TW200839449A - Radiation-sensitive resin composition for immersion exposure and method of forming photoresist pattern - Google Patents

Abstract

A radiation-sensitive resin composition for immersion exposure which can give a satisfactory pattern shape, has an excellent focal depth, and is reduced in the content of components dissolving in an immersion medium, e.g., water, with which the composition is in contact during immersion exposure. It is effective in diminishing bubble defects. Also provided is a method of forming a photoresist pattern from the composition. The radiation-sensitive resin composition for immersion exposure comprises: a polymer (A) which contains fluoroalkyl groups, has a fluorine content of 3 at.% or higher, and becomes alkali-soluble by the action of an acid; a resin (B) which becomes alkali-soluble by the action of an acid and has a fluorine content less than 3 at.%; and a radiation-sensitive acid generator (C).; A photoresist film formed by applying this resin composition to a substrate has an advancing contact angle with water of 95 DEG or smaller.

Description

200839449 九、發明說明 【發明所屬之技術領域】 本發明關於可適用於經由水等的浸潤介質對光阻膜進 行曝光的浸潤式曝光法之浸潤式曝光用敏輻射線性樹脂組 ’成物以及使用其的光阻圖型形成方法。 【先前技術】 Φ 於積體電路元件之製造所代表的微細加工領域中，爲 了得到高的積體度，最近需要可在Ο.ΙΟμπι以下之水平的 微細加工之微影技術。然而，於以往的微影製程中，通常 使用i線等的近紫外線當作輻射線，一般認爲該近紫外線 在次微米程度的微細加工係極困難。因此，爲了使 0.1 0 μιη以下之水平的微細加工成爲可能，檢討更短波長 的輻射線之利用。作爲如此的短波長之輻射線，例如可舉 出水銀線的明線光譜、準分子雷射所代表的遠紫外線、X φ 線、電子線等，但於此等之中，KrF準分子雷射（波長 2 4 8 nm )或ArF準分子雷射（波長1 9 3 nm )係特別受到注 @。 作爲適合於如此的準分子雷射之照射的光阻，利用具 ' 有酸解離性官能基的成分、及經輻射線的照射（以下稱爲 「曝光」）而產生酸的成分（以下稱爲「酸產生劑」）之 化學增幅效果的光阻（以下稱爲「化學增幅型光阻」）係 有多數提案。作爲化學增幅型光阻，例如有提案一種光阻 ，其含有具羧酸的第三丁酯基或苯酚的第三丁基碳酸酯基 -5- 200839449 的樹脂及酸產生劑。此光阻經由曝光所產生 使樹脂中所存在的第三丁酯基或第三丁基碳 ，該樹脂成爲具有羧基或酚性羥基所成的酸 爲利用光阻膜的曝光區域在鹼顯像液中成爲 者。 於如此的微影製程中，今後要求更微細 例如線寬爲45nm左右的微細光阻圖型）。 此4 5nm更微細的圖型形成，考慮如前述地 源波長的短波長化，或增大透鏡的開口數 ，光源波長的短波長化係需要新的高價曝光 透鏡的高NA化，由於解像度與焦點深度成 即使提高解像度，也有焦點深度降低的問題 最近，作爲可能解決如此問題的微影技 潤式曝光（liquid immersion lithography ) 方法爲在曝光時，使在透鏡與基板上的光阻 前述光阻膜上，存在有指定厚度的純水或氟 的液狀折射率介質（浸潤介質）。於該方法 空氣或氮氣等的惰性氣體之曝光光路空間置 η )更大的液體，例如純水等，即便使用相 之光源，也與使用短波長的光源的情況或使 的情況同樣地，可達成高解像性，同時焦點 低。若使用如此的浸潤式曝光，則可使用現 裝的透鏡，實現以低成本、更優異的高解像 度亦優異的光阻圖型之形成，而受到非常的 的酸之作用， 酸酯基被解離 性基，其結果 易溶性的顯像 的圖型形成（ 爲了達成比如 曝光裝置之光 (ΝΑ )。然而 裝置。又，在 權衡的關係， 〇 術，有報告浸 法的方法。此 膜之間的至少 系惰性液體等 中，將以往之 換成折射率（ 同的曝光波長 用筒Ν Α透鏡 深度亦不會降 存的裝置所安 性、且焦點深 注目。 6- 200839449 然而，於前述的浸潤式曝光程序中，由於曝光時光阻 膜係直接接觸水等的浸潤介質，而會從光阻膜中溶出酸產 生劑等。該溶出物的量若多，則會對透鏡造成損傷，有得 不到指定的圖型形狀，得不到充分解像度的問題點。 又，於使用水當作浸潤介質時，曝光時會產生泡（氣 泡），該氣泡達成透鏡的角色，而無法以最初指定的折射 率進行曝光，在氣泡周邊，亦無法形成指定形狀的圖型， 而有產生氣泡缺陷的問題點。 作爲浸潤式曝光裝置所使用的光阻用樹脂，例如有提 案專利文獻1及專利文獻2中記載的樹脂、或專利文獻3 中記載的添加劑等。 然而，即便使用此等樹脂或添加劑的光阻，也不能說 是可充分抑制酸產生劑等溶到水中的溶出物量，氣泡缺陷 亦容易產生。 專利文獻1 :國際公開WO 2 004/0 6 8242號公報 專利文獻2 :特開2005 - 1 73474號公報 專利文獻3 :特開2006-48029號公報 【發明內容】 發明所欲解決的問題 本發明係鑒於上述實情，目的爲提供所得到的圖型形 狀良好，焦點深度優異，對浸潤式曝光時所接觸的水等之 浸潤介質的溶出物之量少，且可抑制氣泡缺陷的產生之浸 潤式曝光用敏輻射線性樹脂組成物以及使用其的光阻圖型 200839449 形成方法。 解決問題的手段 達成前述目的之手段係如以下。 [1] 一種浸潤式曝光用敏輻射線性樹脂組成物，其含 有含氟化烷基，氟含量爲3原子％以上，且藉由酸的作用 成爲鹼可溶性的聚合物（A )，及藉由酸的作用成爲鹼可 溶性，且氟含量爲低於3原子％的樹脂（B )，以及敏輻 射線性酸產生劑（C )，其特徵爲將該浸潤式曝光用敏輻 射線性樹脂組成物塗佈在基板上而形成的光阻膜，對於水 的前進接觸角係95度以下。 [2] 如上述[1]記載的浸潤式曝光用敏輻射線性樹脂組 成物，其中前述樹脂（B)含有含內酯構造的重複單位、 及含藉由酸的作用成爲鹼可溶性之骨架的重複單位。 [3 ]如上述[1 ]或[2]記載的浸潤式曝光用敏輻射線性樹 脂組成物，其中前述聚合物（A)含有含下述通式（1) 所示的重複單位、及含藉由酸的作用成爲鹼可溶性之骨架 的重複單位， [化1] R1 -f c-ch2-}- ⑴ [通式（1)中’ R1表示氫、甲基或三氟甲基’ A表不單鍵 、亞甲基、碳數2〜6的伸院基、氧原子、硫原子、羰氧 基、氧羰基、醯胺基、磺醯胺基或胺甲酸酯基；R2表示 200839449 含有至少一個以上的氟原子之碳數1〜6的直鏈狀或支鏈 狀的烷基、或碳數4〜2 0的1價脂環式烴基或其衍生物] 〇 [4] 如上述[1]至[3]中任一項記載的浸潤式曝光用敏輻 射線性樹脂組成物，其中用於給予前述通式（1 )所示重 複單位的單體係從2,2,2-三氟乙基（甲基）丙烯酸酯、2_ (1，1，1，3,3,3-六氟）丙基（甲基）丙烯酸酯、1-( 2,2,3,3,4,4,5,5-八氟）己基（甲基）丙烯酸酯、1-( 2,2,3,3,4,4,4-七氟）五（甲基）丙烯酸酯及全氟環己基（ 甲基）丙烯酸酯中所選出的至少一種。 [5] 如上述[1]至[4]中任一項記載的浸潤式曝光用敏輻 射線性樹脂組成物，其中以該聚合物（A )及前述樹脂（ B )的合計爲1 00質量％時，該聚合物（A )的含量係0· 1 質量％以上。 [6] —種光阻圖型之形成方法，其特徵爲具備：（1 ) 使用上述[1]至[5]中任一項記載的浸潤式曝光用敏輻射線 性樹脂組成物，在基板上形成光阻膜的步驟；（2 )經由 浸潤介質且通過具有指定圖型的光罩，對前述光阻膜照射 輻射線，進行曝光的步驟；及（3 )將經曝光的光阻膜顯 像，形成光阻圖型的步驟。 發明的效果 若使用本發明的浸潤式曝光用敏輻射線性樹脂組成物 ’則所得到的圖型形狀良好，焦點深度優異，且對浸潤式 -9- 200839449 曝光時所接觸的水等之浸潤介質的溶出物之量可變少。胃 者，由於光阻膜與浸潤介質的前進接觸角爲95度以下， 可抑制浸潤式曝光時的氣泡缺陷之產生。 【實施方式】 實施發明的最佳形態 以下詳細說明本發明。 本發明的浸潤式曝光用敏輻射線性樹脂組成物（以τ 僅稱「敏輻射線性樹脂組成物」或「樹脂組成物」）之特 徵爲含有：含氟化烷基，氟含量爲3原子％以上，且藉_ 酸的作用成爲鹼可溶性的聚合物（A )，及藉由酸的作g 成爲鹼可溶性，且氟含量爲低於3原子％的樹脂（B )， 以及敏輻射線性酸產生劑（C )，其特徵爲將該樹脂組成 物塗佈在基板上而形成的光阻膜，對於水的前進接觸角係 95度以下。 該敏輻射線性樹脂組成物，係在透鏡與光阻膜之間， 經由在波長193nm的折射率比空氣還高之浸潤介質（例 如水等），輻射線照射的含浸潤式曝光之光阻圖型形成方 法中，用於形成光阻膜。 又，於本發明的敏輻射線性樹脂組成物中，將該樹脂 組成物塗佈在基板上而形成的光阻膜，對於水的前進接觸 角係95度以下。於該前進接觸角爲95度以下時，可抑制 高速掃描時的氣泡咬入，抑制氣泡缺陷的產生。再者，本 說明書中的「前進接觸角」，係意味於形成有本發明的樹 -10- 200839449 脂組成物所成的光阻膜之基板上，滴下25 μί的水’然後 以lOpL/min的速度在基板上注入水滴時，液面與基板的 接觸角。具體地，如後述的實施例所示地，可以使用 KRUS公司製「DSA-10」來測定。 又，於本發明的敏輻射線性樹脂組成物中，將該樹脂 組成物塗佈在基板上而形成的光阻膜，對於水的後退接觸 角較佳爲75度以上，尤佳爲80度以上，更佳爲85度以 上。於該後退接觸角爲75度以上時，高速掃描曝光時的 除水性變良好，可抑制水印缺陷的產生。再者，本說明書 中的「後退接觸角」，係意味於形成有本發明的樹脂組成 物所成的光阻膜之基板上，滴下25 μί的水，然後以1〇 pL/min的速度吸引基板上的水滴時，液面與基板的接觸 角。具體地，如後述實施例所示地，可以使用KRUS公司 製「DSA-10」來測定。 <聚合物（A ) > 本發明中的含氟化烷基、氟含量爲3原子％以上、且 藉由酸的作用成爲鹼可溶性的聚合物（A )[以下僅稱「聚 合物（A)」]，係藉由酸的作用成爲鹼可溶性的鹼不溶性 或鹼難溶性的聚合物。此處所言的「鹼不溶性或鹼難溶性 」，係意味於由含有聚合物（A )的敏輻射線性樹脂組成 物所形成的光阻膜來形成光阻圖型時，在所採用的鹼顯像 條件下，代替該光阻膜，僅將使用聚合物（A )的被膜進 行顯像時’該被膜的初期膜厚之50%以上在顯像後殘存的 -11 - 200839449 性質。 由於該聚合物（A )在構造中含有氟化烷基，故作爲 光阻組成物的成分添加及形成光阻膜時，藉由膜中的聚合 物（A )之撥油性特長，其分佈在光阻膜表面有變高的傾 向，可抑制浸潤式曝光時酸產生劑或酸擴散控制劑等對水 等的浸潤介質之溶出。 又，藉由該聚合物（A )的撥水性特長，光阻膜與浸 潤介質的前進接觸角係成爲在指定範圍，可抑制氣泡缺陷 的產生。再者，光阻膜與浸潤介質的後退接觸角會變高， 水滴不會殘留而可高速地掃描曝光。又，藉由倂用以往的 浸潤用上層膜，溶出會更減低，而且光阻的撥水性高，可 更抑制從水印或氣泡缺陷等的浸潤介質而來的缺陷之產生 〇 另外，上述聚合物（A)所含有的氟化烷基之氟含量 ，以聚合物（A)全體爲100原子％時，爲3原子％以上， 較佳爲3〜5 0原子％，更佳爲5〜3 0原子％。 再者，該氟含量可藉由13C-NMR來測定。 本發明中的聚合物（A )只要爲含有氟化烷基，且藉 由酸的作用成爲鹼可溶性者即可，並沒有特別的限定，例 如較佳爲包含··由構造中含有氟化烷基的單體而來的重複 單位、及含有藉由酸的作用成爲鹼可溶性的骨架之重複單 位者。 作爲在構造中含有氟化烷基的單體，可舉出在主鏈含 有氟化烷基者、在側鏈含有氟化烷基者、在主鏈和側鏈含 -12- 200839449 有氟化烷基者。 作爲在主鏈含有氟化烷基的單體，例如可舉出α-三 氟甲基丙烯酸酯化合物、β-三氟甲基丙烯酸酯化合物、 α，β-三氟甲基丙烯酸酯化合物、1種類以上的乙烯基部位 之氫被三氟甲基等的氟化院基取代的化合物等。 又，作爲在側鏈含有氟化烷基的單體，例如可舉出如 原冰片烯之脂環式烯烴化合物的側鏈爲氟化烷基或其衍生 物者，丙烯酸或甲基丙烯酸的側鏈爲氟化烷基或其衍生物 的酯化合物，1種類以上的烯烴之側鏈（不含雙鍵的部位 )爲氟化烷基或其衍生物者。 再者，作爲在主鏈和側鏈含有氟化烷基的單體，例如 可舉出α-三氟甲基丙烯酸、β-三氟甲基丙烯酸、α，β-三氟 甲基丙烯酸等之側鏈爲氟化烷基或其衍生物的酯化合物， 1種類以上的乙烯基部位之氫被三氟甲基等的氟化烷基所 取代的化合物之側鏈經氟化烷基或其衍生物取代者，1種 類以上的脂環式烯烴化合物之雙鍵所鍵結的氫經三氟甲基 等的氟化烷基所取代、且側鏈爲氟化烷基或其衍生物者等 。再者，此處的脂環式烯烴化合物表示環的一部分爲雙鍵 的化合物。 於本發明中，由構造中含有氟化烷基的單體而來的重 複單位，係如以上所示地，並沒有特別的限定，較佳爲下 述通式（1)所示的重複單位（以下稱爲「重複單位（1) j ) ° -13- 200839449 [化2] R1 十卜CH2+ ⑴ [通式（1)中，R1表示氫、甲基或三氟甲基；A表示單鍵 、亞甲基、碳數2〜6的伸烷基、氧原子、硫原子、羰氧 基、氧羰基、醯胺基、磺醯胺基或胺甲酸酯基；R2表示 含有至少一個以上的氟原子之碳數1〜6的直鏈狀或支鏈 狀的烷基、或碳數4〜20的1價脂環式烴基或其衍生物] 〇 於通式（1 )的R2中，作爲含有至少一個以上的氟原 子之碳數1〜6的直鏈狀或支鏈狀的烷基，例如可舉出甲 基、乙基、1-丙基、2-丙基、1· 丁基、2-丁基、2- ( 2-甲 基丙基）基、1-戊基、2-戊基、3-戊基、1- ( 2-甲基丁基 )基、1-(3-甲基丁基）基、2-(2-甲基丁基）基、2-( 3-甲基丁基）基、新戊基、1-己基、2-己基、3-己基、1-(2-甲基戊基）基、1-(3-甲基戊基）基、1-(4-甲基戊 基）基、2-(2-甲基戊基）基、2-(3-甲基戊基）基、2-(4-甲基戊基）基、3-(2-甲基戊基）基、3-(3-甲基戊 基）基等的直鏈狀、支鏈狀的烷基之部分氟化或全氟烷基 等。 又，於通式（1 )的R2中，作爲含有至少一個以上的 氟原子之碳數4〜2G的1價脂環式烴基或其衍生物，可舉 出環戊基、環戊基甲基、1-(1-環戊基乙基）基、1-(2- -14- 200839449 環戊基乙基）基、環己基、環己基甲基、1-(1-環己基乙 基）基、1-(2_環己基乙基）、環庚基、環庚基甲基、Ιο-環庚基 乙基） 基、 1-(2_環庚基 乙基） 基、 2-原冰片 基等的脂環式烷基的部分氟化或全氟烷基等。 作爲給予前述重複單位（1)的單體，可舉出三氟甲 基（甲基）丙烯酸酯、2,2,2-三氟乙基（甲基）丙烯酸酯 、全氟乙基（甲基）丙烯酸酯、全氟正丙基（甲基）丙烯 酸酯、全氟異丙基（甲基）丙烯酸酯、全氟正丁基（甲基 )丙烯酸酯、全氟異丁基（甲基）丙烯酸酯、全氟第三丁 基（甲基）丙烯酸酯、全氟環己基（甲基）丙烯酸酯、2-(1，15153,3,3-六氟）丙基（甲基）丙烯酸酯、1-( 2.2.3.3.4.4.5.5- 八氟）戊基（甲基）丙烯酸酯、1-( 2.2.3.3.4.4.5.5- 八氟）己基（甲基）丙烯酸酯、全氟環己 基甲基（甲基）丙烯酸酯、1- ( 2,2,3,3,3-五氟）丙基（甲 基）丙烯酸酯、1-(2,2,3,3,4,4,4-七氟）五（甲基）丙烯 酸酯、1- ( 3,3,4,4,5,5,6,6,7,7,8,8,9,9，10，10，10-十七氟） 癸基（甲基）丙烯酸酯、1-(5-三氟甲基- 3,3,4,4,5,6,6,6-八氟）己基（甲基）丙烯酸酯等。 於此等單體之中，較佳爲從2,2,2-三氟乙基（甲基） 丙烯酸酯、2- ( 1，1，1，3,3,3-六氟）丙基（甲基）丙烯酸酯 、1-(2,2,3,3,4,4,5,5-八氟）己基（甲基）丙烯酸酯、1-(2,2,3,3,4,4,4·七氟）五（甲基）丙烯酸酯及全氟環己基 (甲基）丙烯酸酯中所選出的至少一種。 前述聚合物（A )可僅含有1種的該重複單位（1 ) -15- 200839449 ，也可含有2種以上。 又，前述含藉由酸的作用成爲鹼可溶性之骨架的重複 單位係沒有特別的限定，較佳爲下述通式（2 )所示的重 複單位（以下稱爲「重複單位（2 )」）。藉由含有該重 複單位（2 )，在曝光時可成爲指定的前進接觸角，顯像 時可成爲鹼可溶性。即，在曝光時保持通式（2 )的構造 ，幾乎不會喪失前述在構造中含有氟化烷基的單體而來的 重複單位之效果，具有指定的前進接觸角，由於藉由酸的 作用使-C(R4)3部分從通式（2)的構造脫離而成爲鹼可溶 [化3] R3 十 C-CH2+ (2) =0 Ο R4_l R4 R4 [通式（2)中，R3表示氫、甲基或三氟甲基。各R4互相 獨立地表示碳數4〜20的1價脂環式烴基或其衍生物、或 碳數1〜4的直鏈狀或支鏈狀的烷基]。 於通式（2 )的R4中，作爲碳數4〜20的1價脂環式 烴基’例如可舉出從原冰片烷、三環癸烷、四環十二烷、 金剛烷、或環丁烷、環戊烷、環己烷、環庚烷、環辛烷等 的環烷類等而來的脂環族環所成的基；此等的脂環族環所 成的基經例如甲基、乙基、正丙基、異丙基、正丁基、2 _ 甲基丙基、1·甲基丙基、第三丁基等的碳數1〜4的直鏈 16- 200839449 狀、支鏈狀或環狀的烷基之1種以上或1個以上所取代的 基等。又，任2個的R4可互相鍵結，與各自所鍵結合的 碳原子一起形成2價脂環式烴基或其衍生物。 於此等脂環式烴基之中，較佳爲從原冰片烷、三環癸 烷、四環十二烷、金剛烷、環戊烷或環己烷而來的脂環族 環所成的基、或此等的脂環族環所成的基經前述烷基所取 代的基等。 又，於通式（2 )的R4中，作爲碳數1〜4的直鏈狀 或支鏈狀的烷基，例如可舉出甲基、乙基、正丙基、異丙 基、正丁基、2-甲基丙基、1-甲基丙基、第三丁基等。 於通式（2 )中，作爲-C(R4)3的例子，可舉出第三丁 基、1-正（1-乙基-1-甲基）丙基、1-正（1，1-二甲基）丙 基、1-正（1，1-二甲基）丁基、1-正（1，1-二甲基）戊基 、二乙基）丙基、1-正（1，1-二乙基）丁基、1-正 (1，1_二乙基）戊基、1-(1-甲基）環戊基、1-(1·乙基 )環戊基、1- ( 1-正丙基）環戊基、1- ( 1-異丙基）環戊 基、1-(1-甲基）環己基、1-(1-乙基）環己基、l-(b 正丙基）環己基、1-(1-異丙基）環己基、-甲基-卜 (2-原冰片基）}乙基、1-{1-甲基-1- ( 2-四環癸基）}乙 基、1-{1_甲基-1- ( 1-金剛烷基）}乙基、2- ( 2-甲基）原 冰片基、2- ( 2-乙基）原冰片基、2- ( 2-正丙基）原冰片 基、2-(2-異丙基）原冰片基、2-(2-甲基）四環癸基、 2-(2-乙基）四環癸基、2-(2-正丙基）四環癸基、2-( 2-異丙基）四環癸基、1-(1-甲基）金剛烷基、1-(卜乙 -17- 200839449 基）金剛烷基、1-(1-正丙基）金剛烷基、1-(丨_異丙基 )金剛院基、或此等的脂環族環所成的基經例如甲基、乙 基、正丙基、異丙基、正丁基、2 -甲基丙基、1-甲基丙基 、第三丁基等之碳數1〜4的直鏈狀、支鏈狀或環狀的烷 基的1種以上或1個以上所取代的基等。 作爲給予前述重複單位（2 )的較佳單體，可舉出（ 甲基）丙烯酸2-甲基金剛烷基-2-基酯、（甲基）丙烯酸 2-甲基-3-羥基金剛烷基-2-基酯、（甲基）丙烯酸2-乙基 金剛烷基-2-基酯、（甲基）丙烯酸2-乙基-3-羥基金剛烷 基-2-基酯、（甲基）丙烯酸2-正丙基金剛烷基-2-基酯、 (甲基）丙烯酸2-異丙基金剛烷基-2-基酯、（甲基）丙 烯酸-2-甲基雙環[2.2.1]庚-2-基酯、（甲基）丙烯酸-2-乙 基雙環[2·2·1]庚-2_基酯、（甲基）丙烯酸-8-甲基三環 [5.2.1.0·2,6]癸烷_8_基酯、（甲基）丙烯酸-8-乙基三環 [5.2.1.0.2,6]癸烷-8_基酯、（甲基）丙烯酸-4-甲基四環 [6·2·13,6·〇2,7]十二烷-4-基酯、（甲基）丙烯酸-4-乙基四 環[6·2·13,6·02,7]十二烷-扣基酯、（甲基）丙烯酸卜（雙 環[2.2.1]庚-2-基）-1_甲基乙酯、（甲基）丙烯酸1-(三 環[5·2·1·〇.2,6]癸烷_8_基）甲基乙酯、（甲基）丙烯酸 1-(四環[6.2.13,6.02,7]十二烷-4-基）-1-甲基乙酯、（甲 基）丙烯酸1-(金剛烷-1-基）-卜甲基乙酯、（甲基）丙 烯酸1· ( 3-羥基金剛烷-1-基）-1-甲基乙酯、（甲基）丙 烯酸1，1-二環己基乙酯、（甲基）丙烯酸1，1 -二（雙環 [2·2·1]庚-2-基）乙酯、（甲基）丙烯酸1，1-二（三環 -18 - 200839449 Μ·2·1·0·2’6]癸院_8·基）乙酯、（甲基）丙烯酸1，1-二（ 四環[6.2.13,6.〇2,7]十二烷|基）乙酯、（甲基）丙烯酸 —（金剛院-1-基）乙酯、（甲基）丙烯酸甲基-b ί哀戊酯、（甲基）丙烯酸1-乙基-i-環戊酯、（甲基）丙 燃酸1-甲基-1-環己酯、（甲基）丙烯酸^乙基4·環己酯 等。 於此等單體之中，特佳爲（甲基）丙烯酸2-甲基金 剛院基-2-基酯、（甲基）丙烯酸2-乙基金剛烷基-2_基酯 、（甲基）丙烯酸-2-甲基雙環[2.2.1]庚-2-基酯、（甲基 )丙烯酸-2-乙基雙環[2.23]庚-2_基酯、（甲基）丙烯酸 1-(雙環[2.2.1]庚-2-基）-1-甲基乙酯、（甲基）丙烯酸 1-(金剛烷-1-基）-h甲基乙酯、（甲基）丙烯酸1-甲基_ 1 -環戊酯、（甲基）丙烯酸丨_乙基-丨_環戊酯、（甲基） 丙烯酸1-甲基-1_環己酯、（甲基）丙嫌酸乙基-丨_環己 酯等。 前述聚合物（A )可僅含有1種的該重複單位（2 ) ，也可含有2種以上。 於聚合物（A)中，除了前述在構造中含有氟化烷基 的重複單位、及前述重複單位（2 )以外，例如亦可含有 1種類以上的用於提高鹼溶解性之具有內酯構造或羥基、 羧基等的重複單位，用於提高蝕刻耐性之由含有脂環式化 合物的重複單位或芳香族化合物而來的重複單位，用於抑 制來自基板的反射之由芳香族化合物而來的重複單位等之 「其它重複單位」。 -19- 200839449 作爲產生前述含有內酯構造的重複單位（以卞稱爲重 複單位（3))之單體，可舉出下述通式（3-1)〜（3-6 )等。 [化4]。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Its photoresist pattern formation method. [Prior Art] Φ In the field of microfabrication represented by the manufacture of integrated circuit components, in order to obtain a high degree of integrated body, a lithography technique capable of microfabrication at a level below Ο.ΙΟμπι has recently been required. However, in the conventional lithography process, near-ultraviolet rays such as i-lines are usually used as radiation, and it is considered that the near-ultraviolet microfabrication is extremely difficult. Therefore, in order to make microfabrication at a level of 0.10 μm or less possible, the use of radiation of shorter wavelengths is reviewed. Examples of such short-wavelength radiation include a bright-line spectrum of a mercury line, a far-ultraviolet light represented by an excimer laser, an X φ line, an electron beam, etc., but among these, a KrF excimer laser (wavelength 2 4 8 nm) or ArF excimer laser (wavelength 193 nm) is particularly affected by @. As a photoresist suitable for the irradiation of such a pseudo-molecular laser, a component having an acid-dissociable functional group and a radiation-irradiated (hereinafter referred to as "exposure") is used to generate an acid (hereinafter referred to as a component). The photoresist of the chemical amplification effect of "acid generator" (hereinafter referred to as "chemical amplification type photoresist") has many proposals. As the chemically amplified photoresist, for example, there is proposed a photoresist comprising a third butyl carbonate group having a carboxylic acid or a third butyl carbonate group of phenol-5-200839449 and an acid generator. The photoresist is subjected to exposure to produce a third butyl ester group or a third butyl carbon which is present in the resin, and the resin is an acid having a carboxyl group or a phenolic hydroxyl group as an exposed region using a photoresist film in alkali imaging. Become the liquid. In such a lithography process, a finer photoresist pattern having a line width of about 45 nm is required in the future. The formation of a finer pattern of 45 nm, considering the short wavelength of the source wavelength as described above, or increasing the number of apertures of the lens, the short wavelength of the wavelength of the light source requires a high NA of the new high-priced exposure lens due to the resolution and The depth of focus becomes a problem of reducing the depth of focus even if the resolution is improved. Recently, as a liquid immersion lithography method that can solve such a problem, the photoresist on the lens and the substrate is exposed to the above-mentioned photoresist at the time of exposure. On the film, there is a liquid refractive index medium (wetting medium) of pure water or fluorine of a specified thickness. In this method, a liquid having a larger exposure light path of an inert gas such as air or nitrogen, such as pure water, may be used in the same manner as or in the case of using a light source of a short wavelength even when a light source of a phase is used. Achieve high resolution and low focus. When such an immersion exposure is used, a ready-to-wear lens can be used to form a photoresist pattern which is excellent in low cost and excellent in high resolution, and is subjected to a very acid action, and the acid ester group is dissociated. The result is the formation of a pattern of readily soluble imaging (in order to achieve light such as exposure (ΝΑ). However, the device. Again, in the trade-off relationship, there is a method of reporting the immersion method. At least the inert liquid or the like is replaced by a conventional refractive index (the same exposure wavelength is not compromised by the depth of the lens, and the focus is deep. 6-200839449 However, in the foregoing In the immersion exposure process, the photoresist film is directly exposed to a wetting medium such as water during exposure, and an acid generator or the like is eluted from the photoresist film. If the amount of the eluted material is large, damage to the lens may occur. If the shape of the pattern is not specified, the problem of sufficient resolution cannot be obtained. Moreover, when water is used as the immersion medium, bubbles (bubbles) are generated during exposure, and the bubble reaches the role of the lens. The method is exposed at a refractive index which is originally specified, and a pattern of a predetermined shape is not formed around the bubble, and there is a problem of occurrence of a bubble defect. As a resist resin used for an immersion exposure apparatus, for example, a patent document is proposed. (1) The resin described in Patent Document 2 or the additive described in Patent Document 3. However, even if the resist of these resins or additives is used, it cannot be said that the amount of the eluted substance dissolved in water such as an acid generator can be sufficiently suppressed. In the case of a bubble defect, the invention is also easy to produce. Patent Document 1: International Publication No. WO 2 004/0 6 8242 Patent Document 2: JP-A-2006-48029 (Patent Document 3) DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a shape having a good shape and excellent depth of focus, and a small amount of eluted matter of a wetting medium such as water contacted during immersion exposure, and can be suppressed. A sensitized radiation linear resin composition for immersion exposure which produces bubble defects and a photoresist pattern 200839449 forming method using the same. The means for achieving the above object is as follows. [1] A sensitized radiation linear resin composition for immersion exposure, which contains a fluorine-containing alkyl group, has a fluorine content of 3 atom% or more, and becomes a base by an action of an acid. a soluble polymer (A), and a resin (B) having an alkali content and having a fluorine content of less than 3 atom%, and a radiation sensitive linear acid generator (C) characterized by the infiltration The resistive film formed by coating the photosensitive resin composition with a radiation-sensitive linear resin composition on the substrate has a contact angle of 95 degrees or less with respect to water. [2] The sensitized radiation linear resin for immersion exposure as described in [1] above. In the composition, the resin (B) contains a repeating unit having a lactone structure and a repeating unit containing a skeleton which becomes alkali-soluble by the action of an acid. [3] The sensitized radiation linear resin composition for immersion exposure according to the above [1], wherein the polymer (A) contains a repeating unit represented by the following formula (1), and The repeating unit of the skeleton of alkali solubility by the action of an acid, [1] R1 -f c-ch2-}- (1) [In the formula (1), 'R1 represents hydrogen, methyl or trifluoromethyl' A a bond, a methylene group, a carbon number of 2 to 6 or more, an oxygen atom, a sulfur atom, a carbonyloxy group, an oxycarbonyl group, a decylamino group, a sulfonylamino group or a urethane group; and R2 means that 200839449 contains at least one The above-mentioned linear or branched alkyl group having 1 to 6 carbon atoms of the fluorine atom or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof] [4] as described above [1] The sensitized radiation linear resin composition for immersion exposure according to any one of [3], wherein the single system for giving the repeating unit represented by the above formula (1) is from 2,2,2-trifluoroethyl (meth) acrylate, 2_(1,1,1,3,3,3-hexafluoro)propyl (meth) acrylate, 1-( 2,2,3,3,4,4,5, 5-octafluoro)hexyl (meth) acrylate, 1-( 2,2,3,3,4,4,4-heptafluoro)penta Yl) acrylate, and at least one perfluoro cyclohexyl (meth) acrylate is selected. [5] The sensitized radiation linear resin composition for immersion exposure according to any one of the above [1] to [4] wherein the total of the polymer (A) and the resin (B) is 100% by mass. The content of the polymer (A) is 0.1% by mass or more. [6] A method for forming a photoresist pattern, comprising: (1) using the immersion-type radiation sensitive linear resin composition according to any one of the above [1] to [5], on a substrate a step of forming a photoresist film; (2) a step of exposing the photoresist film to a radiation pattern by immersing the medium through a mask having a specified pattern; and (3) developing the exposed photoresist film The step of forming a photoresist pattern. Advantageous Effects of Invention When the immersion-type radiation sensitive linear resin composition of the present invention is used, the shape of the pattern obtained is good, the depth of focus is excellent, and the immersion medium of water or the like which is in contact with the immersion type -9-200839449 is exposed. The amount of the eluate can be reduced. In the stomach, since the advancing contact angle of the photoresist film and the immersion medium is 95 degrees or less, generation of bubble defects during immersion exposure can be suppressed. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The immersion-type radiation sensitive linear resin composition of the present invention (hereinafter referred to as "sensitizing radiation linear resin composition" or "resin composition") is characterized by containing a fluorine-containing alkyl group and having a fluorine content of 3 atom%. Above, and by the action of the acid, the alkali-soluble polymer (A), and the acid (as a) which is alkali-soluble by the acid, and having a fluorine content of less than 3 atom%, and the linear acid generated by the sensitive radiation The agent (C) is characterized in that the resist film formed by applying the resin composition on a substrate has a contact angle of 95 degrees or less with respect to water. The sensitive radiation linear resin composition is between the lens and the photoresist film, and is irradiated with a immersion medium having a refractive index higher than air at a wavelength of 193 nm (for example, water, etc.). In the type forming method, it is used to form a photoresist film. Further, in the radiation sensitive linear resin composition of the present invention, the resist film formed by coating the resin composition on the substrate has an advancing contact angle with water of 95 degrees or less. When the advancing contact angle is 95 degrees or less, it is possible to suppress bubble trapping at the time of high-speed scanning and suppress the occurrence of bubble defects. In addition, the "advance contact angle" in the present specification means that 25 μί of water is dripped on the substrate on which the photoresist film formed of the tree-10-200839449 lipid composition of the present invention is formed, and then lOpL/min. The contact angle of the liquid surface to the substrate when the water droplets are injected onto the substrate. Specifically, it can be measured using "DSA-10" manufactured by KRUS Co., Ltd. as shown in the examples below. Further, in the radiation sensitive linear resin composition of the present invention, the resist film formed by applying the resin composition on the substrate has a receding contact angle with respect to water of preferably 75 degrees or more, and more preferably 80 degrees or more. More preferably, it is 85 degrees or more. When the receding contact angle is 75 degrees or more, the water repellency at the time of high-speed scanning exposure becomes good, and generation of watermark defects can be suppressed. In addition, the "retraction contact angle" in the present specification means that 25 μί of water is dripped on the substrate on which the resist film formed of the resin composition of the present invention is formed, and then sucked at a speed of 1 〇pL/min. The contact angle between the liquid surface and the substrate when water droplets on the substrate. Specifically, it can be measured by using "DSA-10" manufactured by KRUS Co., Ltd. as shown in the examples below. <Polymer (A) > The fluorine-containing alkyl group and the fluorine-containing content in the present invention are 3 atom% or more, and the alkali-soluble polymer (A) is acted upon by the action of an acid [hereinafter, simply referred to as "polymer ( A)"] is an alkali-soluble alkali-insoluble or alkali-insoluble polymer by the action of an acid. The term "alkali-insoluble or alkali-insoluble" as used herein means a photoresist pattern formed by a resistive linear resin composition containing a polymer (A) to form a photoresist pattern. Under the condition of the photo-resist film, only the film of the polymer (A) was used for development, and the original film thickness of the film was 50% or more and remained in the -11 - 200839449 property after development. Since the polymer (A) contains a fluorinated alkyl group in the structure, when a photoresist film is added as a component of the photoresist composition, the polymer (A) in the film has an oil-repellent property, and is distributed in The surface of the photoresist film tends to be high, and it is possible to suppress elution of an infiltration medium such as water by an acid generator or an acid diffusion controlling agent during the immersion exposure. Further, by the water-repellent property of the polymer (A), the advancing contact angle of the photoresist film and the wetting medium is within a predetermined range, and generation of bubble defects can be suppressed. Further, the receding contact angle between the photoresist film and the immersion medium becomes high, and water droplets do not remain and can be scanned at high speed. Further, by using the conventional upper layer for infiltration, the elution is further reduced, and the water repellency of the photoresist is high, and the occurrence of defects such as water-immersing or bubble defects can be further suppressed. The fluorine content of the fluorinated alkyl group contained in (A) is 3 atom% or more, preferably 3 to 50 atom%, more preferably 5 to 3 0 when the total amount of the polymer (A) is 100 atom%. atom%. Further, the fluorine content can be measured by 13C-NMR. The polymer (A) in the present invention is not particularly limited as long as it contains a fluorinated alkyl group and is alkali-soluble by the action of an acid. For example, it is preferable to contain a fluorinated alkane in the structure. The repeating unit derived from the monomer of the group and the repeating unit containing the skeleton which becomes alkali-soluble by the action of the acid. Examples of the monomer having a fluorinated alkyl group in the structure include those having a fluorinated alkyl group in the main chain, a fluorinated alkyl group in the side chain, and fluorinated in the main chain and the side chain containing -12-200839449. Alkyne. Examples of the monomer having a fluorinated alkyl group in the main chain include an α-trifluoromethacrylate compound, a β-trifluoromethacrylate compound, and an α,β-trifluoromethacrylate compound. A compound in which the hydrogen of the vinyl group or more is substituted with a fluorinated group such as a trifluoromethyl group. Further, examples of the monomer having a fluorinated alkyl group in the side chain include a side chain in which an alicyclic olefin compound such as norbornene is a fluorinated alkyl group or a derivative thereof, and an acrylic acid or methacrylic acid side. The chain is an ester compound of a fluorinated alkyl group or a derivative thereof, and a side chain (a site containing no double bond) of one or more kinds of olefins is a fluorinated alkyl group or a derivative thereof. In addition, examples of the monomer having a fluorinated alkyl group in the main chain and the side chain include α-trifluoromethacrylic acid, β-trifluoromethylacrylic acid, and α,β-trifluoromethylacrylic acid. The side chain is an ester compound of a fluorinated alkyl group or a derivative thereof, and a side chain of a compound in which one or more kinds of hydrogens of a vinyl group are substituted by a fluorinated alkyl group such as a trifluoromethyl group is subjected to a fluorinated alkyl group or a derivative thereof. The substance is substituted by a hydrogen atom bonded to a double bond of one or more kinds of alicyclic olefin compounds, substituted by a fluorinated alkyl group such as a trifluoromethyl group, and the side chain is a fluorinated alkyl group or a derivative thereof. Further, the alicyclic olefin compound herein means a compound in which a part of the ring is a double bond. In the present invention, the repeating unit derived from the monomer having a fluorinated alkyl group in the structure is not particularly limited as described above, and is preferably a repeating unit represented by the following formula (1). (hereinafter referred to as "repeating unit (1) j ) ° -13- 200839449 [Chemical 2] R1 Xb CH2+ (1) [In the formula (1), R1 represents hydrogen, methyl or trifluoromethyl; A represents a single bond a methylene group, an alkylene group having 2 to 6 carbon atoms, an oxygen atom, a sulfur atom, a carbonyloxy group, an oxycarbonyl group, a decylamino group, a sulfonylamino group or a urethane group; and R2 represents at least one or more a linear or branched alkyl group having 1 to 6 carbon atoms of a fluorine atom or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof is contained in R2 of the formula (1) as The linear or branched alkyl group having 1 to 6 carbon atoms and containing at least one fluorine atom may, for example, be a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group or a 1-butyl group. 2-butyl, 2-(2-methylpropyl), 1-pentyl, 2-pentyl, 3-pentyl, 1-(2-methylbutyl), 1-(3-methyl Butyl), 2-(2-methylbutyl), 2-(3-methylbutyl), neopentyl 1-hexyl, 2-hexyl, 3-hexyl, 1-(2-methylpentyl), 1-(3-methylpentyl), 1-(4-methylpentyl), 2- (2-methylpentyl), 2-(3-methylpentyl), 2-(4-methylpentyl), 3-(2-methylpentyl), 3-(3 a partially fluorinated or perfluoroalkyl group of a linear or branched alkyl group such as a methylpentyl) group, etc. Further, in the R 2 of the formula (1), at least one or more fluorine atoms are contained. The monovalent alicyclic hydrocarbon group having 4 to 2 G carbon atoms or a derivative thereof may, for example, be a cyclopentyl group, a cyclopentylmethyl group, a 1-(1-cyclopentylethyl) group or a 1-(2- 14- 200839449 Cyclopentylethyl), cyclohexyl, cyclohexylmethyl, 1-(1-cyclohexylethyl), 1-(2-cyclohexylethyl), cycloheptyl, cycloheptyl a partially fluorinated or perfluoroalkyl group of an alicyclic alkyl group such as a benzyl group, a Ιο-cycloheptylethyl) group, a 1-(2-cycloheptylethyl) group or a 2-orioleyl group. The monomer of the above repeating unit (1) includes trifluoromethyl (meth) acrylate, 2, 2, 2-trifluoroethyl (meth) acrylate, and perfluoroethyl (meth) acrylate. Ester, perfluoro N-propyl (meth) acrylate, perfluoroisopropyl (meth) acrylate, perfluoro-n-butyl (meth) acrylate, perfluoroisobutyl (meth) acrylate, perfluoro third Butyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2-(1,15153,3,3-hexafluoro)propyl (meth) acrylate, 1-( 2.2.3.3. 4.4.5.5- octafluoro)pentyl (meth) acrylate, 1-( 2.2.3.3.4.4.5.5- octafluoro)hexyl (meth) acrylate, perfluorocyclohexylmethyl (meth) acrylate , 1-( 2,2,3,3,3-pentafluoro)propyl (meth) acrylate, 1-(2,2,3,3,4,4,4-heptafluoro)penta(methyl) Acrylate, 1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro) fluorenyl (methyl) Acrylate, 1-(5-trifluoromethyl-3,3,4,4,5,6,6,6-octafluoro)hexyl (meth) acrylate, and the like. Among these monomers, preferred are 2,2,2-trifluoroethyl (meth) acrylate, 2-(1,1,1,3,3,3-hexafluoro)propyl ( Methyl) acrylate, 1-(2,2,3,3,4,4,5,5-octafluoro)hexyl (meth) acrylate, 1-(2,2,3,3,4,4 At least one selected from the group consisting of: 4·heptafluoro)penta(meth)acrylate and perfluorocyclohexyl (meth)acrylate. The polymer (A) may contain only one type of the repeating unit (1) -15 to 200839449, or may contain two or more kinds. In addition, the repeating unit system containing the skeleton which is alkali-soluble by the action of an acid is not particularly limited, and is preferably a repeating unit represented by the following formula (2) (hereinafter referred to as "repeating unit (2)"). . By including the repeating unit (2), it is possible to have a predetermined advancing contact angle at the time of exposure, and it becomes alkali-soluble at the time of development. That is, the structure of the general formula (2) is maintained at the time of exposure, and the effect of the above-mentioned repeating unit containing the fluorinated alkyl group in the structure is hardly lost, and the specified advancing contact angle is obtained due to the acid The action removes the -C(R4)3 moiety from the structure of the formula (2) to become alkali-soluble [Chemical 3] R3 C-CH2+ (2) =0 Ο R4_l R4 R4 [R3 in the formula (2) Represents hydrogen, methyl or trifluoromethyl. Each R4 independently represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms. In the R4 of the formula (2), the monovalent alicyclic hydrocarbon group of 4 to 20 carbon atoms may, for example, be derived from norbornane, tricyclodecane, tetracyclododecane, adamantane or cyclopentane. a group of an alicyclic ring derived from a cycloalkane such as an alkane, a cyclopentane, a cyclohexane, a cycloheptane or a cyclooctane; or a group formed by such an alicyclic ring, for example, a methyl group a straight chain 16-200839449 having a carbon number of 1 to 4, such as ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1 methylpropyl, and t-butyl. One or more or one or more substituted groups of a chain or a cyclic alkyl group. Further, any two of R4 may be bonded to each other to form a divalent alicyclic hydrocarbon group or a derivative thereof together with the carbon atom to which each bond is bonded. Among these alicyclic hydrocarbon groups, a group derived from an alicyclic ring derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane or cyclohexane is preferred. Or a group in which the alicyclic ring is substituted with the above alkyl group or the like. Further, in R4 of the formula (2), examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group and a n-butyl group. Base, 2-methylpropyl, 1-methylpropyl, tert-butyl, and the like. In the general formula (2), examples of -C(R4)3 include a third butyl group, 1-n-(1-ethyl-1-methyl)propyl group, and 1-n-(1,1). -Dimethyl)propyl, 1-n-(1,1-dimethyl)butyl, 1-n-(1,1-dimethyl)pentyl, diethyl)propyl, 1-正 (1 ,1-diethyl)butyl, 1-n-(1,1-diethyl)pentyl, 1-(1-methyl)cyclopentyl, 1-(1·ethyl)cyclopentyl, 1 - (1-n-propyl)cyclopentyl, 1-(1-isopropyl)cyclopentyl, 1-(1-methyl)cyclohexyl, 1-(1-ethyl)cyclohexyl, 1-. b n-propyl)cyclohexyl, 1-(1-isopropyl)cyclohexyl, -methyl-b (2-originyl)}ethyl, 1-{1-methyl-1-(2-tetra Cyclodecyl)}ethyl, 1-{1_methyl-1-(1-adamantyl)}ethyl, 2-(2-methyl) borneol, 2-(2-ethyl) Borneol base, 2-(2-n-propyl) borneol, 2-(2-isopropyl) borneol, 2-(2-methyl)tetracyclodecyl, 2-(2-ethyl) Tetracyclic fluorenyl, 2-(2-n-propyl)tetracyclodecyl, 2-(2-isopropyl)tetracyclodecyl, 1-(1-methyl)adamantyl, 1-(b -17- 200839449 base) adamantyl, 1-(1-positive-propyl Adamantyl, 1-(anthracene-isopropyl)-glycols, or a group of such alicyclic rings, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, One or more or one or more substituted linear, branched or cyclic alkyl groups having 1 to 4 carbon atoms such as 2-methylpropyl group, 1-methylpropyl group or tert-butyl group; Base. Preferred monomers for the above repeating unit (2) include 2-methyladamantyl-2-yl (meth)acrylate and 2-methyl-3-hydroxyadamantane (meth)acrylate. 2-yl-yl ester, 2-ethyladamantyl-2-yl (meth)acrylate, 2-ethyl-3-hydroxyadamantyl-2-yl (meth)acrylate, (methyl) ) 2-n-propyladamantyl-2-yl acrylate, 2-isopropylidenyl-2-alkyl (meth)acrylate, 2-methylbicyclo(methyl) acrylate [2.2.1 Hept-2-yl ester, 2-ethylbicyclo[2·2·1]hept-2-yl (meth)acrylate, 8-methyltricyclo(methyl)acrylate [5.2.1.0· 2,6]decane-8-yl ester, (meth)acrylic acid-8-ethyltricyclo[5.2.1.0.2,6]decane-8-yl ester, (meth)acrylic acid-4-methyl Tetracycline [6·2·13,6·〇2,7]dodecyl-4-yl ester, (meth)acrylic acid 4-ethyltetracyclo[6·2·13,6·02,7 Dodecane-carboxyl ester, (meth)acrylic acid (bicyclo[2.2.1]hept-2-yl)-1_methylethyl ester, (meth)acrylic acid 1-(tricyclo[5·2] ·1·〇.2,6]decane_8_yl)methylethyl ester, (meth)acrylic acid 1-(four [6.2.13,6.02,7]dodec-4-yl)-1-methylethyl ester, 1-(adamantan-1-yl)-methylethyl (meth)acrylate, (meth)acrylic acid 1 (3-hydroxyadamantan-1-yl)-1-methylethyl ester, 1,1-dicyclohexylethyl (meth)acrylate, 1,1 -di(bicyclo[2][2] ·2·1]hept-2-yl)ethyl ester, 1,1-di(tricyclo-18-200839449 Μ·2·1·0·2'6] 癸院_8·基) Ethyl ester, 1,1-di(tetracyclo[6.2.13,6.〇2,7]dodecane|yl)ethyl (meth)acrylate, (meth)acrylic acid-(金刚院-1-yl) Ethyl ester, methyl-b whey amyl (meth)acrylate, 1-ethyl-i-cyclopentyl (meth)acrylate, 1-methyl-1-cyclohexyl (meth)propanoate Ester, (meth)acrylic acid ethyl 4-cyclohexyl ester, and the like. Among these monomers, 2-methyl-glycolyl-2-yl (meth)acrylate, 2-ethyladamantyl-2-yl (meth)acrylate, (methyl) )-2-methylbicyclo[2.2.1]hept-2-yl acrylate, 2-ethylbicyclo[2.23]hept-2-yl (meth)acrylate, 1-(bicyclo)(meth)acrylate [2.2.1]hept-2-yl)-1-methylethyl ester, 1-(adamantan-1-yl)-h-methylethyl (meth)acrylate, 1-methyl (meth)acrylate _ 1 -cyclopentyl ester, 丨 (ethyl) hydrazine (ethyl) hydrazine - cyclopentyl ester, (methyl) acrylate 1-methyl-1 - cyclohexyl ester, (methyl) acrylic acid ethyl - hydrazine _cyclohexyl ester and the like. The polymer (A) may contain only one type of the repeating unit (2) or two or more types. In the polymer (A), in addition to the above-mentioned repeating unit containing a fluorinated alkyl group in the structure and the above repeating unit (2), for example, one or more types of lactone-containing structures for improving alkali solubility may be contained. Or a repeating unit such as a hydroxyl group or a carboxyl group, or a repeating unit derived from a repeating unit or an aromatic compound containing an alicyclic compound for improving etching resistance, and for repeating an aromatic compound from reflection from a substrate "Other repeating units" such as units. -19- 200839449 The following formula (3-1) to (3-6) and the like are exemplified as the monomer which produces the repeating unit (hereinafter referred to as the repeating unit (3)) having a lactone structure. [Chemical 4]

