫耳％較佳，20〜70莫耳％更佳，30〜60莫耳％最 佳。 (A- 1)成分，更具體而言，其較佳者係具有酸解離 ^ 性溶解抑制基之酚醛清漆樹脂、羥基苯乙烯系樹脂、 -低級烷基）丙烯酸酯樹脂、含有由羥基苯乙烯所衍生之 構成單位及（α -低級烷基）丙烯酸酯所衍生之構成單位 之共聚合樹脂等。 再者，本說明書中，所謂的「（α_低級烷基）丙烯 -15- 200928592 酸」，係指丙烯酸（CH2 = CH - COOH )及α -低級烷基 丙烯酸之一者或二者。α -低級烷基丙烯酸，其在丙烯酸 之羰基結合之碳原子上結合之氫原子，係可以低級烷基而 取代者。「（α -低級烷基）丙烯酸酯」係「（α -低級 烷基）丙烯酸」之酯衍生物，且爲丙烯酸酯及α —低級烷 _ 基丙烯酸酯之一者或二者。所謂的「（α -低級烷基）丙 烯酸酯所衍生之構成單位」，係指（α -低級烷基）丙烯 φ 酸酯之伸乙烯性雙鍵打開所形成之構成單位，以下亦稱爲 (α -低級烷基）丙烯酸酯構成單位。「（α —低級烷 基）丙烯酸酯」係丙烯酸酯及α-低級烷基丙烯酸酯之一 者或二者。所謂的「由羥基苯乙烯所衍生之構成單位」， 係指羥基苯乙烯或α—低級烷基羥基苯乙烯之伸乙烯性雙 鍵打開所形成之構成單位，以下亦稱爲羥基苯乙烯單位。 「α -低級烷基羥基苯乙烯」係在苯基所結合之碳原子上 結合有低級烷基者。 φ 在「α -低級烷基丙烯酸酯所衍生之構成單位」及 「α -低級烷基羥基苯乙烯所衍生之構成單位」中，α位 上所結合之低級烷基，係碳數1〜5之烷基，其係以直鏈 或分支鏈狀之烷基爲較佳，例如有甲基、乙基、丙基、異 * 丙基、η—丁基、異丁基、tert — 丁基、戊基、異戊基、新 戊基等。在工業上以甲基爲較佳。 (A _ 1 )成分，其適合之樹脂成分並無特別之限制， 惟例如有具有：具有下述構成單位（al)之類的苯酚性羥 基之單位、具有選自下述構成單位（a2)及下述構成單位 -16- 200928592 (a3 )之中至少1個的酸解離性溶解抑制基之單位 及，如有必要可使用之下述構成單位（a4 )之類的鹼 性之單位，其等之樹脂成分（以下’亦_稱爲（A _ 1 1 分）。該（A— 11)成分中，藉由因曝光而由酸發生 發生酸之作用，在構成單位（a2)及/或構成單位（ 中會發生開環，從而，最初對於鹼顯像液爲不溶性之 中，其鹼溶解性就會增大。其結果，藉由曝光•顯像 可形成化學增幅型之正型之圖型。 ••構成單位（a 1 ) 構成單位（al )，係具有苯酚性羥基之單位，其 者爲下述一般式（1)所示之羥基苯乙烯所衍生之單位 [化1]BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pattern forming method and a material for forming a coating film, and more particularly to a pattern forming by a double patterning method. The pattern forming method and the pattern forming method are applied to the film forming material. Further, the present invention relates to a pattern forming method and a coating film forming material, and more particularly to a fine pattern of forming a material for forming a coating film using a water-soluble resin composition. The pattern forming method of the type and the material for forming a coating film to which the pattern forming method is applied. [Prior Art] The technique of forming a fine pattern on a substrate and engraving it as a mask to mold the underlayer of the pattern (pattern forming technique) has been used in the 1C production of the semiconductor industry. Widely used, and subject to considerable Φ. The fine pattern is generally composed of an organic material and formed by techniques such as lithography or nanoimprinting. For example, in the lithography method, a "photoresist film" formed of a photoresist composition containing a substrate component such as a resin is formed on a support such as a substrate, and the photoresist film is formed by the predetermined pattern. The photomask (mask pattern) is a step of selectively exposing a radiation pattern such as a light or an electron beam to apply a development process to form a photoresist pattern having a predetermined shape on the photoresist film. The exposed portion of the photoresist which is changed to a dissolved property in the developing solution is referred to as a positive type, and the exposed portion is changed in the developing solution -5 to 200928592 to form a photoresist composition having insoluble characteristics. It is called negative type. Further, the above-described photoresist pattern can be used as a mask, and the substrate can be processed by etching to produce a sequential conductor element or the like. In recent years, due to the advancement of lithography technology, the miniaturization of patterns has been rapidly progressing. The method of miniaturization, in general, is aimed at the short-wavelength of the exposure light source. Specifically, ultraviolet rays represented by g-line and i-line are conventionally used, but semiconductor elements using KrF excimer laser or ArF excimer laser φ are now in mass production, for example, by using an ArF excimer laser. The lithography can form a pattern at a resolution of about 45 nm. In addition, in order to further improve the resolution, F2 excimer lasers, electron beams, EUV (extreme ultraviolet rays) or X-rays, which are shorter wavelengths than these excimer lasers, are also being reviewed. In the photoresist composition, lithographic properties such as sensitivity to such an exposure light source and resolution of a pattern capable of reproducing a fine size are pursued. A photoresist composition which satisfies such a requirement, and which comprises a base material component which changes in alkali solubility due to an action of an acid, and an acid generator which generates an acid due to exposure, and a chemically amplified photoresist composition thereof (Reference Patent Document 1). For example, a positive type chemically amplified photoresist generally has a base material component which contains a resin which can increase the alkali solubility due to the action of an acid, and is formed when the photoresist pattern is formed. The acid generator generates acid, and the exposed portion becomes alkali soluble. One method for further improving the resolution is to expose the liquid between the objective lens and the sample of the exposure machine by sandwiching a liquid having a higher refractive index than the air (immersion medium). (Immersion Exposure) lithography-6 - 200928592 The method is called "Liquid Immersion Lithography (hereinafter also referred to as "immersion exposure") (Non-Patent Document 1 refers to). With the dip-bench exposure, even with a light source of the same exposure wavelength, the same high resolution can be achieved as in the case of using a light source of a shorter wavelength or a higher NA lens, and the depth of focus range is not lowered. In addition, the immersion liquid is exposed and can be applied using an existing exposure apparatus. Therefore, the immersion exposure can be expected to form a photoresist pattern with low cost, high resolution, and excellent depth of focus; and in the manufacture of semiconductor components requiring high equipment investment, regardless of cost Or the lithography characteristics such as resolution can give the semiconductor industry a considerable effect and receive a great deal @. The immersion exposure is effective in the formation of all the pattern shapes, and can be combined with the super-resolution technique such as the phase shifting method and the deformed illumination method in the current review. At present, the immersion exposure technique is mainly actively studied with the technique of using ArF quasi-molecular laser as a light source. In addition, nowadays, the immersion medium is mainly based on water. Recently, one of the newly proposed lithography techniques is a double exposure method in which two patterns are formed to form a pattern (Non-Patent Documents 2 and 3). According to this double exposure method, a finer pattern can be formed than the pattern formed by the patterning of the first time. For example, in Non-Patent Document 2, the method shown in Fig. 3 is described. That is, first, as shown in Fig. 3 (a), a laminate in which the substrate 101, the underlayer film 102, and the hard mask 103 are laminated is prepared. Next, a photoresist film is disposed on the hard mask 1 〇 3, and the photoresist film is imaged as shown in FIG. 3 200928592 (b) by selective exposure through the reticle 10 5 to form an interval. A trench pattern with a width of d/4 and a photoresist pattern with a spacing d. Then, after the photoresist pattern 104 is used as a mask, the hard mask 103 is etched, and the residual photoresist pattern 1〇4 is removed. By this, as shown in Fig. 3(c), a hard light cover 103' having a resist pattern can be obtained. Next, as shown in FIG. 3(d), the position of the mask 105 is moved, and then the photoresist material is coated on the hard mask 103' to form a gap Φ in the hard mask 103'. And a thinner film thickness of the hard mask 103' is thicker than the film thickness of the photoresist film. Furthermore, the photoresist film is selectively exposed through the moving mask 105 to develop a photoresist pattern 106. Then, the photoresist pattern 106 is used as a mask to perform a hard mask 1〇3, and after the uranium is engraved, the residual photoresist pattern 106 is removed. Thereby, as shown in FIG. 3(e), a trench pattern of a plurality of partitions having a width of d / 4 and a hard mask 103 "copied by a pattern having a pitch of d / 2" can be obtained. By etching the hard mask 1 〇 3" as a mask, the pattern of the hard mask ❹ 103" can be copied on the underlying film 1 〇 2 to form the i /2 of the reticle 1 〇 5 used. The pattern of the spacing 102'. Thus, according to the double exposure method, it is possible to form a higher resolution "photograph" pattern using a light source of the same exposure wavelength and using the same photoresist composition. In addition, the double exposure method can be carried out by using an existing exposure apparatus. [Patent Document 1] JP-A-2003-241385 [Non-Patent Document 1] OPTRONICS N0.4 (2003) [Non-Patent Document 2] Proceedings of SPIE 525 6 , 200928592 985 - 994 (2003) » [Non-Patent Document 3] Proceedings of SPIE, Volume 6153, 615301 - 1 to 19 (2006). [Summary of the Invention]. [Disclosure of the Invention] However, in the conventional double exposure method, it is generally necessary to set φ on the substrate. The layer film, in addition, in order to form a pattern on the substrate, the pattern of the photoresist film must be at least 2 times, and the etching of the underlying hard mask is performed at least twice. In the case of the double exposure method, a high-resolution photoresist pattern can be formed, but in recent years, in pursuit of further miniaturization of electronic equipment, a technique of forming a fine photoresist pattern with higher resolution is required. In view of the above, it is an object of the present invention to provide a novel pattern forming method which can reduce the number of steps in the double exposure method, and a material for forming a coating film which is suitable for use in the pattern forming method. An object of the present invention is to provide a novel pattern forming method for forming a finer pattern and a material for forming a coating film which is applied to the pattern forming method. The present inventors have made the above object. As a result of the review, it was found that on the surface of the first photoresist pattern, the coating film formed by using the water-soluble resin composition to form a coating film can be reduced. The present invention has been completed by the number of steps in the low double exposure method. -9 - 200928592 Further, the inventors have found that a coating made of a water-soluble resin composition is formed on the surface of a resist pattern. The film forming material is used to form a coating film, and the photoresist pattern coated by the coating film is exposed and developed. The pattern formed by the coating film component is formed, and a finer pattern can be formed. Thus, the present invention has been completed. More specifically, the present invention includes the invention. That is, the present invention is a pattern forming method characterized by comprising: Φ coating a photoresist composition on a support. a step of forming a photoresist film, a step of selectively exposing and developing the photoresist film through a mask pattern to form a photoresist pattern, and forming a coating film on the surface of the photoresist pattern a step of forming a coating film with a material, and further, a step (i) or (Π) below; (i) on the support formed by the photoresist pattern covered by the coating film Step of coating the second photoresist composition to form a second photoresist film And step (ii) of forming the second photoresist pattern by selectively φ exposure and developing the second photoresist film via the second mask pattern to be covered by the coating film The photoresist pattern is exposed and developed to form a pattern formed by the coating film component. The first aspect of the present invention is a pattern forming method, characterized in that: the step of: coating a first photoresist composition to form a first photoresist film on a support, and The first photoresist film is selectively exposed and developed by the first mask pattern to form a first photoresist pattern, and is used on the surface of the first photoresist pattern. The coating film forming material formed of the water-soluble resin composition forms a coating film, forms a coating pattern, and the second photoresist is applied to the support formed on the coating pattern. a step of forming a second photoresist film, and selectively etching and developing the second photoresist film via the second mask pattern to form a second photoresist pattern step. A second aspect of the present invention is a pattern forming method, characterized in that: a step of forming a photoresist film by coating a positive photoresist composition on a support, and interposing the photoresist film The mask pattern is subjected to selective exposure and development to form a photoresist pattern, and a coating film forming material is formed on the surface of the photoresist pattern by using a material for forming a coating film. The step of forming a film, exposing and developing the photoresist pattern covered by the coating film to form a pattern formed by the coating film component. The third aspect of the present invention is a material for forming a coating film which is a coating film of a water-soluble resin used in the pattern forming method of the first aspect and the second aspect. The forming material is characterized in that it is composed of a material for forming a coating film containing a polymer containing an oxazoline group, or an aqueous solution containing a water-soluble resin and a water-soluble crosslinking agent. According to the above aspect of the table 1 and the third aspect of the present invention, a novel pattern forming method capable of reducing the number of steps in the double exposure method, and a method applicable to the pattern forming method can be provided. A material for forming a film. According to the second aspect and the third aspect of the present invention, it is possible to provide a novel pattern forming method capable of forming a finer pattern, and a coating film forming method applicable to the pattern forming method. material. Further objects, features, and advantages of the present invention will be fully understood from the following description. Further, the benefits of the present invention should be clarified by the following description of the attached drawings with reference to the accompanying drawings. [Embodiment] u [Best Mode of Carrying Out the Invention] [Type 1 of Implementation] _ An embodiment of the present invention will be described below. Further, the embodiment of the present invention is not limited to the following description, and is described in advance. Ο "Formation Method of Pattern of First Aspect" The pattern forming method of the present invention is a pattern forming method using a photoresist composition. Such a photoresist composition is a conventional photoresist composition which can be used by those skilled in the art at the time of implementation of the present invention, but is not limited thereto. Among them, it is preferred to use a chemically amplified photoresist composition. The chemically amplified photoresist composition is not limited, and may be composed of a plurality of chemically amplified photoresist compositions which are proposed as Φ chemically amplified photoresist compositions, depending on the exposure light source used, lithography characteristics, and the like. Choose as appropriate. The chemically amplified photoresist composition may be a negative photoresist composition or a positive photoresist composition, preferably a positive photoresist composition. 'Chemical-amplified photoresist composition, which is generally a substrate component (A) (hereinafter referred to as (A) component) which undergoes alkali solubility change due to the action of acid, and acid acid generation due to exposure The agent component (B) (hereinafter referred to as component (B)) is dissolved in an organic solvent (S) (hereinafter referred to as (S) component). -12-200928592 Here, the term "base material component" means an organic compound having a film forming ability, and an organic compound having a molecular weight of 500 or more is preferably used. By the amount of the organic compound being more than 500, the film forming ability can be improved, and a pattern of nanometer degree can be easily formed. The organic compound having a molecular weight of 500 or more may be a low molecular weight organic compound having a molecular weight of 500 or more and 2000 or less (hereinafter referred to as a low molecular compound), and a high molecular weight resin having a molecular weight of more than 2000 (polymer). ). The aforementioned low molecular compound generally uses a non-polymer. In the case of a resin (polymer), the mass average molecular weight in terms of polystyrene by GPC (gel permeation chromatography) is used. Hereinafter, when it is simply referred to as "resin", it is a resin having a molecular weight of more than 2,000. The component (A) may be a low molecular compound which changes its alkali solubility by the action of an acid, or a resin which changes its alkali solubility by the action of an acid, or may be a mixture thereof. In the φ (A) component, the organic compound which is a component of the substrate for the chemically amplified photoresist can be used singly or in combination of two or more kinds. * When the chemically amplified photoresist composition is a negative-type photoresist composition, the component (A) can be used in addition to the substrate component which is reduced in alkali solubility by the action of an acid, and the negative-type photoresist composition It is also possible to use a crosslinking agent in combination. In such a negative photoresist composition, when an acid is generated in the component (B) due to exposure, cross-linking occurs between the component (A) and the crosslinking agent by the action of the acid, and the component (A) is formed. It will change from alkali solubility to alkali insolubility. In the formation of a photoresist pattern, such as when a photoresist film obtained by coating the negative photoresist composition on a substrate is selectively exposed, the exposed portion becomes alkali-insoluble and relative Since the unexposed portion remains alkali-soluble without change, alkali imaging can be performed. As the component (A) of the negative photoresist composition, an alkali-soluble resin can be generally used. The alkali-soluble resin, for example, has a lower alkyl group selected from α-(hydroxyalkyl)acrylic acid and α-(hydroxyalkyl)acrylic acid. Among the esters, one or more kinds of resins derived from one or more of the esters are preferred because they form a good photoresist pattern with less swelling. Further, α-(hydroxyalkyl)acrylic acid is an acrylic acid having a hydrogen atom bonded to a carbon atom at a 0:position of a carboxyl group, or a hydroxyalkyl group bonded to a carbon atom of the position (preferably A hydroxyalkyl group having 1 to 5 carbon atoms: one or both of hydroxyalkylacrylic acid. For example, when an amine-based crosslinking agent such as glycoluril having a methylol group or an alkoxymethyl group is used, it is preferred to form a good photoresist pattern having less swelling. The amount of the crosslinking agent to be added is preferably 1 to 50 parts by mass based on 100 parts by mass of the alkali-soluble resin. When the chemically amplified photoresist composition is a positive-type photoresist composition, the (Α) component can be used as a substrate component having an acid-dissociable dissolution inhibiting group and having an alkali solubility which is increased by the action of an acid. Such a positive-type photoresist composition is an alkali-insoluble property before exposure, and when an acid is generated from a (Β) component by exposure when a photoresist pattern is formed, acid dissociation dissolution inhibition is caused by the action of the acid. The base will dissociate and the component (A) will become alkali soluble. Therefore, in the formation of the photoresist pattern, such as when the photoresist film obtained by coating the positive-type photoresist composition on the substrate is selectively exposed, the exposed portion becomes alkali-14-200928592 soluble, and the other On the other hand, the unexposed portion remains alkali-insoluble without change, and alkaline imaging can be performed. The component (A) of the positive resist composition may be any one of the following (A-1) component and/or (A-2) component as long as it has an acid dissociable dissolution inhibiting base. _ · (A-1) component: a resin having an acid dissociable dissolution inhibiting group. • (A - 2) component: a low molecular φ compound with an acid dissociative dissolution inhibitory group. Hereinafter, a preferred aspect of the (A-1) component and the (A-2) component will be more specifically described. [(A-1) component] The component (A-1) is preferably a resin containing a constituent unit having an acid dissociable dissolution inhibiting group. In the resin, the ratio of the constituent unit φ of the acid dissociable dissolution inhibiting group is preferably 20 to 80 mol%, more preferably 20 to 70 mol%, based on the total amount of the total constituent units constituting the resin. Good, 30~60 moles is the best. (A-1) component, more specifically, a novolak resin having an acid dissociation dissolution inhibiting group, a hydroxystyrene resin, a -lower alkyl acrylate resin, containing hydroxystyrene A copolymerized resin or the like which is a constituent unit derived from the constituent unit derived from (α-lower alkyl) acrylate. In the present specification, the term "(α_lower alkyl) propylene-15-200928592 acid" means one or both of acrylic acid (CH2 = CH - COOH) and ?-lower alkyl acrylate. The α-lower alkylacrylic acid, which is a hydrogen atom bonded to a carbon atom to which a carbonyl group of acrylic acid is bonded, may be substituted with a lower alkyl group. "(α-Lower alkyl) acrylate" is an ester derivative of "(α-lower alkyl) acrylate" and is one or both of an acrylate and an α-lower alkyl acrylate. The term "constituting unit derived from (α-lower alkyl) acrylate" means a constituent unit formed by the opening of an ethylenic double bond of an (α-lower alkyl) propylene φ acid ester, hereinafter also referred to as ( Α-lower alkyl) acrylate constitutes a unit. "(α-lower alkyl) acrylate" is either or both of an acrylate and an α-lower alkyl acrylate. The "constituting unit derived from hydroxystyrene" means a constituent unit formed by the extension of an ethylenic double bond of hydroxystyrene or α-lower alkyl hydroxystyrene, and is hereinafter also referred to as a hydroxystyrene unit. "α-Lower alkylhydroxystyrene" is a group in which a lower alkyl group is bonded to a carbon atom to which a phenyl group is bonded. φ In the "constituting unit derived from α-lower alkyl acrylate" and "constituting unit derived from α-lower alkyl hydroxystyrene", the lower alkyl group bonded to the α position is a carbon number of 1 to 5 The alkyl group is preferably a linear or branched alkyl group, for example, methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert-butyl, Pentyl, isopentyl, neopentyl and the like. It is preferred to use a methyl group in the industry. The component (A _ 1 ) is not particularly limited, and is, for example, a unit having a phenolic hydroxyl group having the following structural unit (al), and having a constituent unit selected from the following (a2) And a unit of the acid dissociable dissolution inhibiting group of at least one of the following constituent units-16-200928592 (a3) and a basic unit such as the following constituent unit (a4) which may be used, The resin component (hereinafter 'also referred to as (A _ 1 1 point). In the component (A-11), the acid is generated by the acid due to exposure, and the constituent unit (a2) and/or In the constituent unit (the ring is opened in the middle, the alkali solubility is increased in the initial insolubilization of the alkali developing solution. As a result, a chemically amplified type positive pattern can be formed by exposure and development. ••Constituent unit (a 1 ) The constituent unit (al ) is a unit having a phenolic hydroxyl group, which is a unit derived from the hydroxystyrene represented by the following general formula (1) [Chemical Formula 1]

R ❹R ❹

6rV * 5 3 ⑴6rV * 5 3 (1)

4 OH4 OH

[式（1)中，R爲氫原子或低級烷基。] 式（1)中、R爲氫原子或低級烷基。關於低 $ ’其係如上述所示者，並以氫原子或甲基爲較佳。 說明係以下相同。一 〇H在苯環上之結合位置，雖無 ，以 不溶 )成 劑所 a3 ) 樹脂 ，即 較佳 級烷 R之 特別 -17- 200928592 之限制，惟係以式中之4之位置（對位）爲較佳。 構成單位（al) ’基於形成圖型之觀點，係以（A-1 1 )成分中爲40〜80莫耳％、較佳者爲5〇〜75莫耳％含 有者爲理想。藉由在40莫耳％以上，可提升其對於鹼性顯 像液之溶解性，並能獲得圖型形狀之改善效果。藉由在80 _ 莫耳％以下時，則可取得與其他之構成單位之平衡。 此外，基於在圖型上可形成被覆膜之觀點，構成單位 0 (al)，在（A—11)成分中，係以50莫耳％以上含有者 爲較佳’更佳者爲6 0莫耳％以上，最佳者爲7 5莫耳％以 上。其上限並無特別之限制，惟以8 0莫耳％以下爲理想。 如在上述之範圍’藉由苯酚性經基之存在，可在圖型上形 成良好之被覆膜’並可得到良好形狀之圖型。此外，其圖 型與被覆膜之密接性可成爲良好。 ••構成單位（a2) 〇 構成單位（a2 )’係具有酸解離性溶解抑制基之構成 單位，其係下述一般式（2)所示者。[In the formula (1), R is a hydrogen atom or a lower alkyl group. In the formula (1), R is a hydrogen atom or a lower alkyl group. Regarding the lower $', it is as described above, and a hydrogen atom or a methyl group is preferred. The description is the same as the following. The binding position of H on the benzene ring, although not, is in the insoluble) a3) resin, which is the limit of the special grade alkane R, -17-200928592, but is in the position of 4 Bit) is preferred. The constituent unit (al) is preferably 40 to 80 mol%, preferably 5 〇 to 75 mol%, based on the pattern of formation (A-1 1 ). By being 40 mol% or more, the solubility to the alkaline developing solution can be improved, and the effect of the pattern shape can be improved. By being at or below 80 _ mol%, the balance with other constituent units can be obtained. Further, based on the fact that a coating film can be formed on the pattern, the unit 0 (al) is formed, and in the (A-11) component, it is preferably 50 mol% or more. The more preferable one is 60. More than 5% of the moles, the best is more than 7 5 mol%. The upper limit is not particularly limited, but it is preferably 80% or less. As described above, by the presence of a phenolic radical, a good coating film can be formed on the pattern and a good shape can be obtained. Further, the adhesion between the pattern and the coating film can be improved. • constituting unit (a2) 构成 The constituent unit (a2)' is a constituent unit having an acid dissociable dissolution inhibiting group, which is represented by the following general formula (2).

[化2] R[Chemical 2] R

Ο I X -18- 200928592 [式（2 )中、R係與上述相同’ X爲酸解離性溶解抑制 基。] 酸解離性溶解抑制基X，係具有第三輯碳原子之烷 基’例如有該第三級烷基之第三級碳原子結合於酯基[ —c(o)o—]之酸離性溶解抑制基、四氫吡喃基、四氫呋喃 . 基之類的環狀縮醛基等。此種酸解離性溶解抑制基X，例 如在化學增幅型之正型光阻組成物之中所使用者，如上述 0 以外者亦可任意地加以使用。 構成單位（a2)，較佳者例如有下述一般式（3)所 示者等。Ο I X -18- 200928592 [In the formula (2), the R system is the same as the above] X is an acid dissociable dissolution inhibiting group. An acid dissociable dissolution inhibiting group X, which is an alkyl group having a third carbon atom, for example, an acid group having a third-order carbon atom of the third-order alkyl group bonded to an ester group [-c(o)o-] A cyclic acetal group such as a dissolution inhibiting group, a tetrahydropyranyl group or a tetrahydrofuran group. Such an acid dissociable dissolution inhibiting group X, for example, a user of a chemically amplified positive resist composition, or any of the above 0 may be used arbitrarily. The constituent unit (a2) is preferably, for example, the one shown in the following general formula (3).

(3) [式（3)中，R係與上述爲相同者，R11、Ri2、r13係各自 獨立地爲低級烷基（可爲直鏈、分支鏈之任一者，其碳數 係以1〜5爲較佳）。或者，在 係低級烷基，R12可與R13結合而形成單環或多環之脂肪 族環式基。該脂肪族環式基之碳數，係以5〜12爲較佳。] -19- 200928592 在此，所謂的「脂肪族」’係指該基或化合物不具有 芳香族性之意’ 「脂肪族環式基」則係指不具有芳香族性 之單環式基或多環式基。 —(3) In the formula (3), the R system is the same as the above, and the R11, Ri2, and r13 are each independently a lower alkyl group (may be either a linear chain or a branched chain, and the carbon number thereof is 1). ~5 is preferred). Alternatively, in the case of a lower alkyl group, R12 may be bonded to R13 to form a monocyclic or polycyclic aliphatic cyclic group. The carbon number of the aliphatic cyclic group is preferably from 5 to 12. ] -19- 200928592 Here, the term "aliphatic" means that the group or compound does not have an aromatic meaning. "Aromatic ring group" means a monocyclic group having no aromaticity or Polycyclic base. -

Rii、R12、R13如不具有脂肪族環式基時，舉例而 言，R11、R12、R13，其不論何者皆以甲基爲較佳。 、R»2、R13之任一者如具有脂肪族環式基時，脂 肪族環式基如係單環之脂肪族環式基時’構成單位 (a2 )，舉例而言’係以具有環戊基、環己基者等爲較 佳。 脂肪族環式基如係多環之脂環式基時，構成單位 (a2 )，其較佳者例如有下述一般式（4 )所示者。 [化4]When Rii, R12, and R13 do not have an aliphatic cyclic group, for example, R11, R12, and R13 are preferably a methyl group. When any of R»2 and R13 has an aliphatic cyclic group, the aliphatic cyclic group is a monocyclic aliphatic ring group, and the constituent unit (a2), for example, has a ring A pentyl group, a cyclohexyl group or the like is preferred. When the aliphatic cyclic group is a polycyclic alicyclic group, it constitutes a unit (a2), and preferably, for example, those represented by the following general formula (4). [Chemical 4]

[式（4 )中、R係與上述相同，R14爲低級院基（可爲直 鏈、分支鏈之任一者。碳數係以1〜5爲較佳）] 此外，具有包含多環之脂肪族環式基之酸解離性溶解 -20- 200928592 抑制基，係以下述一般式（5 )所示者爲較佳。[In the formula (4), the R system is the same as the above, and R14 is a lower-grade courtyard group (may be any of a straight chain or a branched chain. The carbon number is preferably 1 to 5)] Further, it has a polycyclic ring. Acid dissociable dissolution of aliphatic cyclic group -20- 200928592 The inhibitory group is preferably represented by the following general formula (5).

[式（5 )中，R係與上述相同，R15、R16係各自獨立地爲 低級烷基（可爲直鏈、分支鏈之任一者，碳數係以1〜5 爲較佳）] Φ 構成單位（a2)，在（A— 11)成分中，一般係5〜 50莫耳％，較佳者爲10〜40莫耳％，最佳者爲10〜35莫 ^ 耳％含有者爲理想。 ••構成單位（a3 ) 構成單位（a3 )係具有酸解離性溶解抑制基之構成單 位，其係下述一般式（6)所示者。 -21 - 200928592 [化6]In the formula (5), R is the same as above, and R15 and R16 are each independently a lower alkyl group (may be either a straight chain or a branched chain, and the carbon number is preferably 1 to 5)] Φ The constituent unit (a2), in the component (A-11), is generally 5 to 50 mol%, preferably 10 to 40 mol%, and the most preferred one is 10 to 35 mol%. . • Component (a3) The constituent unit (a3) is a constituent unit having an acid dissociable dissolution inhibiting group and is represented by the following general formula (6). -21 - 200928592 [Chem. 6]

RR

0 [式（6 )中，R係與上述相同，X ’爲酸解離性溶解抑制基] 酸解離性溶解抑制基X’，例如有tert-丁基氧基羰 基、tert —戊基氧基簾基寺之第二級院基氧基鑛基；tert — 丁基氧基羰基甲基、tert - 丁基氧基羰基乙基等之第三級 烷基氧基羰基烷基；tert — 丁基、tert 一戊基等之第三級烷 基；四氫吡喃基、四氫呋喃基等之環狀縮醛基；乙氧基乙 基、甲氧基丙基等之烷氧基烷基等。 其中，又以tert — 丁基氧基羯基、tert — 丁基氧基鑛 〇 基甲基、tert _ 丁基、四氫吡喃基、乙氧基乙基爲較佳。 酸解離性溶解抑制基X’， 例如在化學增幅型之正型 光阻組成物之中所使用者，如上述以外者亦可任意地加以 使用。 * 在一般式（6)中，結合於苯環之基（-OX，）之結合 位置並無特別之限制，惟係以式中所示之4之位置（對 位）爲較佳。 構成單位（a3)，在（A— 11)成分中，一般係5〜 50莫耳％，較佳者爲10〜40莫耳％，最佳者爲1〇〜35莫 -22- 200928592 耳％含有者爲理想。 ••構成單位（a4) - 構成單位（a4)，係鹼不溶性之構成單位’其係下述 一般式（7 )所示者。0 [In the formula (6), the R system is the same as the above, and X' is an acid dissociable dissolution inhibiting group] The acid dissociable dissolution inhibiting group X', for example, tert-butyloxycarbonyl, tert-pentyloxy curtain The second-grade alkyloxy ortho group of the base temple; tert-butyloxycarbonylmethyl, tert-butyloxycarbonylethyl, etc., tertiary alkyloxycarbonylalkyl; tert-butyl, Tert-alkyl group such as tert-pentyl group; cyclic acetal group such as tetrahydropyranyl group or tetrahydrofuranyl group; alkoxyalkyl group such as ethoxyethyl group or methoxypropyl group; and the like. Among them, tert-butyloxyindenyl, tert-butyloxyindolylmethyl, tert-butyl, tetrahydropyranyl or ethoxyethyl are preferred. The acid dissociable dissolution inhibiting group X' can be used, for example, in a chemically amplified positive resist composition, and can be used arbitrarily as described above. * In the general formula (6), the bonding position of the group bonded to the benzene ring (-OX,) is not particularly limited, but the position (alignment) of 4 shown in the formula is preferred. The constituent unit (a3), in the component (A-11), is generally 5 to 50 mol%, preferably 10 to 40 mol%, and the most preferred one is 1 to 35 mol-22-200928592 ear% The inclusion is ideal. ••Constituent unit (a4) - Constituent unit (a4), which is a constituent unit of alkali insolubility', which is shown in the following general formula (7).