(3-1) (3-2) (3-3) R5 ch2=c C=0 1 Ο(3-1) (3-2) (3-3) R5 ch2=c C=0 1 Ο

(3-4) (3-5) (3-6) 通式（3-1)〜（3-6)的各式中，R5表示氫原子或甲 基，R8表示氫原子或碳數1〜4的可有取代基的烷基，R7 表示氫原子或甲氧基。又，A表示單鍵或亞甲基，B表示 氧原子或亞甲基。再者，1表示1〜3的整數，m爲0或1 前述通式（3-1)的R6中，作爲碳數1〜4的可具有 取代基的烷基，例如可舉出甲基、乙基、正丙基、異丙基 -20- 200839449 、正丁基、2-甲基丙基、1-甲基丙基、第三丁基等。 作爲給予前述重複單位（3 )的較佳單體之具體例子 ，可舉出（甲基）丙烯酸-5-氧代-4-氧雜-三環[4.2.1 ·03,7] 壬-2-基酯、（甲基）丙烯酸-9-甲氧羰基-5-氧代-4-氧雜-三環[4.2.1 ·03,7]壬-2-基酯、（甲基）丙烯酸-5-氧代-4-氧 雜-三環[5·2·1·03,8]癸-2-基酯、（甲基）丙烯酸-10-甲氧 羰基-5-氧代-4-氧雜-三環[5.2.1.03,8]壬-2-基酯、（甲基） 丙烯酸-6-氧代-7-氧雜-雙環[3.2.1]辛-2-基酯、（甲基） 丙烯酸-4-甲氧羰基-6-氧代-7-氧雜-雙環[3.2.1]辛-2-基酯 、（甲基）丙烯酸-7-氧代-8-氧雜-雙環[3.3.1]辛-2-基酯 、（甲基）丙烯酸-4-甲氧羰基-7-氧代-8-氧雜-雙環 [3·3·1]辛-2-基酯、（甲基）丙烯酸-2-氧代四氫吡喃-4-基 酯、（甲基）丙烯酸-4-甲基-2-氧代四氫吡喃-4-基酯、（ 甲基）丙烯酸-4-乙基-2-氧代四氫吡喃-4-基酯、（甲基） 丙烯酸-4-丙基-2-氧代四氫吡喃-4-基酯、（甲基）丙烯 酸-5-氧代四氫呋喃-3-基酯、（甲基）丙烯酸-2,2-二甲基-5-氧代四氫呋喃-3-基酯、（甲基）丙烯酸-4,4-二甲基- 5-氧代四氫呋喃-3-基酯、（甲基）丙烯酸-2-氧代四氫呋喃-3-基酯、（甲基）丙烯酸-4,4-二甲基-2-氧代四氫呋喃-3-基酯、（甲基）丙烯酸- 5,5-二甲基-2-氧代四氫呋喃-3-基 酯、（甲基）丙烯酸-2-氧代四氫呋喃-3-基酯、（甲基） 丙烯酸-5-氧代四氫呋喃-2-基甲酯、（甲基）丙烯酸-3,3-二甲基-5-氧代四氫呋喃-2-基甲酯、（甲基）丙烯酸-4，4-二甲基-5 —氧代四氫呋喃-2-基甲酯等。 -21 - 200839449 作爲前述含有脂環式化合物的重複單位（以下 重複單位（4)」），例如可舉出下述通式（4)所 複單位等。 [化5] R8 十 C一 CH2+ (4) /=0 0、(3-4) (3-5) (3-6) In each of the formulae (3-1) to (3-6), R5 represents a hydrogen atom or a methyl group, and R8 represents a hydrogen atom or a carbon number of 1~ An alkyl group which may have a substituent, and R7 represents a hydrogen atom or a methoxy group. Further, A represents a single bond or a methylene group, and B represents an oxygen atom or a methylene group. In addition, 1 represents an integer of 1 to 3, and m is 0 or 1. In the R6 of the above formula (3-1), the alkyl group which may have a substituent of the carbon number of 1 to 4 may, for example, be a methyl group. Ethyl, n-propyl, isopropyl-20-200839449, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and the like. Specific examples of the preferred monomer to which the above repeating unit (3) is given include (meth)acrylic acid-5-oxo-4-oxa-tricyclo[4.2.1 ·03,7] 壬-2. -yl ester, (meth)acrylic acid-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo[4.2.1 ·03,7]non-2-yl ester, (meth)acrylic acid- 5-oxo-4-oxa-tricyclo[5·2·1·03,8]non-2-yl ester, (meth)acrylic acid-10-methoxycarbonyl-5-oxo-4-oxo Hetero-tricyclo[5.2.1.03,8]non-2-yl ester, (meth)acrylic acid-6-oxo-7-oxa-bicyclo[3.2.1]oct-2-yl ester, (methyl Acetyl-4-methoxycarbonyl-6-oxo-7-oxa-bicyclo[3.2.1]oct-2-yl ester, (meth)acrylic acid-7-oxo-8-oxa-bicyclo[ 3.3.1] Oct-2-yl ester, (meth)acrylic acid-4-methoxycarbonyl-7-oxo-8-oxa-bicyclo[3·3·1]oct-2-yl ester, (A 2-oxotetrahydropyran-4-yl acrylate, 4-methyl-2-oxotetrahydropyran-4-yl (meth)acrylate, (meth)acrylic acid-4 -ethyl-2-oxotetrahydropyran-4-yl ester, (meth)acrylic acid-4-propyl-2-oxotetrahydropyran-4-yl, (meth)acrylic acid-5 -oxo Hydrofuran-3-yl ester, (meth)acrylic acid-2,2-dimethyl-5-oxotetrahydrofuran-3-yl ester, (meth)acrylic acid-4,4-dimethyl-5-oxygen Tetrahydrofuran-3-yl ester, 2-oxotetrahydrofuran-3-yl (meth)acrylate, 4,4-dimethyl-2-oxotetrahydrofuran-3-yl (meth)acrylate, (meth)acrylic acid - 5,5-dimethyl-2-oxotetrahydrofuran-3-yl ester, (meth)acrylic acid-2-oxotetrahydrofuran-3-yl ester, (meth)acrylic acid-5- Oxotetrahydrofuran-2-ylmethyl ester, (meth)acrylic acid-3,3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl ester, (meth)acrylic acid-4,4-dimethyl- 5-oxotetrahydrofuran-2-ylmethyl ester and the like. -21 - 200839449 The repeating unit (hereinafter, the repeating unit (4)") containing the alicyclic compound may, for example, be a unit of the following formula (4). [Chemical 5] R8 ten C-CH2+ (4) /=0 0,

XX

[通式（4)中，R8表示氫原子、甲基、或三氟甲基 碳數4〜2 0的脂環式烴基]。 於前述通式（4 )的X中，作爲碳數4〜20的 烴基，例如可舉出從環丁烷、環戊烷、環己院 [2.2.1]庚烷、雙環[2·2·2]辛烷、三環[5.2.1.02,6]癸 環[6·2·13,6·〇2,7]十二烷、三環癸烷等的 而來的脂環族環所成的烴基。 此等由環烷而來的脂環族環係可具有取代基， 經甲基、乙基、正丙基、異丙基、正丁基、2_甲基 1-甲基丙基、第三丁基等的碳數1〜4的直鏈狀、 或環狀的院基之1種以上或1個以上所取代。此等 定於經這些烷基所取代者，亦可爲經羥基、氰基、 〜1 〇的羥烷基、羧基、氧所取代者。 作爲給予前述重複單位（4 )的較佳單體，可 甲基）丙烯酸-雙環[2.2 · 1 ]庚-2 -基酯、（甲基）丙; 環[2.2,2]羊-2-基酯、（甲基）丙烯酸-三環·2·1. 7-基酯、（甲基）丙烯酸-四環[6·2.13,6.02,7]十二 稱爲「 示的重 ，X爲 脂環式 、雙環 烷、四 環烷類 例如可 丙基、 支鏈狀 係不限 碳數1 舉出（ 睹酸·雙 〇2,6]癸· 院-9 -基 -22- 200839449 酯、（甲基）丙烯酸-三環[3.3,1.1s，7]癸-1-基酯、（甲基 )丙烯酸-三環[3.3.1.I3,7]癸-2-基酯等。 又’作爲產生前述由芳香族化合物而來的重複單位（ 以下稱爲「重複單位（5 )」）之較佳單體，例如可舉出 苯乙烯、α-甲基苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、 4-甲基苯乙烯、2-甲氧基苯乙烯、3-甲氧基苯乙烯、4-甲 氧基苯乙烯、4-(2-第三丁氧羰基乙氧基）苯乙烯2-羥基 苯乙烯、3-羥基苯乙烯、4-羥基苯乙烯、2-羥基甲基苯 乙烯、3-羥基-α-甲基苯乙烯、4-羥基-α-甲基苯乙烯、2-甲基-3-羥基苯乙烯、4 -甲基-3-羥基苯乙烯、5 -甲基-3-羥 基苯乙烯、2 -甲基-4-羥基苯乙烯、3 -甲基-4-羥基苯乙烯 、3,4-二羥基苯乙烯、2,4,6-三羥基苯乙烯、扣第三丁氧 基苯乙烯、4 -第三丁氧基·α_甲基苯乙嫌、4- (2 -乙基-2-丙氧基）苯乙烯、4- (2-乙基-2-丙氧基）-α-甲基苯乙烯 、4- ( 1 ·乙氧基乙氧基）苯乙烯、4-(〗_乙氧基乙氧基）-α-甲基苯乙烯、（甲基）丙烯酸苯酯、（甲基）丙烯酸苄 酯、苊烯、5-羥基苊烯、1-乙烯基萘、2_乙烯基萘、2-羥 基-6-乙烯基萘、（甲基）丙烯酸1β萘酯、（甲基）丙烯 酸2-萘酯、（甲基）丙烯酸b萘基甲酯、（甲基）丙烯 酸1-蒽酯、（甲基）丙烯酸2_蒽酯、（甲基）丙烯酸卜 蒽酯、（甲基）丙烯酸9-蒽基甲酯、乙烯基芘等。 於本發明的聚合物（A )中，可含有僅1種的重複單 位（3 )、重複單位（4 )、重複單位（5 )所代表的「其 它重複單位」，也可以含有2種以上。 -23- 200839449 又，本發明的聚合物（A )，例如可藉由使用氫過氧 化物類、二烷基過氧化物類 '二醯基過氧化物類、偶氮化 合物等的自由基聚合引發劑’視需要在鏈轉移劑的存在下 ，於適當的溶劑中’將對應於指定各重複單位的聚合性不 飽和單體聚合而製造。 作爲前述聚合所使用的溶劑’例如可舉出正戊烷、正 己烷、正庚烷、正辛烷、正壬烷、正癸烷等的烷類；環己 烷、環庚烷、環辛烷、十氫萘、原冰片烷等的環烷類；苯 、甲苯、二甲苯、乙苯、異丙苯等的芳香族烴類；氯丁烷 類、溴己烷類、二氯乙烷類、六亞甲基二溴化物、氯苯等 的鹵化烴類；醋酸乙酯、醋酸正丁酯、醋酸異丁酯、丙酸 甲酯等的飽和羧酸酯類；丙酮、2-丁酮、4-甲基-2-庚酮、 2-庚酮等的酮類；四氫呋喃、二甲氧基乙烷類、二乙氧基 乙烷類等的醚類；甲醇、乙醇、1-丙醇、2-丙醇、4-甲基-2-戊醇等的醇類等。此等溶劑可爲單獨或混合2種以上來 使用。 前述聚合的反應溫度通常爲40〜150 °C，較佳爲50〜 1 20 °C，反應時間通常爲1〜48小時，較佳爲1〜24小時 〇 又，本發明的聚合物（A )之由凝膠滲透層析術（ GPC)法所測疋的聚苯乙燒換算重量平均分子星（以下稱 爲「Mw」）較佳爲1，〇〇〇〜50,000，尤佳爲1，〇〇〇〜 40,000，更佳爲1，000〜30,000。該聚合物（A)的Mw若 低於1，〇〇〇，則無法得到充分的前進接觸角。另一方面， -24- 200839449 其Mw若超過5 0,000，則作爲光阻時的顯像性有降 向。 另外，聚合物（A)的Mw與由GPC法所測定 乙烯換算數平均分子量（以下稱「Μη」）之比（ )通常爲1〜5，較佳爲1〜4。 再者，聚合物（Α)係鹵素、金屬等的雜質之 少愈佳’藉此可進一步改善作爲光阻時的感度、解 製程安定性、圖型形狀等。 又，作爲聚合物（A )的精製法，例如可舉出 液-液萃取等的化學精製法，此等的化學精製法與 離心分離等的物理精製法之組合等。 於本發明中，聚合物（A )可爲單獨或混合2 來使用。 又，於本發明中，聚合物（A )的含量，從光 保充分的前進接觸角，可充分抑制來自光阻膜的酸 等之溶出的觀點來看，以該聚合物（A )及後述的 B )之合計爲1 0 0質量％時，較佳爲0 · 1質量％以上 爲0.1〜40質量％，更佳爲0.5〜35質量％。該聚爸 )的含量若低於0 · 1質量％，則無法形成具有指定 觸角的光阻膜，有無法抑制來自光阻膜的酸產生齊jj 出的傾向。另一方面，若該含量超過4 0質量％， 立線的焦點深度變小，產生顯像缺陷之虞。 <樹脂（B ) > 低的傾 的聚苯 M w/Mn 含量愈 像度、 水洗、 超濾、 種以上 阻膜確 產生劑 樹脂（ ，尤佳 r物（a 前進接 等之溶 則有孤 -25- 200839449 本發明之藉由酸的作用成爲鹼可溶性且氟含量爲低於 3原子％的樹脂（B )[以下亦僅稱「樹脂（B )」]，係藉 由酸的作用成爲鹼可溶性的鹼不溶性或鹼難溶性樹脂。此 處所言的「鹼不溶性或鹼難溶性」係意味於從含有樹脂（ B )的敏輻射線性樹脂組成物所形成的光阻膜來形成光阻 圖型時所採用的鹼顯像條件下，將代替該光阻膜而僅用樹 脂（B)的被膜顯像時，該被膜的初期膜厚之50%以上在 顯像後殘留之性質。 作爲前述樹脂（B )，例如可舉出於將原冰片烯衍生 物等聚合而得之主鏈中具有原冰片烷環等的脂環式骨架之 樹脂，於將原冰片烯衍生物與馬來酸酐共聚合而得之主鏈 中具有原冰片烷環及馬來酸酐衍生物之樹脂，於將原冰片 烯衍生物與（甲基）丙烯酸化合物共聚合而得之主鏈中原 冰片烷環與（甲基）丙烯酸骨架混合存在的樹脂，於將原 冰片烯衍生物與馬來酸酐、（甲基）丙烯酸化合物共聚合 而得之主鏈中原冰片烷環與馬來酸酐衍生物和（甲基）丙 烯酸骨架混合存在之樹脂，將（甲基）丙烯酸化合物共聚 合而得之主鏈爲（甲基）丙烯酸骨架的樹脂等。再者，「 (甲基）丙烯酸」表示「丙烯酸」、「甲基丙烯酸」中任 一者或兩者。 於前述樹脂（B)之中，作爲較佳的例子，可舉出含 有藉由酸的作用成爲鹼可溶性之骨架的重複單位、及含有 內酯構造的重複單位。 作爲含有藉由酸的作用成爲鹼可溶性之骨架的重複單 -26- 200839449 位，可舉出前述的重複單位（2 )。再者，用於 複單位（2 )的較佳單體，係與前述者同樣。 又，樹脂（B )可僅含有1種的該重複單位（ 可含有2種以上。 於樹脂（B )中，該重複單位（2 )的含有率 (B)的全部重複單位爲100莫耳％時，較佳爲】 耳°/。，尤佳爲15〜60莫耳％，更佳爲20〜50莫 重複單位（2 )的含有率若低於1 0莫耳％，則作 解像度有降低之虞。另一方面，此含有率若超過 %，則顯像性或曝光寬裕度有惡化之虞。 又，作爲含有內酯構造的重複單位，可舉出 單位（3 )。再者，用於給予此重複單位（3 )的 體係與前述者同樣。 另外，樹脂（B )可僅含有1種的該重複單 也可含有2種以上。 於樹脂（B )中，重複單位（3 )的含有率， B )的全部重複單位爲！〇〇莫耳。/。時，較佳爲5〜 ’尤佳爲10〜70莫耳％，更佳爲15〜60莫耳％ 單位（3 )的含有率若低於5莫耳％，則顯像性 裕度有惡化的傾向。另一方面，此含有率若超過 % ’樹脂（Β )對溶劑的溶解性會惡化，解像度 傾向。 本發明的樹脂（Β )可含有！種或2種以上 複單位（2 )及（3 )以外的重複單位（以下稱爲 給予該重 ：2)，也 ，以樹脂 0〜70莫 ;耳％。該 爲光阻的 70莫耳 前述重複 較佳的單 Ϊ ( 3 )， 以樹脂（ 8 5莫耳％ 。此重複 、曝光寬 85莫耳 有惡化的 的前述重 「其它重 -27- 200839449 複單位」）。 作爲其它重複單位，可舉出前述含有脂環式化合物的 重複單位（4 )、前述由芳香族化合物而來的重複單位（5 )、下述通式（5 )所示的重複單位（以下稱爲重複單位 (6))、下述通式（6 )所示的重複單位（以下稱爲重複 單位（7 ))等。再者，用於給予重複單位（4 )及（5 ) 的較佳單體係各自與前述者同樣。 [化6] R9 (5) 七卜CH2+ /C-0 R1 f3c[In the formula (4), R8 represents a hydrogen atom, a methyl group, or an alicyclic hydrocarbon group having a trifluoromethyl group having 4 to 20 carbon atoms]. In the X of the above formula (4), examples of the hydrocarbon group having 4 to 20 carbon atoms include cyclobutane, cyclopentane, cyclohexyl [2.2.1] heptane, and bicyclo [2·2· 2] octane, tricyclo[5.2.1.02,6] anthracene ring [6·2·13,6·〇2,7] formed by an alicyclic ring derived from dodecane or tricyclodecane Hydrocarbyl group. The cycloaliphatic ring system derived from cycloalkane may have a substituent, and may be substituted with methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methyl-1-methylpropyl, and third. One or more or one or more of the linear or cyclic group having a carbon number of 1 to 4, such as a butyl group, may be substituted. These may be substituted by a hydroxy group, a hydroxy group, a hydroxy group, a carboxyl group or an oxygen group which are substituted by a hydroxy group, a cyano group, or a hydrazine group. As a preferred monomer for the above repeating unit (4), methyl)acrylic acid-bicyclo[2.2 ·1]hept-2-yl ester, (meth)propene; cyclo[2.2,2]-17-yl Ester, (meth)acrylic acid-tricyclo-2.1. 7-yl ester, (meth)acrylic acid-tetracyclo[6·2.13, 6.02,7]12 is called "heavy weight, X is an alicyclic ring" a formula, a bicycloalkane or a tetracycloalkane such as a propyl group or a branched chain is not limited to a carbon number of 1 ( 睹 · 〇 〇 2,6] 癸·院-9-基-22- 200839449 Ester, (A Acetyl-tricyclo[3.3,1.1s,7]non-1-yl ester, (meth)acrylic acid-tricyclo[3.3.1.I3,7]non-2-yl ester, etc. Preferred monomers of the repeating unit derived from the aromatic compound (hereinafter referred to as "repeating unit (5)") include, for example, styrene, α-methylstyrene, 2-methylstyrene, and 3 -methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-(2-tert-butoxycarbonylethoxy) Styrene 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxymethylstyrene, 3-hydroxy-α- Styrene, 4-hydroxy-α-methylstyrene, 2-methyl-3-hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 2- Methyl-4-hydroxystyrene, 3-methyl-4-hydroxystyrene, 3,4-dihydroxystyrene, 2,4,6-trihydroxystyrene, tributyloxystyrene, 4 -T-butoxy-α-methylphenylethyl, 4-(2-ethyl-2-propoxy)styrene, 4-(2-ethyl-2-propoxy)-α-A Styrene, 4-(1·ethoxyethoxy)styrene, 4-(]_ethoxyethoxy)-α-methylstyrene, phenyl (meth)acrylate, (methyl) Benzyl acrylate, decene, 5-hydroxydecene, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-hydroxy-6-vinylnaphthalene, 1β naphthyl (meth)acrylate, (meth)acrylic acid 2-naphthyl ester, b-naphthylmethyl (meth)acrylate, 1-decyl (meth)acrylate, 2-decyl (meth)acrylate, dimethacrylate (meth)acrylate, (meth)acrylic acid 9-fluorenylmethyl ester, vinyl hydrazine, etc. In the polymer (A) of the present invention, it may contain only one repeating unit (3), repeating unit (4) The "other repeating unit" represented by the repeating unit (5) may be contained in two or more types. -23- 200839449 Further, the polymer (A) of the present invention may be, for example, a hydroperoxide. , a radical polymerization initiator of a dialkyl peroxide type 'dimercapto-based peroxide, an azo compound, etc., as needed, in the presence of a chain transfer agent, in a suitable solvent, will correspond to each of the designated repeats A unit of a polymerizable unsaturated monomer is produced by polymerization. Examples of the solvent used for the polymerization include alkane such as n-pentane, n-hexane, n-heptane, n-octane, n-decane or n-decane; cyclohexane, cycloheptane and cyclooctane; , naphthenes such as decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutanes, bromohexanes, dichloroethanes, Halogenated hydrocarbons such as hexamethylene dibromide and chlorobenzene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate; acetone, 2-butanone, 4 a ketone such as methyl-2-heptanone or 2-heptanone; an ether such as tetrahydrofuran, dimethoxyethane or diethoxyethane; methanol, ethanol, 1-propanol, 2 An alcohol such as propanol or 4-methyl-2-pentanol. These solvents may be used singly or in combination of two or more. The reaction temperature of the above polymerization is usually 40 to 150 ° C, preferably 50 to 1 20 ° C, and the reaction time is usually 1 to 48 hours, preferably 1 to 24 hours, and the polymer (A) of the present invention. The polyphenylene bromide-reduced weight average molecular star (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC) is preferably 1, 〇〇〇 50,000, and particularly preferably 1, 〇 〇〇 ~ 40,000, more preferably 1,000 to 30,000. When the Mw of the polymer (A) is less than 1, 〇〇〇, a sufficient advancing contact angle cannot be obtained. On the other hand, -24-200839449, if the Mw exceeds 50,000, the development of the photoresist is lowered. Further, the ratio (M) of the Mw of the polymer (A) to the ethylene equivalent number average molecular weight (hereinafter referred to as "?n") measured by the GPC method is usually from 1 to 5, preferably from 1 to 4. Further, the polymer (Α) is preferably a halogen or a metal having less impurities, whereby the sensitivity, the solution stability, the pattern shape, and the like as a photoresist can be further improved. In addition, examples of the purification method of the polymer (A) include a chemical purification method such as liquid-liquid extraction, a combination of such a chemical purification method and a physical purification method such as centrifugal separation. In the present invention, the polymer (A) may be used singly or in combination 2. Further, in the present invention, the content of the polymer (A) is sufficient to suppress the elution of an acid or the like from the photoresist film from a sufficient advance contact angle of photoprotection, and the polymer (A) and the following will be described later. When the total of B) is 100% by mass, it is preferably 0.1% by mass or more and 0.1 to 40% by mass, more preferably 0.5 to 35% by mass. When the content of the poly dabide is less than 0.1% by mass, a photoresist film having a predetermined antennae cannot be formed, and the acid from the photoresist film cannot be suppressed from being generated. On the other hand, if the content exceeds 40% by mass, the depth of focus of the vertical line becomes small, and a development defect occurs. <Resin (B) > Low tilting polyphenylene M w/Mn content, image, water washing, ultrafiltration, above-mentioned film, resin, (or a good material) Solitary-25-200839449 The resin (B) of the present invention which is alkali-soluble by the action of an acid and having a fluorine content of less than 3 atom% (hereinafter also referred to simply as "resin (B)"] is by the action of an acid It is an alkali-soluble alkali-insoluble or alkali-insoluble resin. The term "alkali-insoluble or alkali-insoluble" as used herein means a photoresist formed from a resistive linear resin composition containing a resin (B). In the case of the alkali development condition used in the pattern, when the film of the resin (B) is used instead of the photoresist film, the initial film thickness of the film is 50% or more and remains after development. The resin (B) may, for example, be a resin having an alicyclic skeleton such as a norbornane ring in a main chain obtained by polymerizing an original borneol derivative or the like, and a norbornene derivative and maleic anhydride. The main chain of copolymerization has an original borneol ring and a maleic anhydride derivative a resin obtained by mixing an ornidyl derivative with a (meth)acrylic compound to obtain a resin in which a norbornane ring and a (meth)acrylic acid skeleton are mixed in a main chain, and a norbornene derivative and maleic anhydride. a resin obtained by copolymerizing a (meth)acrylic acid compound in a main chain in which a norbornane ring is mixed with a maleic anhydride derivative and a (meth)acrylic acid skeleton, and a (meth)acrylic compound is copolymerized to obtain a main chain. Further, "(meth)acrylic acid" means either or both of "acrylic acid" and "methacrylic acid". Among the above resins (B), A preferred example is a repeating unit containing a skeleton which is alkali-soluble by the action of an acid, and a repeating unit having a lactone structure. As a skeleton containing an alkali-soluble skeleton by the action of an acid, it is a repeating single-26-200839449 The above-mentioned repeating unit (2) may be mentioned. The preferred monomer for the complex unit (2) is the same as the above. Further, the resin (B) may contain only one type of the repeat. In the resin (B), when the total repeating unit of the content (B) of the repeating unit (2) is 100 mol%, it is preferably an ear//, more preferably 15 to 60% by mole, more preferably 20 to 50% of the repeating unit (2), if the content is less than 10% by mole, the resolution is lowered. On the other hand, if the content exceeds %, In the case of the repeating unit containing the lactone structure, the unit (3) is also used. The system for giving the repeating unit (3) is the same as the above. In addition, the resin (B) may contain only one type of the repeating unit or two or more types. In the resin (B), the content of the unit (3) is repeated, and all the repeating units of B) are! 〇〇莫耳. /. Preferably, it is 5~', preferably 10 to 70% by mole, more preferably 15 to 60% by mole. If the content of the unit (3) is less than 5 mol%, the developmental margin is deteriorated. Propensity. On the other hand, if the content exceeds %', the solubility of the resin (Β) in the solvent is deteriorated, and the resolution tends to be high. The resin (Β) of the present invention may contain! Or more than two kinds of repeating units other than (2) and (3) (hereinafter referred to as the weight: 2), and also 0 to 70% of the resin; The photoresist is 70 moles of the above-mentioned repeating preferred single Ϊ (3), with resin (85 mil%. This repetition, exposure width 85 mils deteriorated the aforementioned heavy "other heavy -27-200839449 complex unit"). Examples of the other repeating unit include the repeating unit (4) containing the alicyclic compound, the repeating unit (5) derived from the aromatic compound, and the repeating unit represented by the following formula (5) (hereinafter referred to as The repeating unit (6)), the repeating unit represented by the following general formula (6) (hereinafter referred to as repeating unit (7)), and the like. Further, each of the preferred single systems for giving the repeating units (4) and (5) is the same as the above. [6] R9 (5) Seven Bu CH2+ /C-0 R1 f3c

CF, HOCF, HO

[通式（5)中，R9表示氫原子、碳數1〜4的烷基、三氟 甲基、或羥甲基，rig表示2價有機基]。 作爲通式（5 )的R9中之碳數1〜4的烷基，例如可 舉出甲基、乙基、正丙基、異丙基、正丁基、2-甲基丙基 、1-甲基界基、第三丁基等的烷基。 又，作爲通式（5)的R1G中之2價有機基，較佳爲2 價烴基，2價烴基中較佳爲鏈狀或環狀的烴基，亦可爲伸 烷二醇基，也可爲伸烷酯基。 作爲較佳的前述R1 ^，可舉出亞甲基、伸乙基、1，3- 伸丙基或1，2_伸丙基等的伸丙基、四亞甲基、五亞甲基、 六亞甲基、七亞甲基、八亞甲基、九亞甲基、十亞甲基、 十一亞甲基、十二亞甲基、十三亞甲基、十四亞甲基、十 -28- 200839449 五亞甲基、十六亞甲基、十七亞甲基、十八亞甲基、十九 亞甲基、伸二十二基、1-甲基-1，3 -伸丙基、2 -甲基1，3 -伸 丙基、2 -甲基-1，2 -伸丙基、1-甲基-〗，心伸丁基、2 -甲基-1，4-伸丁基、次甲基、亞乙基、亞丙基、或2_亞丙基等的 飽和鏈狀烴基、1，3 -伸環丁基等的伸環丁基、1，3 -伸環戊 基等的伸環戊基、1，4 -伸環己基等的伸環己基、1，5 -伸環 辛基等的伸環辛基等之碳數3〜10的伸環烷基等的環式烴 環基、1，4-伸原冰片基或2,5-伸原冰片基等的伸原冰片基 、1，5-伸金剛烷基、2,6-伸金剛烷基等的伸金剛烷基等之 2〜4環式碳數4〜30的烴環基等之交聯環式烴環基等。 特別地，於含有2價脂肪族環狀烴基當作R1 ^時，較 佳爲在雙三氟甲基-羥基-甲基與該脂肪族環狀烴基之間插 入當作間隔子的碳數1〜4的伸烷基。 又，作爲R1G，較佳爲含有2,5-伸原冰片基的烴基、 1，2-伸乙基、伸丙基。 再者，作爲用於給予重複單位（6 )的特佳單體’可 舉出（甲基）丙烯酸（l，l，l-三氟-2-三氟甲基經基 丙基）酯、（甲基）丙烯酸（I，1，1-三氟三氟甲基邀 基-4-丁基）酯、（甲基）丙烯酸Ο，1，1·三氟·2 —三氟甲 基-2-羥基-5-戊基）酯、（甲基）丙烯酸（m-三氟·2· 三氟甲基-2-羥基-4-戊基）酯、（甲基）丙烯酸2·{[5·( 1，，1，，1，-三氟-2，-三氟甲基-2，-羥基）丙基]雙環[2.2，1]庚 基}酯、（甲基）丙烯酸3-{[8· ( 1，，1，，1’-三氟_2’-三氟甲 基-2，-羥基）丙基]四環[6.2.1.13,6.〇2,7]十二基}酯等。 -29- 200839449In the formula (5), R9 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group or a hydroxymethyl group, and rig represents a divalent organic group. Examples of the alkyl group having 1 to 4 carbon atoms in R9 in the formula (5) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-methylpropyl group, and 1- An alkyl group such as a methyl group or a tributyl group. Further, the divalent organic group in R1G of the formula (5) is preferably a divalent hydrocarbon group, and the divalent hydrocarbon group is preferably a chain or cyclic hydrocarbon group, and may be an alkylene glycol group. It is an alkyl ester group. Preferred examples of the above R1 ^ include a stretching group, a tetramethylene group, a pentamethylene group such as a methylene group, an ethylidene group, a 1,3-propyl group or a 1,2-propyl group. Hexamethylene, heptamethylene, octamethylene, hexamethylene, decamethylene, eleven methylene, dodecamethylene, thirteen methylene, tetradecyl, ten 28- 200839449 Pentamethylene, hexadecyl, heptamethylene, octamethylidene, ninth methylene, thiol-2-yl, 1-methyl-1,3-propanyl , 2-methyl 1,3 -propyl, 2-methyl-1,2-propanyl, 1-methyl-, butyl, 2-methyl-1,4-butylene a saturated chain hydrocarbon group such as a methine group, an ethylene group, a propylene group, or a 2 propylene group, a cyclobutyl group such as a 1,3-cyclobutene group, a 1,3 -cyclopentyl group, or the like. a cyclic hydrocarbon such as a cyclopentene group such as a cyclopentyl group, a 1,4-cyclohexylene group, a cyclopentene group such as a 1,5-cyclohexyl group, or a cycloalkyl group having a carbon number of 3 to 10 An alkaloid group such as a cyclic group, a 1,4-extension borneol group or a 2,5-extension borneol group, a 1,5-adamantyl group, a 2,6-adamantyl group or the like Wait 2~4 A crosslinked cyclic hydrocarbon ring group such as a hydrocarbon ring group having a ring carbon number of 4 to 30 or the like. In particular, when a divalent aliphatic cyclic hydrocarbon group is used as R1^, it is preferred to insert a carbon number as a spacer between the bistrifluoromethyl-hydroxy-methyl group and the aliphatic cyclic hydrocarbon group. ~4 alkylene. Further, as R1G, a hydrocarbon group containing a 2,5-extension borneol group, a 1,2-extended ethyl group, and a propyl group are preferable. Further, as the particularly preferable monomer for giving the repeating unit (6), (1,1,1-trifluoro-2-trifluoromethyl propyl propyl) (meth) acrylate may be mentioned ( Methyl)acrylic acid (I,1,1-trifluorotrifluoromethyl-4-yl)ester, hydrazine (meth)acrylate, 1,1·trifluoro-2-pyridyl-2- Hydroxy-5-pentyl)ester, (meth)acrylic acid (m-trifluoro.2.trifluoromethyl-2-hydroxy-4-pentyl)ester, (meth)acrylic acid 2·{[5·( 1,1,1,1,-trifluoro-2,-trifluoromethyl-2,-hydroxy)propyl]bicyclo[2.2,1]heptyl}ester, (meth)acrylic acid 3-{[8· (1,1,1'-trifluoro-2'-trifluoromethyl-2,-hydroxy)propyl]tetracyclo[6.2.1.13,6.〇2,7]dodecyl}ester. -29- 200839449

[通式（6)中，R11表示氫或甲基，Y表示單鍵或碳數1〜 3的2價有機基，Ζ互相獨立地表示單鍵或碳數1〜3的2 價有機基，R12互相獨立地表示氫原子、羥基、氰基、或 COOR13 基]。 作爲通式（6)中的Υ及Ζ之碳數1〜3的2價有機 基，可舉出亞甲基、伸乙基、伸丙基。 又，通式（6 )的R 1 2中之C Ο Ο R 13基的R 13，表示氫 原子或碳數1〜4的直鏈狀或支鏈狀的烷基、或碳數3〜 20的脂環式烷基。於該R13中，作爲前述碳數1〜4的直 鏈狀或支鏈狀的烷基，可例示甲基、乙基、正丙基、異丙 基、正丁基、2-甲基丙基、1-甲基丙基、第三丁基。 另外，作爲前述碳數3〜20的脂環式烷基，可舉出 ( n爲3〜20的整數）所示的環烷基，例如可舉 出環丙基、環丁基、環戊基、環己基、環庚基、環辛基等 。再者，多環型脂環式烷基，例如可舉出雙環[2.2.1]庚基 、三環[5·2·1·02,6]癸基、四環[6.2.13,6.02’7]十二基、金剛 院基等’或以直鏈狀、支鏈狀或環狀烷基的1種以上或i -30- 200839449 個以上取代環烷基或多環型脂環式烷基的一部分之基等。 又，於3個R12中的至少一個不是氫原子且Y爲單鍵 時，3個Z中的至少一個較佳爲碳數1〜3的2價前述有 機基。 作爲產生前述重複單位（7)的較佳單體，可舉出（ 甲基）丙烯酸3-羥基金剛烷-1-基甲酯、（甲基）丙烯酸 3,5-二羥基金剛烷-1·基甲酯、（甲基）丙烯酸3-羥基- 5-氰基金剛烷-1-基甲酯、（甲基）丙烯酸3-羥基-5-羧基金 剛烷-1-基甲酯、（甲基）丙烯酸3-羥基-5-甲氧羰基金剛 烷-1-基甲酯、（甲基）丙烯酸3-羥甲基金剛烷-1-基甲酯 、（甲基）丙烯酸3,5 -二羥甲基金剛烷-1-基甲酯、（甲 基）丙烯酸3-羥基-5-羥甲基金剛烷-1-基甲酯、（甲基） 丙烯酸3-氰基-5-羥甲基金剛烷-1-基甲酯、（甲基）丙烯 酸3-羥甲基-5-羧基金剛烷-1-基甲酯、（甲基）丙烯酸3-羥甲基-5-甲氧羰基金剛烷-1-基甲酯、（甲基）丙烯酸3-氰基金剛烷-1-基甲酯、（甲基）丙烯酸3,5-二氰基金剛 烷-1-基甲酯、（甲基）丙烯酸3-氰基-5-羧基金剛烷-1-基 甲酯、（甲基）丙烯酸3-氰基-5-甲氧羰基金剛烷-1-基甲 酯、（甲基）丙烯酸3-羧基金剛烷-1-基甲酯、（甲基） 丙烯酸3,5-二羧基金剛烷-1-基甲酯、（甲基）丙烯酸3-羧基-5-甲氧羰基金剛烷-1-基甲酯、（甲基）丙烯酸3-甲 氧羰基金剛烷-1-基甲酯、（甲基）丙烯酸3,5-二甲氧羰 基金剛烷-1-基甲酯、 (甲基）丙烯酸3-羥基-5-甲基金剛烷-1-基酯、（甲 -31 - 200839449 基）丙烯酸3,5-二羥基-7-甲基金剛烷-1-基酯、（甲基） 丙烯酸3-羥基-5-氰基-7-甲基金剛烷-1-基酯、（甲基）丙 嫌酸3 -經基-5-竣基-7-甲基金剛院-1-基醋、（甲基）丙矯 酸3 -經基-5-甲氧碳基-7-甲基金剛垸-1-基醋、（甲基）丙 烯酸3-羥甲基-5-甲基金剛烷-1-基酯、（甲基）丙烯酸 3,5-二羥甲基-7-甲基金剛烷-1-基酯、（甲基）丙烯酸3-羥基-5-羥甲基-7-甲基金剛烷-1-基酯、（甲基）丙烯酸3-氰基-5-羥甲基-7-甲基金剛烷-1-基酯、（甲基）丙烯酸3-羥甲基-5-羧基-7-甲基金剛烷-1-基酯、（甲基）丙烯酸3-羥甲基-5-甲氧羰基-7-甲基金剛烷-1-基酯、（甲基）丙烯 酸3 ·截基-5 -甲基金剛院· 1 -基醋、（甲基）丙矯酸3，5 -二 氰基-7-甲基金剛烷-1-基酯、（甲基）丙烯酸3-氰基-5-羧 基-7-甲基金剛烷-1-基酯、（甲基）丙烯酸3-氰基-5-甲氧 羰基-7-甲基金剛烷-1-基酯、（甲基）丙烯酸3-羧基-5-甲 基金剛烷-1-基酯、（甲基）丙烯酸3,5-二羧基-7-甲基金 剛烷-1-基酯、（甲基）丙烯酸3-羧基-5-甲氧羰基-7-甲基 金剛烷-1-基酯、（甲基）丙烯酸3-甲氧羰基-5-甲基金剛 烷-1-基酯、（甲基）丙烯酸3,5-二甲氧羰基-7-甲基金剛 烷-1-基酯、 (甲基）丙烯酸3-羥基-5-甲基金剛烷-1_基甲酯、（ 甲基）丙烯酸3,5_二羥基-7-甲基金剛烷-1-基甲酯、（甲 基）丙燦酸3 -經基-5 -氣基-7 -甲基金剛院-1-基甲醋、（甲 基）丙烯酸3-羥基-5-羧基-7-甲基金剛烷-1-基甲酯、（甲 基）丙烯酸3-羥基-5-甲氧羰基-7-甲基金剛烷-1-基甲酯、 -32 - 200839449 (甲基）丙烯酸3-羥甲基-5-甲基金剛烷-1-基甲酯、（甲 基）丙烯酸3,5-二羥甲基-7-甲基金剛烷-1-基甲酯、（甲 基）丙烯酸3-羥基-5-羥甲基-7-甲基金剛烷-1-基甲酯、（ 甲基）丙烯酸3-氰基-5 _羥甲基-7-甲基金剛烷-1-基甲酯、 (甲基）丙烯酸3-羥甲基-5-羧基-7-甲基金剛烷-1-基甲酯 、（甲基）丙烯酸3-羥甲基-5-甲氧羰基-7-甲基金剛烷-1_ 基甲酯、（甲基）丙烯酸3-氰基-5-甲基金剛烷-1-基甲酯 、（甲基）丙烯酸3，5-二氰基-7-甲基金剛烷-1-基甲酯、 (甲基）丙烯酸3-氰基-5-羧基-7-甲基金剛烷-1-基甲酯、 (甲基）丙烯酸3-氰基-5-甲氧羰基-7-甲基金剛烷-1-基甲 酯、（甲基）丙烯酸3-羧基-5-甲基金剛烷-1-基甲酯、（ 甲基）丙烯酸3,5-二羧基-7_甲基金剛烷-1-基甲酯、（甲 基）丙細酸3 -殘基-5 -甲氧鑛基-7 -甲基金剛院-1-基甲醋、 (甲基）丙烯酸3-甲氧羰基-5·甲基金剛烷-1-基甲酯、（ 甲基）丙烯酸3,5-二甲氧羰基-7-甲基金剛烷-1-基甲酯、 (甲基）丙烯酸3 -羥基-5,7-二甲基金剛烷-1-基酯、 (甲基）丙烯酸3-羥甲基-5,7-二甲基金剛烷-1-基酯、（ 甲基）丙烯酸3-氰基-5,7-二甲基金剛烷-1-基酯、（甲基 )丙烯酸3-羧基-5,7-二甲基金剛烷-1-基酯、（甲基）丙 烯酸3-甲氧羰基- 5,7-二甲基金剛烷-1-基酯、（甲基）丙 烯酸3-羥基-5,7·二甲基金剛烷-1-基甲酯、（甲基）丙烯 酸3-羥甲基-5，7-二甲基金剛烷-1-基甲酯、（甲基）丙烯 酸3-氰基-5,7-二甲基金剛烷-1-基甲酯、（甲基）丙烯酸 3-羧基- 5,7-二甲基金剛烷-1-基甲酯、（甲基）丙烯酸3- -33- 200839449 甲氧羰基-5，7-二甲基金剛烷-1_基甲酯等。 作爲此等之中的特佳單體，可舉出（甲基）1 羥基金剛烷-卜基甲酯、（甲基）丙烯酸3,5 -二 烷-1-基甲酯、（甲基）丙烯酸3 -氰基金剛烷-1_ (甲基）丙烯酸3 -羧基金剛烷-1 -基甲酯、（甲 酸3 -經基-5-甲基金剛院-1·基酯、（甲基）丙烯 羥基-7 -甲基金剛烷-1 -基酯、（甲基）丙烯酸3 -二甲基金剛烷-卜基酯、（甲基）丙烯酸3_羧基 基金剛烷-1-基酯、（甲基）丙烯酸3-羥基- 5,7-剛烷-1-基甲酯等。 又，本發明中的樹脂（B )，除了前述重複j 、（5) 、（6)及（7)以外，亦可更含有其它 (以下稱爲「再其它重複單位」）。 作爲該再其它重複單位’例如可舉出（甲基 二環戊烯酯、（甲基）丙烯酸金剛烷基甲酯等的 烴骨架的（甲基）丙烯酸酯類；（甲基）丙烯酸 片酯、（甲基）丙烯酸羧基三環癸酯、（甲基） 基四環十一酯等的具有不飽和羧酸的橋式烴骨架 酯類； (甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯 )丙烯酸正丙酯、（甲基.）丙烯酸正丁酯、（甲 酸2 -甲基丙酯、（甲基）丙烯酸1·甲基丙酯、 丙烯酸第三丁酯、（甲基）丙烯酸2-羥乙酯、 丙烯酸2-羥丙酯、（甲基）丙烯酸3-羥丙酯、 弓烯酸3 -羥基金剛 •基甲酯、 基）丙烯 酸 3，5 -二 羥基-5,7--5,7-二甲 二甲基金 _ 位（4) 重複單位 )丙烯酸 具有橋式 羧基原冰 丙烯酸羧 之含羧基 、（甲基 基）丙烯 (甲基） (甲基） (甲基） -34- 200839449 丙烯酸環丙酯、（甲基）丙烯酸環戊酯、（甲基）丙烯酸 環己酯、（甲基）丙烯酸4-甲氧基環己酯、（甲基）丙 烯酸2-環戊氧基羰乙酯、（甲基）丙烯酸2-環己氧基羰 乙酯、（甲基）丙烯酸2- (4-甲氧基環己基）氧基羰乙酯 等之不具有橋式烴骨架的（甲基）丙烯酸酯類； α-羥甲基丙烯酸甲酯、α-羥甲基丙烯酸乙酯、α-羥甲 基丙烯酸正丙酯、α-羥甲基丙烯酸正丁酯等的α-羥甲基丙 烯酸酯類；（甲基）丙烯腈、α-氯丙烯腈、巴豆腈、馬來 腈、富馬腈、中康腈、檸康腈、伊康腈等的不飽和腈化合 物；（甲基）丙烯醯胺、Ν，Ν·二甲基（甲基）丙烯醯胺、 巴豆醯胺、馬來醯胺、富馬醯胺、中康醯胺、檸康醯胺、 伊康醯胺等的不飽和醯胺化合物；Ν-(甲基）丙烯醯基嗎 啉、Ν_乙烯基-ε-己內醯胺、Ν-乙烯基吡咯啶酮、乙烯基 吡啶、乙烯基咪哩等之其它含氮乙烯基化合物·，（甲基） 丙烯酸、巴豆酸、馬來酸、馬來酸酐、富馬酸、伊康酸、 伊康酸酐、檸康酸、檸康酸酐、中康酸等的不飽和羧酸（ 酐）類；（甲基）丙烯酸2 -羧乙酯、（甲基）丙烯酸2-羧丙酯、（甲基）丙烯酸3 -羧丙酯、（甲基）丙烯酸4-羧丁酯、（甲基）丙烯酸4-羧基環己酯等的不具有不飽 和羧酸的有橋式烴骨架的含羧基酯類； 1，2-金剛烷二醇二（甲基）丙烯酸酯、13 —金剛烷二 醇二（甲基）丙烯酸酯、1，4-金剛烷二醇二（甲基）丙烯 酸酯、二環癸基二羥甲基二（甲基）丙烯酸酯等之具有橋 式烴骨架的多官能性單體； •35- 200839449 亞甲二醇二（甲基）丙烯酸酯、乙二醇二（甲基）丙 烯酸酯、丙二醇二（甲基）丙烯酸酯、1，6-己二醇二（甲 基）丙烯酸酯、2,5 -二甲基-2,5 -己二醇二（甲基）丙烯酸 酯、1，8-辛二醇二（甲基）丙烯酸酯、1，9-壬二醇二（甲 基）丙烯酸酯、1，4 -雙（2 -羥丙基）苯二（甲基）丙烯酸 酯、1，3-雙（2-羥丙基）苯二（甲基）丙烯酸酯等之不具 有橋式烴骨架的多官能性單體等之多官能性單體的聚合性 不飽和鍵裂解的單位。 於該再其它重複單位之中，較佳爲具有橋式烴骨架的 (甲基）丙烯酸酯類之聚合性不飽和結合裂解的單位等。 本發明中的樹脂（B )可僅含有一種的選自於此等重 複單位（4 ) 、（ 5 ) 、（ 6 ) 、（ 7 )及再其它重複單位的 重複單位，也可含有2種以上，不論種類爲何。 於樹脂（B )中，前述重複單位（4 )的含有率，以樹 脂（B )的全部重複單位爲1〇〇莫耳％時，通常爲3〇莫耳 %以下’較佳爲2 5莫耳％以下。該重複單位（* )的含有 率右超過3 0旲耳％ ’光阻圖型形狀會惡化，解像度有降 低之虞。 又，前述重複單位（5 )的含有率，以樹脂（B )的全 部重複單位爲1〇〇莫耳％時，通常爲40莫耳％以下，較佳 爲30莫耳％以下。此重複單位（5)的含有率若超過4〇 莫耳％，則輻射線透過率會變低，圖型輪廓有惡化之虞。 另外，前述重複單位（6 )的含有率，以樹脂（B )的 全部重複單位爲100莫耳％時，通常爲3〇莫耳％以下，較 -36- 200839449 佳爲25旲耳％以下。此重複單位（6)的含有率若超過3〇 莫耳％ ’則所得到的光阻膜有容易被鹼顯像液所膨潤之虞 〇 又，前述重複單位（7 )的含有率，以樹脂（B )的全 部重複單位爲1〇〇莫耳％時，通常爲3〇莫耳％以下，較佳 爲2 5旲耳％以下。此重複單位（7 )的含有率若超過3 〇 莫耳°/。’則所得到的光阻膜容易被鹼顯像液所膨潤，對鹼 φ 顯像液的溶解性有降低之虞。 另外，再其它重複單位的含有率，以樹脂（B )的全 部重複單位爲100莫耳％時，通常爲5〇莫耳％以下，較佳 爲4 0莫耳％。 又’於上述樹脂（B )含有氟化烷基時，以樹脂（b )全體爲1 0 G原子％時，其氟含量爲低於3原子％，較佳 爲〇〜2.9原子％，更佳爲〇〜丨.5原子％。 再者’該氟含量係可與前述方法同樣地測定。 φ 又’本發明中的樹脂（B )，例如可藉由使用氫過氧 化物類、一院基過氧化物類、二_基過氧化物類、偶氮化 合物等的自由基聚合引發劑，視需要在鏈轉移劑的存在下 ’於適當的溶劑中，將對應於指定各重複單位的聚合性不 •飽和單體聚合而製造。 作爲前述聚合所使用的溶劑，例如可舉出正戊烷、正 己烷、正庚烷、正辛烷、正壬烷、正癸烷等的烷類；環己 院、環庚烷、環辛烷、十氫萘、原冰片烷等的環烷類·，苯 、甲苯、二甲苯、乙基苯、異丙苯等的芳香族烴類；氯丁 -37- 200839449 烷類、溴己烷類、二氯乙烷類、六亞甲基二溴化物、氯苯 等的鹵化烴類；醋酸乙酯、醋酸正丁酯、醋酸異丁酯、丙 酸甲酯等的飽和羧酸酯類；丙酮、2-丁酮、4-甲基-2-庚酮 、2 -庚酮等的酮類；四氫呋喃、二甲氧基乙烷類、二乙氧 基乙烷類等的醚類等。此等溶劑可爲單獨或混合2種以上 來使用。 前述聚合的反應溫度通常爲40〜150 °C，較佳爲50〜 120°C，反應時間通常爲1〜48小時，較佳爲1〜24小時 〇 又，本發明中的樹脂（B )之由GPC法所測定的Mw 係沒有特別的限定，較佳爲1，000〜1 00,000，更佳爲 1，000〜30,000，特佳爲 1，000〜20,000。該樹月旨（B)的 Mw若低於1，〇〇〇，則作爲光阻時的耐熱性有降低的傾向 。另一方面，其Mw若超過1〇〇,〇〇〇，則作爲光阻時的顯 像性有降低的傾向。 另外，樹脂（B )的Mw與由GPC法所測定的Μη之 比（Mw/Mn)通常爲1〜5，較佳爲1〜3。 又，於樹脂（B )中，從調製造此樹脂（B )時所用 的單體而來的低分子量成分之含量以固體成分換算，對於 100質量％的樹脂而言，較佳爲0.1質量％以下，尤佳爲 〇·〇7質量％以下，更佳爲〇·〇5質量％以下。該含量若爲 〇· 1質量％以下，則可減少對浸潤式曝光時所接觸的水等 的浸潤介質之溶出物的量。再者，光阻保管時在光阻中不 會產生異物，即使光阻塗佈時也不會發生塗佈不均，可充 -38- 200839449 分抑制光阻圖型形成時的缺陷之產生。 作爲從則述單體而來的低分子量成分，可舉出卓體 二聚物、三聚物、寡聚物，可爲Mw500以下的成分。此 Mw5 00以下的成分，例如可藉由水洗、液-液萃取等的化 學精製法，此等的化學精製法與超濾、離心分離等的物理 精製法之組合等來去除。又，可藉由樹脂的高速液體層析 術（HPLC )來進行分析。 再者，樹脂（B)係鹵素、金屬等的雜質之含量愈少 愈佳，藉此可進一步改善作爲光阻時的感度、解像度、製 程安定性、圖型形狀等。 又，作爲樹脂（B )的精製法，例如可舉出水洗、液-液萃取等的化學精製法，此等的化學精製法與超濾、離心 分離等的物理精製法之組合等。 於本發明中，樹脂（B )可爲單獨或混合2種以上來 使用。 又，於本發明中，樹脂（B )的含量，以前述聚合物 (A )與樹脂（B )的合計爲100質量％時，較佳爲99.9 質量％以下，尤佳爲60〜99.9質量％，更佳爲65〜99.5質 量％。此樹脂（B )的含量若在上述範圍內，則光阻膜可 充分確保前進接觸角，可充分抑制來自光阻膜的酸產生劑 等之溶出。 <敏輻射線性酸產生劑（C ) > 本發明中的敏輻射線性酸產生劑（C )[以下亦僅稱「 -39- 200839449 酸產生劑（C)」]，係藉由曝光而產生酸者’藉由所產生 的酸之作用，使樹脂成分中所存在的酸解離性基，具體地 具有重複單位（2)的酸解離性基解離（脫離保護基）， 結果光阻膜的曝光部成爲鹼顯像液中易溶性，具有形成正 型光阻圖型的作用。 作爲如此的酸產生劑（C )，較佳爲含有下述通式（7 )所示的化合物（以下稱爲「酸產生劑1」）者。 [化8]In the formula (6), R11 represents hydrogen or a methyl group, Y represents a single bond or a divalent organic group having 1 to 3 carbon atoms, and fluorene independently represents a single bond or a divalent organic group having 1 to 3 carbon atoms. R12 independently of each other represents a hydrogen atom, a hydroxyl group, a cyano group, or a COOR13 group]. The divalent organic group having 1 to 3 carbon atoms of ruthenium and osmium in the formula (6) includes a methylene group, an ethyl group and a propyl group. Further, R 13 of the C Ο Ο R 13 group in R 1 2 of the formula (6) represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, or a carbon number of 3 to 20 Alicyclic alkyl group. In the above R13, a linear or branched alkyl group having 1 to 4 carbon atoms is exemplified by a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group or a 2-methylpropyl group. , 1-methylpropyl, tert-butyl. In addition, examples of the alicyclic alkyl group having 3 to 20 carbon atoms include a cycloalkyl group (n is an integer of 3 to 20), and examples thereof include a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. , cyclohexyl, cycloheptyl, cyclooctyl and the like. Further, examples of the polycyclic alicyclic alkyl group include a bicyclo [2.2.1] heptyl group, a tricyclo [5·2·1·02, 6] fluorenyl group, and a tetracyclic ring [6.2.13, 6.02'. 7] Twelve bases, Donkey Kong bases, etc. or one or more of linear, branched or cyclic alkyl groups or i -30-200839449 or more substituted cycloalkyl or polycyclic alicyclic alkyl groups Part of the base. Further, when at least one of the three R12 is not a hydrogen atom and Y is a single bond, at least one of the three Z is preferably a divalent organic group having a carbon number of 1 to 3. Preferred examples of the monomer which produces the above repeating unit (7) include 3-hydroxyadamantane-1-yl (meth)acrylate and 3,5-dihydroxyadamantane-1 (meth)acrylate. Methyl ester, 3-hydroxy-5-cyanoxan-2-ylmethyl (meth)acrylate, 3-hydroxy-5-carboxyadamantan-1-yl (meth)acrylate, (methyl) ) 3-hydroxy-5-methoxycarbonyl adamant-1-ylmethyl acrylate, 3-hydroxymethyladamantane-1-yl (meth) acrylate, 3,5-dihydroxy (meth) acrylate Methyl adamantyl-1-ylmethyl ester, 3-hydroxy-5-hydroxymethyladamantane-1-yl (meth)acrylate, 3-cyano-5-hydroxymethyl konjam (meth)acrylate Alkyl-1-ylmethyl ester, 3-hydroxymethyl-5-carboxyadamantane-1-yl (meth)acrylate, 3-hydroxymethyl-5-methoxycarbonyladamantane (meth)acrylate- 1-methylmethyl ester, 3-cyanopredyl-1-ylmethyl (meth)acrylate, 3,5-dicyanostand-1-ylmethyl (meth)acrylate, (meth)acrylic acid 3-cyano-5-carboxyadamantan-1-ylmethyl ester, 3-cyano-5-methoxycarbonyldantakan-1-ylmethyl (meth)acrylate , 3-carboxyadamantane-1-yl (meth)acrylate, 3,5-dicarboxyadamantan-1-yl (meth)acrylate, 3-carboxy-5-methyl (meth)acrylate Oxycarbonyl hydroxy-damant-1-ylmethyl ester, 3-methoxycarbonyldantapan-1-ylmethyl (meth)acrylate, 3,5-dimethoxycarbonyldantapan-1-yl (meth)acrylate Ester, 3-hydroxy-5-methyladamantan-1-yl (meth)acrylate, 3,5-dihydroxy-7-methyladamantan-1-yl (methyl-31-200839449) , (meth)acrylic acid 3-hydroxy-5-cyano-7-methyladamantan-1-yl ester, (meth)acrylic acid 3-cyano-5-mercapto-7-methyl -1-yl vinegar, (methyl) propyl acid 3 - mercapto-5-methoxycarbyl-7-methyl rimanta-1-yl vinegar, 3-hydroxymethyl-5-(meth)acrylate Methyl adamantyl-1-yl ester, 3,5-dihydroxymethyl-7-methyladamantan-1-yl (meth)acrylate, 3-hydroxy-5-hydroxymethyl (meth)acrylate -7-methyladamantan-1-yl ester, 3-cyano-5-hydroxymethyl-7-methyladamantan-1-yl (meth)acrylate, 3-hydroxymethyl (meth)acrylate 5-carboxy--7-methyladamantan-1-yl Ester, 3-hydroxymethyl-5-methoxycarbonyl-7-methyladamantan-1-yl (meth)acrylate, (meth)acrylic acid 3 · cleavage-5-methyl genius, 1 - Base vinegar, (meth)propionic acid 3,5-dicyano-7-methyladamantan-1-yl ester, 3-cyano-5-carboxy-7-methyladamantane (meth)acrylate -1-yl ester, 3-cyano-5-methoxycarbonyl-7-methyladamantan-1-yl (meth)acrylate, 3-carboxy-5-methyladamantane (meth)acrylate- 1-yl ester, 3,5-dicarboxy-7-methyladamantan-1-yl (meth)acrylate, 3-carboxy-5-methoxycarbonyl-7-methyladamantane (meth)acrylate -1-yl ester, 3-methoxycarbonyl-5-methyladamantan-1-yl (meth)acrylate, 3,5-dimethoxycarbonyl-7-methyladamantane (meth)acrylate- 1-yl ester, 3-hydroxy-5-methyladamantane-1-yl methyl (meth)acrylate, 3,5-dihydroxy-7-methyladamantan-1-yl (meth)acrylate Ester, (meth)propanoic acid 3-carbyl-5-carbyl-7-methyl-Golden-1-1-methyl ketone, 3-hydroxy-5-carboxy-7-methyl ketamine (meth)acrylate Alkan-1-ylmethyl ester, (meth)acrylic acid 3- 5--5-methoxycarbonyl-7-methyladamantan-1-ylmethyl ester, -32 - 200839449 3-hydroxymethyl-5-methyladamantan-1-ylmethyl (meth)acrylate, ( 3,5-Dimethylol-7-methyladamantan-1-ylmethylmethyl (meth)acrylate, 3-hydroxy-5-hydroxymethyl-7-methyladamantane-1-(meth)acrylate Methyl ester, 3-cyano-5-hydroxymethyl-7-methyladamantan-1-ylmethyl (meth)acrylate, 3-hydroxymethyl-5-carboxy-7-(meth)acrylate Methyl adamantyl-1-ylmethyl ester, 3-hydroxymethyl-5-methoxycarbonyl-7-methyladamantane-1-yl methyl (meth)acrylate, 3-cyano (meth)acrylate- 5-methyladamantan-1-ylmethyl ester, (meth)acrylic acid 3,5-dicyano-7-methyladamantan-1-ylmethyl ester, (meth)acrylic acid 3-cyano-5 -carboxy-7-methyladamantan-1-ylmethyl ester, 3-cyano-5-methoxycarbonyl-7-methyladamantan-1-ylmethyl (meth)acrylate, (meth)acrylic acid 3-carboxy-5-methyladamantan-1-ylmethyl ester, (meth)acrylic acid 3,5-dicarboxy-7-methyladamantan-1-ylmethyl ester, (methyl)propionic acid 3 -residue-5-methoxy ortho-7-methyl-dragongarten-1-yl-methyl vinegar, 3-methoxycarbonyl-5-methyladamantan-1-ylmethyl (meth)acrylate, 3,5-dimethoxycarbonyl-7-methyladamantan-1-ylmethyl (meth)acrylate , 3-hydroxy-5,7-dimethyladamantan-1-yl (meth)acrylate, 3-hydroxymethyl-5,7-dimethyladamantan-1-yl (meth)acrylate , (meth)acrylic acid 3-cyano-5,7-dimethyladamantan-1-yl ester, (carboxy)acrylic acid 3-carboxy-5,7-dimethyladamantan-1-yl ester, (Meth)acrylic acid 3-methoxycarbonyl- 5,7-dimethyl adamantyl-1-yl ester, 3-hydroxy-5,7-dimethyl adamantyl-1-yl (meth)acrylate , (methyl) acrylate 3-hydroxymethyl-5,7-dimethyl adamantyl-1-yl methyl ester, (meth)acrylic acid 3-cyano-5,7-dimethyl adamantane-1- Methyl ester, 3-carboxy-5,7-dimethyladamantan-1-yl methyl ester, (meth)acrylic acid 3-33-200839449 methoxycarbonyl-5,7-dimethyl Fundane-2-yl methyl ester and the like. Examples of the particularly preferable monomer among these include (meth)1 hydroxyadamantane-bromomethyl ester, (meth)acrylic acid 3,5-dialkyl-1-ylmethyl ester, and (methyl). Acrylic acid 3-cyanopredane-1_ (3-)carboxyadamantane-1-ylmethyl (meth)acrylate, (formic acid 3-carbyl-5-methyl-Golden-1-yl ester, (meth) propylene Hydroxy-7-methyladamantan-1 -yl ester, 3-methyano-cycloalkanyl (meth)acrylate, 3-carboxy-hydroxydanta-1-yl (meth)acrylate, (A) Further, 3-hydroxy-5,7-cycloalkan-1-ylmethyl acrylate, etc. Further, the resin (B) in the present invention, except for the above-mentioned repetitions j, (5), (6) and (7), Others (hereinafter referred to as "other repeating units") may be further included. Examples of the other repeating unit' include, for example, a hydrocarbon such as methyldicyclopentene ester or adamantyl (meth)acrylate. A bridge hydrocarbon having an unsaturated carboxylic acid such as a (meth) acrylate such as a (meth) acrylate tablet, a carboxy tricyclononyl (meth) acrylate or a (meth) quaternary undecyl ester; Skeleton esters; (methyl ) methyl acrylate, ethyl (meth) acrylate) n-propyl acrylate, n-butyl (methyl) acrylate, (2-methyl propyl formate, 1 · methyl propyl (meth) acrylate, acrylic acid Third butyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth) acrylate, 3-hydroxyxanthyl phthalate, methacrylic acid 3 ,5-dihydroxy-5,7--5,7-dimethylene fund_position (4) repeating unit) acrylic acid having a bridged carboxyl group, raw carboxylic acid, carboxyl group, (meth) propylene (methyl) ) (methyl) (methyl) -34- 200839449 cyclopropyl acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-methoxycyclohexyl (meth) acrylate, 2-cyclopentyloxycarbonylethyl (meth)acrylate, 2-cyclohexyloxycarbonylethyl (meth)acrylate, 2-(4-methoxycyclohexyl)oxycarbonyl (meth)acrylate (meth) acrylates having no bridge hydrocarbon skeleton such as esters; α-hydroxymethyl methacrylate, α-hydroxyethyl methacrylate, α-hydroxymethyl acrylate Α-hydroxymethyl acrylate such as ester or n-butyl α-hydroxymethyl acrylate; (meth)acrylonitrile, α-chloroacrylonitrile, crotononitrile, maleonitrile, fumaronitrile, mesocarbonitrile, An unsaturated nitrile compound such as citraconazole or ikononitrile; (meth) acrylamide, hydrazine, hydrazine dimethyl (meth) acrylamide, crotonamide, maleamide, fumarine , an unsaturated decylamine compound such as mesaconamine, citraconazole, and econylamine; Ν-(meth)propenyl morpholine, Ν_vinyl-ε-caprolactam, Ν-ethylene Other nitrogen-containing vinyl compounds such as pyrrolidone, vinylpyridine, vinylidene, etc., (meth)acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, and ito Unsaturated carboxylic acid (anhydride) such as acid anhydride, citraconic acid, citraconic anhydride, mesaconic acid, 2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, (methyl) Carboxylic acid-containing carboxyl group having no bridged hydrocarbon skeleton, such as 3-carboxypropyl acrylate, 4-carboxybutyl (meth)acrylate or 4-carboxycyclohexyl (meth)acrylate Ester; 1,2-adamantanediol di(meth)acrylate, 13-adamantanediol di(meth)acrylate, 1,4-adamantanediol di(meth)acrylate, two a polyfunctional monomer having a bridged hydrocarbon skeleton such as cyclodecyl dimethylol di(meth)acrylate; • 35- 200839449 methylene glycol di(meth) acrylate, ethylene glycol bis (A) Acrylate, propylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2,5-dimethyl-2,5-hexanediol di(meth)acrylic acid Ester, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,4-bis(2-hydroxypropyl)benzenedi(methyl) Polymerizable unsaturated bond of polyfunctional monomer such as acrylate, 1,3-bis(2-hydroxypropyl)benzenedi(meth)acrylate, or the like having no bridged hydrocarbon skeleton The unit of lysis. Among the other repeating units, a polymerizable unsaturated bond-cracking unit of a (meth) acrylate having a bridge hydrocarbon skeleton is preferable. The resin (B) in the present invention may contain only one type of repeating unit selected from the repeating units (4), (5), (6), (7) and other repeating units, or may contain two or more kinds. , regardless of the type. In the resin (B), the content of the repeating unit (4) is usually 3 〇 mol% or less when the total repeating unit of the resin (B) is 1 〇〇 mol%, and preferably 2 5 Less than the ear. The content of the repeating unit (*) is more than 30% of the right. The shape of the photoresist pattern is deteriorated, and the resolution is lowered. Further, when the content of the repeating unit (5) is 1% by mol based on the total repeating unit of the resin (B), it is usually 40 mol% or less, preferably 30 mol% or less. If the content of the repeating unit (5) exceeds 4% by mole, the radiation transmittance becomes low, and the outline of the pattern deteriorates. Further, when the content of the repeating unit (6) is 100 mol% of the total repeating unit of the resin (B), it is usually 3 〇 mol% or less, preferably 25 旲% or less from -36 to 200839449. When the content of the repeating unit (6) exceeds 3 〇 mol %, the obtained resist film is easily swollen by the alkali developing solution, and the content of the repeating unit (7) is resin. When the total repeating unit of (B) is 1% by mole, it is usually 3 〇 mol% or less, preferably 25 旲% or less. The content of this repeating unit (7) is more than 3 莫 mol / °. The photoresist film obtained is easily swollen by the alkali developing solution, and the solubility in the alkali φ developing solution is lowered. Further, when the content of the other repeating unit is 100 mol% based on the total repeating unit of the resin (B), it is usually 5 〇 mol% or less, preferably 40 mol%. Further, when the resin (B) contains a fluorinated alkyl group, when the total amount of the resin (b) is 10 G atom%, the fluorine content is less than 3 atom%, preferably 〇2.9% by atom, more preferably For 〇~丨.5 atomic%. Further, the fluorine content can be measured in the same manner as the above method. φ Further, the resin (B) in the present invention can be, for example, a radical polymerization initiator such as a hydroperoxide, a hospital-based peroxide, a di-based peroxide or an azo compound. It is produced by polymerizing a polymerizable non-saturated monomer corresponding to each designated repeating unit in a suitable solvent in the presence of a chain transfer agent as needed. Examples of the solvent used for the polymerization include alkane such as n-pentane, n-hexane, n-heptane, n-octane, n-decane or n-decane; cyclohexyl, cycloheptane and cyclooctane; , naphthenics such as decalin and norbornane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chloroprene-37-200839449 alkanes, bromohexanes, Halogenated hydrocarbons such as dichloroethane, hexamethylene dibromide, chlorobenzene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate; acetone; a ketone such as 2-butanone, 4-methyl-2-heptanone or 2-heptanone; an ether such as tetrahydrofuran, dimethoxyethane or diethoxyethane; and the like. These solvents may be used singly or in combination of two or more. The reaction temperature of the above polymerization is usually 40 to 150 ° C, preferably 50 to 120 ° C, and the reaction time is usually 1 to 48 hours, preferably 1 to 24 hours. Further, the resin (B) in the present invention The Mw system measured by the GPC method is not particularly limited, and is preferably 1,000 to 1,000,000, more preferably 1,000 to 30,000, particularly preferably 1,000 to 20,000. When the Mw of the tree (B) is less than 1, 〇〇〇, the heat resistance at the time of the photoresist tends to be lowered. On the other hand, if the Mw exceeds 1 Torr, the imageability as a photoresist tends to decrease. Further, the ratio (Mw/Mn) of Mw of the resin (B) to Μη measured by the GPC method is usually from 1 to 5, preferably from 1 to 3. In the resin (B), the content of the low molecular weight component derived from the monomer used for the production of the resin (B) is preferably 0.1% by mass in terms of solid content, based on 100% by mass of the resin. In the following, it is preferably 〇·〇 7 mass% or less, more preferably 〇·〇 5 mass% or less. When the content is 〇·1 mass% or less, the amount of the eluted matter of the wetting medium such as water which is contacted during the immersion exposure can be reduced. Further, in the storage of the photoresist, no foreign matter is generated in the photoresist, and even if the photoresist is applied, uneven coating does not occur, and the defects at the time of forming the photoresist pattern can be suppressed from -38 to 200839449. The low molecular weight component derived from the monomer described above may, for example, be a dimer, a trimer or an oligomer, and may be a component having a Mw of 500 or less. The component of Mw 5 00 or less can be removed by, for example, a chemical purification method such as water washing or liquid-liquid extraction, or a combination of such a chemical purification method and a physical purification method such as ultrafiltration or centrifugation. Further, the analysis can be carried out by high-speed liquid chromatography (HPLC) of a resin. Further, the resin (B) is preferably a content of impurities such as a halogen or a metal, and the like, whereby the sensitivity, the resolution, the process stability, the pattern shape, and the like as the photoresist can be further improved. In addition, as a method of purifying the resin (B), for example, a chemical purification method such as water washing or liquid-liquid extraction, a combination of such a chemical purification method, a physical purification method such as ultrafiltration or centrifugal separation, and the like can be given. In the present invention, the resin (B) may be used singly or in combination of two or more. In the present invention, when the total amount of the polymer (A) and the resin (B) is 100% by mass, the content of the resin (B) is preferably 99.9% by mass or less, and particularly preferably 60 to 99.9% by mass. More preferably, it is 65 to 99.5 mass%. When the content of the resin (B) is within the above range, the photoresist film can sufficiently ensure the advancing contact angle, and the elution of the acid generator or the like from the photoresist film can be sufficiently suppressed. <sensitive radiation linear acid generator (C) > The radiation sensitive linear acid generator (C) of the present invention (hereinafter also referred to simply as "-39-200839449 acid generator (C)"] is exposed by exposure The acid generating person's, by the action of the generated acid, causes the acid dissociable group present in the resin component, specifically, the acid dissociable group dissociation (release protecting group) of the repeating unit (2), resulting in a photoresist film The exposed portion has an effect of being easily soluble in the alkali developing solution and forming a positive resist pattern. As such an acid generator (C), a compound represented by the following formula (7) (hereinafter referred to as "acid generator 1") is preferably contained. [化8]