[式（7)中’ R係與上述相同’ R4’爲低級烷基，n’爲0〜3 之整數] 再者’ R4’之低級烷基，可爲直鏈或分支鏈之任一 者，其碳數係以1〜5爲較佳。η’爲0〜3之整數，惟係以 0爲較佳。 構成單位（a4)，在（Α— 11)成分中，一般係1〜 4 〇莫耳％ ’較佳者爲5〜2 5莫耳％。藉由在1莫耳％以 上，可提高其形狀之改善（尤其膜減少之改善）效果’而 藉由在40莫耳％以下，則可取得與其他構成單位之平衡。 在（A— 11)成分中，前述構成單位（ai)、以及選 自構成單位（a2 )及構成單位（a3 )之中至少1個之構成 -23- 200928592 單位爲必須者，並可任意地含有構成單位（a4 )。此外’ 亦可使用具有此等之各構成單位之全部之共聚物’或者爲 具有1個以上此等構成單位之各聚合物混合物。或者’亦 可爲此等之組合者。 此外，（A- 11)成分，可任意地含有前述構成單位 . (al ) 、（ a2 ) 、（ a3 ) 、（ a4 )以外者，惟此等構成單 位之比例，一般係8 0莫耳％以上，較佳爲9 0莫耳％以上 ❹ （1 〇 〇莫耳％爲最佳）者爲理想。 其中，又以將：「具有前述構成單位（al)及（a3) 之共聚物之任一種、或該共聚物之2種以上之混合物」、 或「具有構成單位（al) 、（a2)、及（a4)之共聚物之 任一種、或該共聚物之2種以上之混合物」，其等各自使 用或混合之態樣，基於可簡便地獲得其效果而爲最佳者。 此外，在提升耐熱性之點上亦爲較佳。 其中，係以：藉由第三級烷基氧基羰基加以保護之聚 〇 羥基苯乙烯、及藉由1_烷氧基烷基加以保護之聚羥基苯 乙烯，其二者之混合物爲較佳。在進行此種此種混合時， 各聚合物之混合比（質量比）（藉由第三級烷基氧基羰基 加以保護之聚羥基苯乙烯/藉由1 一烷氧基烷基加以保護 ' 之聚羥基苯乙烯）係例如1/9〜9/1，較佳者爲2/8〜8 / 2，最佳者則爲2 / 8〜5 / 5。 適合作爲（A- 1)成分之上述（A — 11)成分以外之 樹脂成分，尤其基於耐蝕刻性可形成更低圖型之觀點，係 以含有（〇! —低級烷基）丙烯酸酯樹脂之樹脂成分（（α -24- 200928592 一低級烷基）丙烯酸酯樹脂）爲較佳，並以由（α-低級 烷基）丙烯酸酯樹脂所成之樹脂成分爲最佳。 在（α —低級烷基）丙烯酸酯樹脂中，係以由含有酸 解離性溶解抑制基之（α -低級烷基）丙烯酸酯所衍生之 構成單位（a5 )之樹脂爲較佳。關於α -低級烷基，則與 _ 上述相同。 構成單位（a5)之酸解離性溶解抑制基，其具有在曝 φ 光前使（A - 12)成分整體成爲鹼性不溶之鹼溶解抑制 性，同時，又係在曝光後由於（B)成分發生之酸之作用 而解離，可將此種（A- 12)成分整體改變成爲鹼可溶性 之基。 此外，在（α -低級烷基）丙烯酸酯樹脂成分中，構 成單位（a5)中之酸解離性溶解抑制基，當由（Β)成分 發生之酸而解離時，會生成羧酸。由於此種生成羧酸之存 在，在光阻圖型上形成之被覆膜之密接性就會提升。 Q 酸解離性溶解抑制基，例如可在ArF準分子雷射之光 阻組成物用之樹脂中，由多數被提案者之中適當地加以選 擇。一般而言，廣爲人知者已有：與（α -低級烷基）丙 烯酸之羧基形成環狀或鏈狀之第三級烷基酯之基、或環狀 ^ 或鏈狀之烷氧基烷基等。 在此，所謂的「形成第三級烷基酯之基」，係指藉由 與丙烯酸之羧基之氫原子之取代而形成酯之基。亦即，在 丙烯酸酯之羰基氧基[-c(0)- 0-]之末端之氧原子上， 結合有鏈狀或環狀之第三級烷基之第三級碳原子之構造。 -25- 200928592 該第三級烷基酯中，酸如作用時，氧原子與第三級碳原子 之間的鍵結就會被切斷。 再者’所謂的第三級烷基’係指具有第三級碳原子之 烷基。形成鏈狀之第三級烷基酯之基，例如有tert一丁 基、tert -戊基等。形成環狀之第三級烷基酯之基，例如 . 有與後述之「含有脂環式基之酸解離性溶解抑制基」所例 示爲相同者。 0 「環狀或鏈狀之烷氧基烷基」，係與羧基之氫原子進 行取代而形成酯。亦即，在丙烯酸酯之羰基氧基[-C(O) -〇—]之末端之氧原子上，形成有前述垸氧基院基結合之 構造。此種構造中，藉由酸之作用，在氧原子與烷氧基烷 基之間，其鍵結會被切斷。 此種環狀或鏈狀之烷氧基烷基，例如有1-甲氧基甲 基、1_乙氧基乙基、1 一異丙氧基乙基、1—環己基氧基 乙基、2—金剛烷氧基甲基、1—甲基金剛烷氧基甲基、4 φ —氧基一2_金剛烷氧基甲基、1_金剛烷氧基乙基、2 -金剛烷氧基乙基等。 構成單位（a5)，係以環狀，尤其是包含含有脂肪族 環式基之酸解離性溶解抑制基之構成單位爲較佳。在此， ' 「脂肪族」及「脂肪族環式基」係如上述定義所示者。 脂肪族環式基，可爲單環或多環之任一者’例如在 ArF光阻等中，可由多數被提案者之中適當地加以選擇。 基於耐蝕刻性之觀點係以多環之脂環式基爲較佳。此外’ 脂環式基係以烴基爲較佳’並以飽和之烴基（脂環式基） -26- 200928592 爲最佳。 單環之脂環式基，例如有除去由環鏈烷烴而來的1個 氫原子之基。多環之脂環式基，例如有除去由雙環鏈烷 烴、三環鏈烷烴、四環鏈烷烴等而來的1個氫原子之基 等。 具體而言，單環之脂環式基，例如有環戊基、環己基 等。多環之脂環式基，例如有金剛烷、原菠烷、異菠烷、 三環癸烷、四環十二烷等之由聚環鏈烷烴除去1個氫原子 之基等。此等之中，係以除去由金剛烷而來的1個氫原子 之金剛烷基、除去由原菠烷而來的1個氫原子之原菠烷 基、除去由三環癸烷而來的1個氫原子之三環癸烷基、除 去由四環十二烷而來的1個氫原子之四環十二烷基，爲工 業上較佳者。 更具體而言，構成單位（a5)，係以選自下述一般式 (1，）〜（3’）中之至少1種爲較佳。此外，（α —低級 烷基）丙烯酸酯所衍生之單位，係於其酯部具有上述環狀 之烷氧基烷基之單位，具體而言，較佳者係至少1種選自 2—金剛烷氧基甲基、1 一甲基金剛烷氧基甲基、4 —氧基 —2 -金剛烷氧基甲基、1 —金剛烷氧基乙基、2 —金剛烷 氧基乙基等之可具有取代基由脂肪族多環式烷基氧基低級 烷基（a -低級烷基）丙烯酸酯所衍生之單位。 -27- 200928592 [化8][In the formula (7), the 'R system is the same as the above', R4' is a lower alkyl group, and n' is an integer of 0 to 3. Further, the lower alkyl group of 'R4' may be either a straight chain or a branched chain. The carbon number is preferably from 1 to 5. η' is an integer of 0 to 3, but 0 is preferred. The constituent unit (a4), in the (Α-11) component, is generally 1 to 4 〇 mol% ’, preferably 5 to 2 5 mol%. By improving the shape (especially the improvement of the film reduction) by more than 1 mol%, and by 40 mol% or less, the balance with other constituent units can be obtained. In the component (A-11), the constituent unit (ai) and the constituent -23-200928592 selected from at least one of the constituent unit (a2) and the constituent unit (a3) are essential, and may be arbitrarily Contains the constituent unit (a4). Further, a copolymer having all of the constituent units of these or a polymer mixture having one or more of these constituent units may be used. Or ' can also be a combination of these. Further, the component (A-11) may optionally contain the above-mentioned constituent units. (al), (a2), (a3), and (a4), but the ratio of these constituent units is generally 80% by mole. The above is preferably 90% by mole or more (1% of the molar % is optimal). In addition, "the copolymer of any of the above-mentioned constituent units (al) and (a3) or a mixture of two or more of the copolymers" or "having a constituent unit (al), (a2), Any one of the copolymers of (a4) or a mixture of two or more of the copolymers, which are used or mixed, is preferably based on the fact that the effect can be easily obtained. In addition, it is also preferable in terms of improving heat resistance. Among them, a polyhydroxy styrene protected by a tertiary alkyloxycarbonyl group, and a polyhydroxystyrene protected by a 1-alkoxyalkyl group, a mixture of the two is preferred. . In carrying out such mixing, the mixing ratio (mass ratio) of each polymer (polyhydroxystyrene protected by a tertiary alkyloxycarbonyl group / protected by a monoalkoxyalkyl group) The polyhydroxystyrene) is, for example, 1/9 to 9/1, preferably 2/8 to 8 / 2, and most preferably 2 / 8 to 5 / 5. It is suitable as a resin component other than the above (A-11) component of the component (A-1), and in particular, based on the viewpoint that etching resistance can form a lower pattern, it is a resin containing (〇!-lower alkyl) acrylate resin. The resin component ((α - 24 - 200928592-lower alkyl) acrylate resin) is preferable, and the resin component obtained from the (α-lower alkyl) acrylate resin is preferable. In the (α-lower alkyl) acrylate resin, a resin having a constituent unit (a5) derived from an (α-lower alkyl) acrylate having an acid-dissociable dissolution inhibiting group is preferred. Regarding α-lower alkyl, it is the same as _ above. An acid dissociable dissolution inhibiting group of the constituent unit (a5), which has an alkali dissolution inhibiting property of making the (A - 12) component as a whole alkaline insoluble before exposure to φ light, and is also a component (B) after exposure. The dissociation by the action of the acid can change the entire (A-12) component to an alkali-soluble base. Further, in the (α-lower alkyl) acrylate resin component, the acid dissociable dissolution inhibiting group in the unit (a5) is formed, and when dissociated from the acid generated by the (Β) component, a carboxylic acid is formed. Due to the presence of such a carboxylic acid, the adhesion of the coating formed on the photoresist pattern is improved. The Q-dissociable dissolution-inhibiting group can be appropriately selected from among many of the proprietors, for example, among the resins for the photoresist composition of the ArF excimer laser. In general, it is well known that a carboxyl group or a chain alkoxyalkyl group is formed by forming a cyclic or chain tertiary alkyl ester with a carboxyl group of (α-lower alkyl)acrylic acid. Base. Here, the term "the group forming the third-stage alkyl ester" means a group which forms an ester by substitution with a hydrogen atom of a carboxyl group of acrylic acid. That is, a structure in which a third-order carbon atom of a chain or ring-shaped tertiary alkyl group is bonded to an oxygen atom at the terminal of the carbonyloxy group [-c(0)- 0-] of the acrylate. -25- 200928592 In the third-stage alkyl ester, when the acid acts, the bond between the oxygen atom and the third-order carbon atom is cut off. Further, 'the so-called tertiary alkyl group' means an alkyl group having a third-order carbon atom. The group forming the chain-like tertiary alkyl ester is, for example, tert-butyl, tert-pentyl or the like. The group forming the cyclic third-order alkyl ester is, for example, the same as the "acid-dissociable dissolution inhibiting group containing an alicyclic group" which will be described later. 0 "A cyclic or chain alkoxyalkyl group" which is substituted with a hydrogen atom of a carboxyl group to form an ester. Namely, a structure in which the above-mentioned decyloxy group is bonded is formed on the oxygen atom at the terminal of the carbonyloxy group [-C(O) - fluorene] of the acrylate. In this configuration, the bond between the oxygen atom and the alkoxyalkyl group is cleaved by the action of an acid. Such a cyclic or chain alkoxyalkyl group, for example, 1-methoxymethyl, 1-ethoxyethyl, 1-isopropoxyethyl, 1-cyclohexyloxyethyl, 2-adamantyloxymethyl, 1-methyladamantyloxymethyl, 4 φ-oxy-2-adamantyloxymethyl, 1-adamantyloxyethyl, 2-adamantyloxy Ethyl and the like. The constituent unit (a5) is preferably a cyclic group, particularly a constituent unit containing an acid dissociable dissolution inhibiting group containing an aliphatic cyclic group. Here, 'aliphatic' and 'aliphatic cyclic group' are as defined above. The aliphatic cyclic group may be either a single ring or a polycyclic ring. For example, in an ArF photoresist or the like, it may be appropriately selected among a plurality of proprietors. From the viewpoint of etching resistance, a polycyclic alicyclic group is preferred. Further, the 'alicyclic group is preferably a hydrocarbon group' and is preferably a saturated hydrocarbon group (alicyclic group) -26-200928592. The monocyclic alicyclic group has, for example, a group which removes one hydrogen atom derived from a cycloalkane. The polycyclic alicyclic group may, for example, be a group in which one hydrogen atom is removed by a bicycloalkane, a tricycloalkane or a tetracyclic alkane. Specifically, the monocyclic alicyclic group may, for example, be a cyclopentyl group, a cyclohexyl group or the like. The polycyclic alicyclic group may, for example, be a group in which one hydrogen atom is removed from a polycycloalkane such as adamantane, prorotane, isopentane, tricyclodecane or tetracyclododecane. Among these, an adamantyl group which removes one hydrogen atom derived from adamantane, a raw spinachyl group which removes one hydrogen atom derived from the original spinane, and a tricyclic decane are removed. It is industrially preferred that a tricyclodecane group of one hydrogen atom and a tetracyclododecyl group which removes one hydrogen atom derived from tetracyclododecane are used. More specifically, the constituent unit (a5) is preferably at least one selected from the following general formulas (1) to (3'). Further, the unit derived from the (α-lower alkyl) acrylate is a unit in which the ester moiety has the above cyclic alkoxyalkyl group, and specifically, at least one selected from the group consisting of 2 - King Kong Alkoxymethyl, 1-methyladamantyloxymethyl, 4-oxo-2-adamantyloxymethyl, 1-adamantyloxyethyl, 2-adamantyloxyethyl, etc. The unit may have a substituent derived from an aliphatic polycyclic alkyloxy lower alkyl (a-lower alkyl) acrylate. -27- 200928592 [Chem. 8]

RR

〇 [式（1 ’）中、R係與上述相同，R1爲低級烷基] [化9]〇 [In the formula (1 ′), the R system is the same as the above, and R1 is a lower alkyl group] [Chemical 9]

RR

(21) [式（2’）中，R係與上述相同，R2及R3係各自獨立地爲 低級烷基] -28- 200928592 [化 10](21) [In the formula (2'), R is the same as above, and R2 and R3 are each independently a lower alkyl group] -28- 200928592 [Chemical 10]

c〇〇R4 Q [式（3’）中，R係與上述相同，R4爲第三級烷基] 一般式（1，）〜（3，）中，R之氫原子或低級烷基’ 係與上述丙烯酸酯之α位所結合之氫原子或低級烷基之說 明爲相同者。 R1之低級烷基，係以碳數1〜5之直鏈或分支鏈狀之 烷基爲較佳，具體而言，例如有甲基、乙基、丙基、異丙 基、η - 丁基、異丁基、戊基、異戊基、新戊基等。其 中，又以甲基、乙基，其等由於工業上容易獲得之緣故而 ❹ 較佳。 R2及R3之低級烷基，係以各自獨立地爲碳數1〜5之 直鏈或分支鏈狀之烷基爲較佳。其中，R2及R3係以共同 地爲甲基時，在工業上爲較佳。具體而言，例如有由2— ' (1-金剛烷基）—2 —丙基丙烯酸酯所衍生之構成單位。 R4係鏈狀之第三級烷基或環狀之第三級烷基。鏈狀之 第三級烷基，例如有tert - 丁基或tert—戊基，並以tert - 丁基在工業上爲較佳。環狀之第三級烷基，係與前述之 「含有脂肪族環式基之酸解離性溶解抑制基」所例示者相 -29- 200928592 同’例如有2 —甲基—2-金剛烷基、2 —乙基一 2 -金剛烷 基、2—（1 一金剛烷基）—2 —丙基、1—乙基環己基、1 _乙基環戊基、1—甲基環己基、1—甲基環戊基等。 此外，基- COOR4，可結合於式中所示之四環十二烷 基之3或4之位置，惟其結合位置並無特定。此外，丙烯 酸酯構成單位之羧基殘基亦同樣地可結合於式中所示之8 或9之位置。 構成單位（a5)可使用1種或2種以上之組合。 在（α -低級烷基）丙烯酸酯樹脂成分中，構成單位 (a5 )之比例，相對於構成（α —低級烷基）丙烯酸酯樹 脂成分之全構成單位之總計，係以20〜60莫耳％爲較佳， 3 0〜5 0莫耳％爲更佳，3 5〜4 5莫耳％爲最佳。藉由在下限 値以上可得到圖型，而在上限値以下’則可取得與其他構 成單位之平衡。 (α -低級烷基）丙烯酸酯樹脂’除了前述構成單位 (a5 )，係以進而具有由具有內酯環之丙烯酸酯所衍生之 構成單位（a6)爲較佳。構成單位（a6) ’在提高對於光 阻膜之基板之密接性，及在提高與顯像液之親水性上爲有 效者。此外，並可形成與圖型之密接性高之被覆膜。 在構成單位（a6)中’結合於α位之碳原子者’係低 級烷基或氫原子。α位之碳原子上結合之低級院基’係與 構成單位（a5)之說明相同’其較佳者爲甲基。 構成單位（a6)，例如有在丙燒酸醋之酯側鏈部上， 結合了由內酯環所成之單環式基或具有內醋環之多環的環 -30- 200928592 式基之構成單位。再者，此時所謂的內酯環’係指含有 -〇 — c(o) —構造之1個環，並將其作爲第1個環來計 數。因此’在此如僅內酯環時，稱爲單環式基，如進而具 有其他之環構造時’則無關其構造而稱爲多環式基。 構成單位（a6) ’例如有除去由r 一丁內酯而來的1 . 個氫原子之單環式基、或者除去由含有內酯環之雙環鏈院 烴而來的1個氫原子之多環式基等。 ο 構成單位（a6) ’更具體而言’例如有選自以下之— 般式（4’）〜（7’）之至少1種爲較佳。C〇〇R4 Q [In the formula (3'), R is the same as above, and R4 is a tertiary alkyl group] In the general formula (1,) to (3,), a hydrogen atom of R or a lower alkyl group The description of the hydrogen atom or the lower alkyl group bonded to the α-position of the above acrylate is the same. The lower alkyl group of R1 is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group or a η-butyl group. , isobutyl, pentyl, isopentyl, neopentyl and the like. Among them, a methyl group, an ethyl group, and the like are preferable because they are industrially easy to obtain. The lower alkyl group of R2 and R3 is preferably a linear or branched alkyl group each independently having a carbon number of 1 to 5. Among them, when R2 and R3 are a common methyl group, it is industrially preferable. Specifically, for example, there are constituent units derived from 2-(1-adamantyl)-2-propyl acrylate. R4 is a chain-like tertiary alkyl group or a cyclic tertiary alkyl group. The chain-like tertiary alkyl group, for example, tert-butyl or tert-pentyl, is industrially preferred as tert-butyl. The cyclic tertiary alkyl group is exemplified by the above-mentioned "acid dissociable dissolution inhibiting group containing an aliphatic cyclic group" -29-200928592 with the same 'for example, 2-methyl-2-adamantyl group , 2-ethyl-2-anomantyl, 2-(1-adamantyl)-2-propyl, 1-ethylcyclohexyl, 1-ethylcyclopentyl, 1-methylcyclohexyl, 1 - methylcyclopentyl and the like. Further, the base - COOR4 may be bonded to the position of 3 or 4 of the tetracyclododecyl group shown in the formula, except that the binding position is not specified. Further, the carboxyl residue of the acrylate constituent unit can be similarly bonded to the position of 8 or 9 shown in the formula. The constituent unit (a5) may be used alone or in combination of two or more. In the (α-lower alkyl) acrylate resin component, the ratio of the constituent unit (a5) is 20 to 60 mol with respect to the total of the constituent units constituting the (α-lower alkyl) acrylate resin component. % is better, 3 0~5 0 mol% is better, 3 5~4 5 mol% is the best. The pattern can be obtained above the lower limit ,, and the lower limit 値 can be obtained by balancing the other constituent units. The (α-lower alkyl) acrylate resin ' is preferably a constituent unit (a6) derived from an acrylate having a lactone ring, in addition to the above-mentioned constituent unit (a5). The constituent unit (a6)' is effective in improving the adhesion to the substrate of the resist film and improving the hydrophilicity of the developing solution. Further, it is possible to form a coating film having high adhesion to the pattern. In the constituent unit (a6), the 'carbon atom bonded to the α-position' is a lower alkyl group or a hydrogen atom. The low-grade base group bonded to the carbon atom of the α-position is the same as the description of the constituent unit (a5). The preferred one is a methyl group. The constituent unit (a6) is, for example, a ring of a monocyclic group formed by a lactone ring or a polycyclic ring having a vinegar ring on the side chain portion of the ester of propyl sulphate, and a ring of -30-200928592 Constitute unit. Here, the term "lactone ring" at this time means one ring having a structure of -〇 - c(o) - and is counted as the first ring. Therefore, when it is referred to herein as a lactone ring only, it is referred to as a monocyclic group, and if it has a further ring structure, it is called a polycyclic group irrespective of its structure. The constituent unit (a6) 'for example, has a monocyclic group in which one hydrogen atom is removed from r-butyrolactone, or one hydrogen atom from a double-chain chain hydrocarbon containing a lactone ring. Ring base and the like. ο constituting unit (a6) ‘ More specifically, for example, at least one selected from the following general formulas (4') to (7') is preferable.

' R6係各自獨立地爲 [式（4’）中，R係與上述相同， 氫原子或低級烷基] -31 - 200928592 [化 12]'R6 is each independently [in the formula (4'), and the R is the same as the above, a hydrogen atom or a lower alkyl group] -31 - 200928592 [Chemical 12]

RR

[式（5’）中，R係與上述相同，m爲〇或1] [化 13][In the formula (5'), the R system is the same as described above, and m is 〇 or 1] [Chemical 13]

RR

(6·) [式（6’）中，R係與上述相同] -32- 200928592 [化 14](6·) [In the formula (6'), the R system is the same as the above] -32- 200928592 [Chem. 14]

[式（7’）中，R係與上述相同] 一般式（4’）中，R5、R6係各自獨立地爲氫原子或低 級烷基，較佳爲氫原子。在R5、R6中，低級烷基，其較 佳者爲碳數1〜5之直鏈或分支鏈狀之烷基，例如甲基、 乙基、丙基、異丙基、η-丁基、異丁基、tert_ 丁基、戊 基、異戊基、新戊基等。工業上則以甲基爲較佳。 Φ 在一般式（4’）〜（7’）所示之構成單位中，係以一 般式（4’）所示之構成單位，其便宜而在工業上爲較佳， 在一般式（4’）所示之構成單位中，R爲甲基，R5及R6 爲氫原子，而甲基丙烯酸酯與7· _丁內酯之酯鍵結位置， 則以其內酯環上之α位之α —甲基丙烯醯氧基_ 7 一丁內 酯爲最佳。 構成單位（a6 )可使用1種或2種以上之組合。 在（α —低級烷基）丙烯酸酯樹脂成分中，構成單位 (a6)之比例’相對於構成（α -低級烷基）丙烯酸酯樹 -33- 200928592 脂成分之全構成單位之總計，係以2 0〜6 0莫耳％較佳，2 0 〜5 0莫耳％更佳，3 0〜4 5莫耳％最佳。藉由在下限値以 上，其微影特性可提升’而藉由在上限値以下，則可取得 與其他構成單位之平衡。 (α -低級烷基）丙烯酸酯樹脂成分，除前述構成單 - 位（a5)以外’或者前述構成單位（a5)及（a6)以外， 係以進而具有包含含有極性基之多環式基之丙烯酸酯所衍 Q 生之構成單位（a7)者爲較佳。藉由構成單位（a7)， (α -低級烷基）丙烯酸酯樹脂成分整體之親水性可提 高，與顯像液之親和性可提高，且在曝光部之鹼溶解性可 提升，並可提升其解像性。 在構成單位（a7)中，結合於《位之碳原子者，係低 級烷基或氫原子。結合於α位之碳原子之低級烷基，係與 構成單位（a5)之說明相同，其較佳者爲甲基。極性基， 例如有羥基、氰基、羧基、胺基等’並以羥基爲較佳。多 〇 環式基，可在前述（a5)單位之「含有脂肪族環式基之酸 解離性溶解抑制基」所例示之脂肪族環式基之中’由多環 式者適當地選擇而使用。 構成單位（a7)，係以選自下述一般式（8’）〜 (9 ’）之至少1種爲較佳。 -34- 200928592In the formula (7'), R is the same as defined above. In the general formula (4'), R5 and R6 are each independently a hydrogen atom or a lower alkyl group, preferably a hydrogen atom. In R5, R6, lower alkyl, preferably a linear or branched alkyl group having a carbon number of 1 to 5, such as methyl, ethyl, propyl, isopropyl, η-butyl, Isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, and the like. In the industry, methyl is preferred. Φ In the constituent units shown in the general formulas (4') to (7'), it is a constituent unit represented by the general formula (4'), which is inexpensive and industrially preferable, and is in the general formula (4'). In the structural unit shown, R is a methyl group, R5 and R6 are hydrogen atoms, and the ester bonding position of methacrylate with 7·-butyrolactone is α in the α-position on the lactone ring. —Methyl propylene methoxy -7 —butyrolactone is preferred. The constituent unit (a6) may be used alone or in combination of two or more. In the (α-lower alkyl) acrylate resin component, the ratio of the constituent unit (a6) to the total constituent unit of the fat component constituting the (α-lower alkyl) acrylate tree-33-200928592 is 2 0~6 0 Molar% is better, 2 0 ~ 5 0 Molar% better, 3 0~4 5 Molar% best. By the upper limit 値 or more, the lithographic characteristics can be improved, and by the upper limit 値, the balance with other constituent units can be obtained. The (α-lower alkyl) acrylate resin component further has a polycyclic group containing a polar group in addition to the above-mentioned constituent unit-position (a5) or the above-mentioned constituent units (a5) and (a6). It is preferred that the constituent unit (a7) of the acrylate is derived. By the constituent unit (a7), the hydrophilicity of the (α-lower alkyl) acrylate resin component as a whole can be improved, the affinity with the developing solution can be improved, and the alkali solubility in the exposed portion can be improved and can be improved. Its resolution. In the constituent unit (a7), a carbon atom bonded to the "position" is a lower alkyl group or a hydrogen atom. The lower alkyl group bonded to the carbon atom at the α-position is the same as the description of the constituent unit (a5), and is preferably a methyl group. The polar group is, for example, a hydroxyl group, a cyano group, a carboxyl group, an amine group or the like, and a hydroxyl group is preferred. The polycyclic ring group can be appropriately selected and used by a polycyclic ring among the aliphatic cyclic groups exemplified in the "acid dissociable dissolution inhibiting group containing an aliphatic cyclic group" in the above (a5) unit. . The constituent unit (a7) is preferably at least one selected from the following general formulas (8') to (9'). -34- 200928592

[化 15][化15]

(〇H)„ (81) [式（8’）中，R係與上述相同，η I 一般式（8’）中之 R，係與 (3’）中之R爲相同。在此等之中 合於金剛烷基之第3位者爲較佳。 [化 16] f 1〜3之整數] 上述一般式（1’）〜 ，則以η爲1、羥基結(〇H) „ (81) [In the formula (8'), the R system is the same as described above, and η I is the same as R in the formula (8') and is the same as R in the (3'). It is preferable to use the third group of the adamantyl group. [Chemical Formula 16] The integer of 1 to 3] The above general formula (1')~, η is 1, and the hydroxyl group is

RR

(9〇 [式（9’）中，R係與上述相同，k ί 此等之中，係以k爲1者較佳 1〜3之整數] 。此外，氰基則以結合 -35- 200928592 於原菠烷基之5位或6位者爲較佳。 構成單位（a7)可使用1種或2種以上之組合。 在（α _催級烷基）丙烯酸酯樹脂成分中，構成單位 (a7 )之比例，相對於構成（ct 一低級烷基）丙烯酸酯樹 脂成分之全構成單位之總計，係以10〜50莫耳％較佳，15 〜40莫耳％更佳’ 20〜35莫耳％最佳。藉由在下限値以 上，其微影特性可提升，而藉由在上限値以下，則可取得 φ 與其他構成單位之平衡。 在（α -低級烷基）丙烯酸酯樹脂成分中，此等之構 成單位（a5 )〜（a7 )之總計，相對於全構成單位之總 計，係以70〜100莫耳％較佳，並以80〜100莫耳％最 佳。 (α -低級烷基）丙烯酸酯樹脂成分，亦可含有前述 構成單位（a5 )〜（a7 )以外之構成單位（a8 )。構成單 位（a8 )，只要係未被分類爲上述之構成單位（a5 )〜 0 ( a7 )之其他構成單位即可，並無特別之限制。 例如，較佳者係含有多環之脂肪族烴基、且由（α 一 低級烷基）丙烯酸酯所衍生之構成單位等。該多環之脂肪 族烴基’例如有前述「含有脂肪族環式基之酸解離性溶解 ' 抑制基」所例示之脂肪族環式基之中，由多環式者加以適 當地選擇而使用。其中，又以選自三環癸烷基、金剛烷 基、四環十二烷基、原菠烷基、異菠烷基之至少丨種以 上’其等基於工業上容易獲得等之觀點而較佳。構成單位 (a8 ) ’係以酸非解離性基爲最佳。 -36- 200928592 構成單位（a8)，具體而言，例如有下述（10)〜 (12)之構造者。 [化 17](9〇[Formula (9'), R is the same as above, k ί, etc., k is 1 is preferably an integer of 1 to 3.] In addition, cyano is combined with -35- 200928592 It is preferable to use 5 or 6 of the original spinnyl group. The constituent unit (a7) may be used alone or in combination of two or more. In the (α-hydroxyalkyl) acrylate resin component, the constituent unit ( The ratio of a7) is preferably 10 to 50 mol%, more preferably 15 to 40 mol%, relative to the total constituent unit of the (ct-lower alkyl) acrylate resin component. 20 to 35 The ear % is the best. By the upper limit 値 or more, the lithography characteristics can be improved, and by the upper limit 値, the balance between φ and other constituent units can be obtained. The (α-lower alkyl) acrylate resin component The total of the constituent units (a5) to (a7) of these is preferably 70 to 100 mol%, and is preferably 80 to 100 mol%, based on the total of the total constituent units. The lower alkyl) acrylate resin component may also contain a constituent unit (a8) other than the above constituent units (a5) to (a7). A8) is not particularly limited as long as it is not classified into the other constituent units of the above-mentioned constituent units (a5) to 0 (a7). For example, it is preferred to contain a polycyclic aliphatic hydrocarbon group and a constituent unit derived from (α-lower alkyl) acrylate, etc. The polycyclic aliphatic hydrocarbon group 'for example, the aliphatic ring exemplified by the above-mentioned "acid dissociable dissolution inhibiting group containing an aliphatic cyclic group" Among the bases, a polycyclic formula is appropriately selected and used, and at least one selected from the group consisting of a tricyclodecylalkyl group, an adamantyl group, a tetracyclododecyl group, a raw spintenyl group, and an iso-spinyl group is at least It is preferable that the above is based on the viewpoint of easy availability in the industry, etc. The constituent unit (a8) is preferably the acid non-dissociable group. -36- 200928592 constituent unit (a8), specifically, for example There are the following constructors (10) to (12). [Chem. 17]