R16 (7) 通式（7)中，R14表示氫原子、氟原子、羥基、碳原 子數1〜1 0的直鏈狀或支鏈狀的烷基、碳原子數1〜1 〇的 直鏈狀或支鏈狀的院氧基、碳原子數2〜11的直鏈狀或支 鏈狀的烷氧羰基。又，R15表示碳原子數1〜10的直鏈狀 或支鏈狀的烷基、烷氧基或碳原子數1〜1 〇的直鏈狀、支 鏈狀、環狀的烷磺醯基。再者，R16獨立地表示碳原子數 1〜1 〇的直鏈狀或支鏈狀的烷基、可經取代的苯基或可有 取代基的萘基，或是2個R1 6互相鍵結合而形成碳原子數 2〜1 〇的2價基，此2價基亦可經取代，k爲〇〜2的整數 ，X·表示式：R”CnF2nS03·、r17so3-(式中，R” 表示氟 原子或可經取代的碳原子數1〜12的烴基，η爲1〜10的 整數）、或下述通式（8-1 )或（8-2 )所示的陰離子， -40- 200839449 爲0〜1 0的整數。 [化9] R18R16 (7) In the formula (7), R14 represents a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, and a linear chain having 1 to 1 carbon atoms. A terpenoid or branched alkoxy group or a linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms. Further, R15 represents a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group or a linear, branched or cyclic alkanesulfonyl group having 1 to 1 ring of carbon atoms. Further, R16 independently represents a linear or branched alkyl group having 1 to 1 carbon atom, a substituted phenyl group or a naphthyl group which may have a substituent, or 2 R1 6 bonded to each other. Further, a divalent group having a carbon number of 2 to 1 Å is formed, and the divalent group may be substituted, k is an integer of 〇~2, and X represents a formula: R"CnF2nS03·, r17so3- (wherein R" represents a fluorine atom or a hydrocarbon group having 1 to 12 carbon atoms which may be substituted, η is an integer of 1 to 10), or an anion represented by the following formula (8-1) or (8-2), -40- 200839449 An integer from 0 to 1 0. [Chemical 9] R18

(8-2) Ν_ \ · 18 ^ R (8-1)(8-2) Ν_ \ · 18 ^ R (8-1)