RR

[式（10 )中，R係與上述相同][In the formula (10), the R system is the same as described above]

[式（1 1 )中，R係與上述相同] -37- 200928592 [化 19][In the formula (1 1 ), the R system is the same as the above] -37- 200928592 [Chem. 19]

(12) © [式（12)中，R係與上述相同] 如具有構成單位（a8 )時，在（α —低級烷基）丙烯 酸酯樹脂成分中，構成單位（)之比例，相對於構成 (α -低級烷基）丙烯酸酯樹脂成分之全構成單位之總 計，係以1〜25莫耳％較佳，並以5〜20莫耳％更佳。 (α -低級烷基）丙烯酸酯樹脂成分，其係以至少具 有構成單位（a5) 、（a6)、及（a7)之共聚物爲較佳。 此種共聚物，例如有由上述構成單位（a5) 、（a6)、及 ® (a7)所成之共聚物、由上述構成單位（a5) 、（a6)、 (a7)、及（a8)所成之共聚物等。 . (A - 11)成分，可依據習知之方法將前述構成單位 _ 之單體以聚合而製得。舉例而言，可將各構成單位之單 體，以使用例如偶氮雙異丁腈（AIBN )之類的自由基聚 合開始劑之習知自由基聚合等，使其聚合而製得。 (A- 1)成分，係以質量平均分子量（凝膠滲透色層 分析法之聚苯乙烯換算質量平均分子量，以下相同） 30000以下爲較佳，20000以下較佳，12000以下最佳。下 -38- 200928592 限値只要超過2000者即可，而基於圖型倒塌之抑制、解 像性提升等之點，其較佳者爲4000以上’最佳者爲5000 以上者。 [(A — 2)成分] (A-2)成分，係分子量500以上2000以下者，其 係以具有上述（A - 1)成分之說明所例示之酸解離性溶解 Q 抑制基X或X ’之低分子化合物爲較佳。具體而言，例如 有將具有多數之苯酚骨架之化合物的羥基之氫原子之一 部，以上述酸解離性溶解抑制基X或X’加以取代者。 (A - 2 )成分，舉例而言，係以在非化學增幅型之g 線或i線光阻中已知作爲增感劑或耐熱性提升劑，亦即將 低分子量苯酚化合物之羥基之氫原子之一部以上述酸解離 性溶解抑制基加以取代者爲較佳，可由其等中任意地加以 使用。 〇 此種低分子量苯酚化合物，例如有以下所列舉者。 例如有··雙（4一羥基苯基）甲烷、雙（2,3,4一三羥 基苯基）甲院、2—（4_經基苯基）一 2— (4，—經基苯 基）丙烷、2-（2,3,4 —三羥基苯基）—2— (2，，3，，4，_ 二經基苯基）丙院、三（4 一經基苯基）甲院、雙（4 一經 基一3,5 —二甲基苯基）—2—羥基苯基甲烷、雙（4 一羥 基一2,5— 一甲基苯基）一 2—經基苯基甲院、雙（4 一經 基一3，5—二甲基苯基）— 3,4 —二羥基苯基甲烷、雙（4_ 羥基一2,5—二甲基苯基）—3,4 _二羥基苯基甲烷、雙（4 -39- 200928592 —羥基—3 —甲基苯基）一 3,4—二羥基苯基甲烷 一環己基一 4 一羥基一 6 —甲基苯基）一4_羥基 烷、雙（3 -環己基—4 —經基-6—甲基苯基）-羥基苯基甲烷、丨―tl- (4_羥基苯基）異丙基 [1,1 一雙（4 —羥基苯基）乙基]苯、苯酚、m—甲屆 甲酚或二甲苯酚等之苯酚類之福馬林縮合物之2、. 體等。惟’無庸贅言，並不限於此範圍。 ❹ 再者’酸解離性溶解抑制基亦無特別之限制， 上述列舉者。 < (B )成分> (B)成分，可由傳統上在化學增幅型光阻中 作爲酸發生劑者之任意者中，適當地選擇加以使用 酸發生劑，到目前爲止，已知有碘鎗鹽或鎏鹽等之 酸發生劑、肟磺酸鹽系酸發生劑、雙烷基或雙芳基 〇 二偶氮甲烷類、聚（雙磺醯基）二偶氮甲烷類等之 甲烷系酸發生劑、硝基苄基磺酸鹽系酸發生劑、亞 酸鹽系酸發生劑、二楓系酸發生劑等多種。 鎗鹽系酸發生劑之具體例子，有二苯基碘鑰三 * 磺酸鹽、（4 -甲氧基苯基）苯基碘鑰三氟甲烷磺 雙（p — tert — 丁基苯基）碘鑰三氟甲烷磺酸鹽、三 三氟甲烷磺酸鹽、（4 一甲氧基苯基）二苯基鎏三 磺酸鹽、（4 一甲基苯基）二苯基鎏九氟丁烷磺酸| 一 tert—丁基苯基）二苯基鎏三氟甲烷磺酸鹽、二 雙（3 苯基甲 ;，4 ~~ 二 ]-4 - & ' p — 丨、4核 例如有 ，已知 。此種 鎗鹽系 磺醯基 二偶氮 胺基磺 氟甲院 酸鹽、 苯基鎏 氟甲烷 Ϊ ' ( P 苯基碘 -40- 200928592 鎗九氟丁烷磺酸鹽、雙（P- tert— 丁基苯基）碘鎗九 烷磺酸鹽、三苯基鎏九氟丁烷磺酸鹽。其中，係以氟化院 基磺酸離子作爲陰離子之鎗鹽爲較佳。 肟磺酸鹽化合物之例子，其較佳者有α —（甲基擴醯 基氧基亞胺基）-苯基乙腈、(甲基磺醯基氧基亞胺 . 基）一 Ρ—甲氧基苯基乙腈、(三氟甲基磺醯基氧基 亞胺基）-苯基乙腈、α - （三氟甲基擴醢基氧基亞胺 φ 基）—Ρ—甲氧基苯基乙腈、α—(乙基磺醯基氧基亞胺 基）一 ρ—甲氧基苯基乙腈、α -（丙基磺醯基氧基亞胺 基）-Ρ—甲基苯基乙腈、α—(甲基磺酿基氧基亞胺 基）一 Ρ —溴苯基乙腈等。此等之中，係以α —（甲基擴 醯基氧基亞胺基）-Ρ-甲氧基苯基乙腈爲較佳。 二偶氮甲烷系酸發生劑之具體例子，有雙（異丙基磺 醯基）二偶氮甲烷、雙（Ρ_甲苯磺醯基）二偶氮甲烷、 雙（1,1 一二甲基乙基磺醯基）二偶氮甲烷、雙（環己基 〇 磺醯基）二偶氮甲烷、雙（2,4-二甲基苯基磺醯基）二 偶氮甲烷等。 (Β)成分，可單獨使用1種之酸發生劑，亦可使用 2種以上之組合。 . (Β)成分之使用量，相對於（Α)成分100質量份， 一般係1〜20質量份，較佳係2〜10質量份。藉由在上述 範圍之下限値以上，可進行充分之圖型形成，而藉由在上 述範圍之上限値以下，能容易地獲得溶液之均一性，並能 獲得良好之保存安定性。 -41 - 200928592 <任意成分> 在化學增幅型光阻組成物中，爲提升其圖型形狀、繼 續經時安定性等’亦可進而配合任意成分之含氮有機化合 物（D)(以下’稱爲（D)成分）。該（D)成分，因爲 . 已有各種類被提案之緣故，可由習知者中任意地加以使 用，惟係以胺，特別是第二級低級脂肪族胺或第三級低級 φ 脂肪族胺爲較佳。 在此，所謂的低級脂肪族胺，係指碳數5以下之烷基 或烷基醇類之胺，此種第二級或第三級胺之例子，有三甲 基胺、二乙基胺、三乙基胺、二_n—丙基胺、三—η—丙 基胺、三戊基胺、二乙醇胺、三乙醇胺、三異丙醇胺等， 並以三乙醇胺、三異丙醇胺等之第三級烷醇胺爲較佳。 此等可以單獨使用，亦可將2種以上組合加以使用。 (D)成分’相對於（Α)成分1〇〇質量份，一般係 〇 於〇.〇1〜5.〇質量份之範圍內使用。 此外’化學增幅型光阻組成物中，爲防止因前述 (D)成分之配合而導致感度劣化，或爲提升圖型形狀、 繼續安定性等之目的，亦可進而使其含有任意之成分，例 如有機羧酸或磷之氧基酸或其衍生物（Ε)(以下，稱爲 (Ε)成分）。再者，亦可倂用（D)成分及（Ε)成分， 或者使用其任一種。 有機羧酸，例如有丙二酸、檸檬酸、蘋果酸、琥珀 酸、苯甲酸、水楊酸等。 -42- 200928592 磷之氧基酸或其衍生物，例如有磷酸、磷酸二-η — 丁基酯、磷酸二苯基酯等之磷酸或其等之酯等衍生物、膦 酸、膦酸二甲基酯、膦酸一二一 η — 丁基酯、苯基膦酸、 膦酸二苯基酯、膦酸二苄基酯等之膦酸及其等之酯等衍生 物、次膦酸、苯基次膦酸等之次膦酸及其等之酯等衍生 物，此等之中，又以膦酸爲較佳。 (Ε)成分，一般係以（Α)成分每100質量份，〇.〇1 0 〜5.0質量份之比例加以使用。 化學增幅型光阻組成物中，可進而根據所期望者，而 適當地含有：具有混和性之添加劑，例如用以改良該光阻 組成物之塗佈膜性能之附加性樹脂、用以提升塗佈性之界 面活性劑、溶解抑制劑、可塑劑、安定劑、着色劑、暈光 防止劑等。 化學增幅型光阻組成物，可將材料溶解於有機溶劑 (S )(以下，稱爲（S)成分）而製造。（S)成分，只 〇 要係可將使用之各成分溶解、並作成均一之溶液者即可， 可由傳統上習知作爲光阻組成物之溶劑中，適當地選擇任 意的1種或2種以上加以使用。 具體例子，有r - 丁內酯等之內酯類、丙酮、甲基乙 基酮、環己酮、甲基異戊基酮、2 —庚酮等之酮類、乙二 醇、乙二醇單乙酸酯、二乙二醇、二乙二醇單乙酸酯、丙 二醇、丙二醇單乙酸酯、丙二醇單甲基醚乙酸酯 (PGMEA )、二丙二醇、或二丙二醇單乙酸酯之單甲基 醚、單乙基醚、單丙基醚、單丁基醚或單苯基醚等之多價 -43- 200928592 醇類及其衍生物、或者二噁烷之類的環式醚類、或者乳酸 甲酯、乳酸乙酯（EL)、酢酸甲酯、酢酸乙酯、酢酸丁 酯、丙酮酸甲酯、丙酮酸乙酯、甲氧基丙酸甲酯、乙氧基 丙酸乙酯等之酯類等。此等之中，係以PGMEA、EL、丙 二醇單甲基醚（PGME )爲較佳。此等之有機溶劑可以單 _ 獨使用，亦可作成2種以上之混合溶劑而使用。 (S )成分之使用量並無特別之限制，惟化學增幅型 Q 光阻組成物可使用在支持體上可進行塗佈濃度之液體量。 本發明之圖型形成方法，係包含：在支持體上，塗佈 第一之化學增幅型光阻組成物以形成第一之光阻膜之步驟 (以下’稱爲膜形成步驟（1));將即述第一之光阻 膜，介由第一之光罩圖型進行選擇性曝光、顯像並形成第 一之光阻圖型之步驟（以下，稱爲圖型化步驟（1)); 在前述第一之光阻圖型表面上，形成由水溶性樹脂膜所成 之被覆膜而形成被覆圖型之步驟（以下，稱爲被覆步 ❹ 驟）；在形成有前述被覆圖型之前述支持體上，塗佈第二 之化學增幅型光阻組成物而形成第二之光阻膜之步驟（以 下，稱爲膜形成步驟（2)):以及，將前述第二之光阻 膜，介由第二之光罩圖型進行選擇性曝光、顯像而形成圖 ' 型之步驟（以下，稱爲圖型化步驟（2))。 以下，在本發明之圖型形成方法中，使用圖1來說明 較佳實施型態。本實施型態，係將正型光阻組成物作爲第 一及二之化學增幅型光阻組成物而使用之例子。 在本實施型態中，首先，如圖1(a)所示者，係於支 -44- 200928592 持體1上，塗佈第一之化學增幅型光阻組成物並形成第一 之光阻膜2。接著，如圖1(b)所示者，將第一之光阻膜 2進行選擇性曝光、顯像而形成多數之第一之光阻圖型 3。然後，如圖1(c)所示者，在多數之第一之光阻圖型 3之表面上，各自形成由水溶性樹脂膜所成之被覆膜4而 . 形成多數之被覆圖型5。隨後，如圖1(d)所示者，在形 成有多數之被覆圖型5之支持體1上，塗佈第二之化學增 Q 幅型光阻組成物，而形成塡充在多數之被覆圖型5間之空 隙的第二之光阻膜6。然後，如圖1(e)所示者，將第二 之光阻膜6之，與多數之形成有被覆圖型5之位置爲相異 之位置進行選擇性曝光、顯像。藉由顯像，第二之光阻膜 6之曝光部被除去，其結果，由多數之第二之光阻圖型7 及多數之被覆圖型5所成之圖型（以下，亦可能將由光阻 圖型及被覆圖型所成之圖型稱爲複合圖型），即可在支持 體1上形成。 〇 如此地操作，即可在支持體1上，形成較在圖型化步 驟（1)所形成之光阻圖型3爲更狹間距之複合圖型。 以下，茲就各步驟加以更詳細地說明。 [膜形成步驟（1 )] 支持體1，其並無特別之限制，可使用傳統習知者， 例如有電子零件用之基板、或者在其等上形成有所定之配 線圖型者。更具體而言，例如有矽晶圓、銅、鉻、鐵、鋁 等之金屬製之基板、或玻璃基板等。配線圖型之材料，例 -45- 200928592 如可使用銅、鋁、鎳、金等。 此外，支持體1 ’亦可爲在上述之基板上，設置無機 系及/或有機系之膜者。無機系之膜，有無機防反射膜 (無機B ARC )。有機系之膜，則有有機防反射膜（有機 B ARC )或多層光阻法中之下層膜等有機膜。其中，又以 . 設置有下層膜時，可在基板上形成高深寬比之圖型，係在 半導體之製造等上爲有用而較佳。 φ 在此，所謂的多層光阻法，係指在基板上，設置至少 一層之有機膜（下層膜）及至少一層之光阻膜，並將形成 於上層之光阻膜之光阻圖型作爲光罩，而進行下層之圖型 化之方法，其可形成高深寬比之圖型。多層光阻法中，基 本上可分別：上層之光阻膜及下層膜之二層構造之方法， 以及在此等光阻膜及下層膜之間設置一層以上之中間層 (金屬薄膜等）的三層以上之多層構造之方法。根據多層 光阻法，藉由確保下層膜所要之厚度，就可將光阻膜薄膜 G 化，並形成高深寬比之微細圖型。 如設置有機膜時’有機膜，舉例而言，係將構成有機 膜之樹脂成分等溶解於有機溶劑中之有機膜形成用材料， 以旋轉器等塗佈於基板上，其較佳者係以200〜300 °C、較 佳爲30〜3 00秒’更佳爲60〜180秒之加熱條件，進行烘 烤處理而形成。關於有機膜形成用材料，則詳如後述。 有機膜之厚度，其較佳者爲10〜5 0 Onm，更佳者爲50 〜45 0n m。藉由在範圍内’可形成高深寬比之圖型，並具 有能確保在基板蝕刻時充分之耐蝕刻性等效果。 -46- 200928592 第一之化學增幅型光阻組成物，其並無特別之限 可由上述已被提案作爲化學增幅型光阻組成物之多數 增幅型光阻組成物之中，適當地選擇而使用' 第一之光阻膜2，可將第一之化學增幅型光阻組 塗佈於支持體上而形成。第一之化學增幅型光阻組成 塗佈，可使用旋轉器等傳統習知之方法來進行。 具體而言，例如可將第一之化學增幅型光阻組成 旋轉器等塗佈於支持體上，在80〜150°C之溫度條件 以40〜120秒、較佳者爲60〜90秒進行烘烤處理（ 烤），以使有機溶劑揮發而形成第一之光阻膜。 光阻膜2之厚度，其較佳爲50〜50 Onm，更佳爲 4 5 Onm。藉由在此範圍内，可以高解像度形成光阻圖 並能得到對於蝕刻具有充分耐性等效果。 [圖型化步驟（1 )] 圖型化步驟（1)可利用傳統習知之方法而進行 如可介由形成有所定圖型之光罩（光罩圖型）而將第 光阻膜2進行選擇性曝光，於8 0〜1 5 0°C之溫度條件 以40〜120秒、較佳爲60〜90秒進行烘烤處理（PEB 光後加熱）），例如可將〇· 1〜1 〇質量％濃度之四甲 羥化物（TMAH )水溶液進行鹼顯像，所使用之光阻 物如係正型時，曝光部會被除去；如係負型時，則未 部會被除去，而形成第一之光阻圖型3。 曝光所使用之波長，其並無特別之限制，可使用 制， 化學 成物 物之 物以 下， 預烘 50〜 型，(12) © [In the formula (12), the R system is the same as the above] When the structural unit (a8) is present, the ratio of the constituent unit () in the (α-lower alkyl) acrylate resin component is relative to the constitution. The total of the total constituent units of the (α-lower alkyl) acrylate resin component is preferably from 1 to 25 mol%, more preferably from 5 to 20 mol%. The (α-lower alkyl) acrylate resin component is preferably a copolymer having at least the constituent units (a5), (a6), and (a7). Examples of such a copolymer include copolymers composed of the above constituent units (a5), (a6), and ® (a7), and the above constituent units (a5), (a6), (a7), and (a8). The resulting copolymer and the like. The component (A-11) can be obtained by polymerizing the monomer of the above constituent unit according to a conventional method. For example, a monomer of each constituent unit can be obtained by polymerization using a conventional radical polymerization such as a radical polymerization initiator such as azobisisobutyronitrile (AIBN). The component (A-1) is preferably a mass average molecular weight (the polystyrene-converted mass average molecular weight of the gel permeation chromatography method, the same applies hereinafter) of 30,000 or less, more preferably 20,000 or less, and most preferably 12,000 or less. The next -38-200928592 is limited to more than 2,000, and it is preferably 4000 or more based on the suppression of the collapse of the pattern and the improvement of the resolution. The best one is 5000 or more. [(A - 2) component] The component (A-2) is a molecular weight of 500 or more and 2000 or less, and is an acid dissociable dissolution Q inhibitor X or X' exemplified by the description of the component (A-1). Low molecular compounds are preferred. Specifically, for example, one of the hydrogen atoms of the hydroxyl group of the compound having a plurality of phenol skeletons is substituted with the above-mentioned acid dissociable dissolution inhibiting group X or X'. The (A - 2 ) component, for example, is known as a sensitizer or a heat resistance enhancer in a non-chemically amplified g-line or i-line resist, that is, a hydrogen atom of a hydroxyl group of a low molecular weight phenol compound. One of the parts is preferably substituted with the above-mentioned acid dissociable dissolution inhibiting group, and may be optionally used.此种 Such a low molecular weight phenol compound is, for example, the ones listed below. For example, bis(4-hydroxyphenyl)methane, bis(2,3,4-trihydroxyphenyl)-methyl, 2-(4-diphenyl)-2-(4-diphenyl) Propane, 2-(2,3,4-trihydroxyphenyl)-2-(2,3,4,4-diphenylphenyl)propyl, tris(4-monophenyl) , bis(4-mono-amino-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-monomethylphenyl)-2-phenyl-phenylphenyl , bis(4-monomethyl- 3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxy Phenylmethane, bis(4-39-200928592-hydroxy-3-methylphenyl)-3,4-dihydroxyphenylmethane-cyclohexyl-4-hydroxy-6-methylphenyl)- 4-hydroxyalkane , bis(3-cyclohexyl-4-yl-amino-6-methylphenyl)-hydroxyphenylmethane, 丨-tl-(4-hydroxyphenyl)isopropyl [1,1-double (4-hydroxyl) 2. A quinone condensate of phenol such as phenyl)ethyl]benzene, phenol, m-methyl cresol or xylenol. However, it is not limited to this scope. Further, the acid dissociable dissolution inhibiting group is not particularly limited, and the above enumerated. <Component (B)> The component (B) can be appropriately selected from any of those conventionally used as an acid generator in a chemically amplified photoresist, and an iodine is known so far. An acid generator such as a gun salt or a barium salt, an acid generator of an oxime sulfonate, a dialkyl or bisaryl bisazomethane, or a methane system such as poly(disulfonyl)diazomethane An acid generator, a nitrobenzylsulfonate acid generator, a acid salt generator, and a bismuth acid generator. Specific examples of the gun salt acid generator include diphenyl iodide trisulphonate, (4-methoxyphenyl)phenyl iodide trifluoromethanesulfonate (p-tert-butylphenyl). Iodine trifluoromethanesulfonate, trifluoromethanesulfonate, (4-methoxyphenyl)diphenylphosphonium trisulfonate, (4-methylphenyl)diphenylphosphonium hexafluorobutane Alkanesulfonic acid | tert-butylphenyl)diphenylphosphonium trifluoromethanesulfonate, di-bis(3 phenylmethyl;, 4~~2]-4 - & 'p- 丨, 4 cores Yes, it is known that this kind of gun salt is sulfonyldiazoaminosulfonate, phenyl fluorofluoromethane Ϊ ' (P phenyl iodine-40- 200928592 gun nonafluorobutane sulfonate, Bis(P-tert-butylphenyl) iodine pentane sulfonate, triphenyl sulfonium hexafluorobutane sulfonate. Among them, it is preferred to use a fluorinated sulfonate ion as an anion gun salt. An example of an oxime sulfonate compound, which is preferably α-(methylxyloxyimino)-phenylacetonitrile, (methylsulfonyloxyimine. Oxyphenyl acetonitrile, (trifluoromethylsulfonyl) Iminoamino)-phenylacetonitrile, α-(trifluoromethyl-decyloxyimide φ group)-fluorenyl-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino a ρ-methoxyphenylacetonitrile, α-(propylsulfonyloxyimino)-oxime-methylphenylacetonitrile, α-(methylsulfonic acidoxyimino) - bromophenylacetonitrile, etc. Among them, α-(methylxyloxyimino)-fluorenyl-methoxyphenylacetonitrile is preferred. Diazomethane acid generator Specific examples are bis(isopropylsulfonyl)diazomethane, bis(indolylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazo Methane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, etc. (Β) component, which can be used alone. The amount of the component to be used may be 1 to 20 parts by mass, preferably 2 to 10 parts by mass, per 100 parts by mass of the (Α) component. Above the lower limit of the above range, it can be charged The pattern is formed, and by the upper limit of the above range, the uniformity of the solution can be easily obtained, and good preservation stability can be obtained. -41 - 200928592 < arbitrary composition> In the composition of the resist, in order to enhance the shape of the pattern, to maintain stability over time, etc., it is also possible to further mix a nitrogen-containing organic compound (D) of any component (hereinafter referred to as a component (D)). Since various classes have been proposed, they can be used arbitrarily by a person skilled in the art, but it is preferred to use an amine, particularly a second-stage lower aliphatic amine or a third-order lower φ aliphatic amine. Here, the term "lower aliphatic amine" means an alkyl group having 5 or less carbon atoms or an amine of an alkyl alcohol, and examples of such a second or third stage amine include trimethylamine and diethylamine. Triethylamine, di-n-propylamine, tri-n-propylamine, tripentylamine, diethanolamine, triethanolamine, triisopropanolamine, etc., and triethanolamine, triisopropanolamine, etc. The third stage alkanolamine is preferred. These may be used alone or in combination of two or more. The component (D) is used in an amount of 1 part by mass based on the mass of the Α. Further, in the chemically amplified photoresist composition, in order to prevent deterioration of sensitivity due to the combination of the above component (D), or to enhance the shape of the pattern, to maintain stability, etc., it is possible to further contain an optional component. For example, an organic carboxylic acid or a phosphorus oxyacid or a derivative thereof (hereinafter referred to as a "ruthenium" component). Further, the component (D) and the component (()) may be used, or any of them may be used. The organic carboxylic acid may, for example, be malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid or the like. -42- 200928592 Phosphorous oxyacid or a derivative thereof, for example, phosphoric acid such as phosphoric acid, di-n-butyl phosphate, diphenyl phosphate or the like, or a derivative thereof, phosphonic acid or phosphonic acid a derivative of a methyl ester, a phosphonic acid, a di-n-butyl butyl ester, a phenylphosphonic acid, a diphenyl phosphonate, a dibenzyl phosphonate, or the like, a derivative such as an ester, a phosphinic acid, Among them, a phosphonic acid is preferable to a derivative such as a phosphinic acid such as phenylphosphinic acid or the like. The (Ε) component is generally used in a ratio of Α.〇10 to 5.0 parts by mass per 100 parts by mass of the (Α) component. The chemically amplified photoresist composition may further contain: an additive having a miscibility, such as an additive resin for improving the coating film properties of the photoresist composition, for lifting coating, according to a desired one. A surfactant, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, a light-suppressing agent, and the like. The chemically amplified photoresist composition can be produced by dissolving a material in an organic solvent (S) (hereinafter referred to as a component (S)). The component (S) may be prepared by dissolving each component to be used in a uniform solution, and any one or two kinds of solvents may be appropriately selected from those conventionally known as a photoresist composition. Use above. Specific examples include lactones such as r-butyrolactone, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone, ethylene glycol, and ethylene glycol. Monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, or dipropylene glycol monoacetate Multivalents such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether -43- 200928592 Alcohols and their derivatives, or cyclic ethers such as dioxane Or methyl lactate, ethyl lactate (EL), methyl decanoate, ethyl decanoate, butyl phthalate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate Esters and the like. Among these, PGMEA, EL, and propylene glycol monomethyl ether (PGME) are preferred. These organic solvents may be used singly or in combination of two or more. The amount of the (S) component to be used is not particularly limited, but the chemically amplified Q-resist composition may use a liquid amount which can be applied to the support. The pattern forming method of the present invention comprises the step of coating a first chemically amplified resist composition on a support to form a first photoresist film (hereinafter referred to as a film formation step (1)) a step of selectively exposing, developing, and forming a first photoresist pattern through a first photomask pattern (hereinafter, referred to as a patterning step (1) a step of forming a coating pattern formed of a water-soluble resin film on the surface of the first photoresist pattern to form a coating pattern (hereinafter referred to as a coating step); and forming the above-mentioned coating pattern a step of applying a second chemically amplified photoresist composition to form a second photoresist film (hereinafter referred to as a film formation step (2)) on the support of the type: and the second light The resist film is subjected to selective exposure and development through a second mask pattern to form a pattern (hereinafter referred to as a patterning step (2)). Hereinafter, in the pattern forming method of the present invention, a preferred embodiment will be described using Fig. 1 . In this embodiment, a positive-type photoresist composition is used as the first and second chemically amplified photoresist compositions. In this embodiment, first, as shown in FIG. 1(a), on the holder-44-200928592 holder 1, the first chemically amplified photoresist composition is applied and the first photoresist is formed. Membrane 2. Next, as shown in Fig. 1(b), the first photoresist film 2 is selectively exposed and developed to form a plurality of first photoresist patterns 3. Then, as shown in FIG. 1(c), a coating film 4 made of a water-soluble resin film is formed on the surface of the first photoresist pattern 3, and a plurality of coating patterns are formed. . Subsequently, as shown in FIG. 1(d), a second chemically amplified Q-type photoresist composition is coated on the support 1 on which a plurality of overlying patterns 5 are formed, and a plurality of coatings are formed. A second photoresist film 6 having a gap between the patterns 5. Then, as shown in Fig. 1(e), the second photoresist film 6 is selectively exposed and developed at a position different from the position at which the plurality of patterns 5 are formed. By the development, the exposed portion of the second photoresist film 6 is removed, and as a result, a pattern formed by a plurality of second photoresist patterns 7 and a plurality of overlying patterns 5 (hereinafter, may also be The pattern formed by the photoresist pattern and the overlying pattern is referred to as a composite pattern, and can be formed on the support 1.如此 In this way, a composite pattern which is formed at a narrower pitch than the photoresist pattern 3 formed in the patterning step (1) can be formed on the support 1. Hereinafter, each step will be described in more detail. [Film Forming Step (1)] The support 1 is not particularly limited, and a conventional one can be used, for example, a substrate for an electronic component, or a pattern of a predetermined wiring pattern formed thereon. More specifically, for example, there are a substrate made of a metal such as a germanium wafer, copper, chromium, iron, or aluminum, or a glass substrate. Wiring pattern material, for example -45- 200928592 If copper, aluminum, nickel, gold, etc. can be used. Further, the support 1' may be provided with an inorganic or organic film on the substrate. An inorganic film with an inorganic antireflection film (inorganic B ARC ). The organic film is an organic film such as an organic antireflection film (organic B ARC ) or a multilayer film in a multilayer photoresist method. Further, when the underlayer film is provided, a pattern having a high aspect ratio can be formed on the substrate, which is useful for manufacturing semiconductors and the like. φ Here, the so-called multilayer photoresist method means that at least one organic film (lower film) and at least one photoresist film are provided on the substrate, and the photoresist pattern of the photoresist film formed on the upper layer is used as The mask, and the method of patterning the lower layer, can form a high aspect ratio pattern. In the multilayer photoresist method, basically, the method of the two-layer structure of the upper photoresist film and the lower film, and the intermediate layer (metal film, etc.) between the photoresist film and the lower film are provided. A method of constructing multiple layers of three or more layers. According to the multilayer photoresist method, by ensuring the desired thickness of the underlayer film, the photoresist film can be G-formed and a fine pattern of high aspect ratio can be formed. When the organic film is provided, the organic film is, for example, a material for forming an organic film in which an organic component is dissolved in an organic solvent, and is applied to a substrate by a spinner or the like. It is formed by baking treatment at 200 to 300 ° C, preferably 30 to 300 seconds, more preferably 60 to 180 seconds. The material for forming an organic film will be described later in detail. The thickness of the organic film is preferably from 10 to 50 nm, more preferably from 50 to 45 nm. By forming a pattern having a high aspect ratio in the range, it has an effect of ensuring sufficient etching resistance at the time of substrate etching. -46- 200928592 The first chemically amplified photoresist composition is not particularly limited, and may be appropriately selected and used as a majority of the above-mentioned amplified photoresist composition which has been proposed as a chemically amplified photoresist composition. The first photoresist film 2 can be formed by applying a first chemically amplified photoresist group to a support. The first chemically amplified photoresist composition coating can be carried out by a conventional method such as a spinner. Specifically, for example, the first chemically amplified photoresist composition rotator or the like may be applied to the support, and the temperature may be 40 to 120 seconds, preferably 60 to 90 seconds at 80 to 150 ° C. Baking treatment (bake) to volatilize the organic solvent to form a first photoresist film. The thickness of the photoresist film 2 is preferably 50 to 50 Onm, more preferably 4 5 Onm. By being within this range, the photoresist pattern can be formed with high resolution and an effect of sufficient resistance to etching can be obtained. [Drawing Step (1)] The patterning step (1) can be carried out by a conventionally known method, such as by forming a mask (a mask pattern) of a predetermined pattern. Selective exposure, baking at 40 to 120 ° C for 40 to 120 seconds, preferably 60 to 90 seconds (after PEB light heating), for example, 〇·1~1 〇 Alkaline development is carried out in a mass% concentration of tetramethylhydroxide (TMAH) aqueous solution. When the photoresist used is positive, the exposed portion is removed; if it is negative, the unexposed portion is removed and formed. The first photoresist pattern 3 The wavelength used for the exposure is not particularly limited, and it can be used under the chemical substance, pre-baked 50~ type,