(各式中，R18互相獨立地爲具有氟原子且碳數1〜10的 直鏈狀或支鏈狀的烷基，或2個R18互相鍵結，具有氟原 子且碳數2〜10的2價有機基，此2價有機基亦可具有取 代基）。 通式（7)中，作爲R14、R15及R16的碳原子數1〜 1 0的直鏈狀或支鏈狀的烷基，例如可舉出甲基、乙基、 正丙基、異丙基、正丁基、2-甲基丙基、1-甲基丙基、第 三丁基、正戊基、新戊基、正己基、正庚基、正辛基、2-乙基己基、正壬基、正癸基等。於此等烷基之中’較佳爲 甲基、乙基、正丁基、第三丁基等。 又，作爲R14及R15的碳原子數1〜10的直鏈狀或支 鏈狀的烷氧基，例如可舉出甲氧基、乙氧基、正丙氧基、 異丙氧基、正丁氧基、2-甲基丙氧基、1-甲基丙氧基、第 三丁氧基、正戊氧基、新戊氧基、正己氧基、正庚氧基、 正辛氧基、2 -乙基己氧基、正壬氧基、正癸氧基等。於此 等烷氧基之中，較佳爲甲氧基、乙氧基、正丙氧基、正丁 氧基等。 另外，作爲R14的碳原子數2〜11的直鏈狀或支鏈狀 的烷氧羰基，例如可舉出甲氧羰基、乙氧羰基、正丙氧羰 -41 - 200839449 基、異丙氧羰基、正丁氧羰基、2-甲基丙氧羰基、1-甲基 丙氧鑛基、第三丁氧羰基、正戊氧類基、新戊氧碳基、正 己氧鑛基、正庚氧鑛基、正辛氧鑛基、2 -乙基己氧象基、 正壬氧羰基、正癸氧羰基等。於此等烷氧羰基之中，較佳 爲甲氧羰基、乙氧羰基、正丁氧羰基等。 又，作爲R15的碳原子數1〜1 0的直鏈狀、支鏈狀、 環狀的烷磺醯基，例如可舉出甲烷磺醯基、乙烷磺醯基、 正丙烷磺醯基、正丁烷磺醯基、第三丁烷磺醯基、正戊烷 磺醯基、新戊烷磺醯基、正己烷磺醯基、正庚烷磺醯基、 正辛烷磺醯基、2 -乙基己烷磺醯基正壬烷磺醯基、正癸烷 磺醯基、環戊烷磺醯基、環己烷磺醯基等。於此等烷磺醯 基之中，較佳爲甲烷磺醯基、乙烷磺醯基、正丙烷磺醯基 、正丁烷磺醯基、環戊烷磺醯基、環己烷磺醯基等。 而且，r較佳爲0〜2。 於通式（7 )中，作爲R16的可經取代的苯基’例如 可舉出苯基、鄰甲苯基、間甲苯基、對甲苯基、2,3·二甲 基苯基、2，4 -二甲基苯基、2,5 -二甲基苯基、2,6 -二甲基 苯基、3,4 -二甲基苯基、3二甲基苯基、2，4,6 -二甲基苯 基、4-乙基苯基、4_第三丁基苯基、4-環己基苯基、4_氟 苯基等的苯基或經碳原子數1〜1〇的直鏈狀、支鏈狀或環 狀的烷基所取代的苯基；此等的苯基或纟完基取代苯基經1 個以上的淫基、羧基、氰基、硝基、烷氧基、烷氧基烷基 、院氧鑛基、烷氧基羰氧基等的至少一種之基所取代的基 等。 -42- 200839449 於對於苯基及烷基取代苯基的取代基之中，作爲前述 院氧基，例如可舉出甲氧基、乙氧基、正丙氧基、異丙氧 基、正丁氧基、2-甲基丙氧基、1_甲基丙氧基、第三丁氧 基、環戊氧基、環己氧基等的碳原子數1〜20的直鏈狀、 支鏈狀或環狀的烷氧基等。 又，作爲前述烷氧基烷基，例如可舉出甲氧基甲基、 乙氧基甲基、1-甲氧基乙基、2-甲氧基乙基、1-乙氧基乙 基、2·乙氧基乙基等的碳原子數2〜21的直鏈狀、支鏈狀 或環狀的烷氧基烷基等。 另外，作爲前述烷氧羰基，例如可舉出甲氧羰基、乙 氧羰基 '正丙氧羰基、異丙氧羰基、正丁氧羰基、2-甲基 丙氧羰基、1-甲基丙氧羰基、第三丁氧羰基、環戊氧羰基 、環己氧羰基等的碳原子數2〜2 1的直鏈狀、支鏈狀或環 狀的烷氧羰基等。 又’作爲刖述丨兀氧基鑛興基’例如可舉出甲氧鑛氧基 、乙氧基羰氧基、正丙氧基羰氧基、異丙氧基羰氧基、JE 丁氧基鑛氧基、第三丁氧基猿氧基、環戊氧鑛基、環己氧 羰基等的碳原子數2〜21的直鏈狀、支鏈狀或環狀的烷氧 基羰氧基等。 作爲通式（7 )中的R15之可經取代的苯基，較佳爲 苯基、4-環己基苯基、4-第三丁基苯基、4_甲氧基苯基、 4-第三丁氧基苯基等。 又，作爲R 1 6的可經取代的萘基，例如可舉出1 -萘基 、2-甲基-1-萘基、3-甲基-1-萘基、4-甲基-1-萘基、4-甲 -43- 200839449 基-1-萘基、5-甲基-1-萘基、6-甲基-1-萘基、7-甲: 基、8-甲基-1-萘基、2,3-二甲基-1-萘基、2,4-二 萘基、2,5-二甲基-1-萘基、2,6_二甲基-1-萘基、2 基-1-萘基、2,8-二甲基-1-萘基、3,4-二甲基-1-萘3 二甲基-1-萘基、3,6-二甲基-1-萘基、3,7-二甲基 、3,8-二甲基-1-萘基、4,5·二甲基-1-萘基、5,8-二 萘基、4·乙基-1-萘基2-萘基、1-甲基-2-萘基、3-萘基、4-甲基-2-萘基等的萘基或經碳原子數1〜1 鏈狀、支鏈狀或環狀的烷基所取代的萘基；此等的 烷基取代萘基經1個以上的羥基、羧基、氰基、硝 氧基、烷氧基烷基、烷氧羰基、烷氧基羰氧基等的 種之基所取代之基等。 作爲前述取代基的烷氧基、烷氧基烷基、烷氧 烷氧基羰氧基，例如可舉出就前述苯基及烷基取代 例示的基。 作爲通式（7 )中的R16之可經取代的萘基， 1-萘基、1-(4-甲氧基萘基）基、1_(4_乙氧基萘 、1-(4-正丙氧基萘基）基、1-(4-正丁氧萘基） (7-甲氧基萘基）基、2-(7-乙氧基萘基）基、2 丙氧基萘基）基、2- (7_正丁氧基萘基）基等。 又，作爲2個R16互相鍵結合而形成的碳原子 1 〇的2價基，宜爲與通式（7 )中的硫原子一起形 或6員的環之基，特佳爲形成5員的環（即，四氫 )之基。 -1-萘 甲基-1- ,7-二甲 ^ 、 3,5--1-萘基 甲基-1 - 甲基-2- 0的直 萘基或 基、烷 至少1 振悬及 苯基所 較佳爲 基）基 基、2· -(7-正 數2〜 成5員 噻吩環 -44- 200839449 另外，作爲對於前述2價基的取代基’例如可舉出前 述作爲對於苯基及烷基取代苯基的取代基所例示的羥基、 羧基、氰基、硝基、烷氧基、烷氧基烷基、烷氧羰基、烷 氧基羰氧基等。 作爲通式（7)中的R16，較佳爲甲基、乙基、苯基 、4-甲氧基苯基、1-萘基、2個R16互相鍵結合而與硫原 子一起形成四氫噻吩環構造的2價基等。 通式（7)中的 X·爲 R17CnF2nS03·、R17S03·、或前述 通式（8-1 )或（8-2 )所示的陰離子。X-爲R17CnF2nS03· 時的-CnF2n-基，係碳原子數η的全氟伸烷基’但此基可爲 直鏈狀或支鏈狀。此處，η較佳爲1、2、4或8。 又，作爲R 17中的可經取代的碳原子數1〜1 2的烴基 ，較佳爲碳數1〜1 2的烷基、環烷基、有橋脂環式烴基。 具體地，可舉出甲基、乙基、正丙基、異丙基、正丁 基、2-甲基丙基、1-甲基丙基、第三丁基、正戊基、新戊 基、正己基、環己基、正庚基、正羊基、2 -乙基己基、正 壬基、正癸基、原冰片基、原冰片基甲基、經基原冰片基 、金剛烷基等。 又，X-爲前述通式（8-1)或（8-2)所示的陰離子時 ，R18互相獨立地可爲具有氟原子且碳數1〜10的直鏈狀 或支鏈狀的烷基，2個R18可互相鍵結，具氟原子’且爲 碳數2〜1 0的2價有機基’於該情況下’ 2價有機基亦可 具有取代基。 通式（8-1 )或（8-2)中，化18爲碳數1〜1〇的直鏈 -45- 200839449 狀或支鏈狀的烷基時，可舉出三氟甲基、五氟乙基、七氟 丙基、九氟丁基、十二氟戊基、全氟辛基等。 又，於R18爲碳數2〜1 0的2價有機基時，可舉出四 氟伸乙基、六氟伸丙基、八氟伸丁基、十氟伸戊基、十一 氟伸己基等。 因此，作爲前述通式（7)中的較佳陰離子X~，可舉 出三氟甲烷磺酸根陰離子、全氟正丁烷磺酸根陰離子、全 氟正辛烷磺酸根陰離子、2-雙環[2.2.1]庚-2-基-1，1，2,2·四 氟乙烷磺酸根陰離子、2-雙環[2·2·1]庚-2-基-1，1·二氟乙 烷磺酸根陰離子、下述式（9-1)〜（9-7)所示的陰離子 等。 [化 10](In each formula, R18 is independently a linear or branched alkyl group having a fluorine atom and having a carbon number of 1 to 10, or two R18 groups bonded to each other, and having a fluorine atom and having a carbon number of 2 to 10; The valent organic group may have a substituent. In the general formula (7), examples of the linear or branched alkyl group having 1 to 10 carbon atoms of R14, R15 and R16 include a methyl group, an ethyl group, a n-propyl group and an isopropyl group. , n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, positive壬基,正癸基, etc. Among these alkyl groups, 'preferably, a methyl group, an ethyl group, a n-butyl group, a t-butyl group or the like. Further, examples of the linear or branched alkoxy group having 1 to 10 carbon atoms of R14 and R15 include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a n-butyl group. Oxy, 2-methylpropoxy, 1-methylpropoxy, tert-butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2 Ethylhexyloxy, n-decyloxy, n-decyloxy and the like. Among these alkoxy groups, a methoxy group, an ethoxy group, a n-propoxy group, a n-butoxy group or the like is preferable. Further, examples of the linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms of R14 include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl-41-200839449 group, and an isopropoxycarbonyl group. , n-Butoxycarbonyl, 2-methylpropoxycarbonyl, 1-methylpropoxylate, third butoxycarbonyl, n-pentyloxy, neopentyloxy, n-hexyloxy, n-hepteoxy A group, a n-octyloxy group, a 2-ethylhexyloxy group, a n-decyloxycarbonyl group, a n-decyloxycarbonyl group or the like. Among these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group, a n-butoxycarbonyl group and the like are preferable. Further, examples of the linear, branched or cyclic alkanesulfonyl group having 1 to 10 carbon atoms of R15 include a methanesulfonyl group, an ethanesulfonyl group, and a n-propanesulfonyl group. N-butanesulfonyl, third butanesulfonyl, n-pentanesulfonyl, neopentanesulfonyl, n-hexanesulfonyl, n-heptanesulfonyl, n-octanesulfonyl, 2 Ethyl hexylsulfonyl n-decanesulfonyl, n-decanesulfonyl, cyclopentanesulfonyl, cyclohexanesulfonyl and the like. Among the alkanesulfonyl groups, preferred are methanesulfonyl, ethanesulfonyl, n-propanesulfonyl, n-butanesulfonyl, cyclopentanesulfonyl, cyclohexanesulfonyl. Wait. Moreover, r is preferably 0 to 2. In the general formula (7), as the substitutable phenyl group of R16, for example, a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,3·dimethylphenyl group, and 2, 4 may be mentioned. - dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3 dimethylphenyl, 2,4,6- a phenyl group such as dimethylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-cyclohexylphenyl or 4-fluorophenyl or a linear chain having a carbon number of 1 to 1 fluorene a phenyl group substituted with a branched, branched or cyclic alkyl group; such phenyl or fluorenyl substituted phenyl groups having more than one thiol, carboxyl, cyano, nitro, alkoxy, alkane A group substituted with at least one of an oxyalkyl group, a oxyalkylene group, an alkoxycarbonyloxy group or the like. -42- 200839449 Among the substituents for the phenyl group and the alkyl-substituted phenyl group, examples of the above-mentioned alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a n-butyl group. a linear or branched chain having 1 to 20 carbon atoms such as an oxy group, a 2-methylpropoxy group, a 1-methylpropoxy group, a tert-butoxy group, a cyclopentyloxy group or a cyclohexyloxy group. Or a cyclic alkoxy group or the like. Further, examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a 2-methoxyethyl group, and a 1-ethoxyethyl group. 2. A linear, branched or cyclic alkoxyalkyl group having 2 to 21 carbon atoms such as an ethoxyethyl group. Further, examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl 'n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, and a 1-methylpropoxycarbonyl group. a linear, branched or cyclic alkoxycarbonyl group having 2 to 2 carbon atoms such as a third butoxycarbonyl group, a cyclopentyloxycarbonyl group or a cyclohexyloxycarbonyl group. Further, 'for example, a methoxyl group, a methoxycarbonyloxy group, a n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, and a JE butoxy group are mentioned. a linear, branched or cyclic alkoxycarbonyloxy group having 2 to 21 carbon atoms such as a mineral oxygen group, a third butoxy methoxy group, a cyclopentyloxy group or a cyclohexyloxycarbonyl group. . The phenyl group which may be substituted as R15 in the formula (7) is preferably a phenyl group, a 4-cyclohexylphenyl group, a 4-tert-butylphenyl group, a 4-methoxyphenyl group, or a 4-position. Tributyloxyphenyl and the like. Further, examples of the optionally substituted naphthyl group of R 16 include 1-naphthyl group, 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, and 4-methyl-1- Naphthyl, 4-methyl-43- 200839449-1-naphthyl, 5-methyl-1-naphthyl, 6-methyl-1-naphthyl, 7-methyl:yl, 8-methyl-1- Naphthyl, 2,3-dimethyl-1-naphthyl, 2,4-dinaphthyl, 2,5-dimethyl-1-naphthyl, 2,6-dimethyl-1-naphthyl, 2-1-naphthyl, 2,8-dimethyl-1-naphthyl, 3,4-dimethyl-1-naphthalene 3 dimethyl-1-naphthyl, 3,6-dimethyl- 1-naphthyl, 3,7-dimethyl, 3,8-dimethyl-1-naphthyl, 4,5·dimethyl-1-naphthyl, 5,8-dinaphthyl, 4·B a naphthyl group such as a 1-naphthyl 2-naphthyl group, a 1-methyl-2-naphthyl group, a 3-naphthyl group or a 4-methyl-2-naphthyl group, or a chain of 1 to 1 carbon atoms; a naphthyl group substituted by a branched or cyclic alkyl group; these alkyl substituted naphthyl groups have one or more hydroxyl groups, carboxyl groups, cyano groups, nitroxide groups, alkoxyalkyl groups, alkoxycarbonyl groups, and alkane groups. A group substituted with a group such as an oxycarbonyloxy group. The alkoxy group, the alkoxyalkyl group or the alkoxycarbonyloxy group as the substituent may, for example, be a group exemplified by the above-mentioned phenyl group and alkyl group. As a substitutable naphthyl group of R16 in the formula (7), 1-naphthyl group, 1-(4-methoxynaphthyl) group, 1-(4-ethoxynaphthalene, 1-(4-positive) Propylnaphthyl), 1-(4-n-butoxynaphthyl) (7-methoxynaphthyl), 2-(7-ethoxynaphthyl), 2 propoxynaphthyl) Base, 2-(7-n-butoxynaphthyl)yl and the like. Further, the divalent group of the carbon atom 1 形成 which is formed by bonding two R16 to each other is preferably a ring having a ring shape of 6 or more together with a sulfur atom in the formula (7), and particularly preferably a member having 5 members. The base of the ring (ie, tetrahydro). 1-naphthylmethyl-1-, 7-dimethyl^, 3,5--1-naphthylmethyl-1 -methyl-2-0, straight naphthyl or aryl, at least 1 suspension and benzene The base is preferably a base group, 2·-(7-positive number 2 to a 5-membered thiophene ring-44-200839449, and the substituent for the above-mentioned divalent group) is exemplified as the phenyl group and a hydroxy group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group or the like exemplified as the substituent of the alkyl-substituted phenyl group. R16 is preferably a methyl group, an ethyl group, a phenyl group, a 4-methoxyphenyl group or a 1-naphthyl group, and two R16 groups are bonded to each other to form a tetravalent thiophene ring structure and a divalent group together with a sulfur atom. X. in the general formula (7) is an anion represented by R17CnF2nS03·, R17S03· or the above formula (8-1) or (8-2), and X- is a —CnF2n- group at the time of R17CnF2nS03· a perfluoroalkylene group having a carbon number η, but the group may be linear or branched. Here, η is preferably 1, 2, 4 or 8. Further, as a substitutable in R 17 a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, or a cycloalkane And a alicyclic hydrocarbon group. Specifically, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, and a third group are mentioned. Base, n-pentyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, n-henyl, 2-ethylhexyl, n-decyl, n-decyl, borneol, ornidyl, methyl Further, when X- is an anion represented by the above formula (8-1) or (8-2), R18 may independently have a fluorine atom and have a carbon number of 1 to 10; a linear or branched alkyl group, two R18 groups may be bonded to each other, and a fluorine atom 'and a carbon number of 2 to 10 carbonic acid'. In this case, the 'divalent organic group may also have a substitution In the formula (8-1) or (8-2), when the formula 18 is a linear -45-200839449- or branched alkyl group having a carbon number of 1 to 1 fluorene, a trifluoromethyl group is exemplified. , pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, dodecafluoropentyl, perfluorooctyl, etc. Further, when R18 is a divalent organic group having 2 to 10 carbon atoms, four Fluorine-extended ethyl, hexafluoro-propyl, octafluoro-butyl, decafluoro-pentyl, eleven fluoride The hexyl group or the like. The preferred anion X~ in the above formula (7) includes a trifluoromethanesulfonate anion, a perfluoro-n-butanesulfonate anion, a perfluoro-n-octanesulfonate anion, and 2- Bicyclo[2.2.1]hept-2-yl-1,1,2,2·tetrafluoroethanesulfonate anion, 2-bicyclo[2·2·1]hept-2-yl-1,1·difluoro An ethanesulfonate anion, an anion represented by the following formulas (9-1) to (9-7), etc. [Chemical 10]

(9-1> (9-2) (9-3) (9-4) (9-5) (9-6) (9-7) 又，作爲通式（7)的較佳具體例子，可舉出三苯基 毓三氟甲烷磺酸鹽、三第三丁基苯基鏟三氟甲烷磺酸鹽、 • 4-環己基苯基-二苯基鐘三氟甲烷磺酸鹽、4-甲磺醯基苯 基-二苯基鏡三氟甲烷磺酸鹽、1-( 3，5-二甲基-4-羥基苯 基）四氫噻吩鐵三氟甲烷磺酸鹽、1 - ( 4-正丁氧基萘基） 四氫噻吩鑰三氟甲烷磺酸鹽、 三苯基锍全氟正丁烷磺酸鹽、三第三丁基苯基毓全氟 正丁烷磺酸鹽、4-環己基苯基-二苯基銃全氟正丁烷磺酸 鹽、4-甲烷磺醯基苯基·二苯基鏡全氟正丁烷磺酸鹽、卜 -46 - 200839449 (3,5-二甲基-4-羥基苯基）四氫噻吩鑰全氟正丁烷磺酸鹽 、1-(4-正丁氧基萘基）四氫噻吩鑰全氟正丁烷磺酸鹽、 三苯基銃全氟正辛烷磺酸鹽、三第三丁基苯基毓全氟 正辛烷磺酸鹽、4-環己基苯基-二苯基毓全氟正辛烷磺酸 鹽、4-甲烷磺醯基苯基-二苯基毓全氟正辛烷磺酸鹽、^ (3，5 -二甲基-4-羥基苯基）四氫噻吩鑰全氟正辛烷磺酸鹽 、1_ ( 4-正丁氧基萘基）四氫噻吩鑰全氟正辛烷磺酸鹽、(9-1> (9-2) (9-3) (9-4) (9-5) (9-6) (9-7) Further, as a preferable specific example of the general formula (7), Triphenylphosphonium trifluoromethanesulfonate, tri-tert-butylphenyl shovel trifluoromethanesulfonate, • 4-cyclohexylphenyl-diphenyl clock trifluoromethanesulfonate, 4-methyl Sulfohydroxyphenyl-diphenyl mirror trifluoromethanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene iron trifluoromethanesulfonate, 1 - ( 4- n-Butoxynaphthyl) Tetrahydrothiophene trifluoromethanesulfonate, triphenylsulfonium perfluoro-n-butanesulfonate, tri-tert-butylphenylphosphonium perfluoro-n-butanesulfonate, 4- Cyclohexylphenyl-diphenylfluorene perfluoro-n-butane sulfonate, 4-methanesulfonylphenyl-diphenyl mirror perfluoro-n-butane sulfonate, Bu-46 - 200839449 (3,5- Dimethyl-4-hydroxyphenyl)tetrahydrothiophene perfluoro-n-butane sulfonate, 1-(4-n-butoxynaphthyl)tetrahydrothiophene-perfluoro- n-butane sulfonate, triphenyl Based on perfluoro-n-octane sulfonate, tri-tert-butylphenyl fluorene perfluoro-n-octane sulfonate, 4-cyclohexyl phenyl-diphenyl fluorene perfluoro-n-octane sulfonate, 4- Methanesulfonylphenyl - Diphenylphosphonium perfluoro-n-octane sulfonate, (3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene-perfluoro- n-octane sulfonate, 1-(4-n-butoxy) Naphthyl)tetrahydrothiophene perfluorooctane sulfonate,

三苯基锍2-(雙環[2.2.1]庚- 2，-基）-1,1，2,2 -四氟乙 烷磺酸鹽、三第三丁基苯基鏡2-(雙環[m]庚_2，_基）_ 1，1，2，2 -四氟乙烷磺酸鹽、4 -環己基苯基-二苯基鏡2 _ (雙 環[2·2·1]庚-2’-基）-1，1，2,2 -四氟乙烷磺酸鹽、4-甲烷磺 醯基苯基-二苯基銃2-(雙環[2·2·1]庚-2，-基）-1,i，2,2-四 氟乙院磺酸鹽、1-( 3，5 -二甲基-4-經基苯基）四氫噻吩鑰 2-(雙環[2·2·1]庚·2、基）·ΐ，ι，2,2-四氟乙烷磺酸鹽、丨·（ 4-正丁氧基萘基）四氫噻吩鑰2-(雙環[2.2.1]庚- 2，-基）-1，1，2,2-四氟乙烷磺酸鹽、 二苯基锍2-(雙環[2.2.1]庚·2，-基）-丨山二氟乙烷磺 酸鹽、三第三丁基苯基毓2-(雙環[2.2.1]庚-2，_基）-1，1_ 二氟乙烷磺酸鹽、4 -環己基苯基-二苯基毓2 _ (雙環 [2·2·1]庚- 2’-基）-1，1-一氟乙烷磺酸鹽、4•甲烷磺醯基苯 基-二苯基毓2-(雙環[2.2.1]庚-2，_基）•二氟乙烷磺 酸鹽、卜（3,5 -一甲基-4 -羥基苯基）四氫噻吩_ 2_ (雙環 [2.2.1]庚-2’-基）-1，1-二氟乙烷磺酸鹽、〗_ ( ‘正丁氧基 萘基）四氫噻吩鑰2-(雙環[2·2·1]庚_2，-基）-1卜二氟乙 -47- 200839449 烷磺酸鹽、下述式B 1〜B 1 5所示的化合物等。 [化 11]Triphenylphosphonium 2-(bicyclo[2.2.1]hept-2,yl)-1,1,2,2-tetrafluoroethanesulfonate, tri-t-butylphenyl mirror 2-(bicyclo[ m]g_2,_yl)_ 1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyl-diphenyl mirror 2 _ (bicyclo[2·2·1]g- 2'-yl)-1,1,2,2-tetrafluoroethanesulfonate, 4-methanesulfonylphenyl-diphenylfluorene 2-(bicyclo[2·2·1]heptane-2, -yl)-1,i,2,2-tetrafluoroethane sulfonate, 1-(3,5-dimethyl-4-phenylphenyl)tetrahydrothiophene 2-(bicyclo[2·2 ·1] Geng·2, base)·ΐ, ι, 2,2-tetrafluoroethane sulfonate, 丨·(4-n-butoxynaphthyl)tetrahydrothiophene key 2-(bicyclo[2.2.1 Geng-2,-yl)-1,1,2,2-tetrafluoroethanesulfonate, diphenylphosphonium 2-(bicyclo[2.2.1]heptan-2-yl-yl)-fluorene difluoride Ethane sulfonate, tri-tert-butylphenyl fluorene 2-(bicyclo[2.2.1]heptan-2,-yl)-1,1-difluoroethane sulfonate, 4-cyclohexylphenyl-di Phenylindole 2 _ (bicyclo[2·2·1]heptyl-2'-yl)-1,1-fluoroethanesulfonate, 4•methanesulfonylphenyl-diphenylphosphonium 2-( Bicyclo[2.2.1]heptane-2,_yl)•difluoroethane sulfonate, Bu (3,5 - Methyl-4 -hydroxyphenyl)tetrahydrothiophene_ 2_(bicyclo[2.2.1]heptan-2'-yl)-1,1-difluoroethanesulfonate, __ (n-butoxynaphthalene) Tetrahydrothiophene key 2-(bicyclo[2·2·1]heptyl-2,-yl)-1difluoroethane-47- 200839449 alkane sulfonate, represented by the following formula B 1 to B 1 5 Compounds, etc. [化11]

[化 12][化 12]

[化 13][Chem. 13]

[化 14][Chem. 14]

48- 200839449 [化 15]48- 200839449 [Chem. 15]

[化 16][Chemistry 16]

B11B11

B12B12

[化 17][Chem. 17]