，例 一之 下， (曝 基銨 組成 曝光 KrF -47-, Example 1, under the exposure of ammonium composition exposure KrF -47-

200928592 準分子雷射、ArF準分子雷射、F2準分子雷 紫外線）、VUV (真空紫外線）、EB (電子 線、軟X射線等放射線而進行。 此時，第一之光阻膜2之選擇性曝光， 氣等不活性氣體中進行’其可爲通常之曝光（ 亦可藉由浸液曝光而進行。 浸液曝光，如上所述，於曝光時，傳統』 或氮氣等不活性氣體所充滿之透鏡與晶圓上之 部分，以具有較空氣之折射率爲大之折射率之 媒介）充滿之狀態下進行曝光。更具體而言， 係將上述操作所得之光阻膜與曝光裝置之最1 間’以具有較空氣之折射率爲大之折射率的淬 介）充滿，並在該狀態下，介由所期望之光譯 光（浸漬曝光）而實施。 浸液媒介’係以使用較空氣之折射率爲犬 本發明之正型光阻組成物所形成之光阻膜所貝 爲小之折射率的溶劑爲較佳。此種溶劑之折象 前述範圍内即可’並無特別之限制。 具有較空氣之折射率爲大、且較光阻膜之 之折射率的溶劑，例如有水、氟系不活性液 劑、烴系溶劑等。 氟系不活性液體之具體例子，有 C4F9OCH3、c4f9〇c2h5、c5h3F7 等以氟系化名 分之液體等’其沸點係以70〜180t者爲較佳 f、EUV (極 線）、X射 ’於空氣或氮 乾曝光）， 係將以空氣 光阻膜間之 溶劑（浸液 浸液曝光， 位置之透鏡 劑（浸液媒 圖型進行曝 ，且較使用 有之折射率 率，只要在 折射率爲小 體、矽系溶 C3HC12F5、 物作爲主成 ，並以8 0〜 -48 - 200928592 1 60 °C者爲更佳。氟系不活性液體如具有上述範圍之沸點 時，在曝光終了後，其浸液所使用之媒介的除去，即可以 簡便方法進行之故而較佳。 氟系不活性液體，尤其以烷基之全部氫原子皆以氟原 子加以取代之全氟烷基化合物爲較佳。全氟烷基化合物， . 具體而言，例如有全氟烷基醚化合物或全氟烷基胺化合 物。 〇 進而’具體而言，前述全氟烷基醚化合物，例如有全 氟（2—丁基一四氫呋喃）（沸點1〇2。(：），前述全氟烷基 胺化合物例如有全氟三丁基胺（沸點1 741 )。 [被覆步驟] 接著，在形成之多數之第一之光阻圖型3表面上，係 各自使用由水溶性樹脂組成物所成之被覆膜形成用材料， 形成被覆膜4而形成多數之被覆圖型5。 © 被覆膜4之形成方法’其較佳可使用含有水溶性樹脂 所成之水溶液’且該水溶性樹脂係使用含有噁唑啉基之聚 . 合物之被覆膜形成用材料的方法。關於被覆膜形成用材 料’係詳細說明於後述之本發明之被覆膜形成用材料中。 使用被覆膜形成用材料時，被覆膜4，例如可將該被 覆膜形成用材料塗佈於圖型之表面而形成塗膜後，再於該 塗膜上施加烘烤處理而形成。此外，亦可於烘烤處理前， 以80°C〜18CTC之溫度’ 30秒〜180秒左右，在塗膜上進 行預烘烤處理之操作。 -49- 200928592 被覆膜形成用材料之塗佈方法，可使用習知之方法， 例如將形成有第一之光阻圖型3之支持體1，以浸漬於被 覆膜形成用材料中之方法（浸漬式塗布法）、將被覆膜形 成用材料以旋轉塗佈法塗佈於該支持體1上之方法等。 被覆步驟中，係於被覆膜形成用材料之塗佈後，在塗 _ 膜上施加烘烤處理。藉由施加烘烤處理，可促進由第一之 光阻圖型3而來之酸拡散，並在第一之光阻圖型3及塗膜 0 之界面中發生交聯反應。而藉由該交聯反應，在第一之光 阻圖型之表面上可形成被覆膜4。 在烘烤處理中，烘烤溫度，係以70 °C〜180 °C較佳， 80 °C〜170 °C更佳。藉由在此範圍内，可形成強固之被覆 膜4。烘烤時間，其並無特別之限制，惟考慮其烘烤處理 之效果、圖型形狀之安定性等，以30秒〜300秒較佳，60 秒〜1 8 0秒更佳。 被覆步驟中，在被覆膜形成用材料之塗佈後，將支持 φ 體1表面以洗淨液加以洗淨者爲較佳。藉此，即使在支持 體1上，不存在光阻膜之部分（非圖型部分）之表面上附 著有多餘之水溶性樹脂，亦會藉由該洗淨液而被洗掉，或 濃度變得非常薄。另一方面，光阻圖型3表面之水溶性樹 ' 脂，則因爲交聯之故而繼續殘留。其結果，在光阻圖型3 表面上可充分地形成水溶性樹脂膜，惟在支持體1上之非 圖型部表面則不形成或幾乎不形成水溶性樹脂膜，而可以 高度被覆選擇性在光阻圖型3表面形成水溶性樹脂膜（被 覆膜4)。 -50- 200928592 進而，藉由洗淨，被覆膜4可成爲膜厚度薄且均一 者。亦即，在進行洗淨時，可除去光阻圖型3上之未交聯 的多餘水溶性樹脂，另一方面，由於交聯而強固地結合於 圖型表面之水溶性樹脂則均一地殘留於圖型表面。因此， 奈米程度之水溶性樹脂之薄膜，就可以均一之膜厚度，極 . 佳之精度且高度之再現性而形成。 洗淨液，只要係可將未交聯之水溶性樹脂等溶解並除 φ 去者即可，例如有與後述被覆膜形成用材料之溶劑所例示 爲相同者。 洗淨，可使用習知之方法，例如將洗淨液以噴霧法 等，供給於由被覆膜形成用材料所成塗膜之表面上之後， 將多餘之洗淨液在減壓下以吸引而施行之方法、或在洗淨 液中浸漬洗淨之方法、噴霧洗淨之方法、蒸氣洗淨之方 法、將洗淨液以旋轉塗佈法塗佈於支持體上之方法等，尤 以旋轉塗佈法爲較佳。洗淨條件（洗淨時間、洗淨液之使 〇 用量等），可考慮洗淨方法等而適當地加以設定。例如在 以旋轉塗佈法進行洗淨時’可於100〜5000rpm、1〜100 秒左右之範圍内適當地加以調節。 洗淨，係以進行至被覆膜形成用材料所成之塗膜中之 ' 溶劑，完全地揮發前爲較佳。該溶劑是否已完全地揮發， 係以目視來確認。 被覆膜4之厚度’較佳爲〇_lnm以上，更佳爲0.5〜 50nm，最佳爲1〜30nm。藉由在O.lnm以上，可獲得對於 蝕刻，例如氧氣電漿蝕刻等乾蝕刻爲充足之耐性之效果。 -51 - 200928592 [膜形成步驟（2)] 接著’在形成有多數之被覆圖型5之支持體1上，塗 佈第二之化學增幅型光阻組成物，而形成塡充有多數之被 覆圖型5間之空隙的第二之光阻膜6。 . 在本實施型態中，第二之化學增幅型光阻組成物，係 使用正型光阻組成物。在前述膜形成步驟（1)，第一之 0 化學增幅型光阻組成物如係使用正型光阻組成物時，所謂 的第一之化學增幅型光阻組成物與第二之化學增幅型光阻 組成物，可使用相同者，亦可使用相異者。 第二之光阻膜6，可與第一之光阻膜2相同地，以傳 統習知之方法而形成。第二之光阻膜6之膜厚度，係以至 少與被覆圖型5之高度相同、或較其厚者爲較佳。亦即， 將支持體1由第二之光阻膜6側來觀察時，其表面係平坦 者爲較佳。 ❹ [圖型化步驟（2)] 接著，將第二之光阻膜6中，與多數之形成有被覆圖 型5之位置爲相異之位置進行選擇性曝光、顯像。藉此， * 可在支持體1上，形成由多數之被覆圖型5、以及在第二 之光阻膜6上剛剛形成之多數第二之光阻圖型7，所共同 形成之複合圖型。 在此，本發明中，除與在被覆步驟形成之被覆圖型爲 完全一致之情形以外，全部皆爲「與形成被覆圖型之位置 -52- 200928592 爲相異之位置」’且包含全部不重複之情形，及一部重複 之情形。 本發明中，係以形成被覆圖型之位置、與在圖型化步 驟（2)進行選擇性曝光之位置，全部不重複者爲較佳。 藉此，就可以形成較圖型化步驟（1 )所形成之光阻圖 型，其圖型間之間隔（間距）更狹窄之狹間距之圖型。 與形成被覆圖型之位置爲相異位置之選擇性曝光，例 如可將圖型化步驟（1)所使用之光罩圖型，在水平方向 上移動而進行。此種光罩圖型之移動，可藉由調節所使用 之曝光装置之程式而實施。光罩圖型，可以在1個方向上 平行地移動，亦可使其旋轉地移動。舉例而言，在形成圖 型時，圖型化步驟（1 )中，可使用多數之線以一定間距 配置於線/間距之光罩圖型而形成線/間距圖型後，再於 圖型化步驟（2)中，將該光罩圖型，以相對於線之方向 爲垂直方向而進行平行地移動，並藉由在圖型化步驟 (1 )所形成之線圖型與線圖型之中間位置上，形成線圖 型，而使最初形成之線/間距之間距，其約1 / 2之間距 上，可形成線/間距之複合圖型。 例如，在形成線寬l〇〇nm、線寬：間隔寬度=1:3之 線/間距圖型後，藉由將光罩圖型以相對於線之方向爲垂 直方向上平行移動200nm，以形成線寬1 〇〇nm、線寬：間 隔寬度=1 : 3之線/間距圖型’即可形成線寬1 0 0 nm、線 寬：間隔寬度=1 : 1之線/間距圖型。 此外，將圖型化步驟（1)所使用之光罩圖型進行旋 -53- 200928592 轉移動’並使用與圖型化步驟（1)所 相異之光罩圖型，即可形成多様之複合丨 除了使光罩圖型移動之方法以外， 曝光機中之載台（承載基板之台座）移丨 本發明之圖型形成方法中，上述 • 後，亦可進而在所形成之複合圖型之表 水溶性樹脂膜所成之被覆膜的第二之被 〇 複合圖型中’第二之光阻膜6上所形成 7之表面’即可由水溶性樹脂膜所成之 提升其蝕刻耐性等。 本發明之圖型形成方法中，上述 後’亦可進而多次重複：上述被覆穿 (2)、圖型化步驟（2)之一連串之操 複：在形成之複合圖型表面上，形成由 之被覆膜而形成被覆圖型，並在該被覆 〇 體1上塗佈化學增幅型光阻組成物而形 光阻膜進行選擇性曝光、顯像而形成複 此，即可進而形成狹間距之圖型、及複g 本發明之圖型形成方法中，上述 後，亦可將所形成之複合圖型作爲光罩 1之蝕刻。亦即，如在基板上設置有機 膜之鈾刻，在該有機膜上，可以形成忠 (有機膜圖型），進而將此等之圖型（ 圖型）作爲光罩而進行基板之蝕刻。複 使用之光罩圖型爲 圖型。 其他方法還包括將 訪之方法。 圖型化步驟（2 ) 面上，進行形成由 覆步驟。藉此，在 之第二之光阻圖型 被覆膜所被覆，而 圖型化步驟（2 ) —驟、膜形成步驟 作。亦即，多次重 水溶性樹脂膜所成 圖型所形成之支持 成光阻膜，再將該 合圖型之操作。藉 唯形狀之圖型。 圖型化步驟（2 ) 使用而進行支持體 膜時，可進行有機 於複合圖型之圖型 複合圖型及有機膜 合圖型如直接形成 -54- 200928592 於基板上時，可直接將複合圖型作爲光罩，而進行基板之 蝕刻。藉由如此地將基板進行蝕刻，即可製造半導體設備 等。 飩刻之方法，可利用習知之方法，例如有機膜之蝕刻 係乾蝕刻爲較佳。其中，基於被覆膜對於其等之蝕刻之耐 . 性爲筒之觀點、生產效率之觀點，尤以氧氣電獎餓刻、或 _ 使用cf4氣體或CHF3氣體之蝕刻爲較佳，並以氧氣電漿 Φ 蝕刻爲最佳。基板之蝕刻，係以使用鹵素氣體之蝕刻爲較 佳，使用氟化碳系氣體之蝕刻較佳，尤以使用CF4氣體或 chf3氣體之蝕刻最佳。 [有機膜形成用材料] 在上述膜形成步驟（1)所使用之支持體1中，用以 形成可在基板上形成之有機膜之有機膜形成用材料，未必 需要有如光阻膜的對於電子射線或光之感受性。在半導體 © 元件或液晶表示元件之製造中，可使用一般使用之光阻或 樹脂。 _ 此外，藉由使用以被覆膜所被覆之被覆圖型，進行有 機膜之蝕刻，可將該被覆圖型複印到有機膜上，並在可形 成有機膜圖型之情形下，有機膜形成用材料係以蝕刻，尤 其是形成可進行乾鈾刻之有機膜之材料爲較佳。其中，又 以形成可進行氧氣電漿蝕刻等蝕刻之有機膜之材料爲較 佳。 此種有機膜形成用材料，可爲傳統上用以形成有機 -55- 200928592 B ARC等之有機膜之材料。舉例而言，有「普路瓦科學」 公司製之ARC系列、「羅門哈斯」公司製之AR系列、東 京應化工業公司製之SWK系列等。 其中，如上所述，係以在蝕刻步驟中使用氧氣電漿蝕 刻時，可容易地以氧氣電漿蝕刻將有機膜進行蝕刻，且對 . 於鹵氣體，具體而言，係CF4氣體或CHF3氣體等氟化碳 系氣體之耐性較高之材料所構成者爲較佳。 φ 此外’在上述有機BARC與基板之間’亦可形成含有 至少一種選自下述樹脂成分之有機膜，該成分包括：酚醛 清漆樹脂、丙烯酸樹脂及可溶性聚醯亞胺所成之群。 此等之材料除了容易進行氧氣電漿蝕刻等之蝕刻以 外，對於氟化碳系氣體之耐性亦強，而適用於本發明中。 亦即，一般而言，因爲基板等之蝕刻係使用氟化碳系氣體 等鹵氣體之故，藉由構成由此種材料所成之有機膜，除了 在形成有機膜圖型時使用氧氣電漿鈾刻可提升加工性以 φ 外’在後步驟中使用氟化碳系氣體等鹵氣體將基板等進行 蝕刻時，亦能提升耐蝕刻性。 此等之樹脂成分可以單獨使用1種，亦可2種以上混 合加以使用。 ' 上述之中，又以酚醛清漆樹脂、及在側鏈上具有脂環 式部位或芳香族環之丙烯酸樹脂，其可被便宜而廣泛地使 用，且對於使用氟化碳系氣體之乾蝕刻具有優良耐性之 故，而爲較佳者。 酚醛清漆樹脂，可以在正型光阻組成物作爲一般之使 -56- 200928592 用’亦可在含有酚醛清漆樹脂作爲主成分之i線或g線用 之正型光阻使用。 酚醛清漆樹脂，例如係將具有苯酚性羥基之芳香族化 合物（以下，簡稱爲「苯酚類」）及醛類在酸觸媒之存在 下進行加成縮合而製得之樹脂。 . 苯酚類，例如有苯酚、〇 —甲酚、m—甲酚、P —甲 — 酚、〇 —乙基苯酚、m—乙基苯酚、p_乙基苯酚、〇 — 丁基 ❹ 苯酚、m— 丁基苯酚、p— 丁基苯酚、2,3 —二甲苯酚、2,4 —二甲苯酚、2,5 -二甲苯酚、2,6—二甲苯酚、3，4 —二甲 苯酚、3,5 —二甲苯酚、2,3,5 —三甲基苯酚、3,4,5—三甲 基苯酚、p —苯基苯酚、間苯二酚、氫醌、氫醌單甲基 醚、焦掊酚、間苯三酚、羥基二苯基、雙苯酚A、没食子 酸、没食子酸酯、α —萘酚、；8 -萘酚等。 醛類，例如甲醛、糠醛、苯甲醛、硝基苯甲醛、乙醛 等。 ❹ 加成縮合反應時之觸媒，並無特別之限制，惟例如在 酸觸媒下，可使用鹽酸、硝酸、硫酸、犠酸、草酸、酢酸 酚醛清漆樹脂，亦可使用市售者。 酚醛清漆樹脂之質量平均分子量（Mw)之下限値， 係以3000以上爲較佳，5000以上爲更佳，6000以上爲最 佳，7000以上爲極佳。上限値，係以50000以下爲較佳’ 30000以下爲更佳，1 0000以下爲最佳，9000以下爲極 佳。 -57- 200928592200928592 excimer laser, ArF excimer laser, F2 excimer laser), VUV (vacuum ultraviolet), EB (electronic line, soft X-ray, etc.). At this time, the choice of the first photoresist film 2 Exposure, gas and other inert gases are carried out 'which can be the usual exposure (can also be carried out by immersion exposure. immersion exposure, as described above, during exposure, conventional) or inert gas such as nitrogen The lens and the portion on the wafer are exposed in a state filled with a medium having a refractive index greater than that of air. More specifically, the photoresist film obtained by the above operation and the exposure device are the most One of the 'spaces' is filled with a quenched medium having a refractive index greater than that of air, and in this state, it is carried out by a desired photo-transfer (immersion exposure). The liquid immersion medium is preferably a solvent having a refractive index which is smaller than the refractive index of the light resisting film formed by the positive resist composition of the present invention. The refractive index of such a solvent is not particularly limited as long as it is within the above range. The solvent having a refractive index larger than that of air and having a refractive index higher than that of the photoresist film may, for example, be water, a fluorine-based inactive liquid, or a hydrocarbon-based solvent. Specific examples of the fluorine-based inactive liquid include a liquid having a fluorine-based name such as C4F9OCH3, c4f9〇c2h5, and c5h3F7, etc., and a boiling point of 70 to 180 tons is preferable to f, EUV (polar line), and X-ray. Air or nitrogen dry exposure), the solvent between the air photoresist film (the liquid immersion liquid exposure, the position of the lens agent (immersion liquid pattern exposure), and the use of the refractive index, as long as the refractive index It is preferably a small body, a lanthanide-soluble C3HC12F5, as a main component, and is preferably 80 to -48 - 200928592 1 60 ° C. When a fluorine-based inactive liquid has a boiling point of the above range, after the end of exposure, The removal of the medium used for the immersion liquid is preferably carried out in a simple manner. A fluorine-based inactive liquid, particularly a perfluoroalkyl compound in which all hydrogen atoms of the alkyl group are substituted with a fluorine atom is preferred. The perfluoroalkyl compound, specifically, for example, a perfluoroalkyl ether compound or a perfluoroalkylamine compound. Further, the above-mentioned perfluoroalkyl ether compound, for example, has perfluoro(2-butyl) Base-tetrahydrofuran) (boiling point 1〇 2. (:), the perfluoroalkylamine compound is, for example, perfluorotributylamine (boiling point 1 741 ). [Coating step] Next, on the surface of the first plurality of photoresist patterns 3 formed, Each of the coating film forming materials formed of the water-soluble resin composition is used to form a coating film 4 to form a plurality of coating patterns 5. The method for forming the coating film 4 is preferably a water-soluble resin. A method of forming a material for forming a coating film containing a oxazoline group-containing polymer. The material for forming a coating film is described in detail in the present invention described later. In the material for forming a coating film, when the coating film forming material is used, the coating film 4 can be applied to the surface of the pattern to form a coating film, for example, and then applied to the coating film. It is formed by applying a baking treatment. Further, it is also possible to perform a prebaking treatment on the coating film at a temperature of 80 ° C to 18 CTC for about 30 seconds to 180 seconds before the baking treatment. -49- 200928592 A coating method of a material for forming a film can be carried out by a conventional method For example, the support 1 in which the first photoresist pattern 3 is formed is immersed in a material for forming a coating film (immersion coating method), and the material for forming a coating film is coated by spin coating. a method of coating the support 1 or the like. In the coating step, after the coating of the coating film forming material, a baking treatment is applied to the coating film. By applying the baking treatment, the first coating can be promoted. The photoresist pattern 3 is acid-dissipated, and a cross-linking reaction occurs in the interface between the first photoresist pattern 3 and the coating film 0. By the crosslinking reaction, the first photoresist pattern is formed. The coating film 4 can be formed on the surface. In the baking treatment, the baking temperature is preferably 70 ° C to 180 ° C, more preferably 80 ° C to 170 ° C. By this range, a strong coating film 4 can be formed. The baking time is not particularly limited, but it is preferably 30 seconds to 300 seconds, preferably 60 seconds to 180 seconds, in consideration of the effect of the baking treatment and the stability of the shape of the pattern. In the coating step, it is preferred to wash the surface of the support φ body 1 with a cleaning liquid after application of the material for forming a coating film. Thereby, even on the support 1, the excess water-soluble resin adheres to the surface of the portion (non-pattern portion) where the photoresist film is not present, and is washed away by the cleaning liquid, or the concentration is changed. Very thin. On the other hand, the water-soluble tree 'lipid on the surface of the photoresist pattern 3 continues to remain due to cross-linking. As a result, the water-soluble resin film can be sufficiently formed on the surface of the resist pattern 3, but the surface of the non-pattern portion on the support 1 does not form or hardly forms a water-soluble resin film, and can be highly coated selectively. A water-soluble resin film (coating film 4) is formed on the surface of the resist pattern 3. Further, by washing, the coating film 4 can be made thin and uniform in film thickness. That is, when the cleaning is performed, the uncrosslinked excess water-soluble resin on the resist pattern 3 can be removed, and on the other hand, the water-soluble resin strongly bonded to the surface of the pattern due to crosslinking is uniformly left. On the surface of the pattern. Therefore, a film of a water-soluble resin having a nanometer degree can be formed by uniform film thickness, excellent precision, and high reproducibility. The washing liquid is not particularly limited as long as it dissolves the uncrosslinked water-soluble resin or the like, and is exemplified as a solvent which is a material for forming a coating film to be described later. The washing can be carried out by a conventional method, for example, by applying a cleaning solution to the surface of the coating film formed of the material for forming a coating film by a spray method or the like, and then sucking the excess cleaning liquid under reduced pressure. a method of performing the method, a method of immersing and washing in a washing liquid, a method of spray washing, a method of steam washing, a method of applying a washing liquid to a support by a spin coating method, and the like, in particular, rotating A coating method is preferred. The washing conditions (washing time, amount of the washing liquid, etc.) can be appropriately set in consideration of the washing method and the like. For example, when it is washed by a spin coating method, it can be appropriately adjusted in the range of 100 to 5000 rpm and about 1 to 100 seconds. It is preferred to carry out the "solvent" in the coating film formed by the material for forming a coating film before completely volatilizing. Whether or not the solvent has completely volatilized is visually confirmed. The thickness ' of the coating film 4' is preferably 〇_lnm or more, more preferably 0.5 to 50 nm, most preferably 1 to 30 nm. By being above 0.1 nm, an effect of sufficient resistance to etching such as dry etching such as oxygen plasma etching can be obtained. -51 - 200928592 [Film Forming Step (2)] Next, a second chemically amplified resist composition is applied onto the support 1 on which a plurality of overlying patterns 5 are formed, and a plurality of coatings are formed. A second photoresist film 6 having a gap between the patterns 5. In the present embodiment, the second chemically amplified photoresist composition uses a positive photoresist composition. In the film forming step (1), when the first zero chemically amplified photoresist composition uses a positive photoresist composition, the so-called first chemically amplified photoresist composition and the second chemically amplified type The photoresist composition can be the same or a different one. The second photoresist film 6 can be formed in the same manner as the first photoresist film 2 by a conventionally known method. The film thickness of the second photoresist film 6 is preferably at least the same as or higher than the height of the coated pattern 5. That is, when the support 1 is viewed from the side of the second photoresist film 6, the surface is flat. ❹ [Picture patterning step (2)] Next, the second photoresist film 6 is selectively exposed and developed at a position different from the position at which the plurality of patterns 5 are formed. Thereby, a composite pattern formed by a plurality of coating patterns 5 and a plurality of second photoresist patterns 7 formed on the second photoresist film 6 can be formed on the support 1 . Here, in the present invention, except for the case where the overlay pattern formed in the coating step is completely identical, all of them are "positions different from the position at which the overlay pattern is formed - 52 - 200928592" and all of them are not included. Repeated situations, and a repeated situation. In the present invention, it is preferable that all of the positions at which the pattern of the coating pattern is formed and the position where the patterning step (2) is selectively exposed are not repeated. Thereby, it is possible to form a pattern of a photoresist pattern formed by the patterning step (1), and a narrow pitch pattern in which the interval (pitch) between the patterns is narrower. The selective exposure at a position different from the position at which the pattern of the overlay is formed can be performed, for example, by moving the mask pattern used in the patterning step (1) in the horizontal direction. The movement of such a mask pattern can be implemented by adjusting the program of the exposure apparatus used. The reticle pattern can be moved in parallel in one direction or it can be rotated. For example, when forming a pattern, in the patterning step (1), a plurality of lines may be arranged at a certain pitch to form a line/pitch mask pattern to form a line/space pattern, and then the pattern In the step (2), the reticle pattern is moved in parallel in a direction perpendicular to the direction of the line, and the line pattern and the line pattern formed by the patterning step (1) In the middle position, a line pattern is formed, and the line/pitch distance between the initially formed lines/pitch is formed at a distance of about 1/2, and a line/pitch composite pattern can be formed. For example, after forming a line/space pattern of line width l〇〇nm, line width: interval width=1:3, by moving the reticle pattern in parallel with respect to the direction of the line in the vertical direction by 200 nm, Line width 1 〇〇 nm, line width: interval width = 1: 3 line / pitch pattern ' can form line width 1 0 0 nm, line width: interval width = 1: 1 line / spacing pattern. In addition, the reticle pattern used in the patterning step (1) is rotated by -53-200928592 and the reticle pattern different from the patterning step (1) is used to form a smear pattern. In addition to the method of moving the mask pattern, the stage (the pedestal carrying the substrate) in the exposure machine is moved in the pattern forming method of the present invention, and the above-mentioned composite pattern can be further formed. In the second towed composite pattern of the coating film formed of the water-soluble resin film, the surface 7 formed on the second photoresist film 6 can be improved by the water-soluble resin film. Wait. In the pattern forming method of the present invention, the above-mentioned 'after repeated' may be repeated a plurality of times: a series of operations of the overcoating (2) and the patterning step (2): on the surface of the formed composite pattern, formed by Forming a coating pattern on the coating film, applying a chemically amplified photoresist composition to the covering body 1 and selectively exposing and developing the photoresist film to form a narrow gap In the pattern forming method of the present invention, the formed composite pattern may be etched as the mask 1 after the above. That is, if an uranium engraving of an organic film is provided on a substrate, a loyalty (organic film pattern) can be formed on the organic film, and these patterns (patterns) can be used as a mask to etch the substrate. The reticle pattern used is the pattern. Other methods include the method of interviewing. On the surface of the patterning step (2), the formation step is performed. Thereby, the second photoresist pattern coating is coated, and the patterning step (2) is performed, and the film forming step is performed. That is, a plurality of heavy water-soluble resin films are formed into a pattern to form a photoresist film, and the pattern is operated. Borrow the shape of the shape. When the patterning step (2) is used to support the body film, the pattern of the composite pattern and the organic film pattern can be organically combined with the composite pattern, such as directly forming -54-200928592 on the substrate, and the compound can be directly compounded. The pattern is used as a mask to etch the substrate. By etching the substrate in this manner, a semiconductor device or the like can be manufactured. The etching method can be preferably carried out by a conventional method such as etching of an organic film. Among them, based on the viewpoint that the coating film is resistant to the etching of the film, the viewpoint of production efficiency, especially oxygen oxygen award hungry, or etch using cf4 gas or CHF3 gas is preferable, and oxygen is used. Plasma Φ etching is optimal. The etching of the substrate is preferably performed by etching using a halogen gas, and etching using a fluorinated carbon-based gas is preferable, and etching using CF4 gas or chf3 gas is particularly preferable. [Material for Organic Film Forming] In the support 1 used in the film formation step (1), an organic film forming material for forming an organic film which can be formed on a substrate does not necessarily have to be a photoresist film. The sensibility of rays or light. In the manufacture of a semiconductor © element or a liquid crystal display element, a photoresist or a resin which is generally used can be used. Further, by etching the organic film by using the coating pattern coated with the coating film, the coating pattern can be copied onto the organic film, and the organic film can be formed in the case where the organic film pattern can be formed. The material is preferably etched, especially a material which forms an organic film which can be subjected to dry uranium engraving. Among them, a material which forms an organic film which can be etched by oxygen plasma etching or the like is preferable. Such a material for forming an organic film may be a material conventionally used for forming an organic film of organic -55-200928592 B ARC or the like. For example, there are ARC series manufactured by "Pulova Science", AR series manufactured by Rohm and Haas Company, and SWK series manufactured by Tokyo Chemical Industry Co., Ltd. Wherein, as described above, the organic film can be easily etched by oxygen plasma etching when etching with oxygen plasma in the etching step, and the halogen gas, specifically, CF4 gas or CHF3 gas A material having a high resistance to a fluorinated carbon-based gas is preferred. Further, φ may be formed between the organic BARC and the substrate to form an organic film containing at least one resin component selected from the group consisting of a novolak resin, an acrylic resin, and a soluble polyimine. These materials are excellent in resistance to fluorinated carbon-based gases, and are suitable for use in the present invention, in addition to being easily etched by oxygen plasma etching or the like. In other words, in general, since the etching of the substrate or the like uses a halogen gas such as a fluorinated carbon-based gas, an organic film made of such a material is used, and oxygen plasma is used in addition to the formation of the organic film pattern. The uranium engraving can improve the workability. When the substrate or the like is etched using a halogen gas such as a fluorinated carbon-based gas in the subsequent step, the etching resistance can be improved. These resin components may be used singly or in combination of two or more. In the above, a novolak resin and an acrylic resin having an alicyclic portion or an aromatic ring in a side chain, which can be used inexpensively and widely, and have a dry etching using a fluorinated carbon-based gas It is better because of its excellent tolerance. The novolak resin can be used as a positive type resist for i-line or g-line which contains a novolak resin as a main component in a positive-type photoresist composition. The novolak resin is, for example, a resin obtained by addition-condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter, abbreviated as "phenol") and an aldehyde in the presence of an acid catalyst. Phenols, for example, phenol, decyl cresol, m-cresol, P-methyl phenol, hydrazine-ethyl phenol, m-ethyl phenol, p-ethyl phenol, hydrazine-butyl hydrazine, m — butyl phenol, p-butyl phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol , 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl Ether, pyrogallol, phloroglucinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, 8-naphthol, and the like. Aldehydes such as formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, and the like.触 The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, citric acid, oxalic acid, decanoic acid novolac resin may be used under an acid catalyst, and a commercially available one may also be used. The lower limit 质量 of the mass average molecular weight (Mw) of the novolac resin is preferably 3,000 or more, more preferably 5,000 or more, most preferably 6,000 or more, and most preferably 7,000 or more. The upper limit is preferably 50,000 or less, more preferably 30,000 or less, and most preferably less than 10,000, and 9000 or less is excellent. -57- 200928592