B15 再者，於本發明中，酸產生劑1可爲單獨或混合2種 以上來使用。 又，作爲敏輻射線性酸產生劑（C )所可使用的前述 酸產生劑1以外的敏輻射線性酸產生劑（以下稱爲「其它 酸產生劑」），例如可舉出鑰鹽化合物、含鹵素化合物、 重氮酮化合物、礪化合物 '磺酸化合物等。作爲此等的其 -49- 200839449 它酸產生劑，例如可舉出下述者。 鑰鹽化合物： 作爲鑰鹽化合物，例如可舉出碘鑰鹽、毓鹽、 重氮鑰鹽、吡啶鐵鹽等。 作爲鑰鹽化合物的具體例，可舉出二苯基碘鑰 烷磺酸鹽、二苯基碘鐵九氟正丁烷磺酸鹽、二苯基 氟正辛烷磺酸鹽、二苯基碘鑰2-雙環[2·2·1]庚 φ 1，1，2,2·四氟乙烷磺酸鹽、雙（4-第三丁基苯基） 氟甲烷磺酸鹽、雙（4-第三丁基苯基）碘鑰九氟 磺酸鹽、雙（4 -第三丁基苯基）碘鑰全氟正辛烷磺 雙（4-第三丁基苯基）碘鑰2-雙環[2.2.1]庚-2-基-] 四氟乙烷磺酸鹽、環己基· 2 -氧代環己基·甲基锍三 磺酸鹽、二環己基· 2-氧代環己基锍三氟甲烷磺酸 氧代環己基二甲基鏡二氟甲院磺酸鹽等。 含鹵素化合物： φ 作爲含鹵素化合物，例如可舉出含鹵烷基的烴 、含鹵烷基的雜環式化合物等。 作爲含鹵素化合物的具體例子，可舉出苯基雙 甲基）-S-三哄、4-甲氧基苯基雙（三氯甲基）-S·三 奈基雙（二氯甲基）-二哄等的（三氯甲基）-S -二 物、1，1-雙（4 -氯本基）-2,2,2 -三氯乙垸等。 重氮酮化合物： 作爲重氮酮化合物，例如可舉出1，3 -二酮基 化合物、重氮苯醌化合物、重氮萘醌化合物等。 鐵鹽、 三氟甲 碘鑰全 -2-基- 碘鑰三 正丁烷 酸鹽、 .，1，2,2· 氟甲烷 鹽、2- 化合物 (三氯 哄、1 · 哄衍生 2-重氮 -50- 200839449 作爲重氮酮的具體例子，可舉出1，2-萘醌二疊氮基- 4- 磺醯氯、1，2-萘醌二疊氮基-5-磺醯氯、2,3,4,4’-四羥基 二苯甲酮的1，2-萘醌二疊氮基-4-磺酸酯或1，2-萘醌二疊 氮基-5-磺酸酯、三（4-羥基苯基）乙烷的1，2-萘醌 二疊氮基-4-磺酸酯或1，2-萘醌二疊氮基-5-磺酸酯等。 礪化合物： 作爲碾化合物，例如可舉出β-酮基礪、β_磺醯基颯、 或此等的化合物之α-重氮化合物等。 作爲礪化合物的具體例子，可舉出4-三苯甲醯甲基 颯、釆基苯甲醯甲基礪、雙（苯基磺醯基）甲烷等。 磺酸化合物： 作爲磺酸化合物’例如可舉出烷基磺酸酯、烷基磺酸 醯亞胺、鹵烷基磺酸酯、芳基磺酸酯、亞胺基磺酸酯等。 作爲磺酸化合物的具體例子，可舉出苯偶姻甲苯磺酸 酯、焦掊酚的三（三氟甲烷磺酸鹽）、硝苯基-9,10-二乙 氧基蒽-2-磺酸鹽、三氟甲烷磺醯基雙環[2.2.1]庚-5-烯_ 2，3-二碳化二亞胺、九氟正丁烷磺醯基雙環[2 ·2.1]庚- 5-烯-2，3-二碳化二亞胺、全氟正辛烷磺醯基雙環[2.2.1 ]庚- 5- 烯-2,3-二碳化二亞胺、2_ 雙環[2·2·1]庚-2-基·1，1，2,2-四 氟乙烷磺醯基雙環卩·2·1]庚_5_烯·2,3-二碳化二亞胺、Ν- (三氟甲烷磺醯氧基）琥珀醯亞胺、Ν-(九氟正丁烷磺醯 氧基）琥珀醯亞胺、Ν_(全氟正辛烷磺醯氧基）琥珀醯亞 胺、Ν-(2-雙環[2.2.1]庚-2-基- i5l，2,2-四氟乙烷磺醯氧基 )琥珀醯亞胺、萘二羧酸醯亞胺三氟甲烷磺酸鹽、 •51 - 200839449 1，8-萘二羧酸醯亞胺九氟正丁烷磺酸鹽、1，8-萘二羧酸醯 亞胺全氟正辛烷磺酸鹽等。 於此等其它酸產生劑之中，較佳爲二苯基碘鑰三氟甲 烷磺酸鹽、二苯基碘鑰九氟正丁烷磺酸鹽、二苯基碘鑰全 氟正辛烷磺酸鹽、二苯基碘鑰 2-雙環[2.2.1]庚-2-基-1，1，2,2-四氟乙烷磺酸鹽、雙（4-第三丁基苯基）碘鐵三 氟甲烷磺酸鹽、雙（4-第三丁基苯基）碘鐵九氟正丁烷磺 酸鹽、雙（4-第三丁基苯基）碘鐵全氟正辛烷磺酸鹽、雙 (4-第三丁基苯基）碘鑰2-雙環[2.2.1]庚-2-基·1，1，2,2-四 氟乙烷磺酸鹽、環己基· 2-氧代環己基·甲基鏡三氟甲烷磺 酸鹽、二環己基· 2-氧代環己基毓三氟甲烷磺酸鹽、2-氧 代環己基二甲基銃三氟甲烷磺酸鹽、 三氟甲烷磺醯基雙環[2.2.1]庚-5-烯-2,3-二碳化二亞 胺、九氟正丁烷磺醯基雙環[2.2.1]庚-5-烯-2,3-二碳化二 亞胺、全氟正辛烷磺醯基雙環[2.2.1]庚-5-烯-2,3-二碳化 二亞胺、2-雙環[2.2.1]庚-2-基-1，1，2,2-四氟乙烷磺醯基雙 環[2.2.1]庚-5-烯-2,3-二碳化二亞胺、Ν-(三氟甲烷磺醯 氧基）琥珀醯亞胺、Ν-(九氟正丁烷磺醯氧基）琥珀醯亞 胺、Ν-(全氟正辛烷磺醯氧基）琥珀醯亞胺、Ν- ( 2-雙環 [2.2.1]庚-2-基-1，1，2,2-四氟乙烷磺醯氧基）琥珀醯亞胺、 1，8-萘二羧酸醯亞胺三氟甲烷磺酸鹽等。 前述其它酸產生劑可爲單獨或混合2種以上來使用。 於本發明中，酸產生劑1與其它酸產生劑的合計使用 量’從確保作爲光阻的感度及顯像性之觀點來看，對於聚 -52- 200839449 合物（A)與樹脂（B)的合計100質量份而言，通常爲 0.1〜20質量份，較佳爲0.5〜10質量份。該合計使用量 若低於〇. 1質量份，則感度及顯像性有降低的傾向。另一 方面，若超過20質量份，則對於輻射線的透明性會降低 ，有變成難以得到矩形的光阻圖型之傾向。 又，其它酸產生劑的使用比例，對於酸產生劑1與其 它酸產生劑的合計100質量％而言，通常爲80質量％以下 ，較佳爲60質量％以下。 <含氮化合物（D) > 又，於本發明的敏輻射線性樹脂組成物中，作爲具有 控制由於曝光而從酸產生劑所產生的酸在光阻膜中的擴散 顯像，抑制非曝光區域中的不宜化學反應之作用的酸擴散 控制劑，可使含有含氮化合物[以下稱爲含氮化合物（D ) ]。藉由摻合如此的酸擴散控制劑，可提高所得到的敏輻 射線性樹脂組成物之儲存安定性。而且，可更提高作爲光 阻的解像度，同時可抑制從曝光到曝光後的加熱處理爲止 的擱置時間（PED)的變動所致的光阻圖型之線寬變化， 可得到製程安定性極優異的組成物。 作爲前述含氮化合物（D )，例如可舉出3級胺化合 物、其它胺化合物、含醯胺基的化合物、脲化合物、及其 它含氮雜環化合物等。 作爲前述3級胺化合物，例如較佳爲正己胺、正庚胺 、正辛胺、正壬胺、正癸胺、環己胺等的單（環）烷基胺 -53- 200839449 類；二正丁胺、二正戊胺、二正己胺、二正庚胺、二正辛 胺、二正壬胺、二正癸胺、環己基甲胺、二環己胺等的二 (環）烷基胺類；三乙胺、三正丙胺、三正丁胺、三正戊 胺、三正己胺、三正庚胺、三正辛胺、三正壬胺、三正癸 胺、環己基二甲胺、甲基二環己胺、三環己胺等的三（環 )烷基胺類；2,2’，2”-硝基三乙醇等的取代烷基胺；苯胺 、N•甲基苯胺、N，N-二甲基苯胺、2-甲基苯胺、3 —甲基 苯胺、4 一甲基苯胺、4 一硝基苯胺、二苯基胺、三苯基胺 、萘基胺、2,4,6-三第三丁基-N-甲基苯胺、N-苯基二乙醇 胺、2,6-二異丙基苯胺等。 作爲前述其它胺化合物，例如伸乙二胺、N，N，N’，N’-四甲基伸乙二胺、四亞甲基二胺、六亞甲二胺、4,4’-二胺 基二苯基甲烷、4,4’-二胺基二苯基醚、4，4’-二胺基二苯 甲酮、4,4’-二胺基二苯基胺、2,2-雙（4-胺基苯基）丙烷 、2- ( 3-胺基苯基）-2- ( 4-胺基苯基）丙烷、2- ( 4-胺基 苯基）-2- ( 3-羥基苯基）丙烷、2- ( 4-胺基苯基）-2- ( 4-羥基苯基）丙烷、1，4-雙[1-(4-胺基苯基）-1-甲基乙基] 苯、1，3-雙[1- (4-胺基苯基）-1-甲基乙基]苯、雙（2-二 甲基胺基乙基）醚、雙（2-二乙基胺基乙基）醚、1-(2-羥乙基）-2-咪唑啉二酮、2-喹噁啉醇、N，N，N’，N’-四（2- 羥丙基）伸乙二胺、N，N，N’，N”，N”-五甲基二伸乙三胺等 〇 作爲前述含醯胺基的化合物，例如較佳爲N-第三丁 氧羰基二正辛胺、N-第三丁氧羰基二正壬胺、N-第三丁氧 -54- 200839449 羰基二正癸胺、N-第三丁氧羰基二環己胺、N_第三丁氧鑛 基-1-金剛烷基胺、N-第三丁氧羰基-2-金剛烷基胺、^第 三丁氧羰基-N-甲基-1-金剛烷基胺、αχ·)·!·(第三丁氧 羰基）-2·吡咯啶甲醇、（R)-( + )-l -(第三丁氧羰基）-2_口比 咯啶甲醇、N-第三丁氧羰基-4-羥基哌啶、N-第三丁氧鑛 基吡咯啶、N-第三丁氧羰基哌哄、N-第三丁氧羰基脈陡、 N，N -一第二丁氧鑛基-1-金剛院基胺、n，N -二第三丁氧鑛 基-N_甲基-1-金剛烷基胺、N_第三丁氧羰基-4,4，_二胺基 二苯基甲烷、N，N’-二第三丁氧羰基六亞甲基二胺、 N，N，N’，N’-四第三丁氧羰基六亞甲基二胺、n，N，-二第三 丁氧羰基-1,7-二胺基庚烷、N，N’-二第三丁氧羰基-丨，訌二 胺基辛烷、N，N、二第三丁氧羰基-i，9-二胺基壬烷、n，n，_ 二第三丁氧簾基-1，10 -二胺基癸燒、n，n，_二第三丁氧鑛 基-1，12-二胺基十二烷、N，N’-二第三丁氧羰基_4,4，·二胺 基二苯基甲烷、N-第三丁氧羰基苯并咪唑、第三丁氧幾 基-2-甲基苯并咪唑、N-第三丁氧羰基_2_苯基苯并咪唑等 的N -第三丁氧羰基含有胺基化合物，以及、甲醯胺、N _ 甲基甲醯胺、N，N-二甲基甲醯胺、乙醯胺、N-甲基乙醯胺 、N，N-二甲基乙醯胺、丙醯胺、苯甲醯胺、吡咯啶酮、N_ 甲基吡咯啶酮、N -乙醯基· 1-金剛烷基胺、異氰尿酸三（ 2-羥乙基）酯等。 作爲前述脲化合物，例如較佳爲尿素、甲脲、1，1 ·二 甲基脲' 1，3 -二甲基脲、1，1，3,3 -四甲基脲、1,3 -二苯基脲 、三正丁基硫脲等。 -55- 200839449 作爲前述其它含氮雜環化合物，例如可舉出咪唑、4-甲基咪唑、4-甲基_2_苯基咪唑、苯并咪唑、2-苯基苯并咪 唑' 1-卞基_2·甲基咪唑、丨·苄基_2_甲基_1H_咪唑等的咪 11坐類，啦D定、2·甲基吡啶、甲基吡啶、2_乙基吡啶、4_ 乙基吡啶、2-苯基吡啶、苯基吡啶、2_甲基_4_苯基吡啶 、於鹼、菸鹼酸、菸鹼酸醯胺、喹啉、4 _羥基喹啉、8 _羥 基嗤啉、ίΤΐΙ定、2,2，：6，，2，，三聯吡啶等的吡啶類；哌哄、1_ (2-經乙基）哌哄等的哌哄類，以及吡哄、吡唑、嗒哄、醌 西、嘌呤、吡咯啶、哌啶、哌啶乙醇、3 _哌啶基-〗，2 _丙烷 一醇、嗎啉、4 -甲基嗎啉、丨_ ( 4 -嗎啉基）乙醇、4 -乙醯 基嗎啉、3- ( Ν_嗎啉基）-1 ,2-丙二醇、1，4-二甲基哌哄、 1，4-二氮雜雙環[2.2.2]辛烷等。 前述含氮化合物（D )可爲單獨或混合2種以上來使 用。 如此的酸擴散控制劑[含氮化合物（D )]之配合量， 對於聚合物（A )與樹脂（Β )的合計1 0 0質量份而言， 較佳爲15質量份以下，尤佳爲〇·0〇ι〜1〇質量份，、更佳 爲0 · 0 1〜5質量份。該酸擴散控制劑的配合量若超過i 5 質量份，則作爲光阻的感度會降低。另一方面，若低於 0.001質量份，則隨著製程條件，作爲光阻的圖型形狀或 尺寸忠實度有降低之虞。 <溶劑（E ) > 本發明的敏輻射線性樹脂組成物於使用時，以總固體 -56 - 200839449 成分濃度成爲通常1〜50質量％、較佳1〜25質量％的方 式’溶解在溶劑中後，例如經由孔徑〇·2μπι左右的過濾器 來過濾，調製成爲樹脂組成物溶液。 作爲前述溶劑（Ε )，例如可舉出2-丁酮、2-庚酮、 3-甲基-2-丁酮、2-己酮、4_甲基-2-庚酮、3-甲基-2-庚酮 、3，3-二甲基-2-丁酮、2-庚酮、2-辛酮等的直鏈狀或支鏈 狀的酮類；環庚酮、3-甲基環庚酮、環己酮、2-甲基環己 酮、2,6_二甲基環己酮、異佛爾酮等的環狀的酮類；丙二 醇單甲基醚醋酸酯、丙二醇單乙基醚醋酸酯、丙二醇單正 丙基醚醋酸酯、丙二醇單異丙基醚醋酸酯、丙二醇單正丁 基醚醋酸酯、丙二醇單異丁基醚醋酸酯、丙二醇單第二丁 基醚醋酸酯、丙二醇單第三丁基醚醋酸酯等的丙二醇單烷 基醚醋酸酯類；2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥 基丙酸正丙酯、2-羥基丙酸異丙酯、2-羥基丙酸正丁酯、 2-羥基丙酸異丁酯、2-羥基丙酸第二丁酯、2-羥基丙酸第 三丁酯等的2-羥基丙酸烷基類；3-甲氧基丙酸甲酯、3-甲 氧基丙酸乙酯、3 -乙氧基丙酸甲酯、3_乙氧基丙酸乙酯等 的3-烷氧基丙酸烷基類，及 正丙醇、異丙醇、正丁醇、第三丁醇、環己醇、乙二 醇單甲基醚、乙二醇單乙基醚、乙二醇單正丙基醚、乙二 醇單正丁基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、 二乙二醇二正丙基醚、二乙二醇二正丁基醚、乙二醇單甲 基醚醋酸酯、乙二醇單乙基醚醋酸酯、乙二醇單正丙基醚 醋酸酯、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單正 -57- 200839449 丙基醚、甲苯、二甲苯、2-羥基-2-甲基丙酸乙酯、乙氧 基醋酸乙酯、羥基醋酸乙酯、2-羥基-3-甲基丁酸甲酯、3_ 甲氧基丁基醋酸酯、3-甲基-3-甲氧基丁基醋酸酯、3-甲 基-3-甲氧基丁基丙酸酯、3-甲基-3-甲氧基丁基丁酸酯、 醋酸乙酯、醋酸正丙酯、醋酸正丁酯、乙醯基醋酸甲酯、 乙醯基醋酸乙酯、.丙酮酸甲酯、丙酮酸乙酯、N-甲基吡咯 啶酮、N，N-二甲基甲醯醯胺、N，N-二甲基乙醯胺、苄基乙 基醚、二正己基醚、二乙二醇單甲基醚、二乙二醇單乙基 醚、己酸、辛酸、1-辛醇、1-壬醇、苯甲醇、醋酸苄酯、 苯甲酸乙酯、草酸二乙酯、馬來酸二乙酯、γ-丁內酯、碳 酸伸乙酯、碳酸伸丙酯等。 於此等之中，較佳爲直鏈狀或支鏈狀的酮類、環狀的 酮類、丙二醇單烷基醚醋酸酯類、2_羥基丙酸烷酯類、3_ 烷氧基丙酸烷酯類、γ-丁內酯等。 此等溶劑（Ε )可爲單獨或混合2種以上來使用。 <添加劑> 於本發明的敏輻射線性樹脂組成物中，視需要可摻合 脂環族添加劑、界面活性劑、增感劑等的各種添加劑。 前述脂環族添加劑係顯示進一步改善乾飩刻耐性、圖 型形狀、與基板的接著性等之作用的成分。 作爲如此的脂環族添加劑，例如可舉出1 -金剛烷羧 酸、2-金剛烷酮、1-金剛烷羧酸第三丁酯、^金剛烷羧酸 第三丁氧羰基甲酯、b金剛烷羧酸α-丁內酯酯、13 —金剛 -58 - 200839449 烷二羧酸二第三丁酯、1-金剛烷乙酸第三丁酯、1·金剛烷 乙酸第三丁氧羰基甲基、1，3-金剛烷二乙酸二第三丁酯、 2,5·二甲基-2,5·二（金剛烷基羰氧基）己烷等的金剛烷衍 生物類；脫氧膽酸第三丁酯、脫氧膽酸第三丁氧羰基甲酯 、脫氧膽酸2-乙氧基乙酯、脫氧膽酸2-環己基氧基乙酯 、脫氧膽酸3 -氧代環己酯、脫氧膽酸四氫吡喃酯、脫氧 膽酸甲羥戊內酯等的脫氧膽酸酯類；石膽酸第三丁酯、石 膽酸第三丁氧羰基甲酯、石膽酸2 -乙氧基乙酯、石贍酸 2 -環己基氧基乙酯、石膽酸3-氧代環己酯、石膽酸四氫吡 喃酯、石膽酸甲羥戊內酯等的石膽酸酯類；己二酸二甲酯 、己二酸二乙酯、己二酸二丙酯、己二酸二正丁酯、己二 酸二第三丁酯.等的烷基羧酸酯類、或3-[2-羥基-2,2-雙（ 三氟甲基）乙基]四環[4·4·〇·1 十二烷等。 此等脂環族添加劑可爲單獨或混合2種以上來使用。 又，前述界面活性劑係爲顯示改良塗佈性、輝紋、顯 像性等之作用的成分。 作爲如此的界面活性劑，例如可舉出聚氧化乙烯月桂 基醚、聚氧化乙烯硬脂基醚、聚氧化乙烯油基醚、聚氧化 乙烯正辛基苯基醚、聚氧化乙烯正壬基苯基醚、聚乙二醇 二月桂酸酯、聚乙二醇二硬脂酸酯等的非離子系界面活性 劑，以及以下商品名：KP341 (信越化學工業株式會社製 )、P〇iyfi〇wNo·75、同ν〇·95(共榮社化學株式會社製 )、Eftop EF301、同 EF3 03、同 EF3 5 2 ( ΤΟΗΚΕΜ PRODUCTS 株式會社製）、Megafac F171、同 F173(大 -59- 200839449 日本油墨化學工業株式會社製）、Florad FC430、同 FC43 1 (住友 3M 株式會社製）、Asahiguard AG710、 Surflon S-3 82、同 SC-101、同 SC-102、同 SC-103、同 SC-104、同 SC-105、同SC-106 (旭硝子株式會社製）等 。此等界面活性劑可爲單獨或混合2種以上來使用。 又，前述增感劑，係顯示吸收輻射線的能量，將其能 量傳達給酸產生劑（C )，藉此而增加酸的生成量之作用 者，敏輻射線性樹脂組成物具有提高敏輻射線性組成物的 表觀感度之效果。 作爲如此的增感劑，例如可舉出咔唑類、苯乙酮類、 二苯甲酮類、萘類、酚類、聯乙醯、曙紅、玫瑰紅、芘類 、蒽類、啡噻哄類等。再者，此等增感劑可爲單獨或混合 2種以上來使用。 又，藉由摻合染料或顏料，使曝光部的潛像成爲可見 化，可以緩和曝光時的暈光之影響，藉由摻合接著助劑， 可以改善與基板的接著性。 再者，作爲前述以外的添加劑，可舉出鹼可溶性樹脂 、具有酸解離性的保護基之低分子鹼溶解性控制劑、防暈 光劑、保存安定化劑、消泡劑等。 <光阻圖型的形成方法> 本發明的浸潤式曝光用敏輻射線性樹脂組成物係特別 適用作爲化學增幅型光阻。於化學增幅型光阻中，藉由曝 光而從酸產生劑所產生的酸之作用，使樹脂成分[主要爲 -60- 200839449 樹脂（B )]中的酸解離性基進行解離，產生羧基，結果光 阻的曝光部對於鹼顯像液的溶解性變高，該曝光部可被鹼 顯像液所溶解、去除，而得到正型光阻圖型。 本發明的光阻圖型形成方法具備：（1 )使用前述浸 潤式曝光用敏輻射線性樹脂組成物，在基板上形成光阻膜 的步驟[以下亦稱爲「步驟（1 )」]，（2 )經由浸潤介質 且通過具有指定圖型的光罩，對所形成的光阻膜照射輻射 線，進行曝光的步驟[以下亦稱爲「步驟（2 )」]，及（3 )將經曝光的光阻膜顯像，形成光阻圖型的步驟[以下亦 稱爲「步驟（3 )」]。 於前述步驟（1 )中，將本發明的樹脂組成物溶解在 溶劑中而得之樹脂組成物溶液，藉由旋轉塗佈、流延塗佈 、輥塗佈等的適當之塗佈手段，例如塗佈在矽晶圓、經鋁 所被覆的晶圓等之基板上，而形成光阻膜。具體地，以所 得到的光阻膜成爲指定膜厚的方式，塗佈樹脂組成物溶液 後，藉由預烘烤（PB )，以使用塗膜中的溶劑揮發，而 形成光阻膜。 光阻膜的厚度係沒有特別的限定，通常爲〇.1〜5μπι ，更佳爲0.1〜2μιη。 又，預烘烤的加熱條件係隨著敏輻射線性樹脂組成物 的摻合組成而變化，但通常爲3 0〜2 0 0 °C左右，較佳爲5 0 〜150〇C。 再者，於本發明中，爲了以最大限度引出敏輻射線性 組成物的潛在能力，例如亦可像特公平6_ 1 2452號公報（ -61 - 200839449 特開昭59-93448號公報）等中所揭示地，於所使用的基 板上預先形成有機系或無機系的抗反射膜。又，爲了防止 環境氣氛中所含有的鹼性雜質等之影響，例如也可像特開 平5 - 1 8 8 5 9 8號公報等中所揭示地，於光阻膜上設置保護 膜。再者，爲了防止從光阻膜流出酸產生劑等，例如亦可 像特開200 5-3 523 84號公報等中所揭示地，於光阻膜上設 置浸潤用保護膜。又，也可倂用此等技術。 φ 於前述步驟（2 )中，經由水等的浸潤介質，對步驟 (1 )所形成的光阻膜照射輻射線，使曝光。再者，於此 情況下，通過具有指定圖型的光罩，照射輻射線。 作爲前述輻射線’可按照所使用的酸產生劑之種類， 適當地選擇可見光線、紫外線、遠紫外線、X射線、荷電 粒子線等來使用，但較佳爲A r F準分子雷射（波長1 9 3 n m )或KrF準分子雷射（波長24 8nm )所代表的遠紫外線， 特佳爲ArF準分子雷射（波長193nm)。 # 又，曝光量等的曝光條件，係按照敏輻射線性樹脂組 成物的摻合組成或添加劑的種類等來適宜選定。於本發明 中，在曝光後較佳進行加熱處理（PEB )。藉由PEB，可 圓滑地進行樹脂成分中的酸解離性基之解離反應。該pEB 的加熱條件係隨著敏輻射線性樹脂組成物的摻合組成而變 化，但通常爲30〜200 °C，較佳爲50〜170 °C。 於前述步驟（3 )中，藉由對經曝光的光阻膜進行顯 像，形成指定的光阻圖型。作爲該顯像所使用的顯像液， 例如較佳爲溶解有氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉 -62- 200839449 、偏矽酸鈉、氨水、乙胺、正丙胺、二乙胺、二正丙胺、 三乙胺、甲基二乙基胺、乙基二甲基胺、三乙醇胺、氫氧 化四甲銨、吡略、哌啶、膽鹼、1，8 -二氮雜雙環-[5.4 · 〇 ]-7-H 烯、U5 -二氮雜雙環-[4·3·0]-5 -壬烯等的鹼性化合 物中至少一種的驗性水溶液。前述驗性水溶液的濃度通常 爲1 0質量％以下。於該情況下，鹼性水溶液的濃度若超 過1 G質量％，則有非曝光部亦會溶解在顯像液中之虞， 而係不宜。 又，於由前述鹼性水溶液所成的顯像液中，例如亦可 添加有機溶劑。作爲前述有機溶劑，例如可舉出丙酮、甲 基乙基酮、甲基異丁基酮、環庚酮、環己酮、3 -甲基環庚 酮、2,6-二甲基環己酮等的酮類·，甲醇、乙醇、正丙醇、 異丙醇、正丁醇、第三丁醇、環戊醇、環己醇、1，4-己二 醇、1，4-己烷二甲醇等的醇類；四氫呋喃、二噁烷等的醚 類；乙酸乙酯、乙酸正丁酯、乙酸異戊酯等的酯類；甲苯 、二甲苯等的芳香族烴類，或苯酚、丙酮基丙酮、二甲基 甲醯胺等。此等有機溶劑可爲單獨或混合2種以上來使用 。此有機溶劑的使用量，對於鹼性水溶液而言，較佳爲 1 00容量％以下。於該情況下，有機溶劑的使用量若超過 1 00容量％，則顯像性降低，曝光部的顯像殘渣有變多之 虞。又，於由鹼性水溶液所成的顯像液中，也可添加適量 的界面活性劑等。 再者，由鹼性水溶液所成的顯像液來顯像後，—^ 水洗淨及進行乾燥。 -63- 200839449 實施例 以下舉出實施例來更具體說明本發明的實施形態。但 是，本發明完全不受此等實施例所限制。此處，只要沒有 特別預先指明，則份係以質量爲基準。 <聚合物（A-1)〜（A-3)及樹脂（Β·1)〜（B-4)的合 成> 以下說明各聚合物（A )及各樹脂（Β )的合成例。 再者，於下述的各合成例中，各測定及評價係藉由下述要 領來進行。 (1 ) Mw 及 Μη 使用東曹（股）製GPC管柱（2支G2000HXL、1支 G3000HXL、1支G4000HXL )，在流量爲 1 .〇毫升/分鐘 、洗提溶劑爲四氫呋喃、管柱溫度爲40°C的分析條件下， 以單分散聚苯乙烯當作標準，藉由凝膠滲透層析術（GPC )來測定。又，分散度Mw/Mn係由測定結果來算出。 (2 ) "C-NMR 分析 各聚合物的13 C-NMR分析係使用日本電子（股）製 「JNM-EX270」來測定。 又，以下顯示下述各合成中所用的單體[(M-1)〜（ Μ - 9 )]之構造。 -64- 200839449Further, in the present invention, the acid generator 1 may be used alone or in combination of two or more. In addition, as the sensitive radiation linear acid generator (hereinafter referred to as "other acid generator") other than the acid generator 1 which can be used as the radiation-sensitive linear acid generator (C), for example, a key salt compound may be mentioned. A halogen compound, a diazoketone compound, an anthracene compound 'sulfonic acid compound, and the like. As such an -49-200839449, the acid generator thereof is exemplified by the following. Key salt compound: Examples of the key salt compound include an iodine salt, a phosphonium salt, a diazo salt, and a pyridinium salt. Specific examples of the key salt compound include diphenyl iodine sulfonate, diphenyl iodonium nonafluoro n-butane sulfonate, diphenyl fluoride n-octane sulfonate, and diphenyl iodine. Key 2-bicyclo[2·2·1]g φ 1,1,2,2·tetrafluoroethane sulfonate, bis(4-t-butylphenyl)fluoromethanesulfonate, bis(4- Ternyl butyl phenyl iodide hexafluoro sulfonate, bis(4-tributylphenyl) iodine perfluoro-n-octane sulfonate (4-tert-butylphenyl) iodine 2-bicyclo [2.2.1]Hept-2-yl-]tetrafluoroethanesulfonate, cyclohexyl-2-oxocyclohexylmethylsulfonate, dicyclohexyl-2-oxocyclohexylsulfonate Fluoromethanesulfonate oxocyclohexyl dimethyl mirror difluoromethyl sulfonate and the like. Halogen-containing compound: φ As the halogen-containing compound, for example, a halogenated alkyl group-containing hydrocarbon or a halogenated alkyl group-containing heterocyclic compound can be given. Specific examples of the halogen-containing compound include phenylbismethyl)-S-triazine, 4-methoxyphenylbis(trichloromethyl)-S.trinylbis(dichloromethyl)- (Trichloromethyl)-S-dioxide, 1,1-bis(4-chlorobenzyl)-2,2,2-trichloroacetamidine, etc. The diazoketone compound: Examples of the diazoketone compound include a 1,3 -dione group compound, a diazonium benzoquinone compound, and a diazonaphthoquinone compound. Iron salt, trifluoromethyl iodide all-2-yl-iodyl tri-n-butanoate, ., 1,2,2·fluoromethane salt, 2-compound (trichloropurine, 1 · hydrazine derived 2-weight Nitrogen-50- 200839449 Specific examples of the diazoketone include 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonyl chloride. 1,2-naphthoquinonediazide-4-sulfonate or 1,2-naphthoquinonediazide-5-sulfonate of 2,3,4,4'-tetrahydroxybenzophenone, Tris(4-hydroxyphenyl)ethane 1,2-naphthoquinonediazide-4-sulfonate or 1,2-naphthoquinonediazide-5-sulfonate, etc. Examples of the milled compound include β-keto oxime, β-sulfonyl hydrazine, or an α-diazo compound of such a compound. Examples of the ruthenium compound include 4-trityl guanidine. a sulfonic acid compound: a sulfonic acid compound, for example, an alkyl sulfonate, an alkyl sulfonate, or an alkyl sulfonate Haloalkyl sulfonate, aryl sulfonate, imino sulfonate, etc. Specific examples of the sulfonic acid compound include Benzoin tosylate, tris(trifluoromethanesulfonate) of pyrogallol, nitrophenyl-9,10-diethoxyindole-2-sulfonate, trifluoromethanesulfonylbicyclo[ 2.2.1] hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, Perfluoro-n-octanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, 2_bicyclo[2·2·1]hept-2-yl·1,1,2 ,2-tetrafluoroethanesulfonylbicycloindole·2·1]hept-5-ene·2,3-dicarbodiimide, fluorene-(trifluoromethanesulfonyloxy) amber quinone imine, hydrazine -(nonafluoro-n-butanesulfonyloxy) amber imine, Ν-(perfluoro-n-octanesulfonyloxy) amber quinone imine, Ν-(2-bicyclo[2.2.1]heptan-2-yl - i5l,2,2-tetrafluoroethanesulfonyloxy) succinimide, phthalimide naphthalene diamine trifluoromethane sulfonate, • 51 - 200839449 1,8-naphthalene dicarboxylate Nonafluoro-n-butane sulfonate, octadecyl 1,8-naphthalene dicarboxylate, perfluoro-n-octane sulfonate, etc. Among other acid generators, diphenyl iodine trifluoromethane is preferred. Methanesulfonate, diphenyl iodide, nonafluoro-n-butane sulfonate Diphenyl iodide perfluoro-n-octane sulfonate, diphenyl iodide 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate, double (4-tert-butylphenyl)-iodo-iron trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodo-iron nonafluoro-n-butane sulfonate, bis(4-tert-butylbenzene) Iodine iron perfluoro-n-octane sulfonate, bis(4-tert-butylphenyl) iodide 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoro Ethane sulfonate, cyclohexyl 2-oxocyclohexylmethyl mirror trifluoromethanesulfonate, dicyclohexyl 2-oxocyclohexylfluorene trifluoromethanesulfonate, 2-oxocyclohexyl Dimethyl sulfonium trifluoromethanesulfonate, trifluoromethanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo[2.2 .1]hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, 2 -bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonylbicyclo[2.2.1]hept-5-ene-2,3-dicarbodiimide, Ν-(Trifluoromethanesulfonyloxy) succinimide, Ν-(nonafluoro-n-butane sulfonyloxy) amber Amine, Ν-(perfluoro-n-octanesulfonyloxy) succinimide, Ν-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate Alkoxy) amber imine, 1,8-naphthalene dicarboxylate, trifluoromethanesulfonate, and the like. The above-mentioned other acid generators may be used alone or in combination of two or more. In the present invention, the total amount of use of the acid generator 1 and other acid generators is 'from the viewpoint of ensuring sensitivity and developability as a photoresist, for the poly-52-200839449 compound (A) and resin (B). The total amount of 100 parts by mass is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass. When the total amount used is less than 0.1 part by mass, the sensitivity and developability tend to be lowered. On the other hand, when it exceeds 20 parts by mass, the transparency to the radiation is lowered, and it tends to be difficult to obtain a rectangular photoresist pattern. In addition, the ratio of use of the other acid generator is usually 80% by mass or less, preferably 60% by mass or less, based on 100% by mass of the total of the acid generator 1 and the other acid generator. <Nitrogen-containing compound (D) > Further, in the radiation sensitive linear resin composition of the present invention, as a diffusion display for controlling the acid generated from the acid generator due to exposure in the resist film, the inhibition is suppressed. The acid diffusion controlling agent which is not suitable for the chemical reaction in the exposed region may contain a nitrogen-containing compound [hereinafter referred to as a nitrogen-containing compound (D)]. By incorporating such an acid diffusion controlling agent, the storage stability of the obtained radiation sensitive resin composition can be improved. Further, the resolution of the photoresist can be further improved, and the line width variation of the resist pattern due to the fluctuation of the shelf life (PED) from the exposure to the heat treatment after the exposure can be suppressed, and the process stability can be excellent. Composition. Examples of the nitrogen-containing compound (D) include a tertiary amine compound, another amine compound, a guanamine group-containing compound, a urea compound, and other nitrogen-containing heterocyclic compounds. As the above-mentioned tertiary amine compound, for example, a mono(cyclo)alkylamine-53-200839449 type such as n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine or cyclohexylamine; Di(cyclo)alkylamines such as butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-decylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine Class; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, tri-n-decylamine, cyclohexyldimethylamine, a tri(cyclo)alkylamine such as methyldicyclohexylamine or tricyclohexylamine; a substituted alkylamine such as 2,2',2"-nitrotriethanol; aniline, N-methylaniline, N , N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-monoaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,4, 6-tri-tert-butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisopropylaniline, etc. As the other amine compounds, for example, ethylenediamine, N, N, N' , N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylene Diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diamine Diphenylamine, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane, 2-(4-amino group Phenyl)-2-(3-hydroxyphenyl)propane, 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane, 1,4-bis[1-(4-amino) Phenyl)-1-methylethyl]benzene, 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene, bis(2-dimethylaminoethyl) Ether, bis(2-diethylaminoethyl)ether, 1-(2-hydroxyethyl)-2-imidazolidinone, 2-quinoxaline alcohol, N,N,N',N' - tetrakis(2-hydroxypropyl)-extended ethylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine or the like as the above-mentioned guanamine-containing compound, for example, preferably N-tert-butoxycarbonyldi-n-octylamine, N-tert-butoxycarbonyldi-n-decylamine, N-tert-butoxy-54-200839449 carbonyl di-n-decylamine, N-tert-butoxycarbonyl dicyclohexyl Amine, N_third butoxy- ortho-adamantylamine, N-third butoxycarbonyl-2-adamantylamine, ^ third carbonyl-N-methyl-1-adamantylamine, αχ·····(Tertidinoxycarbonyl)-2·pyrrolidinemethanol, (R)-( + )-l -(T-butoxycarbonyl) - 2_ mouth pyrrolidine methanol, N-third butoxycarbonyl-4-hydroxypiperidine, N-third butoxy-oxopyrrolidine, N-third butoxycarbonyl piperazine, N-third Oxycarbonyl ruthenium, N,N-a second butoxy- ortho-yl-l-Gumantylamine, n,N-di-tert-butoxy-based-N-methyl-1-adamantylamine, N_ Third butoxycarbonyl-4,4,-diaminodiphenylmethane, N,N'-di-t-butoxycarbonylhexamethylenediamine, N,N,N',N'-fourth third Butoxycarbonylhexamethylenediamine, n,N,-di-tert-butoxycarbonyl-1,7-diaminoheptane, N,N'-di-tert-butoxycarbonyl-indole, anthracenediamine Octane, N, N, di-tert-butoxycarbonyl-i,9-diaminodecane, n,n,_dt-butoxybutyryl-1,10-diaminopyrene, n,n , _ two third butoxy- orion-1,12-diaminododecane, N,N'-di-t-butoxycarbonyl-4,4,diaminodiphenylmethane, N-third Butoxycarbonylbenzimidazole, third butoxymethyl-2-methylbenzimidazole, N- N-tert-butoxycarbonyl group such as butoxycarbonyl-2-phenylbenzimidazole contains an amine compound, and formamide, N-methylformamide, N,N-dimethylformamide, Acetamide, N-methylacetamide, N,N-dimethylacetamide, acetamide, benzamide, pyrrolidone, N-methylpyrrolidone, N-ethenyl 1 - adamantylamine, tris(2-hydroxyethyl) isocyanurate, and the like. As the aforementioned urea compound, for example, urea, methyl urea, 1,1, dimethylurea '1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3 - two are preferable. Phenylurea, tri-n-butyl thiourea, and the like. -55- 200839449 Examples of the other nitrogen-containing heterocyclic compound include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, and 2-phenylbenzimidazole ' 1- Molecular 11 such as fluorenyl-2-methylimidazole, hydrazino-benzyl-2-methyl-1H-imidazole, D-, 2-methylpyridine, methylpyridine, 2-ethylpyridine, 4_ Ethylpyridine, 2-phenylpyridine, phenylpyridine, 2-methyl-4-phenylpyridine, base, nicotinic acid, nicotinic acid decylamine, quinoline, 4-hydroxyquinoline, 8-hydroxyl Pyridines such as porphyrin, ruthenium, 2,2,6,2, and terpyridine; piperidines such as piperidine, 1-(2-ethyl) piperidine, and pyridinium, pyrazole,嗒哄, 醌, 嘌呤, pyrrolidine, piperidine, piperidine ethanol, 3-piperidinyl-, 2, propanol, morpholine, 4-methylmorpholine, 丨_(4-morpholino Ethanol, 4-ethionylmorpholine, 3-(indolylmorpholinyl)-1,2-propanediol, 1,4-dimethylpiperidinium, 1,4-diazabicyclo[2.2.2] Octane and so on. The nitrogen-containing compound (D) may be used singly or in combination of two or more. The amount of the acid-diffusion controlling agent [nitrogen-containing compound (D)] is preferably 15 parts by mass or less, more preferably 15 parts by mass or less, based on the total of the polymer (A) and the resin (Β). 〇·0〇ι~1〇 parts by mass, more preferably 0·0 1~5 parts by mass. When the amount of the acid diffusion controlling agent exceeds i 5 parts by mass, the sensitivity as a photoresist is lowered. On the other hand, if it is less than 0.001 part by mass, the pattern shape or dimensional fidelity as a photoresist may be lowered depending on the process conditions. <Solvent (E) > The radiation sensitive linear resin composition of the present invention is dissolved in the form of a total solid-56 - 200839449 component concentration of usually 1 to 50% by mass, preferably 1 to 25% by mass. After the solvent is passed through, for example, it is filtered through a filter having a pore size of about 2 μm to prepare a resin composition solution. Examples of the solvent (Ε) include 2-butanone, 2-heptanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-heptanone, and 3-methyl group. a linear or branched ketone such as 2-heptanone, 3,3-dimethyl-2-butanone, 2-heptanone or 2-octanone; cycloheptanone, 3-methyl ring a cyclic ketone such as heptanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone or isophorone; propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-isopropyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol mono-butyl ether acetate, Propylene glycol monoalkyl ether acetate such as propylene glycol monobutyl ether acetate; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, n-propyl 2-hydroxypropionate, 2-hydroxypropionic acid 2-hydroxypropionic acid alkyl group such as isopropyl ester, n-butyl 2-hydroxypropionate, isobutyl 2-hydroxypropionate, second butyl 2-hydroxypropionate, and tert-butyl 2-hydroxypropionate Class; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate 3-Alkoxypropionic acid alkyl such as ethyl ethoxypropionate, and n-propanol, isopropanol, n-butanol, tert-butanol, cyclohexanol, ethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl Ethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-57- 200839449 propyl ether, toluene, xylene, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate, Methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropane Acid ester, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoxyacetate, ethyl acetoxyacetate, pyruvic acid Methyl ester, ethyl pyruvate, N-methylpyrrolidone, N,N-dimethyl Indoleamine, N,N-dimethylacetamide, benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, caproic acid, octanoic acid, 1- Octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethyl carbonate, propyl carbonate, and the like. Among these, a linear or branched ketone, a cyclic ketone, a propylene glycol monoalkyl ether acetate, a 2-hydroxypropionic acid alkyl ester, and a 3-alkoxypropionic acid are preferable. Alkyl esters, γ-butyrolactone, and the like. These solvents (Ε) may be used singly or in combination of two or more. <Additive> In the radiation sensitive linear resin composition of the present invention, various additives such as an alicyclic additive, a surfactant, a sensitizer, and the like may be blended as needed. The alicyclic additive system exhibits a component which further improves the effects of dry etching resistance, pattern shape, adhesion to a substrate, and the like. Examples of such an alicyclic group-containing additive include 1-adamantanecarboxylic acid, 2-adamantanone, 1-butylantanecarboxylic acid tert-butyl ester, adamantanecarboxylic acid, third butoxycarbonylmethyl ester, and b. Alpha-butyrolactone of adamantane, 13-King Kong-58 - 200839449 Di-tert-butyl dialkyl dicarboxylate, tert-butyl 1-adamantane acetate, tributyloxycarbonyl methyl 1 adamantane acetate , adamantane derivatives such as 1,3-adamantane diacetate di-t-butyl ester, 2,5-dimethyl-2,5.di(adamantylcarbonyloxy)hexane; deoxycholic acid Tributyl ester, third butoxycarbonyl methyl deoxycholate, 2-ethoxyethyl deoxycholate, 2-cyclohexyloxyethyl deoxycholate, 3-oxocyclohexyl deoxycholate, deoxygenated Deoxycholate such as tetrahydropyranyl cholate, mevalonate deoxycholate, etc.; tert-butyl lithochate, third butoxycarbonyl methyl lithate, 2-ethoxygen lithocholic Glycolate such as ethyl ethyl ester, 2-cyclohexyloxyethyl phosphinate, 3-oxocyclohexyl lithate, tetrahydropyranyl lithate, and mevalonate lithochalate Class; dimethyl adipate, diethyl adipate, Alkyl carboxylates such as dipropyl diacrylate, di-n-butyl adipate, di-tert-butyl adipate, or 3-[2-hydroxy-2,2-bis(trifluoromethyl) Ethyl]tetracyclo[4·4·〇·1 dodecane, etc. These alicyclic additives may be used singly or in combination of two or more. Further, the surfactant is a component which exhibits an effect of improving coatability, striation, and imaging properties. Examples of such a surfactant include polyethylene oxide lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, and polyoxyethylene n-nonylbenzene. A nonionic surfactant such as a base ether, polyethylene glycol dilaurate or polyethylene glycol distearate, and the following trade names: KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), P〇iyfi〇wNo ·75, ν〇·95 (manufactured by Kyoeisha Chemical Co., Ltd.), Eftop EF301, EF3 03, EF3 5 2 (manufactured by ΤΟΗΚΕΜ PRODUCTS Co., Ltd.), Megafac F171, and F173 (large-59-200839449 Japanese ink Chemical Industry Co., Ltd., Florad FC430, FC43 1 (manufactured by Sumitomo 3M Co., Ltd.), Asahiguard AG710, Surflon S-3 82, SC-101, SC-102, SC-103, SC-104, It is the same as SC-105 and SC-106 (made by Asahi Glass Co., Ltd.). These surfactants can be used singly or in combination of two or more. Further, the sensitizer is a function of absorbing radiation energy and transmitting the energy to the acid generator (C), thereby increasing the amount of acid generated, and the sensitive radiation linear resin composition has a linearity of sensitivity radiation. The effect of the apparent sensitivity of the composition. Examples of such a sensitizer include oxazoles, acetophenones, benzophenones, naphthalenes, phenols, hydrazine, ruthenium, rose bengal, anthraquinones, anthraquinones, and thiophenes Ape and so on. Further, these sensitizers may be used singly or in combination of two or more. Further, by blending a dye or a pigment, the latent image of the exposed portion can be visualized, the effect of blooming at the time of exposure can be alleviated, and the adhesion to the substrate can be improved by blending the bonding aid. In addition, examples of the additives other than the above include an alkali-soluble resin, a low molecular alkali solubility control agent having an acid dissociable protecting group, an antihalation agent, a storage stabilizer, and an antifoaming agent. <Formation Method of Photoresist Pattern> The sensitized radiation linear resin composition for immersion exposure of the present invention is particularly suitable as a chemical amplification type resist. In the chemically amplified photoresist, the acid dissociable group in the resin component [mainly -60-200839449 resin (B)] is dissociated by the action of an acid generated by the acid generator by exposure to produce a carboxyl group. As a result, the solubility of the exposed portion of the resist is high in the alkali developing solution, and the exposed portion can be dissolved and removed by the alkali developing solution to obtain a positive resist pattern. The photoresist pattern forming method of the present invention comprises: (1) a step of forming a photoresist film on a substrate by using the immersion-type sensitive radiation linear resin composition (hereinafter also referred to as "step (1)"), ( 2) a step of exposing the formed photoresist film to radiation by passing through a medium and passing through a mask having a specified pattern (hereinafter also referred to as "step (2)"), and (3) exposing The step of developing the photoresist film to form a photoresist pattern [hereinafter also referred to as "step (3)"]. In the above step (1), the resin composition solution obtained by dissolving the resin composition of the present invention in a solvent is suitably coated by spin coating, cast coating, roll coating, or the like, for example. It is coated on a substrate such as a germanium wafer or a wafer coated with aluminum to form a photoresist film. Specifically, the resin composition solution is applied so that the obtained photoresist film has a predetermined film thickness, and then a pre-bake (PB) is used to volatilize the solvent in the coating film to form a photoresist film. The thickness of the photoresist film is not particularly limited and is usually from 0.1 to 5 μm, more preferably from 0.1 to 2 μm. Further, the heating condition of the prebaking varies depending on the blending composition of the sensitive radiation linear resin composition, but is usually about 30 to 200 ° C, preferably 5 0 to 150 ° C. Further, in the present invention, in order to maximize the potential ability of the radiation-sensitive linear composition, for example, it can be used in, for example, Japanese Patent Publication No. Hei. No. Hei 59-93448 (JP-A-59-93448). It is disclosed that an organic or inorganic antireflection film is formed in advance on the substrate to be used. In addition, a protective film may be provided on the photoresist film, as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. In addition, a protective film for wetting is provided on the photoresist film, as disclosed in JP-A-200-5-3 523 84, for example, in order to prevent the acid generator from flowing out of the photoresist film. Also, these techniques can be used. φ In the above step (2), the photoresist film formed in the step (1) is irradiated with radiation through a wetting medium such as water to expose the film. Further, in this case, the radiation is irradiated by the mask having the specified pattern. The radiation line ' can be appropriately selected depending on the type of the acid generator to be used, such as visible light, ultraviolet light, far ultraviolet light, X-ray, charged particle beam, etc., but is preferably an Ar F excimer laser (wavelength) The far ultraviolet rays represented by the 1 9 3 nm or KrF excimer laser (wavelength 24 8 nm) are particularly excellent ArF excimer lasers (wavelength 193 nm). # Further, the exposure conditions such as the exposure amount are appropriately selected in accordance with the blending composition of the sensitive radiation linear resin composition, the type of the additive, and the like. In the present invention, heat treatment (PEB) is preferably carried out after exposure. By PEB, the dissociation reaction of the acid dissociable group in the resin component can be smoothly carried out. The heating condition of the pEB varies depending on the blending composition of the sensitive radiation linear resin composition, but is usually 30 to 200 ° C, preferably 50 to 170 ° C. In the foregoing step (3), a predetermined photoresist pattern is formed by developing the exposed photoresist film. As the developing solution used for the development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate-62-200839449, sodium metasilicate, ammonia, ethylamine, n-propylamine, and the like are preferably dissolved. Ethylamine, di-n-propylamine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrolipid, piperidine, choline, 1,8-diaza An aqueous test solution of at least one of a basic compound such as bicyclo-[5.4 · 〇]-7-H-ene, U5-diazabicyclo-[4·3·0]-5-decene. The concentration of the aforementioned aqueous solution is usually 10% by mass or less. In this case, if the concentration of the alkaline aqueous solution exceeds 1 G% by mass, the non-exposed portion may be dissolved in the developing solution, which is not preferable. Further, for example, an organic solvent may be added to the developing solution formed of the alkaline aqueous solution. Examples of the organic solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cycloheptanone, cyclohexanone, 3-methylcycloheptanone, and 2,6-dimethylcyclohexanone. Ketones, etc., methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexane An alcohol such as methanol; an ether such as tetrahydrofuran or dioxane; an ester such as ethyl acetate, n-butyl acetate or isoamyl acetate; an aromatic hydrocarbon such as toluene or xylene; or phenol or acetone. Acetone, dimethylformamide, and the like. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent to be used is preferably 100% by volume or less for the alkaline aqueous solution. In this case, when the amount of the organic solvent used exceeds 100% by volume, the developability is lowered, and the development residue of the exposed portion is increased. Further, an appropriate amount of a surfactant or the like may be added to the developing solution made of an aqueous alkaline solution. Further, after developing with a developing solution made of an alkaline aqueous solution, the water is washed and dried. -63- 200839449 EXAMPLES Hereinafter, examples of the present invention will be described more specifically by way of examples. However, the invention is not limited at all by these examples. Here, the parts are based on mass unless otherwise specified. <Synthesis of Polymers (A-1) to (A-3) and Resins (Β·1) to (B-4)> A synthesis example of each polymer (A) and each resin (Β) will be described below. Further, in each of the following synthesis examples, each measurement and evaluation was carried out by the following procedures. (1) Mw and Μη use GCC column (two G2000HXL, one G3000HXL, one G4000HXL) made by Tosoh Co., Ltd. at a flow rate of 1. 〇ml/min, the elution solvent is tetrahydrofuran, and the column temperature is The measurement was carried out by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of 40 °C. Further, the degree of dispersion Mw/Mn was calculated from the measurement results. (2) "C-NMR analysis The 13 C-NMR analysis of each polymer was carried out using "JNM-EX270" manufactured by JEOL Ltd. Further, the structure of the monomer [(M-1) to ((-9)] used in each of the following synthesises is shown below. -64- 200839449