Mw如在3 000以上時，在以高溫烘烤時將難以昇華， 装置不易被汚染。此外，Mw如在5000以上時，對於氟化 碳系氣體等之耐蝕刻性優良而較佳。此外，Mw如在 5 000 0以下時，其對於具有微細凹凸之基板具有良好之塡 塞特性。尤其在10000以下時，乾蝕刻有容易進行之傾向 . 而較佳。 酚醛清漆樹脂，一般Mw爲5000〜50000爲理想，較 D 佳者爲8 00 0〜30000，且分子量爲500以下之低核體，較 佳爲200以下之低核體，其含有量係於凝膠滲透色層分析 法中爲1質量％以下，最佳者則爲〇·8質量％以下之酚醛清 漆樹脂爲理想。低核體之含有量係越少越好，較佳者爲0 質量％。 在具有上述範圍内之Mw之酚醛清漆樹脂中，藉由分 子量5 00以下之低核體之含有量在1質量％以下，其對於 具有微細凹凸之基板具有良好之塡塞特性。低核體之含有 〇 量減低，其塡塞特性會變佳之理由尙未明瞭，惟推測應係 分散度變小所致者。 . 在此，所謂的「分子量500以下之低核體」，係指以 聚苯乙烯爲標準藉由GPC法進行分析時’被檢測出分子 量500以下之低分子部分（Fraction )者。在「分子量 5 00以下之低核體」中，會因爲未聚合之單體’或聚合度 低者（例如分子量）而不同’惟包含苯酚類2〜5分子與 醛類進行縮合者等。 分子量500以下之低核體之含有量（質量％)，可將 -58- 200928592 依GPC法進行之分析結果，在横軸上取部分（Fraction) 編號，縦軸取濃度而作圖，求出相對於全曲線下面積，分 子量500以下之低分子部分（Fraction)之曲線下面積之 比例（％)而測定。 丙烯酸樹脂，可使用一般正型光阻組成物上所使用 - 者，例如一種丙烯酸樹脂，其係具有醚結合之聚合性化合 _ 物所衍生之構成單位，以及具有羧基之聚合性化合物所衍 〇 生之構成單位。 具有醚結合之聚合性化合物，例如有2—甲氧基乙基 (甲基）丙烯酸酯、甲氧基三乙二醇（甲基）丙烯酸酯、 3—甲氧基丁基（甲基）丙烯酸酯、乙基卡必醇（甲基） 丙烯酸酯、苯氧基聚乙二醇（甲基）丙烯酸酯、甲氧基聚 丙二醇（甲基）丙烯酸酯、四氫糠基（甲基）丙烯酸酯等 之具有醚結合及酯結合之（甲基）丙烯酸衍生物等。此等 之化合物可以單獨或使用2種以上之組合。再者，在本說 © 明書中，（甲基）丙烯酸酯係丙烯酸酯及甲基丙烯酸酯之 —者或二者。 . 具有羧基之聚合性化合物，例如有丙烯酸、甲基丙烯 酸、巴豆酸等之單羧酸；馬來酸、富馬酸、衣康酸等之二 羧酸；2—甲基丙烯醯氧基乙基琥珀酸、2 -甲基丙烯醯氧 基乙基馬來酸、2-甲基丙烯醯氧基乙基苯二酸、2—甲基 丙烯醯氧基乙基六氫苯二酸等之具有羧基及酯結合之化合 物等’其較佳者爲丙烯酸、甲基丙烯酸。此等之化合物單 獨或使用2種以上之組合。 -59- 200928592 所謂的可溶性聚醯亞胺，係指可藉由有機溶劑成爲液 狀之聚醯亞胺。 有機膜形成用材料中，亦可進而根據所期望者而適當 地含有具混和性之添加劑，例如：用以改良有機膜之性能 之加成性樹脂、用以提升塗佈性之界面活性劑、溶解抑制 . 劑、可塑劑、安定劑、着色劑、暈光防止劑等。 有機膜形成用材料，可將上述樹脂成分等材料溶解於 φ 有機溶劑中而製造。有機溶劑，例如可使用上述作爲化學 增幅型光阻組成物之（S )成分所例示者。 再者，在光阻膜與有機膜之間，亦可使用矽系材料所 成之硬光罩層。 [實施之型態2] 茲說明本發明之其他實施型態，惟在本實施之型態 中，與上述實施型態1重複之部分則省略其說明，並以相 〇 異部分爲重點加以說明。因此，在本實施之型態中，可適 當地援用上述實施型態1之相關記載。 《第二之態樣之圖型形成方法》 本發明之其他實施型態之圖型形成方法，係可使用正 型光阻組成物之圖型形成方法。此種光阻組成物，可使用 本發明實施時點中，該業者可利用之習知之正型光阻組成 物，其並無特別之限制。其中，又以使用化學增幅型之正 型光阻組成物爲較佳。 -60- 200928592 化學增幅型光阻組成物，其並無特別之限制， 爲化學增幅型光阻組成物所提案之多數化學增幅型 成物之中，根據所使用之曝光光源、微影特性等而 選擇使用。 此外，在本實施之型態中，其可使用之化學增 . 阻組成物之說明，係援用上述實施型態1之記載， 之型態中不加以詳細說明。在本實施之型態中，如 Φ 明示者，所謂化學增幅型光阻組成物或光阻組成物 正型光阻組成物之意。 本實施型態之圖型形成方法，係於支持體上形 之圖型形成方法，其係包含：在支持體上，塗佈正 組成物而形成光阻膜之步驟（以下，稱爲膜形 (1)):將前述光阻膜介由光罩圖型進行選擇性 顯像，而形成光阻圖型之步驟（以下，稱爲圖型 (1));在前述光阻圖型之表面上，使用由水溶 〇 組成物所成之被覆膜形成用材料以形成被覆膜之步 下，稱爲被覆步驟）；將以前述被覆膜加以被覆之 阻圖型進行曝光、顯像，而形成由前述被覆膜成分 圖型之步驟（以下，稱爲圖型化步驟（2))。 * 以下，就本發明之圖型形成方法，利用圖2說 佳實施型態。 本實施型態中，首先，如圖2 ( a )所示者，在 21上，將化學增幅型之正型光阻組成物加以塗佈而 阻膜22。接著，如圖2 ( b )所示者，將光阻膜22 可由作 光阻組 適當地 幅型光 本實施 無特別 ，係指 成圖型 型光阻 成步驟 曝光、 化步驟 性樹脂 驟（以 前述光 所成之 明其較 支持體 形成光 進行選 -61 - 200928592 擇性曝光、顯像’而形成多數之光阻圖型23。接著，如圖 2(c)所示者，在多數之光阻圖型23之表面上，各自塗 佈由水溶性樹脂組成物所成之被覆膜形成用材料24a。此 時之被覆膜形成用材料，係以塗佈成與光阻圖型23相同 之膜厚度或更薄之膜厚度者爲較佳。接著，如圖2(d)所 - 示者’僅在光阻圖型23之周圍使被覆膜24殘存著。接 • 著，如圖2(e)所示者，將由被覆膜24所被覆之光阻圖 0 型23進行曝光、顯像，再由支持體1上除去，而形成由 被覆膜24所成之被覆圖型25。 如此地進行操作，而在支持體21上，形成較圖型化 步驟（1 )所形成之光阻圖型23爲更狹間距之圖型25 (由 被覆膜24成分所成之圖型25)。 以下，就各步驟更詳細地加以說明，惟與上述實施型 態1重複之部分，則援用適當實施型態1之說明，並省略 其說明。本實施之型態中，係說明與上述實施型態1相異 〇 之部分。 [膜形成步驟（1 )] 本膜形成步驟（1)中，可使用之化學增幅型光阻組 成物，其並無特別之限制，如以上所述者，可適當地由被 提案作爲化學增幅型光阻組成物之多數之化學增幅型光阻 組成物中選擇而使用。 光阻膜22，可藉由將化學增幅型光阻組成物在支持體 上進行塗佈而形成。第一之化學增幅型光阻組成物之塗 -62- 200928592 佈，可藉由使用旋轉器等傳統習知之方法而進行。 具體而言，例如可將化學增幅型光阻組成物在支持體 上以旋轉器等進行塗佈，並在80〜150°C之溫度條件下， 施加40〜120秒、較佳者爲60〜90秒之烘烤處理（預烘 烤），並使其有機溶劑揮發而形成光阻膜2。 . 光阻膜22之厚度，較佳者爲50〜500nm，更佳者爲 50〜450nm。藉由控制在此範圍内，可以高解像度而形成 Q 光阻圖型，並獲得對於蝕刻具有完全耐性等之效果。 [圖型化步驟（1 )] 圖型化步驟（1 )可利用傳統習知之方法而進行，舉 例而言，可介由所定之圖型所形成之光罩（光罩圖型）而 將光阻膜22進行選擇性曝光，並在80〜150 °C之溫度條件 下，施加40〜120秒、較佳者爲 60〜90秒之烘烤處理 (P E B (曝光後加熱）），再以例如0 · 1〜1 0質量％濃度之 G 四甲基銨羥化物（TMAH )水溶液進行鹼性顯像時，其曝 光部及可被除去而形成光阻圖型23。If the Mw is above 3,000, it will be difficult to sublimate when baking at high temperature, and the device is not easily contaminated. Further, when Mw is 5,000 or more, it is preferable because it is excellent in etching resistance to a carbon fluoride-based gas or the like. Further, when Mw is 5,000 or less, it has good clogging characteristics for a substrate having fine unevenness. In particular, when it is 10,000 or less, dry etching tends to proceed easily. A novolak resin, generally having a Mw of 5,000 to 50,000, preferably a dimethyl group having a molecular weight of 500 or less, and a low nucleus having a molecular weight of 500 or less, preferably a low nucleus of 200 or less. In the gel permeation chromatography method, it is preferably 1% by mass or less, and most preferably a novolak resin of 8% by mass or less. The content of the low core body is preferably as small as possible, preferably 0% by mass. In the novolak resin having a molecular weight of Mw in the above range, the content of the low core body having a molecular weight of 500 or less is 1% by mass or less, which has good clogging characteristics for a substrate having fine unevenness. The reason why the nucleus content of the low-nuclear body is reduced and the clogging characteristics are better is not clear, but it is presumed that the dispersion is small. Here, the "low-nuclear body having a molecular weight of 500 or less" refers to a low-molecular portion (Fraction) having a molecular weight of 500 or less detected when analyzed by the GPC method using polystyrene as a standard. In the "low-nuclear body having a molecular weight of 500 or less", the unpolymerized monomer or the polymerization degree is low (for example, the molecular weight) is different, and only the phenolic 2 to 5 molecules are condensed with the aldehyde. The content of the low-nuclear body having a molecular weight of 500 or less (% by mass) can be obtained by analyzing the results of the GPC method from -58 to 200928592, taking the Fraction number on the horizontal axis, and plotting the concentration on the x-axis. The ratio (%) of the area under the curve of the low molecular weight (Fraction) having a molecular weight of 500 or less was measured with respect to the area under the full curve. The acrylic resin may be used in a general positive type resist composition, for example, an acrylic resin which is a constituent unit derived from an ether-bonded polymerizable compound, and a polymerizable compound having a carboxyl group. The constituent unit of life. A polymerizable compound having an ether bond, for example, 2-methoxyethyl (meth) acrylate, methoxy triethylene glycol (meth) acrylate, 3-methoxy butyl (meth) acrylate Ester, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate Such as (meth)acrylic acid derivatives having an ether bond and an ester bond. These compounds may be used singly or in combination of two or more kinds. Furthermore, in the text of this book, the (meth)acrylate-based acrylate and methacrylate or both. A polymerizable compound having a carboxyl group, for example, a monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid; a dicarboxylic acid such as maleic acid, fumaric acid or itaconic acid; 2-methylpropenyloxyl B Succinic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxyethyl phthalic acid, 2-methylpropenyloxyethyl hexahydrophthalic acid, etc. A compound in which a carboxyl group and an ester are combined, etc., which are preferably acrylic acid or methacrylic acid. These compounds may be used singly or in combination of two or more. -59- 200928592 The so-called soluble polyimine refers to a polyimine which can be liquidized by an organic solvent. In the material for forming an organic film, an additive having a compatibility may be appropriately contained, for example, an additive resin for improving the performance of the organic film, a surfactant for improving coating properties, and Dissolution inhibition. Agents, plasticizers, stabilizers, colorants, smudge inhibitors, etc. The material for forming an organic film can be produced by dissolving a material such as the above resin component in a φ organic solvent. As the organic solvent, for example, those exemplified as the (S) component of the chemically amplified photoresist composition can be used. Further, a hard mask layer made of a lanthanoid material may be used between the photoresist film and the organic film. [Embodiment 2] Other embodiments of the present invention will be described. However, in the present embodiment, the description of the portions overlapping with the above-described embodiment 1 will be omitted, and the description will be focused on the different portions. . Therefore, in the form of the present embodiment, the related description of the above-described embodiment 1 can be appropriately applied. <<Formation Method of Pattern of Second Aspect>> A pattern forming method of another embodiment of the present invention is a pattern forming method using a positive resist composition. Such a photoresist composition can be used in the practice of the present invention, and the conventional positive-type photoresist composition which the manufacturer can utilize is not particularly limited. Among them, a positive-type resist composition using a chemical amplification type is preferred. -60- 200928592 The chemically amplified photoresist composition is not particularly limited, and is a plurality of chemically amplified types of products proposed by chemically amplified photoresist compositions, depending on the exposure light source used, lithography characteristics, and the like. And choose to use. Further, in the present embodiment, the chemical composition can be used. The description of the resist composition is described in the above-described embodiment 1, and the description thereof will not be described in detail. In the form of the present embodiment, as the Φ is shown, the so-called chemically amplified photoresist composition or the photoresist composition is intended to be a positive photoresist composition. The pattern forming method of the present embodiment is a pattern forming method of a support upper form, which comprises the step of forming a photoresist film by coating a positive composition on a support (hereinafter, referred to as a film shape). (1)): a step of selectively developing the photoresist film via a mask pattern to form a photoresist pattern (hereinafter referred to as pattern (1)); on the surface of the photoresist pattern In the above, the coating film forming material formed by the water-soluble cerium composition is used to form a coating film, which is referred to as a coating step), and the resisting pattern coated with the coating film is exposed and developed. Further, a step of forming a pattern of the coating film component (hereinafter referred to as a patterning step (2)) is formed. * Hereinafter, with respect to the pattern forming method of the present invention, a preferred embodiment will be described using FIG. In the present embodiment, first, as shown in Fig. 2(a), a chemically amplified positive-type photoresist composition is applied to the resist film 22 at 21. Next, as shown in FIG. 2(b), the photoresist film 22 can be implemented as a photo-resistance group, and the photo-type photo-pattern is not particularly limited, and is referred to as a pattern-type photo-resistance step exposure process. It is formed by the above-mentioned light that the light is formed by the support-selective exposure, and the majority of the photoresist pattern 23 is formed. Then, as shown in Fig. 2(c), in the majority The surface of the photoresist pattern 23 is coated with a material for forming a coating film 24a made of a water-soluble resin composition. The material for forming a coating film at this time is coated with a photoresist pattern. It is preferable that the same film thickness or thin film thickness is 23. Next, as shown in Fig. 2(d), the coating film 24 is left only around the photoresist pattern 23. As shown in Fig. 2(e), the photoresist pattern 0 type 23 covered by the coating film 24 is exposed and developed, and then removed from the support 1 to form a coating pattern formed by the coating film 24. Type 25. By operating in this manner, on the support 21, the photoresist pattern 23 formed by the patterning step (1) is formed as a narrower pitch pattern. 25 (pattern 25 formed by the coating film 24). Hereinafter, each step will be described in more detail. However, in the case of the portion overlapping with the above-described embodiment 1, the description of the appropriate embodiment 1 is used, and the description is omitted. In the present embodiment, a portion different from the above-described embodiment 1 will be described. [Film Forming Step (1)] In the film forming step (1), a chemically amplified photoresist composition can be used. The material is not particularly limited, and as described above, it can be suitably selected from the chemically amplified photoresist composition proposed as a chemically amplified photoresist composition. The photoresist film 22 can be used. It is formed by coating a chemically amplified photoresist composition on a support. The first chemically amplified photoresist composition is coated with a conventional method known as a spinner. Specifically, for example, the chemically amplified resist composition may be applied to a support by a spinner or the like, and applied at a temperature of 80 to 150 ° C for 40 to 120 seconds, preferably 40 60 to 90 seconds of baking treatment (pre-baking), and The organic solvent is volatilized to form the photoresist film 2. The thickness of the photoresist film 22 is preferably 50 to 500 nm, more preferably 50 to 450 nm. By controlling within this range, Q can be formed with high resolution. The photoresist pattern is obtained and has the effect of being completely resistant to etching, etc. [Drawing step (1)] The patterning step (1) can be carried out by a conventional method, for example, by setting The photomask (mask pattern) formed by the pattern is selectively exposed to the photoresist film 22, and applied at a temperature of 80 to 150 ° C for 40 to 120 seconds, preferably 60 to 90 seconds. After the baking treatment (PEB (post-exposure heating)), and performing alkaline development with an aqueous solution of G tetramethylammonium hydroxide (TMAH) at a concentration of, for example, 0·1 to 10% by mass, the exposed portion thereof can be The photoresist pattern 23 is formed by removal.

_ 曝光所使用之波長，其並無特別之限制，可使用KrF 準分子雷射、ArF準分子雷射、F2準分子雷射、EUV (極 紫外線）、VUV (真空紫外線）、EB (電子線）、X線、 軟X線等放射線而進行。 此時’光阻膜22之選擇性曝光，可爲在空氣或氮氣 等不活性氣體中所進行之通常之曝光（乾曝光），亦可爲 以浸液曝光所進行者。 -63- 200928592 [被覆步驟] . 接著，在所形成之多數之光阻圖型23之表面上，各 自地使用由水溶性樹脂組成物所成之被覆膜形成用材料而 形成被覆膜24並形成多數之被覆圖型25。此時，在光阻 . 圖型23之上方，水溶性樹脂組成物所成之層，係以不形 . 成厚者爲較佳。亦即’將被覆膜形成用材料進行塗佈時， 〇 係以與前述光阻圖型23之膜厚度爲相同之膜厚度或更薄 者爲較佳。 被覆膜24之形成方法，其較佳係使用包含由含有水 溶性樹脂及水溶性交聯劑所成之水溶液之被覆膜形成用材 料的方法。關於被覆膜形成用材料，將於後述之本發明之 被覆膜形成用材料中，再詳細地說明。 被覆步驟中，其較佳係於被覆膜形成用材料之塗佈 後，利用洗淨液將支持體21表面進行洗淨。藉此，即使 〇 在支持體21上、光阻膜不存在之部分（非圖型之部分） 之表面上有多餘的水溶性樹脂附著，也會因該洗淨液而被 . 洗掉、或濃度變得非常薄。另一方面，光阻圖型23表面 之水溶性樹脂，由於交聯之故而殘留。其結果，在光阻圖 型23表面上雖可充分地形成水溶性樹脂膜，惟在支持體 2 1上之非圖型部表面上則不會形成水溶性樹脂膜，或者幾 乎不會形成，並可以高被覆選擇性而在光阻圖型23表面 上形成水溶性樹脂膜（被覆膜24)。此外，在光阻圖型 23之上面’因爲水溶性樹脂幾乎不附著之故，水溶性樹脂 64 - 200928592 膜幾乎不會形成。 進而，藉由洗淨之進行，被覆膜24，其膜厚度會變薄 ^且爲均一者。亦即，如進行洗淨時，在光阻圖型23上之 未交聯的多餘水溶性樹脂可被除去，另一方面，藉由交聯 而強固地結合於圖型表面之水溶性樹脂則會均一地殘留於 . 圖型表面。因此，奈米程度之水溶性樹脂之薄膜，其可以 均一之膜厚度’且精度極佳地、高再現性地形成。 0 洗淨液’如係可將未交聯之水溶性樹脂等溶解而除去 者即可’例如，可使用後述作爲被覆膜形成用材料之溶劑 所例示之相同者。 [圖型化步驟（2 )] 接著’將利用被覆膜24所被覆之光阻圖型23進行曝 光、顯像’並由支持體21上除去，而形成由被覆膜24成 分所成之圖型25。藉此，可在支持體21上，形成多數之 〇 圖型25 » 其中，本發明之光阻圖型23，雖由被覆膜24所被 . 覆，惟因曝光之故，可藉由鹼性顯像而除去。此曝光亦可 爲不使用光罩之全面曝光。另一方面，在光阻圖型23之 側面所形成（附著）之被覆膜24，則在顯像後繼續殘留。 再者，光阻圖型23之上部如形成有被覆膜24時，在以顯 像處理除去光阻圖型23時，亦可同時地被除去。此係在 光阻圖型23之上部所形成之被覆膜很薄，而對於鹼性顯 像不具有耐性之故。 -65- 200928592 再者，本圖型化步驟（2)中，亦可不將光阻圖型23 全部除去，而使一部之光阻圖型23選擇性地殘存。此 哼’就會形成由光阻圖型23及被覆膜24成分所成之圖型 25之複合圖型。關於何者之光阻圖型23被留下，可根據 其目的•用途而適當地加以設定，並無特定之限制。 - 本發明之圖型形成方法中，亦可在上述圖型化步驟 . (2)後，進而多次地重複上述膜形成步驟（1)、圖型化 ❹ 步驟（1)、被覆步驟、圖型化步驟（2)之一連串操作。 亦即，亦可多次重複：在支持體21上所形成之被覆圖型 25表面上，塗佈光阻組成物而形成光阻膜，將該光阻膜選 擇性地進行曝光、顯像而形成光阻圖型後，使用由水溶性 樹脂組成物所成之被覆膜形成用材料形成被覆膜並形成被 覆圖型之操作。藉此，就可進而形成狹間距之圖型，或形 成複雑形狀之圖型。 本發明之圖型形成方法中，亦可在上述圖型化步驟 〇 (2)後，將所形成之被覆圖型25(或複合圖型）作爲光 罩使用而進行支持體21之蝕刻。亦即，如在基板上設置 有機膜時，可進行有機膜之蝕刻，可在該有機膜上形成忠 於複合圖型之圖型（有機膜圖型），進而，可將此等之圖 ' 型（複合圖型及有機膜圖型）作爲光罩而進行基板之蝕 刻。複合圖型如直接形成於基板上時，可直接將複合圖型 作爲光罩，而進行基板之蝕刻。藉由如此地進行基板之蝕 刻，即可製造半導體設備等。 -66 - 200928592 [有機膜形成用材料] 關於有機膜形成材料，因爲可利用與上述實施型態工 爲相同者，故省略其說明。 [實施之型態3] . 《第三之態樣之被覆膜形成用材料》 . 本發明之被覆膜形成用材料，係由水溶性樹脂組成物 〇 所成之被覆膜形成材料’並係由以下之（i)或（ii)之組 成物所成之被覆膜取成材料。例如’在前述本發明之圖型 形成方法中，可用於形成前述被覆膜。 (i) 一種被覆膜形成用材料，其特徵爲其係由含有 水溶性樹脂所成之水溶液構成的被覆膜形成用材料，前述 水溶性樹脂係包含至少含有噁唑啉基之聚合物 (ii) 一種被覆膜形成用材料’其特徵爲其係由含有 水溶性樹脂及水溶性交聯劑所成之水溶液構成者 〇 [被覆膜形成用材料（i)] . 本發明之被覆膜形成用材料，其係由含有水溶性樹脂 所成之水溶液構成的被覆膜形成用材料，前述水溶性樹脂 係包含至少含有嚼哩啉基之聚合物。例如，前述本發明之 圖型形成方法中，可用以形成前述被覆膜。 所謂的「含有噁唑啉基之聚合物」，係指在分子中含 有噁唑啉骨架之聚合物即可’其具體之構造並無特別之限 制。舉例而言’不僅具有嚼哩啉骨架之單體之聚合物，還 -67- 200928592 含有具有噁唑啉骨架之單體及不具有噁唑啉骨架之單體之 共聚物。再者’本說明書中，所謂的「聚合物」’係指包 含2倍_體以上之低聚物者。 「噁唑啉骨架」，例如有下述構造式（13— 1)所示 之2一噁唑啉、構造式（13 - 2)所示之3 —噁唑啉、構造 . 式（1 3 — 3 )所示之4 -噁唑啉，以及其等之取代物。_ The wavelength used for exposure is not particularly limited. KrF excimer laser, ArF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electronic line) can be used. ), X-ray, soft X-ray and other radiation. At this time, the selective exposure of the photoresist film 22 may be a normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or may be performed by immersion exposure. -63-200928592 [Cladding Step] Next, a coating film forming material is formed on each of the surface of the plurality of formed resist patterns 23 by using a material for forming a coating film made of a water-soluble resin composition. And form a majority of the overlay pattern 25 . At this time, above the photoresist pattern 23, the layer formed of the water-soluble resin composition is preferably formed in a thickness. That is, when the material for forming a film is coated, it is preferable that the film has the same film thickness as the film thickness of the photoresist pattern 23 or less. In the method of forming the coating film 24, a method of forming a material for forming a coating film comprising an aqueous solution containing a water-soluble resin and a water-soluble crosslinking agent is preferably used. The material for forming a coating film will be described in detail in the material for forming a coating film of the present invention to be described later. In the coating step, it is preferable to apply the material for forming a coating film, and then wash the surface of the support 21 with a cleaning liquid. Thereby, even if the excess water-soluble resin adheres to the surface of the support 21 and the portion where the photoresist film does not exist (the portion of the non-pattern), it is washed off by the cleaning liquid, or The concentration becomes very thin. On the other hand, the water-soluble resin on the surface of the resist pattern 23 remains due to crosslinking. As a result, the water-soluble resin film can be sufficiently formed on the surface of the resist pattern 23, but the water-soluble resin film is not formed on the surface of the non-pattern portion on the support 21, or is hardly formed. Further, a water-soluble resin film (coating film 24) can be formed on the surface of the resist pattern 23 with high coating selectivity. Further, on the top of the photoresist pattern 23, since the water-soluble resin hardly adheres, the water-soluble resin 64 - 200928592 film hardly forms. Further, by the cleaning, the film thickness of the coating film 24 is reduced and uniform. That is, when the cleaning is performed, the uncrosslinked excess water-soluble resin on the resist pattern 23 can be removed, and on the other hand, the water-soluble resin strongly bonded to the surface of the pattern by crosslinking is Will remain uniformly on the surface of the pattern. Therefore, a film of a water-soluble resin having a nanometer degree can be formed with a uniform film thickness and excellent reproducibility with high precision. In the case where the water-soluble resin or the like which has not been crosslinked is dissolved, the same can be used. For example, the same as exemplified as the solvent for the material for forming a coating film to be described later can be used. [Drawing Step (2)] Next, 'the photoresist pattern 23 coated with the coating film 24 is exposed and developed' and removed by the support 21 to form a film 24 composition. Figure 25. Thereby, a plurality of pattern patterns 25 can be formed on the support body 21. Among them, the photoresist pattern 23 of the present invention is covered by the coating film 24, but may be exposed by alkali due to exposure. Sexual imaging is removed. This exposure can also be a full exposure without the use of a reticle. On the other hand, the coating film 24 formed (attached) on the side surface of the resist pattern 23 continues to remain after development. Further, when the coating film 24 is formed on the upper portion of the photoresist pattern 23, the photoresist pattern 23 can be removed at the same time when the photoresist pattern 23 is removed by the image forming process. This is a thin film formed on the upper portion of the photoresist pattern 23, and is not resistant to alkaline imaging. Further, in the patterning step (2), all of the photoresist pattern 23 may not be removed, and a portion of the photoresist pattern 23 may be selectively left. This 哼' forms a composite pattern of the pattern 25 formed by the photoresist pattern 23 and the coating film 24. Regarding which of the photoresist pattern 23 is left, it can be appropriately set according to its purpose and use, and there is no particular limitation. - In the pattern forming method of the present invention, the film forming step (1), the patterning step (1), the coating step, and the pattern may be repeated a plurality of times after the patterning step (2). One of the modeling steps (2) is a series of operations. That is, it may be repeated a plurality of times: a photoresist composition is applied on the surface of the overlying pattern 25 formed on the support 21 to form a photoresist film, and the photoresist film is selectively exposed and developed. After the photoresist pattern is formed, an operation of forming a coating film using a material for forming a coating film made of a water-soluble resin composition to form a coating pattern is used. Thereby, it is possible to form a pattern of a narrow pitch or a pattern of a reticular shape. In the pattern forming method of the present invention, after the patterning step 〇 (2), the formed pattern 25 (or composite pattern) may be used as a mask to etch the support 21. That is, when an organic film is provided on a substrate, an organic film can be etched, and a pattern (organic film pattern) loyal to the composite pattern can be formed on the organic film, and further, the pattern can be formed. (Composite pattern and organic film pattern) The substrate is etched as a mask. When the composite pattern is formed directly on the substrate, the composite pattern can be directly used as a mask to etch the substrate. By etching the substrate in this manner, a semiconductor device or the like can be manufactured. -66 - 200928592 [Material for forming an organic film] The organic film forming material is the same as the above-described embodiment, and the description thereof will be omitted. [Form 3 of the invention] The material for forming a coating film of the third aspect. The material for forming a coating film of the present invention is a coating material for forming a coating film of a water-soluble resin composition ' It is a coating material obtained from the composition of the following (i) or (ii). For example, in the pattern forming method of the present invention described above, it can be used to form the above-mentioned coating film. (i) A material for forming a coating film, which is characterized in that it is a material for forming a coating film comprising an aqueous solution containing a water-soluble resin, and the water-soluble resin contains a polymer containing at least an oxazoline group ( Ii) A material for forming a coating film, which is characterized by being composed of an aqueous solution containing a water-soluble resin and a water-soluble crosslinking agent, [material for forming a coating film (i)]. The coating film of the present invention The material for forming is a material for forming a coating film comprising an aqueous solution containing a water-soluble resin, and the water-soluble resin is a polymer containing at least a chewing porphyrin group. For example, in the above-described pattern forming method of the present invention, it is possible to form the above-mentioned coating film. The "polymer containing oxazoline group" means a polymer having an oxazoline skeleton in the molecule. The specific structure is not particularly limited. For example, 'a polymer having not only a monomer having a chelate porphyrin skeleton, but also a copolymer having a monomer having an oxazoline skeleton and a monomer having no oxazoline skeleton. In the present specification, the term "polymer" as used herein means an oligomer containing 2 times or more of a body. The "oxazoline skeleton" is, for example, a 2-oxazoline represented by the following structural formula (13-1), a 3-oxazoline represented by the structural formula (13-2), and a structure. 3) The 4-oxazoline shown, and the substitutions thereof.

(13-1) (13-2) (13-3) 該取代物，例如有上述構造式13所示之噁唑啉之碳 原子或氮原子所結合之氫原子，被以碳數1〜6之取代或 未取代之低級烷基、羧基、羥基、鹵基所取代之化合物。 ❹ 上述經取代低級烷基，例如有羥基烷基、（低級烷氧基） 烷基等，惟並不限於此等例示之範圍。 • 本發明之被覆膜形成用材料所含之水溶性樹脂之中， . 其含有噁唑啉基之聚合物之配合量，較佳者係至少1〜50 質量％，更佳者爲1〜3 0質量％。如未達1質量％時，難以 獲得所期望之效果，另一方面，基於必要膜厚度之観點， 當超過50質量％，將難以得到配合量所預期效果之提升。 本發明可使用之含有噁唑啉基之聚合物，例如係以具 -68- 200928592 有以下之一般式（14)所示構造者爲最佳。 [化 21](13-1) (13-2) (13-3) The substituent, for example, a hydrogen atom to which a carbon atom or a nitrogen atom of an oxazoline represented by the above structural formula 13 is bonded is a carbon number of 1 to 6 a substituted or unsubstituted compound substituted with a lower alkyl group, a carboxyl group, a hydroxyl group or a halogen group. ❹ The above substituted lower alkyl group may, for example, be a hydroxyalkyl group or a (lower alkoxy)alkyl group, but is not limited to the scope of these examples. In the water-soluble resin contained in the material for forming a coating film of the present invention, the amount of the oxazoline group-containing polymer is preferably at least 1 to 50% by mass, more preferably 1 to 1%. 30% by mass. If it is less than 1% by mass, it is difficult to obtain the desired effect. On the other hand, when it exceeds 50% by mass based on the thickness of the necessary film thickness, it is difficult to obtain an improvement in the effect expected from the blending amount. The oxazoline group-containing polymer which can be used in the present invention is preferably, for example, a structure represented by the following general formula (14) having -68 to 200928592. [Chem. 21]

(14) ❹ 本發明之被覆膜形成用材料，亦可包含含有上述噁唑 啉基之聚合物以外之水溶性樹脂（以下，稱爲「其他之水 溶性樹脂」）。以下’就其他之水溶性樹脂加以說明。 &lt;其他之水溶性樹脂&gt; 本發明之被覆膜形成用材料所可使用之其他之水溶性 樹脂，其只要係可在室溫下以水溶解之樹脂即可，並無特 Q 別之限制，惟本發明可含有至少1種選自丙烯酸系樹脂、 乙烯系樹脂、纖維素系樹脂、及醯胺系樹脂。 丙烯系樹脂，例如有以丙烯酸、丙烯酸甲酯、甲基丙 烯酸、甲基丙烯酸甲酯、N，N-二甲基丙烯基醯胺、Ν,Ν-• 二甲基胺丙基甲基丙烯基醯胺、Ν,Ν -二甲基胺丙基丙烯 基醯胺、Ν—甲基丙烯基醯胺、二丙酮丙烯基醯胺、Ν,Ν — 二甲基胺乙基甲基丙烯酸酯、Ν，Ν —二乙基胺乙基甲基丙 稀酸酯、Ν，Ν-二甲基胺乙基丙烯酸酯、丙烯醯基嗎啉等 之單體爲構成成分之聚合物或共聚物° -69- 200928592 乙烯系樹脂，例如有N—乙烯耻咯烷酮、乙烯咪唑啉 二酮'酔酸乙烯等之單體爲構成成分之聚合物或共聚物。 纖維素系樹脂，例如有羥基丙基甲基纖維素苯二甲酸 酯、羥基丙基甲基纖維素乙酸酯苯二甲酸酯、羥基丙基甲 基纖維素六氫苯二甲酸酯、羥基丙基甲基纖維素乙酸酯琥 珀酸酯、羥基丙基甲基纖維素、羥基丙基纖維素、羥基乙 ^ 基纖維素、纖維素乙酸酯六氫苯二甲酸酯、羧基甲基纖維 〇 素、乙基纖維素、甲基纖維素等。 進而’亦可使用在醯胺系樹脂之中爲水溶性者。 其中’係以乙烯系樹脂爲較佳，並以聚乙烯吡咯烷酮 或聚乙烯醇類爲較佳。 此水溶性樹脂，可以單獨使用，亦可混合2種以上而 使用。 水溶性樹脂之配合量，爲將被覆膜作成在使用上所必 要之充分膜厚度起見，在被覆膜形成用材料之固態成分 〇 中，係以1〜99質量％左右爲較佳，並以40〜99質量％左 右爲更佳，另以65〜99質量％左右爲最佳。 &lt;水溶性交聯劑&gt; 本發明之被覆膜形成用材料，亦可含有水溶性交聯 劑。水溶性交聯劑，在其構造中係具有至少1個之氮原 子。此種水溶性交聯劑，其較佳係使用至少2個氫原子以 羥基烷基及/或烷氧基烷基所取代、且具有胺基及/或亞 胺基之含氮化合物。此等含氮化合物，例如有胺基之氫原 -70- 200928592 子以經甲基或烷氧基甲基或其二者所取代者，其三聚氰胺 系衍生物、尿素系衍生物、鳥糞胺系衍生物、乙胍畊系衍 生物、苯并鳥糞胺系衍生物、琥珀醯基醯胺系衍生物、或 亞胺基之氫原子被取代之甘脲系衍生物、伸乙烯尿素系衍 生物等。 • 在此等含氮化合物之中，基於交聯反應性之觀點，係 . 以具有至少2個氫原子以羥甲基、或（低級烷氧基）甲 〇 基、或其二者所取代之胺基或亞胺基，其苯并鳥糞胺系衍 生物、鳥糞胺系衍生物、三聚氰胺系衍生物等之三嗪衍生 物、甘脲系衍生物、及尿素系衍生物中之1種以上爲較 佳。 水溶性交聯劑之配合量，在被覆膜形成用材料之固態 成分中，係以1〜99質量％左右爲較佳，1〜60質量％左右 爲更佳，並以1〜35質量％左右爲最佳。 〇 〈溶劑〉 本發明之被覆膜形成用材料，一般係使用水溶液，其 , 係含有水溶性樹脂所成者，且該水溶性樹脂係包含含有上 述噁唑啉基之聚合物者。此被覆膜形成用材料，係以使用 3〜5 0質量％濃度之水溶液爲較佳，並以5〜20質量％濃度 之水溶液爲最佳。濃度如未達3質量％時，對於光阻圖型 可能會有被覆不良之虞，另一方面，如超過50質量％時， 則無法得到濃度提高所預期效果之提升，故基於處理性之 觀點並不佳。 -71 - 200928592 再者’溶劑，可使用水與醇類 類系溶劑’例如有甲基醇類、乙基 基醇類、甘油、乙二醇、丙二醇、 二醇、2,3— 丁二醇等。此等之醇 水爲3 0質量％作爲上限而混合使用 &lt;任意成分&gt; 〇 被覆膜形成用材料，除了水溶 所述配合任意成分。 •界面活性劑 被覆膜形成用材料，例如可配 性劑’其並無特別之限制，惟須對 解性高，且不發生懸浮等之特性。 之界面活性劑，特別可抑制在被覆 Φ 所產生之氣泡（微泡），並可達到 之缺陷之發生的目的。基於上述之 基吡咯烷酮系界面活性劑、第4級 氧基伸乙烯之磷酸酯系界面活性劑 ' 中之1種以上爲較佳。 N-烷基吡咯烷酮系界面活性: (15)所示者爲較佳。 系溶劑之混合溶劑。醇 醇類、丙基醇類、異丙 1,2— 丁 二醇、1，3 -丁 漬系溶劑，可以相對於 性樹脂之外，亦可如下 合界面活性劑。界面活 於上述水溶性樹脂之溶 藉由使用滿足此種特性 膜形成用材料之塗佈時 防止與此微泡產生有關 點，係以使用：N —烷 銨鹽系界面活性劑、聚 、非離子系界面活性劑 射’其係以下述一般式 -72- 200928592(14) The material for forming a coating film of the present invention may further contain a water-soluble resin (hereinafter referred to as "other water-soluble resin") other than the polymer containing the oxazoline group. The following is described with respect to other water-soluble resins. &lt;Other water-soluble resin&gt; The other water-soluble resin which can be used for the material for forming a coating film of the present invention is not particularly limited as long as it is a resin which can be dissolved in water at room temperature. However, the present invention may contain at least one selected from the group consisting of an acrylic resin, a vinyl resin, a cellulose resin, and a guanamine resin. Acrylic resin, for example, acrylic acid, methyl acrylate, methacrylic acid, methyl methacrylate, N,N-dimethylpropenylamine, hydrazine, hydrazine-•dimethylaminopropyl propyl methacrylate Hydrazine, hydrazine, hydrazine - dimethylaminopropyl propyl decylamine, hydrazine - methacryl decylamine, diacetone acrylamide, hydrazine, hydrazine - dimethylamine ethyl methacrylate, hydrazine , Ν-diethylamine ethyl methacrylate, hydrazine, hydrazine-dimethylamine ethyl acrylate, acryl hydrazinomorpholine and other monomers are constituent polymers or copolymers ° -69 - 200928592 A vinyl-based resin, for example, a polymer or a copolymer having a monomer such as N-vinylpyrrolidone or ethylene imidazolidindione-ethylene phthalate as a constituent component. Cellulose-based resins such as hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate phthalate, hydroxypropylmethylcellulose hexahydrophthalate , hydroxypropyl methyl cellulose acetate succinate, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, cellulose acetate hexahydrophthalate, carboxyl Methylcellulose, ethylcellulose, methylcellulose, and the like. Further, it is also possible to use a water-soluble one of the amide-based resins. Among them, a vinyl resin is preferred, and polyvinylpyrrolidone or polyvinyl alcohol is preferred. These water-soluble resins may be used singly or in combination of two or more. The amount of the water-soluble resin is preferably from about 1 to 99% by mass in the solid content of the material for forming a coating film, in order to form the coating film as a sufficient film thickness for use. It is preferably about 40 to 99% by mass, and preferably about 65 to 99% by mass. &lt;Water-soluble cross-linking agent&gt; The material for forming a coating film of the present invention may further contain a water-soluble cross-linking agent. The water-soluble crosslinking agent has at least one nitrogen atom in its structure. Such a water-soluble crosslinking agent is preferably a nitrogen-containing compound having at least two hydrogen atoms substituted with a hydroxyalkyl group and/or an alkoxyalkyl group and having an amine group and/or an amine group. Such nitrogen-containing compounds, such as amine-based hydrogenogen-70-200928592, are substituted by methyl or alkoxymethyl or both, melamine-based derivatives, urea-based derivatives, and guanamine a derivative, an acetaminophen derivative, a benzoguanamine derivative, an amber decylamine derivative, or a glycoluril derivative in which a hydrogen atom of an imine group is substituted, and an ethylene urea-based derivative Things and so on. • Among such nitrogen-containing compounds, based on the viewpoint of crosslinking reactivity, is substituted with at least 2 hydrogen atoms with a hydroxymethyl group, or a (lower alkoxy)methyl fluorenyl group, or both thereof. An amine group or an imine group, one of a triazine derivative such as a benzoguanamine derivative, a guanamine derivative, or a melamine derivative, a glycoluril derivative, and a urea derivative. The above is preferred. The amount of the water-soluble crosslinking agent is preferably from about 1 to 99% by mass, more preferably from about 1 to 60% by mass, and preferably from about 1 to about 35% by mass, based on the solid content of the material for forming a coating film. For the best. <Solvent> The material for forming a coating film of the present invention is generally an aqueous solution containing a water-soluble resin, and the water-soluble resin contains a polymer containing the above oxazoline group. The material for forming a coating film is preferably an aqueous solution having a concentration of 3 to 50% by mass, and preferably an aqueous solution having a concentration of 5 to 20% by mass. If the concentration is less than 3% by mass, there may be a problem with the photoresist pattern. On the other hand, if it exceeds 50% by mass, the effect of increasing the concentration cannot be obtained, so based on the viewpoint of handling. Not good. -71 - 200928592 In addition, 'solvent can use water and alcohol-based solvents' such as methyl alcohols, ethyl alcohols, glycerin, ethylene glycol, propylene glycol, glycols, 2,3-butanediol Wait. The above-mentioned alcohol water is used in an amount of 30% by mass as an upper limit. &lt;Optional component&gt; 材料 The material for forming a coating film is mixed with an optional component in addition to water. • Surfactant The material for forming a coating film, for example, the dispensable agent' is not particularly limited, but has high reactivity and does not exhibit such characteristics as suspension. The surfactant can specifically suppress the bubbles (microbubbles) generated by the coating of Φ, and can achieve the purpose of occurrence of defects. One or more of the above-mentioned pyrrolidone-based surfactant and the fourth-stage oxygen-extended ethylene phosphate-based surfactant are preferred. N-alkylpyrrolidone interfacial activity: (15) is preferred. A mixed solvent of a solvent. Alcohols, propyl alcohols, isopropyl 1,2-butanediol, and 1,3-butyric solvents may be used in combination with an organic resin or a surfactant. The interface is active in the above-mentioned water-soluble resin, and is prevented from being associated with the microbubble when it is coated with a material which satisfies such a characteristic film, and is used: N-alkane salt-based surfactant, poly, non- The ionic surfactants are injected in the following general formula -72- 200928592

[式（15)中，R2()係碳數6以上之烷基] 此種N-烷基吡咯烷酮系界面活性劑，具體而言，例 如有N-己基—2 —吡咯烷酮、N-庚基_2-吡咯烷酮、N —辛基_2_啦咯院酮、N —壬基一 2 —卩比略院酮、N —癸 基一2_吡咯烷酮、\ 一癸基一2-吡咯烷酮、——烷 基一 2 —啦略院酮、N--h二院基一2—吡略院酮、N-十 三烷基—2 —吡咯烷酮、N —十四烷基一 2 —吡咯烷酮、N —十五烷基一 2 —吡咯烷酮、N -十六烷基—2 一吡咯烷 _、N—十七院基一 2—卩比略院酮、n —十八院基一 2—口比 略院酮等。其中並以使用N —辛基一 2 一吡咯烷酮 (「SURFADONE LPIOO」；ISP 公司製）爲較佳。 第4級銨系界面活性劑’例如有下述—般式（16)所 不者爲較佳。 [化 23] χ- (16) ^21 «22 N-R24 R23 -73- 200928592 [式（16 )中、R21、R22、R23、R24，係各自獨立地爲 或羥基烷基（惟，其中之至少1個爲碳數6以上之烷 羥基烷基），X·爲羥化物離子或鹵離子。】 此種第4級銨系界面活性劑，具體而言，例如有 烷基三甲基銨羥化物、十三烷基三甲基銨羥化物、十 - 基三甲基銨羥化物、十五烷基三甲基銨羥化物、十六 . 三甲基銨羥化物、十七烷基三甲基銨羥化物、十八烷 〇 甲基銨羥化物等。其中，並以十六烷基三甲基銨羥化 較佳。 聚氧基伸乙烯之磷酸酯系界面活性劑，其係以下 般式（17)所示者爲較佳。 [化 24] OR, 烷基 基或 十二 四烷 烷基 基三 物爲 述一[In the formula (15), R 2 () is an alkyl group having 6 or more carbon atoms] such an N-alkylpyrrolidone-based surfactant, specifically, for example, N-hexyl-2-pyrrolidone or N-heptyl group 2-pyrrolidone, N-octyl_2_laprofenone, N-mercapto-2-indolyl ketone, N-fluorenyl-2-pyrrolidone, \-mercapto- 2-pyrrolidone, -alkane基一二 - Laiyuan ketone, N--h second hospital base 2- 2-pyridone, N-tridecyl-2-pyrrolidone, N-tetradecyl-2-pyrrolidone, N-15 Alkyl-2-pyrrolidone, N-hexadecyl-2-pyrrolidine _, N-seven-seven-in-one-two-indolyl ketone, n-eighteen-yard base-two-mouth ratio . Among them, N-octyl-2-pyrrolidone ("SURFADONE LPIOO"; manufactured by ISP) is preferred. The fourth-order ammonium-based surfactant is preferably, for example, the following formula (16). Χ- (16) ^21 «22 N-R24 R23-73- 200928592 [In the formula (16), R21, R22, R23, R24 are each independently or a hydroxyalkyl group (only, At least one is an alkylhydroxyalkyl group having 6 or more carbon atoms, and X· is a hydroxylate ion or a halide ion. Such a fourth-order ammonium-based surfactant, specifically, for example, an alkyltrimethylammonium hydroxide, a tridecyltrimethylammonium hydroxide, a decyltrimethylammonium hydroxide, and fifteen An alkyltrimethylammonium hydroxide, a hexamethylammonium hydroxide, a heptadecyltrimethylammonium hydroxide, an octadecylmethylammonium hydroxide, or the like. Among them, hydroxylation with cetyltrimethylammonium is preferred. The polyoxyalkylene phosphate-based surfactant is preferably the one represented by the following formula (17). OR, alkyl or dodecanealkyl group is described as one

L250~(- CH2CH2〇-j~^ —OH 0 (17) [式（17)中，R25爲碳數1〜10之烷基或烷基烯丙 R26爲氫原子或（CH2CH20)R25 ( R25係如上述所定義者 X爲1〜20之整數。] 此種聚氧基伸乙烯之磷酸酯系界面活性劑，具 言，係以「普萊塞夫A2 12E」、「普萊塞夫A2 10G」 上，皆爲第一工業製藥（股）製）等市售者爲較佳。 非離子性界面活性劑，係以聚氧基烷撐之烷基醚 基， )， 體而 (以 化物 -74- 200928592 或烷基胺氧化物化合物爲較佳。 聚氧基烷撐之烷基醚化物，係以下述一般式（18)或 (19)所示之化合物爲較佳。 [化 25] . R27~(~A〇-^R28 (18) ❹ H2‘ ⑽ R27——c -(-A〇-^-R28 (19) 上述一般式（18) 、（19)中係碳數1〜 22之直鏈狀、分支鏈狀或環狀之烷基、具有經基之院基、 或烷基苯基。Αο係以選自氧基烷撐基、氧基乙撐、氧基丙 撐、及氧基丁撐基之中至少1種爲較佳。y係整數。 烷基胺氧化物化合物，其較佳係下述—般式（20 )或 ® ( 2 1 )所示之化合物。 [化 26] '29L250~(-CH2CH2〇-j~^-OH 0 (17) [In the formula (17), R25 is an alkyl group having 1 to 10 carbon atoms or an alkyl allylic group R26 is a hydrogen atom or (CH2CH20)R25 (R25 system) X is an integer of 1 to 20 as defined above.] The polyoxyethylene-based phosphate ester surfactant is, in other words, "Plesef A2 12E" and "Pressev A2 10G". It is preferred by the first industrial pharmaceutical (share) system, etc. Nonionic surfactants are based on polyalkylene alkyl ether groups, ), and (----74- 200928592 Or an alkylamine oxide compound is preferred. The polyalkylene alkyl ether compound is preferably a compound represented by the following general formula (18) or (19). R27~( ~A〇-^R28 (18) ❹ H2' (10) R27——c -(-A〇-^-R28 (19) The above general formula (18), (19) is a linear chain of carbon numbers 1 to 22 a branched or cyclic alkyl group having a transradical group or an alkylphenyl group. The oxime is selected from the group consisting of an oxyalkylene group, an oxyethylene group, an oxypropylene group, and an oxybutyl group. At least one of the groups is preferred. The y is an integer. Alkylamine oxide compound Preferably, it is a compound represented by the following formula (20) or ® (2 1 ). [Chem. 26] '29

CpH2p+l •N· Ο (20)CpH2p+l •N· Ο (20)

CpH2p+iCpH2p+i

(21) -75- 200928592 上述一般式（20) 、（21)中，R29係可以氧原 斷之碳數8〜20之烷基或羥基烷基，P及q係1〜5 數。 _ 上述一般式（20) 、（21)所示之烷基胺氧化物 物，其例如有辛基二甲基胺氧化物、十二烷基二甲基 . 化物、癸基二甲基胺氧化物、月桂基二甲基胺氧化物 蠟基二甲基胺氧化物、硬脂醯基二甲基胺氧化物、異 Q 二乙基胺氧化物、壬基二乙基胺氧化物、月桂基二乙 氧化物、異十五烷基甲基乙基胺氧化物、硬脂醯基甲 基胺氧化物、月桂基二（羥基乙基）胺氧化物、鯨蠘 乙醇胺氧化物、硬脂醯基二（羥基乙基）胺氧化物、 烷基氧基乙氧基乙氧基乙基二（甲基）胺氧化物、硬 基氧基乙基二（甲基）胺氧化物等。 此等之界面活性劑之中，又基於減低缺陷之觀點 以非離子系界面活性劑爲較佳。 〇 界面活性劑之配合量，在被覆膜形成用材料之固 分中，係以0.1〜10質量％左右爲較佳，並以0.2〜2 %左右爲最佳。如在上述配合量範圍之外時，有可能 生塗佈性之惡化、或一種稱爲微泡之塗佈時所發生的 等之可能性’其被認爲與缺陷之發生有深厚關係。 •水溶性氟化合物 在被覆膜形成用材料中，亦可配合水溶性氟化合 水溶性氟化合物，其並無特別之限制，惟必須具有對 子中 之整 化合 胺氧 、鯨 己基 基胺 基丙 基二 十二 脂醯 ，係 態成 質量 會發 氣泡 物。 於上 -76- 200928592 述水溶性樹脂之溶解性高，且不發生懸浮等特性。藉由使 用滿足此種特性之水溶性氟化合物，就可提升其平整性 (被覆膜形成用材料之擴展左右）。平整性之目的雖可藉 由添加界面活性劑所致之降低接觸角而達成，惟界面活性 劑添加量爲過剩時，就無法達到一定左右以上之塗佈提升 . 性，或因爲過剩量之緣故，使得在塗佈時，因塗佈條件而 在被覆膜上發生氣泡（微泡），並成爲缺陷之原因。藉由 0 配合此種水溶性氟化合物，可抑制此種發泡、降低接觸 角、並提升其平整性。 此種水溶性氟化合物，較佳可使用氟烷基醇類、氟烷 基羧酸類等。氟烷基醇類，例如有2—氟_1_乙醇、2，2 —二氟—1_乙醇、三氟乙醇、四氟丙醇、八氟戊醇等。 氟烷基羧酸類，例如有三氟酢酸等。惟並不限於此等例示 之範圍’只要係具有水溶性之氟化物，並能達成上述之效 果者即可。其中’尤以碳數6以下之氟烷基醇類爲較佳。 Φ 又基於容易取得之觀點，其係以三氟乙醇爲最佳。 水溶性氟化合物之配合量，在被覆膜形成用材料之固 . 態成分中’係以〇 · 1〜3 0質量％左右者爲較佳，並以〇 .!〜 1 5質量％左右者爲最佳。如未達到上述配合量範圍時，塗 佈性有惡化之虞。又如較上述配合量爲過剩量配合時，則 無法期待該配合量所應提升之平整性。 •含醯胺基之單體 在被覆膜形成用材料中，亦可配合含醯胺基之單體。 -77- 200928592 含醯胺基之單體，其並無特別之限制，惟須具有對於上述 水溶性樹脂之溶解性高，且不發生懸浮等之特性。 此種含醯胺基之單體，其較佳係下述一般式（22 )所 示之醯胺化合物。(21) -75- 200928592 In the above general formulas (20) and (21), R29 is an alkyl group having a carbon number of 8 to 20 or a hydroxyalkyl group, and P and q are 1 to 5 numbers. _ alkylamine oxides of the above general formulas (20) and (21), which are, for example, octyldimethylamine oxide, dodecyldimethylamine, decyldimethylamine oxide , lauryl dimethylamine oxide waxy dimethylamine oxide, stearyl dimethylamine oxide, iso-Q-diethylamine oxide, mercapto diethylamine oxide, lauryl Diethoxylate, isopentadecylmethylethylamine oxide, stearylmethylamine oxide, lauryl bis(hydroxyethyl)amine oxide, whale oxime ethanolamine oxide, stearic acid sulfhydryl Di(hydroxyethyl)amine oxide, alkyloxyethoxyethoxyethylbis(methyl)amine oxide, hard oxyethyldi(methyl)amine oxide, and the like. Among these surfactants, nonionic surfactants are preferred from the viewpoint of reducing defects. The amount of the surfactant to be added is preferably from 0.1 to 10% by mass in terms of the solid content of the material for forming a coating film, and is preferably about 0.2 to 2%. When it is outside the above-mentioned range of the compounding amount, there is a possibility that the coating property is deteriorated, or the possibility of occurrence of a kind of microbubble coating, which is considered to have a deep relationship with the occurrence of defects. • The water-soluble fluorine compound may be blended with a water-soluble fluorinated water-soluble fluorine compound in the material for forming a coating film, and is not particularly limited, but it must have a hydrazine amine or a cetylamino group in the pair. Propyl icosuccinate, which is a quality bubble. In the above -76-200928592, the water-soluble resin has high solubility and does not exhibit characteristics such as suspension. By using a water-soluble fluorine compound which satisfies such characteristics, the flatness can be improved (the expansion of the material for forming a coating film). Although the purpose of the flatness can be achieved by reducing the contact angle caused by the addition of the surfactant, when the amount of the surfactant added is excessive, it is impossible to achieve a coating improvement of a certain degree or more, or because of the excess amount. At the time of coating, bubbles (microbubbles) are generated on the coating film due to the coating conditions, which causes defects. By blending this water-soluble fluorine compound with 0, it is possible to suppress such foaming, lower the contact angle, and improve the flatness. As such a water-soluble fluorine compound, a fluoroalkyl alcohol or a fluoroalkyl carboxylic acid or the like can be preferably used. Examples of the fluoroalkyl alcohols include 2-fluoro-1-ethanol, 2,2-difluoro-1-ethanol, trifluoroethanol, tetrafluoropropanol, and octafluoropentanol. The fluoroalkylcarboxylic acid is, for example, trifluoroantimonic acid or the like. However, it is not limited to the scope of these illustrations as long as it has a water-soluble fluoride and can achieve the above effects. Among them, fluoroalkyl alcohols having a carbon number of 6 or less are preferred. Φ is based on the viewpoint of easy availability, and it is preferably trifluoroethanol. The amount of the water-soluble fluorine compound is preferably in the range of 〇·1 to 30% by mass in the solid state component of the material for forming a coating film, and is preferably about !. For the best. If the above blending amount range is not reached, the coating property is deteriorated. Further, if the blending amount is an excess amount, the flatness of the blending amount should not be expected. • Monoamine-containing monomer A monomer containing a guanamine group may be blended in the material for forming a coating film. -77- 200928592 The monomer containing amidino group is not particularly limited, but has a property of having high solubility to the above water-soluble resin and not causing suspension or the like. Such a guanamine group-containing monomer is preferably a guanamine compound represented by the following general formula (22).

上述一般式（22)中，R3G係氫原子、碳數1〜5之烷 基、或羥基烷基，R31係碳數1〜5之烷基，R3 2係氫原子 或甲基，z係0〜5之數。上述之中，其烷基、羥基烷基均 包含直鏈、分支鏈。 上述一般式（22)中，並以R30係氫原子、甲基、或 乙基，z係0之含醯胺基之單體爲最佳。此種含醯胺基之 單體，具體而言，例如有丙烯基醯胺、甲基丙烯基醯胺、 N，N-二甲基丙烯基醯胺、Ν,Ν —二甲基甲基丙烯基醯胺、 Ν,Ν—二乙基丙烯基醯胺、ν，Ν-二乙基甲基丙烯基醯胺、 Ν —甲基丙烯基醯胺、Ν_甲基甲基丙烯基醯胺、Ν —乙基 丙烯基醯胺、Ν—乙基甲基丙烯基醯胺等。其中，又以丙 烯基醯胺、甲基丙烯基醯胺爲最佳。 含醯胺基之單體之配合量，在被覆膜形成用材料之固 態成分中，係以0.1〜30質量％左右者爲較佳，並以1〜 -78- 200928592 15質量％左右爲最佳。如未達到0.1質量％時，難以獲得 所期望之效果，另一方面，如超過3 0質量％時，則無法期 待該配合量所應提升之效果。 ^ •至少具有氧原子及/或氮原子之雜環式化合物 在被覆膜形成用材料，亦可配合至少具有氧原子及/ 或氮原子之雜環式化合物。 此種雜環式化合物，較佳係選自：具有噁嗖二啉骨架 之化合物、具有噁唑啉骨架之化合物、具有噁唑烷酮骨架 之化合物、及具有嚼唾院二酮（oxazolidinone)骨架之化 合物中，至少1種。 具有噁唑二啉骨架之化合物，例如有下述構造式 (23)所示之噁唑啉、及其取代物。 [化 28] ❹ 〇 (23)In the above general formula (22), R3G is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group, R31 is an alkyl group having 1 to 5 carbon atoms, R3 2 is a hydrogen atom or a methyl group, and z is 0. ~ 5 number. Among the above, the alkyl group and the hydroxyalkyl group each contain a linear or branched chain. In the above general formula (22), a monomer having an R30-based hydrogen atom, a methyl group or an ethyl group, and a z-based oxime group is preferred. Such a mercapto group-containing monomer, specifically, for example, propenylamine, methacrylamide, N,N-dimethylpropenylamine, hydrazine, hydrazine-dimethylmethacryl Base amine, hydrazine, hydrazine-diethylpropenyl decylamine, ν, Ν-diethyl methacryl decylamine, hydrazine-methacryl decylamine, hydrazine-methyl methacryl decylamine, Ν Ethyl acrylamide, hydrazine-ethyl methacryl decylamine, and the like. Among them, propenylamine and methacrylamide are preferred. The amount of the amide group-containing monomer is preferably from 0.1 to 30% by mass in the solid content of the material for forming a coating film, and is preferably from 1 to -78 to 200928592 15% by mass. good. If it is less than 0.1% by mass, it is difficult to obtain the desired effect. On the other hand, if it exceeds 30% by mass, the effect that the amount of the compounding should be improved cannot be expected. ^Heterocyclic compound having at least an oxygen atom and/or a nitrogen atom The material for forming a coating film may be a heterocyclic compound having at least an oxygen atom and/or a nitrogen atom. Such a heterocyclic compound is preferably selected from the group consisting of a compound having an oxobiline skeleton, a compound having an oxazoline skeleton, a compound having an oxazolidinone skeleton, and a skeleton having an oxazolidinone skeleton. At least one of the compounds. The compound having an oxazoline structure has, for example, an oxazoline represented by the following structural formula (23), and a substituted product thereof. [化 28] ❹ 〇 (23)

NH 該取代物，例如有：上述構造式（23 )所示之噁唑啉 之碳原子或氮原子所結合之氫原子，以碳數1〜6之取代 或未取代之低級烷基、羧基、羥基、鹵基加以取代之化合 物。上述被取代低級烷基，例如有羥基烷基、（低級烷氧 基）烷基等，惟並不限於此等之範圍。 具有噁唑啉骨架之化合物，例如有下述構造式（24 - -79- 200928592 1)所示之2 —嚼哩琳、構造式（24 - 2)所不之3 — II惡哩 啉、構造式（24 - 3)所示之4-噁唑啉、及其等之取代 物。 — [化 29]The substituent of the NH is a hydrogen atom to which a carbon atom or a nitrogen atom of the oxazoline represented by the above structural formula (23) is bonded, a lower alkyl group or a carboxyl group substituted or unsubstituted with a carbon number of 1 to 6. A compound in which a hydroxyl group or a halogen group is substituted. The above substituted lower alkyl group may, for example, be a hydroxyalkyl group or a (lower alkoxy)alkyl group, but is not limited thereto. The compound having an oxazoline skeleton is, for example, a 2-carboline represented by the following structural formula (24--79-200928592 1), a 3- oxaporphyrin having a structural formula (24-2), and a structure. a 4-oxazoline represented by the formula (24-3), and the like thereof. — [Chem. 29]

(24-2) (24-3) ❹（24-1) 該取代物，例如有：具有上述構造式（24 — 1 )〜 (24 - 3)所示之噁唑啉骨架之化合物之碳原子或氮原子 所結合之氫原子，以碳數1〜6之取代或未取代之低級烷 基、羧基、羥基、鹵基加以取代之化合物。上述被取代低 級烷基，例如有羥基烷基、（低級烷氧基）烷基等，惟並 不限於此等之範圍。 © 具有該噁唑啉骨架之化合物之中’其較佳係使用下述 構造式（24 — 1—A)所示之2 —甲基2—噁唑啉。 [it 3〇](24-2) (24-3) ❹(24-1) The substituent is, for example, a carbon atom of a compound having an oxazoline skeleton represented by the above structural formula (24-1) to (24-3) Or a hydrogen atom to which a nitrogen atom is bonded, a compound substituted with a substituted or unsubstituted lower alkyl group, a carboxyl group, a hydroxyl group or a halogen group having 1 to 6 carbon atoms. The above substituted lower alkyl group may, for example, be a hydroxyalkyl group or a (lower alkoxy)alkyl group, but is not limited thereto. The compound having the oxazoline skeleton is preferably a 2-methyl-2-oxazoline represented by the following structural formula (24-1-A). [it 3〇]

'-N (24-1-A) 具有噁唑烷酮骨架之化合物，例如有：下述構造式 -80- 200928592 (25 — 1)所示之5(4) -嚼哩酮、下述構造式（25 一 2) 所示之5(2)—噁唑酮、下述構造式（25_3)所示之4 (5) —噁唑酮、下述構造式（25— 4)所示之2(5)—噁 唑酮、下述構造式（25 - 5)所示之2(3) 一噁唑酮、及 其等之取代物。 [化 3 1]'-N (24-1-A) A compound having an oxazolidinone skeleton, for example, 5(4)-choke ketone represented by the following structural formula -80-200928592 (25-1), the following structure 5(2)-oxazolone represented by the formula (25-2), 4(5)-oxazolone represented by the following structural formula (25_3), 2 shown by the following structural formula (25-4) (5) Oxazolone, a 2(3)-oxazolone represented by the following structural formula (25-5), and the like. [Chem. 3 1]

該取代物，例如有：具有上述構造式（25_1)〜 (25 - 5)所示之噁唑烷酮骨架之化合物之碳原子或氮原 子所結合之氫原子’以碳數1〜6之取代或未取代之低級 烷基、羧基、羥基、鹵基加以取代之化合物。上述被取代 低級院基’例如有經基院基、（低級院氧基）院基等，惟 並不限於此等之範圍。 具有噁唑烷二酮（oxazolidinone)骨架之化合物（或 具有2 -噁唑烷酮骨架之化合物），例如有下述構造式 (26)所示之卩惡哩院二酮（oxazolidinone)(或2 —嗯哩 烷酮）、及其取代物。 -81 - 200928592 [化 32]The substituent is, for example, a hydrogen atom in which a carbon atom or a nitrogen atom of a compound having an oxazolidinone skeleton represented by the above structural formula (25_1) to (25-5) is substituted with a carbon number of 1 to 6. Or a compound substituted with an unsubstituted lower alkyl group, a carboxyl group, a hydroxyl group or a halogen group. The above-mentioned substituted low-grade hospital bases are, for example, based on the base of the base, the base of the (lower grade hospital), and the like, but are not limited to these ranges. A compound having an oxazolidinone skeleton (or a compound having a 2-oxazolidinone skeleton), for example, an oxazolidinone (or 2) represented by the following structural formula (26) - um decyl ketone), and its substitutes. -81 - 200928592 [化32]

該取代物，例如有：上述構造式（26)所示之噁唑烷 二酮（oxazolidinone)(或惡哩院酮）之碳原子或氮 原子所結合之氫原子，以碳數1〜6之取代或未取代之低 級烷基、羧基、羥基、鹵基加以取代之化合物。上述被取 代低級烷基，例如有羥基烷基、（低級烷氧基）烷基等， 惟並不限於此等之範圍。 具有該噁唑烷二酮（oxazolidinone )骨架之化合物之 中，係以使用下述構造式（26— 1)所示之3_甲基—2 — 噁唑烷酮爲較佳。The substituent is, for example, a hydrogen atom to which a carbon atom or a nitrogen atom of an oxazolidinone (or oxazolone) represented by the above structural formula (26) is bonded, and has a carbon number of 1 to 6 A compound substituted with a substituted lower alkyl group, a carboxyl group, a hydroxyl group or a halogen group. The above substituted lower alkyl group may, for example, be a hydroxyalkyl group or a (lower alkoxy)alkyl group, but is not limited thereto. Among the compounds having the oxazolidinone skeleton, a 3-methyl-2-oxazolidinone represented by the following structural formula (26-1) is preferably used.

(26-1) ch3 © [化 33] 至少具有氧原子及/或氮原子之雜環式化合物之配合 量，相對於上述水溶性樹脂，係以1〜50質量％爲較佳， 並以3〜20質量％爲最佳。如未達1質量％時，難以獲得 所期望之效果，另一方面，超過5 0質量％時，則無法期待 -82- 200928592 該配合量所應提升之效果° •至少在同一環内具有2個以上之氮原子之雜環式化合物 被覆膜形成用材料中，亦可配合至少在同一環内具有 2個以上之氮原子之雜環式化合物。 • 此種雜環式化合物，例如有吡哩、3，5 — 一甲基啦 唑、2—吡唑啉、5—吡唑啉酮、3 —甲基一 1—苯基—5 — © 吡唑啉酮、2,3 —二甲基一1—苯基_5—吡唑啉酮、2,3一 二甲基一 4 一二甲基胺基一 1—苯基—卩比哩啉酮、本并 吡唑等之吡唑系化合物；咪唑、甲基咪唑、2,4,5 一三苯基 咪唑、4— (2—胺基乙基）咪唑、2 —胺基一3 - （4 一咪 唑基）丙酸等之咪唑系化合物；2—咪唑啉、2,4,5 -三苯 基一 2 —咪唑啉、2_ (1 -萘基甲基）一 2_咪唑啉等之咪 唑啉系化合物；咪唑烷、2 —咪唑烷酮、2，4一咪唑烷二 酮、1—甲基_2,4 —咪唑烷二酮、5-甲基—2，4一咪唑烷 〇 二酮、5 —羥基—2,4-咪唑烷二酮一 5 -羧酸、5 —脲基一 2,4 —咪唑烷二酮、2_亞胺基一 1 一甲基—4_咪唑烷酮、 2-硫代基- 4-咪唑烷酮等之咪唑烷系化合物；苯并咪 唑、2-苯基苯并咪唑、2_苯并咪唑啉酮等之苯并咪唑系 化合物；1,2 —二嗪、1,3 — 二嗪、1，4 一 二嗪、2，5 —二甲 基吡嗪等之二嗪系化合物；2,4 ( 1H,3H )嘧啶二酮' 5 一 甲基尿嘧D定、5 —乙基一 5 —苯基—4,6 —全—氫嘧啶二 酮、2 —硫代基—4 (1H,3H)—嘧啶酮、4 一亞胺基一 2 (1H，3H) —嘧啶、2,4,6 ( 1H，3H，5H) —嘧啶三酮等之氫 -83- 200928592 嘧啶系化合物；噌啉、酞嗪、喹唑啉、唾喔啉、魯米諾等 之苯并二嗪系化合物；苯并西諾啉、吩嗪、5,10一二氫吩 嗪等之二苯并二嗪系化合物；1H — 1,2,3—三唑、iH〜 1，2,4 —三唑、4 —胺基—1，2,4 —三唑等之三唑系化合物； 苯并三唑、5 —甲基苯并三唑等之苯并三唑系化合物； . 1，3,5 —三嗪、1，3,5 —三嗪一 2,4,6—三醇 ' 2,4,6 — 三甲氧 基一1，3,5 —三嗪 ' 1,3,5 —三嗓一 2,4,6 —三硫醇、1，3,5 — 0 三嗪_2,4,6 —三胺、4,6 —二胺基—1，3,5 —三嗪一 2-醇等 之三嗪系化合物等，惟並不限於此等之範圍。 其中，基於處理容易性，以及，進而容易獲得性等觀 點，其較佳係使用咪唑系化合物之單量體，並以咪唑爲最 佳。 至少在同一環内具有2個以上之氮原子之雜環式化合 物，其配合量，相對於上述水溶性樹脂，係以1〜1 5質量 %左右爲較佳，並以2〜10質量％左右爲最佳。如未達1 G 質量％時，難以獲得期望之效果，另一方面，如超過1 5質 量％時，則除了難以獲得期望之效果以外，同時還有發生 缺陷之風險提高之問題。 ^ •水溶性胺化合物 被覆膜形成用材料中，亦可配合水溶性胺化合物°藉 由使用此種水溶性胺化合物，可以防止雜質之發生、及11 整pH等。 此種水溶性胺化合物，例如有2 5。(：之水溶液中之PKa -84- 200928592 (酸解離定數）爲7.5〜13之胺類。具體而言，例如有： 單乙醇胺、二乙醇胺、三乙醇胺、2— (2 —胺乙氧基）乙 醇、N，N —二甲基乙醇胺、N，N-二乙基乙醇胺、N,N_-二 丁基乙醇胺、N—甲基乙醇胺、N -乙基乙醇胺、N — 丁基 乙醇胺、N —甲基二乙醇胺、單異丙醇胺、二異丙醇胺、 . 三異丙醇胺等之烷醇胺類；二伸乙烯三胺、三伸乙烯四 胺、伸丙基二胺、N，N —二乙基伸乙基二胺、1，4 一 丁烷二 φ 胺、N -乙基一伸乙基二胺、1,2 —丙烷二胺、1，3 —丙烷 二胺、1，6 —己烷二胺等之聚伸烷基聚胺類；2 -乙基—己 基胺、二辛基胺、三丁基胺、三丙基胺、三烯丙基胺、庚 基胺、環己基胺等之脂肪族胺類；苄基胺、二苯基胺等之 芳香族胺類；哌嗪、N-甲基-哌嗪、羥基乙基哌嗪等之 環狀胺類等。其中，係以沸點140°C以上（760mmHg )者 爲較佳，例如有單乙醇胺、三乙醇胺等即爲理想。 水溶性胺化合物之配合量，在被覆膜形成用材料之固 Ο 態成分中，係以ο·1〜30質量％左右爲較佳，並以2〜15 質量％左右爲最佳。如未達〇 · 1質量％時，會有因經時所導 • 致液體劣化之虞’另一方面’如超過30質量％時，則將有 光阻圖型之形狀惡化之可能。 •非胺系水溶性有機溶劑 被覆膜形成用材料中，亦可配合非胺系水溶性有機溶 劑。藉由使用此種非胺系水溶性有機溶劑，可抑制缺陷之 發生。 -85- 200928592 此種非胺系水溶性有機溶劑，其只要係能與水混和之 非胺系有機溶劑即可，例如有··二甲基亞颯等之亞碾類； 二甲基楓、二乙基颯、雙（2—羥基乙基）颯、四伸甲碁 楓等之楓類；N，N —二甲基甲醯胺、n —甲基甲醯胺、N，N —二甲基乙醯胺' N —甲基乙醯胺、n，N —二乙基乙醯胺等 • 之醯胺類；N -甲基—2~吡咯烷酮、N —乙基一 2 —吡咯 烷酮、N-丙基—2_吡咯烷酮、n —羥基甲基_2 —吡咯 Q 烷酮、N —羥基乙基—2 —吡咯烷酮等之內醯胺類；ι，3 -二甲基一2 —咪唑啉二酮、ι，3 —二乙基一 2 -咪唑啉二 酮、1，3 —二異丙基一 2 —咪唑啉二酮等之咪唑啉二酮類； 乙二醇、乙二醇單甲基醚、乙二醇單乙基醚 '乙二醇單丁 基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、 二乙二醇、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙 二醇單丁基醚、丙二醇、丙二醇單甲基醚、甘油、1，2 -丁二醇、1，3_ 丁二醇、2,3 — 丁二醇等之多價醇類及其衍 ❹ 生物。其中，又基於抑制缺陷發生等之觀點，係以多價醇 類及其衍生物爲較佳，並以甘油爲最佳。非胺系水溶性有 機溶劑，可使用1種或2種以上。 非胺系水溶性有機溶劑之配合量，相對於上述水溶性 ' 樹脂，係以〇 . 1〜3 0質量％左右者爲較佳，並以0 5〜1 5 質量％左右者爲最佳。如未達0.1質量％時，其缺陷減低之 效果會降低，另一方面，如超過30質量％時，在與光阻圖 型之間可能會形成混合層而不理想。 -86- 200928592 [被覆膜形成用材料（π)] 本發明之被覆膜形成用材料，係由含有水溶性樹脂及 水溶性交聯劑之水溶液所構成者，在前述本發明之圖型形 成方法中，係用以形成前述被覆膜者。 . &lt;水溶性樹脂&gt; 本發明之被覆膜形成用材料所可使用之水溶性樹脂， &lt;έ φ 其只要係室溫下可溶解於水之樹脂即可，並無特別之限 制’惟在本發明中，可含有至少1種選自：含有丙烯酸系 樹脂、乙烯系樹脂、纖維素系樹脂、醯胺系樹脂、及含噁 唑啉基之聚合物等聚合物者。 丙烯酸系樹脂，例如有以丙烯酸、丙烯酸甲酯、甲基 丙烯酸、甲基丙烯酸甲酯、Ν，Ν —二甲基丙烯基醯胺、Ν，Ν —二甲基胺丙基甲基丙烯基醯胺、Ν，Ν—二甲基胺丙基丙 烯基醯胺、Ν-甲基丙烯基醯胺、二丙酮丙烯基醯胺、ν,Ν 〇 -二甲基胺基乙基甲基丙烯酸酯、Ν,Ν—二乙基胺基乙基 甲基丙烯酸酯、Ν，Ν—二甲基胺基乙基丙烯酸酯、丙烯醯 基嗎啉等之單體爲構成成分之聚合物或共聚物。 乙烯系樹脂，例如有Ν_乙烯吡咯烷酮、乙烯咪唑啉 二酮、酢酸乙烯等之單體爲構成成分之聚合物或共聚物。 纖維素系樹脂，例如有羥基丙基甲基纖維素苯二甲酸 酯、經基丙基甲基纖維素乙酸醋苯二甲酸酯、經基丙基甲 基纖維素六氫苯二甲酸酯、羥基丙基甲基纖維素乙酸酯琥 珀酸酯、羥基丙基甲基纖維素、羥基丙基纖維素、羥基乙 -87- 200928592 基纖維素、纖維素乙酸酯六氫苯二甲酸酯、羧基甲基纖維 素、乙基纖維素、甲基纖維素等。 進而，在醯胺系樹脂之中，亦可使用水溶性者。 其中，又以乙烯系樹脂爲較佳，並以聚乙烯吡咯烷酮 或聚乙烯醇類爲最佳。 . 關於「含有噁唑啉基之聚合物」之說明，由於係與上 述[被覆膜形成用材料（i)]相同之故，在此省略。 ❹ &lt;水溶性交聯劑&gt; 水溶性交聯劑，係其構造中至少具有1個之氮原子。 此種水溶性交聯劑，其較佳係至少2個之氫原子被以羥基 垸基及/或烷氧基烷基所取代，且具有胺基及/或亞胺基 之含氮化合物。此等含氮化合物，例如有胺基之氫原子被 以經甲基或烷氧基甲基或其二者所取代之三聚氰胺系衍生 物、尿素系衍生物、鳥糞胺系衍生物、乙脈畊系衍生物、 G 苯并鳥糞胺系衍生物、琥珀醯基醯胺系衍生物、或亞胺基 之氫原子被取代之甘脲系衍生物、伸乙基尿素系衍生物 等。 此等含氮化合物之中，基於交聯反應性之觀點，係以 至少2個之氫原子以羥甲基、或（低級烷氧基）甲基、或 其二者加以取代’且具有胺基或亞胺基之苯幷鳥糞胺系衍 生物、鳥糞胺系衍生物、三聚氰胺系衍生物等之三嗪衍生 物、甘脈系衍生物、及尿素系衍生物之中之1種以上者爲 較佳。 -88- 200928592 水溶性交聯劑之配合量’在被覆膜形成用材料之固態 成分中，係以1〜99質量％左右爲較佳，並以1〜60質量 %左右爲更佳，另以1〜3 5質量％左右爲最佳。 &lt;溶劑&gt; • 本發明之被覆膜形成用材料，一般係使用含有上述水 . 溶性樹脂及水溶性交聯劑所成之水溶液。此種被覆膜形成 〇 用材料’係以3〜50質量％濃度之水溶液爲較佳，並以5 〜20質量％濃度之水溶液使用爲最佳。濃度如未達3質量 %時，光阻圖型上恐有被覆不良之問題，另一方面，如超 過5 0質量％時，則無法期待其提高濃度之相對應效果，故 基於處理性之觀點並不理想。 再者’溶劑亦可使用水及醇類系溶劑之混合溶劑。醇 類系溶劑，例如有甲基醇類、乙基醇類、丙基醇類、異丙 基醇類、甘油、乙二醇 '丙二醇、1，2 一丁二醇、i，3 — 丁 ® 二醇、2，3 一丁二醇等。此等之醇類系溶劑，係以相對於 水爲30質量％作爲上限而加以混合使用者。 &lt;任意成分&gt; 被覆膜形成用材料’除了水溶性樹脂及水溶性交聯劑 以外’亦可配合任意成分。本任意成分，由於係與上述 [被覆膜形成用材料（i)]相同之故，在此省略其說明。 本發明並不限於上述之實施型態，在請求項所示範圍 內亦可作各種之變更。亦即，在請求項所示範圍內作適當 -89- 200928592 改變之技術上手段之組合所得到之實施型態，亦包含於;^ 發明之技術範圍中。 [實施例] 以下，利用實施例進一步詳細地說明本發明，惟本發 明當然不限於此等之實施例。 〇 [實施例1] 將ArF光阻組成物「TArF—P6111」（東京應化工業 股份公司製），在8英吋矽基板上進行旋轉塗佈，並施加 14(TC、60秒之條件下之預烘烤處理（PAB )，以形成膜 厚度243 nm之光阻膜。接著，將此光阻膜，使用KrF準分 子雷射曝光機NSR— S203 (Nikon公司製、NA = 0.68、σ =〇·75 )，介由線寬250nm、間距750nm之光罩進行選擇 性曝光。然後，再以140 °C、60秒之條件進行烘烤處理 Q ( PEB)後，使用2.38質量％四甲基銨羥化物水溶液進行 30秒顯像，再以去離子水洗淨20秒。其結果，在光阻膜 上，形成了線寬270nm之線圖型以等間隔進行配置之光阻 圖型（以下，稱爲圖型（1))。 另外，將水溶性樹脂之含嚼唑啉基之聚合物「（產品 名稱）艾波克洛斯WS-5 〇〇」（日本觸媒公司製）利用水 調整成全固態成分濃度=40質量％者，而作成被覆膜形成 用材料。 將該被覆膜形成用材料，於前述圖型（1)上，以旋 -90- 200928592 轉塗佈加以均一地塗佈之後，另以130。(：、60秒之條件施 加烘烤處理’再以去離子水洗淨60秒。其結果，形成了 圖型（1 )之表面被以均一被覆膜（水溶性樹脂膜）加以 被覆之被覆線圖型。 接著，於被覆線圖型所形成之基板上，將光阻溶劑之 丙二醇單甲基醚乙酸酯（以下，稱爲r PGMEA」）進行旋 轉塗佈’再以140 °C進行60秒乾燥處理之後，在該光阻膜 爲無光罩之情形下施加全面曝光，然後，再與上述相同之 條件進行顯像’並以去離子水洗淨20秒。其結果，被覆 線圖型並無發生尺寸之變動。 [實施例2] 將上述實施例1所使用之被覆膜形成用材料，除水溶 性樹脂係使用含有噁唑啉基之聚合物「（產品名稱）艾波 克洛斯WS-500」（日本觸媒公司製）及聚乙嫌醇類 〇 「（產品名稱）PVAK30」 （BASF公司製），且調整全 固態成分濃度=1 0質量％以外，其餘均以相同之方法，進 行光阻之耐性試驗。再者，在被覆膜形成用材料Φ之水 '溶 性樹脂之固態成分比率，係相對於聚乙烯醇類，胃w卩惡_ ' 啉之聚合物爲10質量％。 其結果’與實施例1相同地’確認其被覆線圖型之尺 寸並未發生變動，推測光阻組成物在塗佈於 狀並未溶解而可維持。 -91 - 200928592 [實施例3] 將ArF光阻組成物「TArF—P6111」（東京應化工業 股份公司製），在8英吋矽基板之上進行旋轉塗佈，並施 加140°C、60秒之條件下之預烘烤處理（PAB)，以形成 膜厚度243 nm之光阻膜。接著，將此光阻膜，使用KrF準 分子雷射曝光機NSR-S203 (Nikon公司製、NA=0.68、 σ=0·75)，介由線寬250nm、間距75 0nm之光罩進行選 0 擇性曝光。然後，再以140°C、60秒之條件進行烘烤處理 (PEB )後，使用2.38質量％四甲基銨羥化物水溶液進行 30秒顯像，再以去離子水洗淨20秒。其結果，在光阻膜 上，形成了線寬270nm之線圖型以等間隔進行配置之光阻 圖型（以下，稱爲圖型（1))。 另外，將水溶性樹脂之含噁唑啉基之聚合物「（產品 名稱）艾波克洛斯WS-500」（日本觸媒公司製）利用水 調整成全固態成分濃度=10質量％者，而作成被覆膜形成 ❹ 用材料。 將此被覆膜形成用材料，在前述圖型（1)上，以旋 轉塗佈加以均一地塗佈之後，另以1 3(TC、60秒之條件施 加烘烤處理’再以去離子水洗淨60秒。其結果，形成了 圖型（1)之表面被以均一被覆膜（水溶性樹脂膜）加以 被覆之被覆線圖型。 接著’於被覆線圖型所形成之基板上，再度地將前述 光阻組成物以與上述相同之條件進行塗佈，並施加預烘烤 處理形成光阻膜。將該光阻膜在無光罩之情形下進行全面 -92- 200928592 曝光之後，以與上述相同之條件進行顯像’再以去離子水 洗淨20秒。其結果’被覆線圖型之形狀及尺寸均未見到 任何變化。 根據上述之結果’確認了使用本發明之被覆膜形成用 材料，即使第2次之光阻膜形成在形成、曝光、顯像處理 後，被覆線圖型在光阻組成物塗佈於其上前之形狀並未溶 解而可以維持。 〇 [實施例4] 將上述實施例3所使用之被覆膜形成用材料，除使用 含有噁唑啉基之聚合物「（產品名稱）艾波克洛斯」（日 本觸媒公司製）及聚乙烯醇類「（產品名稱）PVA K30」 (BASF公司製）作爲溶性樹脂，使成爲全固態成分濃度 =1 0質量°/。以外，其餘以完全相同之方法，進行光阻之耐 性試驗。再者’被覆膜形成用材料上之水溶性樹脂之固態 φ 成分比率’係相對於聚乙烯醇類，含有噁唑啉之聚合物成 爲10質量％者。 其結果’與實施例3相同地，確認其被覆線圖型之尺 寸並未發生變動，光阻組成物在塗佈於其上之前的形狀並 ' 未溶解而可維持’即使第2次之光阻膜形成在形成、曝 光、顯像處理後’被覆線圖型在光阻組成物塗佈於其上前 之形狀並未溶解而可以維持。 [比較例1 ] -93- 200928592 除不使用被覆膜形成用材料以外，其餘以與上述實施 例4相同之手法進行光阻圖型之形成、光阻組成物之耐性 試驗。其結果’第一之光阻圖型在基板上完全消失。 [比較例2] • 除將上述實施例1所使用之被覆膜形成用材料，使用 聚乙嫌醇類「（產品名稱）PVA K30」 （BASF公司 φ 製），並調整成全固態成分濃度=3 0質量％以外，其餘以 完全相同之方法，進行光阻之耐性試驗。 其結果，第一之光阻圖型在基板上完全消失。 [實施例5] 將ArF光阻組成物「TArF— P6111」（東京應化工業 股份公司製），在8英吋矽基板上進行旋轉塗佈，並施加 140°C、60秒之條件下之預烘烤處理（PAB )，以形成膜 φ 厚度243nm之光阻膜。接著，將此光阻膜，使用KrF準分 子雷射曝光機 NSR — S203 (Nikon公司製、NA = 0.68' σ =0.75 )，介由線寬250nm、間距750nm之光罩進行選擇 性曝光。然後，再以140 °C、60秒之條件進行烘烤處理 * ( PEB )後，使用2 · 3 8質量％四甲基銨羥化物水溶液進 行30秒顯像，再以去離子水洗淨20秒。其結果’在光阻 膜上，形成了線寬270nm之線圖型以等間隔進行配置之光 阻圖型（以下，稱爲圖型（1) ) ° 另外，將水溶性樹脂之含噁唑啉基之聚合物「（產品 -94- 200928592 名稱）艾波克洛斯WS-5 00」（日本觸媒公司製）利用水 調整成全固態成分濃度=20質量％者，而作成被覆膜形成 用材料。 將該被覆膜形成用材料，於前述圖型（1)上，以旋 轉塗佈使前述圖型（1)之膜厚度成爲約80 %左右之厚度 後’再以13〇°C、60秒之條件進行烘烤處理，另以去離子 水洗淨60秒。其結果，圖型（1 )之表面均以水溶性樹脂 Q 膜加以被覆。 接著，在以水溶性樹脂膜加以被覆之圖型（1 )所形 成之基板上，將光阻溶劑之丙二醇單甲基醚乙酸酯（以 下’稱爲「PGMEA」）進行旋轉塗佈，於140°c下以60 秒進行乾燥處理後，另於無光罩之情形下施加全面曝光， 然後，以與上述相同之條件進行顯像，並以去離子水洗淨 20秒。其結果，可除去上述圖型（1)，而僅形成由水溶 性樹脂所成之圖型。 ❹ [實施例6] 將ArF光阻組成物「TArF— P6111」（東京應化工業 股份公司製），在8英吋矽基板上進行旋轉塗佈，並施加 ' 140°C、60秒之條件下之預烘烤處理（PAB )，以形成膜 厚度243nm之光阻膜。接著’將此光阻膜，使用KrF準分 子雷射曝光機NSR—S203 (Nikon公司製、：ΝΑ=0·68、σ = 0.75)，介由線寬250nm、間距750nm之光罩進行選擇 性曝光。然後，再以140°C、60秒之條件進行烘烤處理 -95- 200928592 (PEB )後，使用2 · 3 8質量％四甲基銨羥化物水溶液進行 3 0秒顯像，再以去離子水洗淨2 0秒。其結果，在光阻膜 上，形成了線寬2 7 0 nm之線圖型以等間隔進行配置之光阻 圖型（以下，稱爲圖型（1))。 另外，將水溶性樹脂之聚乙烯吡咯烷酮「PVP K30」 . (BASF公司製）、水溶性交聯劑之尿素系交聯劑「N- 83 1 4」（三和化學公司製）以相對於水溶性樹脂爲5質量 ❹ % ’又將界面活性劑之月桂基二甲基胺氧化物以相對於整 體量爲500ppm所進行配合之水溶液（作成全固態成分濃 度=5質量％)，而調製該被覆膜形成用材料。 將此被覆膜形成用材料，在前述圖型（1)之上，以 旋轉塗佈使前述圖型（1)之膜厚度成爲約80 %左右之厚 度後，施加1 3 0 °C、6 0秒之條件下之烘烤處理，再以去離 子水洗淨60秒。其結果，圖型（1)之表面均以被覆膜 (水溶性樹脂膜）加以被覆，而形成被覆線圖型。 ❹ 接著’在被覆線圖型所形成之基板上，將光阻溶劑之 丙二醇單甲基醚乙酸酯（以下，亦稱爲「PGMEA」）進行 旋轉塗佈’再以140°C進行60秒乾燥處理之後，在該光阻 膜爲無光罩之情形下施加全面曝光，然後，再與上述相同 之條件進行顯像，以去離子水洗淨2 0秒。其結果，可除 去上述圖型（1 )，而僅形成由水溶性樹脂所成之圖型。 [產業上之利用可能性] 根據本發明，不僅在半導體產業之IC製作，即使在 -96- 200928592 所謂奈米科技領域上亦可進行廣泛產業上之利用。 再者，在用以實施發明之最佳型態中所例示之具體實 施態樣或實施例，係用以使本發明之技術內容爲明確者， 惟本發明不應被狹義地解釋爲限於此種具體例，在本發明 之精神及申請專利範圍所記載之範圍內，係可以作各種變 更而實施者。 0 【圖式簡單說明】 [圖1]係用以說明本發明之圖型形成方法之較佳實施 型態的槪略步驟圖。 [圖2]係用以說明本發明之圖型形成方法之另一較佳 實施型態的槪略步驟圖。 [圖3]係用以說明傳統之雙重曝影法之一例的槪略步 驟圖。 φ 【主要元件符號說明】 1 :支持體 2 :第一之光阻膜 3 :第一之光阻圖型 4 :被覆膜 5 :被覆圖型 6 :第二之光阻膜 7:第二之光阻圖型 21 :支持體 -97- 200928592 22 ： 光阻膜 23 ： 光阻圖型 24a :被覆膜形成用材料 24 : 被覆膜 25 : 被覆圖型（由被覆膜成分所成之圖型 10 1 :基板 102 :下層膜 〇 103 :硬光罩 104 =光阻圖型 105 :光罩 106 :光阻圖型 ❹ -98-(26-1) ch3 © The compounding amount of the heterocyclic compound having at least an oxygen atom and/or a nitrogen atom is preferably 1 to 50% by mass based on the water-soluble resin, and is 3 ~20% by mass is the best. If it is less than 1% by mass, it is difficult to obtain the desired effect. On the other hand, when it exceeds 50% by mass, it is impossible to expect -82-200928592. The effect of the blending amount should be improved. • At least 2 in the same ring. Further, a heterocyclic compound having at least two or more nitrogen atoms in the same ring may be blended in the material for forming a heterocyclic compound coating film of the above nitrogen atom. • such heterocyclic compounds, for example, pyridinium, 3,5-monomethyloxazole, 2-pyrazoline, 5-pyrazolone, 3-methyl-1-phenyl-5--pyridyl Oxazolinone, 2,3-dimethyl-1,4-phenyl-5-pyrazolone, 2,3-dimethyl-4-tetramethylamino-1-phenyl-pyridinium porphyrin Pyrazole-based compounds such as benzopyrazole; imidazole, methylimidazole, 2,4,5-triphenylimidazole, 4-(2-aminoethyl)imidazole, 2-amino-amino-3 - (4 Imidazole-based compound of monoimidazolyl)propionic acid; imidazoline of 2-imidazoline, 2,4,5-triphenyl-2-imidazoline, 2-(1-naphthylmethyl)-2-imidazoline a compound; an imidazolidine, a 2-imidazolidinone, a 2,4-imidazolidinedione, a 1-methyl-2,4-imidazolidinedione, a 5-methyl-2,4-imidazolidinedione, 5-Hydroxy-2,4-imidazolidinedione-5-carboxylic acid, 5-ureido- 2,4-imidazolidinedione, 2-imino-1-1-methyl-4-imidazolidinone, 2 -imidazolidine compounds such as thio- 4-imidazolidinone; benzimidazole, 2-phenylbenzimidazole, 2-benzimidazolidinone a benzimidazole compound; a diazine compound such as 1,2-diazine, 1,3-diazine, 1,4-diazine, 2,5-dimethylpyrazine; 2,4 (1H, 3H)pyrimidinedione' 5 monomethyluridine D, 5-ethyl-5-phenyl-4,6-per-hydropyrimidinedione, 2-thioxo-4(1H,3H)-pyrimidine Ketone, 4-iminoamino-2(1H,3H)-pyrimidine, 2,4,6 (1H,3H,5H)-pyrimidinetrione, etc. Hydrogen-83-200928592 Pyrimidine compounds; porphyrins, pyridazines, a benzodiazide compound such as quinazoline, salivary porphyrin or luminol; a dibenzodiazine compound such as benzoxanol, phenazine or 5,10-dihydrophenazine; 1H-1 , a triazole compound such as 2,3-triazole, iH~1,2,4-triazole, 4-amino-1,2,4-triazole; benzotriazole, 5-methylbenzene a benzotriazole compound such as triazole; . 1,3,5-triazine, 1,3,5-triazine- 2,4,6-triol' 2,4,6-trimethoxy-1 ,3,5-triazine' 1,3,5-tris- 2,4,6-trithiol, 1,3,5-0 triazine 2,4,6-triamine, 4,6 — Diamine- 1,3,5-triazine-2-alcohol, etc. Triazine-based compounds, but are not limited to the scope of these. Among them, it is preferred to use a monomeric body of an imidazole-based compound, and it is preferable to use imidazole, based on the ease of handling and further availability. The heterocyclic compound having at least two nitrogen atoms in the same ring is preferably used in an amount of from 1 to 15% by mass, and preferably from 2 to 10% by mass, based on the water-soluble resin. For the best. If it is less than 1 G mass%, it is difficult to obtain the desired effect. On the other hand, if it exceeds 15 mass%, it is difficult to obtain the desired effect, and there is also a problem that the risk of occurrence of defects increases. ^ Water-soluble amine compound The material for forming a coating film may be blended with a water-soluble amine compound. By using such a water-soluble amine compound, it is possible to prevent the occurrence of impurities and the pH of the liquid. Such a water-soluble amine compound has, for example, 25. (In the aqueous solution, PKa-84-200928592 (acid dissociation number) is an amine of 7.5 to 13. Specifically, for example, monoethanolamine, diethanolamine, triethanolamine, 2-(2-amine ethoxylate) Ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N- Alkanolamines such as methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine; diethylenetriamine, triamethylenetetraamine, propyldiamine, N, N-diethylethylenediamine, 1,4-butane bis-amine, N-ethyl-extended ethyldiamine, 1,2-propanediamine, 1,3-propanediamine, 1,6- a polyalkylene amine such as hexanediamine; 2-ethylhexylamine, dioctylamine, tributylamine, tripropylamine, triallylamine, heptylamine, cyclohexylamine Or an aliphatic amine; an aromatic amine such as a benzylamine or a diphenylamine; a cyclic amine such as piperazine, N-methyl-piperazine or hydroxyethylpiperazine; Boiling point above 140 ° C (760 mmHg) The amount of the water-soluble amine compound is preferably ο·1 to 30% by mass in the solid-state component of the material for forming a coating film, which is preferably a monoethanolamine or a triethanolamine. Preferably, it is preferably about 2 to 15% by mass. If it is less than 1% by mass, there may be a deterioration of the liquid caused by the passage of time, and if it exceeds 30% by mass, The shape of the photoresist pattern may be deteriorated. • A non-amine water-soluble organic solvent coating film forming material may be blended with a non-amine water-soluble organic solvent. The organic solvent can suppress the occurrence of defects. -85- 200928592 The non-amine-based water-soluble organic solvent is not limited to a non-amine organic solvent which can be mixed with water, for example, dimethyl hydrazine or the like. Sub-milling; Maple such as dimethyl maple, diethyl hydrazine, bis(2-hydroxyethyl) fluorene, tetra-extension thyroxine; N, N-dimethylformamide, n-methyl Indoleamine, N,N-dimethylacetamide 'N-methylacetamide, n,N-diethylacetamide, etc. Amidoxime; N-methyl-2~pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, n-hydroxymethyl-2-pyrrole Q-alkanone, N-hydroxyethyl- 2 - an internal amide such as pyrrolidone; i, 3, dimethyl-2-imidazolidinone, iota, 3-diethyl-2-imidazolidinone, 1,3 - diisopropyl-2 - imidazolinediones such as imidazolidinone; ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether 'ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate Ester, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl Polyvalent alcohols such as phenyl ether, glycerin, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol, and their derivatives. Among them, based on the viewpoint of suppressing the occurrence of defects, etc., polyvalent alcohols and derivatives thereof are preferred, and glycerin is preferred. The non-amine-based water-soluble organic solvent may be used alone or in combination of two or more. The amount of the non-amine-based water-soluble organic solvent is preferably from about 1 to 30% by mass based on the above-mentioned water-soluble resin, and is preferably from about 0 5 to about 15 % by mass. If it is less than 0.1% by mass, the effect of reducing the defects is lowered. On the other hand, if it exceeds 30% by mass, a mixed layer may be formed between the photoresist pattern and the photoresist pattern. -86-200928592 [Material for forming a coating film (π)] The material for forming a coating film of the present invention is composed of an aqueous solution containing a water-soluble resin and a water-soluble crosslinking agent, and is formed in the pattern of the present invention. In the method, it is used to form the aforementioned coating film. &lt;Water-Soluble Resin&gt; The water-soluble resin which can be used for the material for forming a coating film of the present invention, &lt; έ φ is not particularly limited as long as it is a resin which can be dissolved in water at room temperature. In the present invention, at least one selected from the group consisting of polymers containing an acrylic resin, an ethylene resin, a cellulose resin, a guanamine resin, and a oxazoline group-containing polymer may be contained. Acrylic resin, for example, acrylic acid, methyl acrylate, methacrylic acid, methyl methacrylate, hydrazine, hydrazine-dimethylpropenyl decylamine, hydrazine, hydrazine-dimethylaminopropyl propyl methacryl hydrazine Amine, hydrazine, hydrazine-dimethylaminopropylpropenyl decylamine, hydrazine-methylpropenyl decylamine, diacetone acrylamide, ν, hydrazine-dimethylaminoethyl methacrylate, A monomer or a copolymer of ruthenium-diethylaminoethyl methacrylate, hydrazine, hydrazine-dimethylaminoethyl acrylate or acryloyl morpholine is a constituent polymer or copolymer. Examples of the vinyl resin include a polymer or a copolymer of a monomer such as fluorene-vinylpyrrolidone, ethylene imidazolinedione or ethylene phthalate. Cellulose resin, for example, hydroxypropylmethylcellulose phthalate, propylmethylcellulose acetate phthalate, propylmethylcellulose hexahydrophthalic acid Ester, hydroxypropyl methylcellulose acetate succinate, hydroxypropylmethylcellulose, hydroxypropylcellulose, hydroxyethyl-87-200928592-based cellulose, cellulose acetate hexahydrophthalate Acid ester, carboxymethyl cellulose, ethyl cellulose, methyl cellulose, and the like. Further, among the amide-based resins, water-soluble ones can also be used. Among them, a vinyl resin is preferred, and polyvinylpyrrolidone or polyvinyl alcohol is preferred. The description of the "oxazoline group-containing polymer" is the same as the above-mentioned [coating film forming material (i)], and is omitted here. ❹ &lt;Water-soluble cross-linking agent&gt; The water-soluble cross-linking agent has at least one nitrogen atom in its structure. Such a water-soluble crosslinking agent is preferably a nitrogen-containing compound having at least two hydrogen atoms substituted with a hydroxy fluorenyl group and/or an alkoxyalkyl group and having an amine group and/or an imine group. These nitrogen-containing compounds, for example, a hydrogen atom having an amine group, are substituted with a methyl group or an alkoxymethyl group or a melamine-based derivative, a urea-based derivative, a guanamine derivative, and an ethylene vein. A cultivated derivative, a G benzoguanamine derivative, an amber mercaptoamine derivative, or a glycoluril derivative or an extended ethyl urea derivative in which a hydrogen atom of an imine group is substituted. Among these nitrogen-containing compounds, based on crosslinking reactivity, at least two hydrogen atoms are substituted with a hydroxymethyl group, or a (lower alkoxy)methyl group, or both thereof, and have an amine group. Or one or more of a triazine derivative, a glycine derivative, and a urea derivative such as an imine benzoguanamine derivative, a guanamine derivative, or a melamine derivative. It is better. -88-200928592 The amount of the water-soluble crosslinking agent is preferably from about 1 to 99% by mass, more preferably from about 1 to 60% by mass, based on the solid content of the material for forming a coating film, and more preferably 1 to 3 5 mass% is the best. &lt;Solvent&gt; • The material for forming a coating film of the present invention is generally an aqueous solution containing the above-mentioned water, a soluble resin, and a water-soluble crosslinking agent. The coating material for forming a coating material is preferably an aqueous solution having a concentration of 3 to 50% by mass, and is preferably used in an aqueous solution having a concentration of 5 to 20% by mass. When the concentration is less than 3% by mass, there is a problem that the photoresist pattern is poorly coated. On the other hand, if it exceeds 50% by mass, the corresponding effect of increasing the concentration cannot be expected, so based on the viewpoint of handling property. Not ideal. Further, the solvent may be a mixed solvent of water and an alcohol solvent. Alcohol-based solvents such as methyl alcohols, ethyl alcohols, propyl alcohols, isopropyl alcohols, glycerin, ethylene glycol 'propylene glycol, 1,2-butylene glycol, i, 3-butyl® Glycol, 2,3-butanediol, and the like. These alcohol-based solvents are mixed with the upper limit of 30% by mass based on water. &lt;Optional component&gt; The material for forming a coating film 'may be mixed with an optional component other than the water-soluble resin and the water-soluble crosslinking agent. This optional component is the same as the above-mentioned [substrate for forming a coating film (i)], and the description thereof is omitted here. The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims. That is, the implementation form obtained by combining the technical means of the appropriate -89-200928592 change within the scope of the claims is also included in the technical scope of the invention. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is of course not limited to the examples.实施 [Example 1] An ArF photoresist composition "TArF-P6111" (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was spin-coated on a 8-inch substrate, and 14 (TC, 60 seconds) was applied. Prebaking treatment (PAB) to form a photoresist film having a film thickness of 243 nm. Next, this photoresist film was subjected to KrF excimer laser exposure machine NSR-S203 (manufactured by Nikon, NA = 0.68, σ = 〇·75 ), selective exposure by a mask with a line width of 250 nm and a pitch of 750 nm. Then, after baking (QB) at 140 ° C for 60 seconds, use 2.38 mass % tetramethyl The ammonium hydroxide aqueous solution was developed for 30 seconds, and then washed with deionized water for 20 seconds. As a result, a photoresist pattern having a line width of 270 nm and arranged at equal intervals was formed on the photoresist film (hereinafter, In addition, the chelate-based polymer of the water-soluble resin "(product name) Apollo WS-5 〇〇" (made by Nippon Shokubai Co., Ltd.) is adjusted with water. When the solid content concentration is 40% by mass, the material for forming a coating film is formed. On the above pattern (1), after application by spin-90-200928592 transfer coating, it is uniformly coated with 130. (:, 60 seconds to apply baking treatment) and then washed with deionized water 60 As a result, a coated line pattern in which the surface of the pattern (1) is covered with a uniform coating film (water-soluble resin film) is formed. Next, a photoresist is formed on the substrate formed by the covered pattern. The solvent propylene glycol monomethyl ether acetate (hereinafter referred to as r PGMEA) was spin-coated and then dried at 140 ° C for 60 seconds, and then applied to the photoresist film without a mask. After exposure, the image was developed under the same conditions as above and washed with deionized water for 20 seconds. As a result, the size of the covered line pattern did not change. [Example 2] The above Example 1 was used. In addition to the water-soluble resin, a polymer containing an oxazoline group ("product name" Apoclos WS-500" (manufactured by Nippon Shokubai Co., Ltd.) and polyethyl alcohol 〇" (product name) PVAK30" (made by BASF), and adjusted all solid The resistivity test was carried out in the same manner except for the component concentration of 10% by mass. Further, the solid content ratio of the water-soluble resin in the film forming material Φ was relative to polyvinyl alcohol. In the same manner as in the first embodiment, it was confirmed that the size of the coated line pattern did not change, and it was estimated that the photoresist composition was applied. -91 - 200928592 [Example 3] The ArF photoresist composition "TArF-P6111" (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was spin-coated on a 8-inch substrate. A prebaking treatment (PAB) at 140 ° C for 60 seconds was applied to form a photoresist film having a film thickness of 243 nm. Next, this photoresist film was selected using a KrF excimer laser exposure machine NSR-S203 (manufactured by Nikon Corporation, NA=0.68, σ=0·75) through a mask having a line width of 250 nm and a pitch of 75 nm. Selective exposure. Then, after baking treatment (PEB) at 140 ° C for 60 seconds, development was carried out for 30 seconds using a 2.38 mass % tetramethylammonium hydroxide aqueous solution, followed by washing with deionized water for 20 seconds. As a result, a photoresist pattern (hereinafter referred to as a pattern (1)) in which line patterns having a line width of 270 nm are arranged at equal intervals is formed on the resist film. In addition, the oxazoline group-containing polymer of the water-soluble resin "(product name) Apoclos WS-500" (manufactured by Nippon Shokubai Co., Ltd.) is adjusted to have an all-solid component concentration = 10% by mass. The coating film forms a material for use. This coating film-forming material was uniformly applied by spin coating on the above-mentioned pattern (1), and then subjected to baking treatment under the conditions of TC, 60 seconds, and deionized water. After washing for 60 seconds, the surface of the pattern (1) is covered with a uniform coating film (water-soluble resin film). Next, on the substrate formed by the covered pattern, The photoresist composition is coated again under the same conditions as described above, and a prebaking treatment is applied to form a photoresist film. After the photoresist film is exposed to a full mask -92-200928592, The image was developed under the same conditions as above and washed again with deionized water for 20 seconds. As a result, no change was observed in the shape and size of the covered wire pattern. According to the above results, it was confirmed that the use of the present invention was confirmed. In the material for forming a film, even if the second photoresist film is formed, exposed, and developed, the shape of the coating line before the photoresist composition is applied thereon is not dissolved and can be maintained. [Embodiment 4] The above Embodiment 3 is used. In addition to the oxazoline group-containing polymer "(product name) Apoclos" (manufactured by Nippon Shokubai Co., Ltd.) and polyvinyl alcohol "(product name) PVA K30" (BASF Corporation) As a solvent resin, the resistivity test was carried out in the same manner as the all-solid component concentration = 10 mass%. Further, the water-soluble resin on the material for forming a film was used. The solid φ component ratio ' is 10% by mass based on the polyvinyl alcohol and the oxazoline-containing polymer. As a result, it was confirmed that the size of the covered line pattern did not change as in Example 3. The shape of the resist composition before being applied thereto is 'undissolved and can be maintained'. Even if the second photoresist film is formed after formation, exposure, and development processing, the coated pattern is coated on the photoresist composition. The shape of the upper surface was not dissolved and was maintained. [Comparative Example 1] -93- 200928592 The formation of the photoresist pattern was carried out in the same manner as in the above-described Example 4 except that the material for forming a coating film was not used. Light resistance composition As a result, the first photoresist pattern disappeared completely on the substrate. [Comparative Example 2] • In addition to the material for forming a coating film used in the above Example 1, a polyethyl alcohol was used. (product name) PVA K30" (manufactured by BASF Corporation φ), and adjusted to the total solid content concentration = 30% by mass, the photoresist resistance test was carried out in exactly the same way. As a result, the first photoresist pattern was obtained. The pattern completely disappeared on the substrate. [Example 5] An ArF photoresist composition "TArF-P6111" (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was spin-coated on a 8-inch substrate and 140 ° C was applied thereto. Prebaking treatment (PAB) under conditions of 60 seconds to form a photoresist film having a film thickness of 243 nm. Next, this photoresist film was selectively exposed by a KrF quasi-laser laser exposure machine NSR-S203 (manufactured by Nikon Corporation, NA = 0.68' σ = 0.75) through a mask having a line width of 250 nm and a pitch of 750 nm. Then, after baking treatment (PEB) at 140 ° C for 60 seconds, the image was developed for 30 seconds using an aqueous solution of 2 · 38 % by mass of tetramethylammonium hydroxide, and then washed with deionized water. second. As a result, a photoresist pattern in which a line pattern having a line width of 270 nm is arranged at equal intervals is formed on the photoresist film (hereinafter, referred to as pattern (1)). Further, the oxazole containing the water-soluble resin is formed. "Polyphenyl-based polymer" (product-94-200928592 name) Apollo WS-5 00" (manufactured by Nippon Shokubai Co., Ltd.) is used to form a coating film by adjusting the concentration of all solid components to 20% by mass with water. material. The material for forming a coating film is spin-coated on the pattern (1) so that the film thickness of the pattern (1) is about 80%, and then 13 〇 ° C, 60 seconds. The conditions were baked and washed with deionized water for 60 seconds. As a result, the surface of the pattern (1) was coated with a water-soluble resin Q film. Next, a propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") of a photoresist solvent is spin-coated on a substrate formed by a pattern (1) coated with a water-soluble resin film. After drying at 140 ° C for 60 seconds, full exposure was applied in the absence of a reticle, and then development was carried out under the same conditions as above, and washed with deionized water for 20 seconds. As a result, the above pattern (1) can be removed, and only a pattern formed of a water-soluble resin can be formed.实施 [Example 6] An ArF photoresist composition "TArF-P6111" (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was spin-coated on a 8-inch substrate and subjected to '140 ° C, 60 seconds. The prebaking treatment (PAB) was performed to form a photoresist film having a film thickness of 243 nm. Then, the photoresist film was selectively bonded using a KrF excimer laser exposure machine NSR-S203 (manufactured by Nikon Co., Ltd.: ΝΑ=0.68, σ = 0.75) through a mask having a line width of 250 nm and a pitch of 750 nm. exposure. Then, after baking treatment at -140 ° C for 60 seconds, -95-200928592 (PEB), the image was developed for 30 seconds using an aqueous solution of 2 · 38 % by mass of tetramethylammonium hydroxide, and then deionized. Wash with water for 20 seconds. As a result, a photoresist pattern (hereinafter referred to as a pattern (1)) in which line patterns having a line width of 270 nm are arranged at equal intervals is formed on the resist film. In addition, the polyvinylpyrrolidone of the water-soluble resin "PVP K30" (manufactured by BASF Corporation) and the urea-based crosslinking agent "N-83 1 4" (manufactured by Sanwa Chemical Co., Ltd.) of the water-soluble crosslinking agent are relatively water-soluble. The resin was made up to 5 mass % ' %', and the surfactant was added with an aqueous solution of 95 ppm of the total amount of the lauryl dimethylamine oxide (the total solid content concentration = 5 mass %) to prepare the coating. A material for film formation. The material for forming a coating film is applied to the pattern (1) by spin coating so that the film thickness of the pattern (1) is about 80%, and then applied at 130 ° C, 6 The baking treatment was carried out under conditions of 0 seconds, and then washed with deionized water for 60 seconds. As a result, the surface of the pattern (1) is covered with a coating film (water-soluble resin film) to form a covered line pattern. ❹ Next, 'the propylene glycol monomethyl ether acetate (hereinafter also referred to as "PGMEA") of the photoresist is spin-coated on the substrate formed by the covered pattern, and then subjected to 140 ° C for 60 seconds. After the drying treatment, full exposure was applied while the photoresist film was a mask, and then developed under the same conditions as above, and washed with deionized water for 20 seconds. As a result, the above pattern (1) can be removed, and only a pattern formed of a water-soluble resin can be formed. [Industrial Applicability] According to the present invention, not only in the semiconductor industry, but also in the so-called nanotechnology field of -96-200928592, it can be used in a wide range of industries. In addition, the specific embodiments or examples exemplified in the best mode for carrying out the invention are intended to clarify the technical content of the present invention, but the invention should not be construed as being limited thereto. The specific examples are within the scope of the spirit of the invention and the scope of the claims. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] is a schematic diagram showing a preferred embodiment of a pattern forming method of the present invention. Fig. 2 is a schematic view showing the steps of another preferred embodiment of the pattern forming method of the present invention. [Fig. 3] is a schematic diagram showing an example of a conventional double exposure method. φ [Description of main component symbols] 1 : Support 2 : First photoresist film 3 : First photoresist pattern 4 : Coating film 5 : Cover pattern 6 : Second photoresist film 7 : Second Photoresist pattern 21 : Support -97- 200928592 22 : Photoresist film 23 : Photoresist pattern 24a : Material for forming a film 24 : Coating film 25 : Coating pattern (by coating film composition) Figure 10 1 : Substrate 102 : Lower film 〇 103 : Hard mask 104 = photoresist pattern 105 : reticle 106 : photoresist pattern ❹ -98-

Claims (1)

200928592 十、申請專利範圍 1. 一種圖型形成方法，其特徵係包含： - 在支持體上，塗佈光阻組成物而形成光阻膜之步驟、 及 將該光阻膜介由光罩圖型進行選擇性曝光、顯像而形 . 成光阻圖型之步驟、及 __ 在該光阻圖型之表面上，使用被覆膜形成用材料而形 f) 成被覆膜之步驟、及 進而，以下之（i )或（ii )之步驟； (i)在以該被覆膜所被覆之該光阻圖型形成之該支 持體上，塗佈第二之光阻組成物而形成第二之光阻膜之步 驟、及 將該第二之光阻膜介由第二之光罩圖型進行選擇性曝 光、顯像而形成第二之光阻圖型之步驟 (Π )將以該被覆膜所被覆之該光阻圖型進行曝光、 〇 顯像，而形成由該被覆膜成分所成之圖型之步驟。 2. 如申請專利範圍第1項之圖型形成方法，其中係包 含： 在支持體上’塗佈第一之光阻組成物而形成第一之光 阻膜之步驟、及 將該第一之光阻膜介由第一之光罩圖型進行選擇性曝 光、顯像而形成第一之光阻圖型之步驟、及 在該第一之光阻圖型之表面上，使用水溶性樹脂組成 物所成之被覆膜形成用材料形成被覆膜，並形成被覆圖型 -99- 200928592 之步驟、及 在該被覆圖型形成之該支持體上塗佈第二之光阻組成 -物並形成第二之光阻膜之步驟、及 將該第二之光阻膜介由第二之光罩圖型進行選擇性曝 光、顯像而形成第二之光阻圖型之步驟。 - 3 .如申請專利範圍第2項之圖型形成方法，其中該被 . 覆膜形成用材料係由含有水溶性樹脂所成之水溶液構成 〇 者’且該水溶性樹脂係包含含有噁唑啉基之聚合物。 4 · 一種被覆膜形成用材料，其係由含有水溶性樹脂所 成之水溶液構成之被覆膜形成用材料，其特徵爲該水溶性 樹脂係包含至少含有噁唑啉基之聚合物。 5.如申請專利範圍第4項之被覆膜形成用材料，其中 其係於申請專利範圍第2項之圖型形成方法中所使用者。 6 ·如申請專利範圍第2項之圖型形成方法，其中該被 覆膜形成用材料係由至少含有水溶性樹脂及水溶性交聯劑 © 所成之水溶液構成者。 7. 如申g靑專利範圍第6項之圖型形成方法，其中該水 溶性樹脂係含有選自丙烯酸系樹脂、乙烯系樹脂、纖維素 系樹脂、醯胺系樹脂、及含有嚼哩啉基之聚合物所成群之 至少1種之樹脂者。 8. 如申請專利範圍第6項之圖型形成方法，其中該水 溶性樹脂係含有選自聚乙烯吡咯烷酮、及聚乙烯醇類所成 群之至少1種之樹脂者。 9_如申請專利範圍第6〜8項中任一項之圖型形成方 -100- 200928592 法’其中該水溶性交聯劑係含有選自三嗪衍生物、甘脲衍 生物、及尿素衍生物所成群之至少1種之物質者。 - 1〇. 一'種被覆膜形成用材料，其係申請專利範圍第2 項之圖型形成方法上使用之被覆膜形成材料，其特徵係由 至少含有水溶性樹脂及水溶性交聯劑所成之水溶液構成 . 者。 . 11.如申請專利範圍第1項之圖型形成方法，其中包 ❹ 含： 在支持體上’塗佈正型光阻組成物而形成光阻膜之步 驟、及 將該光阻膜介由光罩圖型進行選擇性曝光、顯像而形 成光阻圖型之步驟、及 在該光阻圖型之表面上’使用水溶性樹脂組成物所成 之被覆膜形成用材料而形成被覆膜之步驟、及 將以該被覆膜所被覆之該光阻圖型進行曝光、顯像而 Ο 形成由該 被覆膜成分所成之圖型之步驟。 12.如申請專利範圍第11項之圖型形成方法，其中該 ， 被覆膜形成用材料係由含有水溶性樹脂所成之水溶液構成 者，且該水溶性樹脂係包含含有噁唑啉基之聚合物。 13_ —種被覆膜形成用材料，其係由含有水溶性樹脂 所成之水溶液構成之被覆膜形成用材料，其特徵爲該水溶 性樹脂係包含至少含有噁唑啉基之聚合物。 14.如申請專利範圍第13項之被覆膜形成用材料，其 中其係於申請專利範圍第11項之圖型形成方法中所使用 -101 - 200928592200928592 X. Patent application scope 1. A pattern forming method, characterized in that: - a step of coating a photoresist composition to form a photoresist film on a support, and passing the photoresist film through a mask pattern a step of selectively exposing and developing a pattern, forming a photoresist pattern, and __ a step of forming a coating film by using a material for forming a coating film on the surface of the photoresist pattern, And further, the step (i) or (ii) below; (i) applying a second photoresist composition to the support formed on the photoresist pattern covered by the coating film a step of the second photoresist film and a step of selectively exposing and developing the second photoresist film to form a second photoresist pattern via the second mask pattern (将) The photoresist pattern covered by the coating film is subjected to exposure and 〇 development to form a pattern formed by the coating film component. 2. The method of forming a pattern according to the first aspect of the patent application, comprising: a step of: coating a first photoresist composition to form a first photoresist film on the support, and the step of forming the first The photoresist film is selectively exposed and developed by the first mask pattern to form a first photoresist pattern, and is formed of a water-soluble resin on the surface of the first photoresist pattern. Forming a coating film by the material for forming a coating film, forming a coating pattern of -99-200928592, and applying a second photoresist composition to the support formed on the coating pattern a step of forming a second photoresist film and a step of selectively exposing and developing the second photoresist film via the second mask pattern to form a second photoresist pattern. The method of forming a pattern according to the second aspect of the patent application, wherein the material for forming a film is composed of an aqueous solution containing a water-soluble resin, and the water-soluble resin contains oxazoline. Base polymer. 4. A material for forming a coating film, which is a material for forming a coating film comprising an aqueous solution containing a water-soluble resin, characterized in that the water-soluble resin contains a polymer containing at least an oxazoline group. 5. The material for forming a film according to item 4 of the patent application, which is the user of the pattern forming method of the second item of the patent application. [6] The pattern forming method according to the second aspect of the invention, wherein the material for forming a coating film is composed of an aqueous solution containing at least a water-soluble resin and a water-soluble crosslinking agent. 7. The method for forming a pattern according to item 6 of the patent application, wherein the water-soluble resin contains an acrylic resin, an ethylene resin, a cellulose resin, a guanamine resin, and a chewing porphyrin group. At least one type of resin in which the polymers are grouped. 8. The pattern forming method according to the sixth aspect of the invention, wherein the water-soluble resin contains at least one resin selected from the group consisting of polyvinylpyrrolidone and polyvinyl alcohol. The method of forming a method according to any one of claims 6 to 8 wherein the water-soluble crosslinking agent is selected from the group consisting of a triazine derivative, a glycoluril derivative, and a urea derivative. At least one of the groups of substances. - a coating film forming material which is a coating film forming material used in the pattern forming method of the second application of the patent application, characterized in that it contains at least a water-soluble resin and a water-soluble crosslinking agent. The resulting aqueous solution constitutes. 11. The method for forming a pattern according to claim 1, wherein the package comprises: a step of forming a photoresist film by coating a positive photoresist composition on the support, and interposing the photoresist film The mask pattern is subjected to selective exposure and development to form a photoresist pattern, and a coating film forming material is formed on the surface of the photoresist pattern by using a water-soluble resin composition. The step of forming a film and exposing and developing the photoresist pattern covered by the coating film to form a pattern formed by the coating film component. 12. The pattern forming method according to claim 11, wherein the material for forming a coating film is composed of an aqueous solution containing a water-soluble resin, and the water-soluble resin contains an oxazoline group. polymer. A material for forming a coating film, which is a material for forming a coating film comprising an aqueous solution containing a water-soluble resin, characterized in that the water-soluble resin contains a polymer containing at least an oxazoline group. 14. The material for forming a coating film according to claim 13 of the patent application, wherein the method for forming a pattern according to item 11 of the patent application scope is used -101 - 200928592 15. 如申請專利範圍第n項之圖型形成方法，其中該 被覆膜形成用材料係由至少含有水溶性樹脂及水溶性交聯 劑所成之水溶液構成者。 16. 如申請專利範圍第15項之圖型形成方法，其中該 • 水溶性樹脂係含有選自丙烯酸系樹脂、乙烯系樹脂、纖維 ， 素系樹脂、醯胺系樹脂、及含有噁唑啉基之聚合物所成群 〇 之至少1種之樹脂者。 17. 如申請專利範圍第15項之圖型形成方法，其中該 水溶性樹脂係含有選自聚乙烯吡咯烷酮、及聚乙烯醇類所 成群之至少1種之樹脂者。 18. 如申請專利範圍第15〜17項中任一項之圖型形成 方法’其中該水溶性交聯劑係含有選自三嗪衍生物、甘脲 衍生物、及尿素衍生物所成群之至少1種之物質者。 19. 一種被覆膜形成用材料，其係申請專利範圍第η © 項之圖型形成方法上使用之被覆膜形成材料，其特徵係由 至少含有水溶性樹脂及水溶性交聯劑所成之水溶液構成 者。 -102-15. The method for forming a pattern according to item n of the patent application, wherein the material for forming a coating film is composed of an aqueous solution containing at least a water-soluble resin and a water-soluble crosslinking agent. 16. The method for forming a pattern according to claim 15, wherein the water-soluble resin is selected from the group consisting of an acrylic resin, a vinyl resin, a fiber, a resin, a guanamine resin, and an oxazoline group. The resin is a group of at least one type of resin. 17. The pattern forming method according to claim 15, wherein the water-soluble resin contains at least one resin selected from the group consisting of polyvinylpyrrolidone and polyvinyl alcohol. The method for forming a pattern of any one of the above-mentioned items of the present invention, wherein the water-soluble crosslinking agent contains at least a group selected from the group consisting of a triazine derivative, a glycoluril derivative, and a urea derivative. One of the substances. A material for forming a coating film, which is a coating film forming material used in a method for forming a pattern of the invention of the present invention, which is characterized in that it comprises at least a water-soluble resin and a water-soluble crosslinking agent. The composition of the aqueous solution. -102-
TW097130829A 2007-08-28 2008-08-13 Method for forming patterns and material for coating film TW200928592A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI408502B (en) * 2009-08-05 2013-09-11 Shinetsu Chemical Co Pattern forming process, chemically amplified positive resist composition, and resist-modifying composition
US9368396B1 (en) 2015-01-12 2016-06-14 Powerchip Technology Corporation Gap fill treatment for via process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI408502B (en) * 2009-08-05 2013-09-11 Shinetsu Chemical Co Pattern forming process, chemically amplified positive resist composition, and resist-modifying composition
US8658346B2 (en) 2009-08-05 2014-02-25 Shin-Etsu Chemical Co., Ltd. Pattern forming process, chemically amplified positive resist composition, and resist-modifying composition
US9368396B1 (en) 2015-01-12 2016-06-14 Powerchip Technology Corporation Gap fill treatment for via process
TWI550769B (en) * 2015-01-12 2016-09-21 力晶科技股份有限公司 Gap fill treatment for via process

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