[化 18][Chem. 18]

[聚合物（A-l )的合成] 將4〇·7〇克（85莫耳％ )前述單體（ (15旲耳％)單體（Μ-3 )溶解於70克 入5·44克二甲基2,2，_偶氮雙（2_甲基戸 體溶液’以氮氣沖洗已投入有30克2-丁 口燒瓶3〇分鐘。氮氣沖洗後，邊攪拌 80C ’使用滴液漏斗費3小時滴下事前葬 液。以滴下的開始當作聚合開始時間，實 反應。聚合結束後，藉由水冷將聚合溶液[Synthesis of polymer (Al)] 4 〇·7 克 (85 mol%) of the above monomer ((15 旲 ear%) monomer (Μ-3) was dissolved in 70 g of 5.44 g of dimethyl Base 2, 2, _ azobis (2-methyl steroid solution 'with nitrogen flushing has been charged with 30 g 2-butry flask for 3 。 minutes. After nitrogen rinsing, stir 80 C'. Use the dropping funnel for 3 hours. Drop the pre-burial burial liquid. The start of the dripping is used as the polymerization start time, and the reaction is completed. After the end of the polymerization, the polymerization solution is cooled by water cooling.

’將該聚合溶液移到2 L的分液漏斗內。 正己烷來稀釋該聚合溶液，投入600克亏 入30克蒸餾水，再攪拌，靜置30分鐘。 ’當作丙二醇單甲基醚醋酸酯溶液。該植 分（聚合物）之物性値係如以下，收率爲 Μ - 1 )及 9 · 3 0 克 2 - 丁酮中，再投 [酸酯）以準備單 酮的5 00mL之三 反應釜邊加熱到 ;備的前述單體溶 施6小時的聚合 冷卻到3 0 °C以下 接著，以150克 I醇及混合後，投 然後，回收下層 f脂溶液的固體成 5 0%。此聚合物 -65- 200839449 的 Mw = 4300 ’ Mw/Mn=1.3，"C-NMR 分析的結 含量=8·98原子％，由單體（m-ι)及（M_3)而 複單位之含有率係8 6 · 3 ·· 1 3 · 7 (莫耳％ )的共聚物 合物當作聚合物（A -1 )。 [聚合物（A-2)的合成] 將35.81克（70莫耳％)前述單體（M-1) 克（3 〇旲耳％ )單體（Μ - 2 )溶解於7 0克2 - 丁 投入3.23克二甲基2，2’-偶氮雙（2 -甲基丙酸酯 單體溶被’以氮氣沖洗已投入有3 0克2 - 丁酮的 三口燒瓶30分鐘。氮氣沖洗後，邊攪拌反應釜 8 0 °C，使用滴液漏斗費3小時滴下事前準備的前 液。以滴下的開始當作聚合開始時間，實施6小 反應。聚合結束後，藉由水冷將聚合溶液冷卻到 ’將該聚合溶液移到2L的分液漏斗內。接著， 正己烷來稀釋該聚合溶液，投入6 〇 〇克甲醇及混 入2 1克蒸餾水，再攪拌，靜置3 〇分鐘。然後， ，當作丙二醇單甲基醚醋酸酯溶液。該樹脂溶液 分（聚合物）之物性値係如以下，收率爲60%。 爲 Mw = 7300，Mw/Mn=1.6，13C-NMR 分析的結 含量= 9.60原子％，由單體（M-1)及（m-2)而 複單位之含有率係70.5:29.5 (莫耳％)的共聚物 合物當作聚合物（A - 2 )。 田 ^ 采爲.氣 來的各重 。將此聚 及 14.17 酮中，再 )以準備 5 0 0 m L 之 邊加熱到 述單體溶 時的聚合 3 0 °C以下 以1 5 0克 合後，投 回收下層 的固體成 此聚合物 果爲 ·氣 來的各重 。以此聚 -66-The polymerization solution was transferred to a 2 L separatory funnel. The polymerization solution was diluted with n-hexane, and 600 g of a reduced amount of distilled water was added thereto, stirred, and allowed to stand for 30 minutes. 'As a propylene glycol monomethyl ether acetate solution. The physical properties of the plant (polymer) are as follows, in the yields of Μ - 1 ) and 9 · 30 g of 2-butanone, and the [ester] is further added to prepare a 500 cc three-reactor for the monoketone. The mixture was heated until the monomer was dissolved for 6 hours, and the polymerization was cooled to 30 ° C or lower. Then, 150 g of the alcohol was mixed and then added, and then the solid of the lower f-fat solution was recovered to 50%. Mw = 4300 ' Mw / Mn = 1.3 of this polymer-65- 200839449, "Cate content of C-NMR analysis = 8.98 atom%, unit by unit (m-ι) and (M_3) A copolymer composition having a content ratio of 8 6 · 3 ·· 1 3 · 7 (mole %) was used as the polymer (A -1 ). [Synthesis of Polymer (A-2)] 35.81 g (70 mol%) of the aforementioned monomer (M-1) g (3 〇旲%) monomer (Μ - 2 ) was dissolved in 70 g 2 - Dilute 3.23 g of dimethyl 2,2'-azobis(2-methylpropionate monomer solution) was flushed with nitrogen to a three-necked flask containing 30 g of 2-butanone for 30 minutes. After nitrogen purge While stirring the reaction vessel at 80 ° C, the pre-prepared liquid was added dropwise using a dropping funnel for 3 hours. The start of the dropwise addition was used as the polymerization start time, and 6 small reactions were carried out. After the completion of the polymerization, the polymerization solution was cooled by water cooling. Transfer the polymerization solution to a 2 L separatory funnel. Then, dilute the polymerization solution with n-hexane, add 6 g of methanol, and mix 21 g of distilled water, stir, and let stand for 3 minutes. Then, It is regarded as a propylene glycol monomethyl ether acetate solution. The physical properties of the resin solution (polymer) are as follows, and the yield is 60%. Mw = 7300, Mw / Mn = 1.6, and the knot content of 13C-NMR analysis. = 9.60 atom%, a copolymer of a monomer (M-1) and (m-2) and a content ratio of 70.5:29.5 (mole %) as a poly Compound (A - 2 ). The field is collected as the weight of the gas. This is condensed into the 14.17 ketone, and then heated to the side of the preparation of 500 ° L to the polymerization of 30 ° ° After the C is combined with 150 g, the solid of the lower layer is collected and the weight of the polymer is taken as the gas. With this poly-66-

200839449 [聚合物（Ad )的合成] 將35.81克（70莫耳％)前述單體（M-1) 克（30旲耳％)單體（M-2)溶解於7〇克2 -丁 投入5·81克一甲基2,2’-偶氮雙（2_甲基丙酸酯 卓體i谷液’以Ml氣沖洗已投入有3 〇克2 - 丁酮的 三口燒瓶3 0分鐘。氮氣沖洗後，邊攪拌反應釜 8 0 °C，使用滴液漏斗費3小時滴下事前準備的前 液。以滴下的開始當作聚合開始時間，實施6小 反應。聚合結束後，藉由水冷將聚合溶液冷卻到 ，將該聚合溶液移到2L的分液漏斗內。接著， 正己烷來稀釋該聚合溶液，投入600克甲醇及混 入30克蒸餾水，再攪拌，靜置30分鐘。然後， ，當作丙二醇單甲基醚醋酸酯溶液。該樹脂溶液 分（聚合物）之物性値係如以下，收率爲55%。200839449 [Synthesis of polymer (Ad)] 35.81 g (70 mol%) of the above monomer (M-1) g (30 mol%) monomer (M-2) was dissolved in 7 g of 2-butene 5·81 g of monomethyl 2,2'-azobis(2-methylpropionate-rich i-solution) was rinsed with M1 gas into a three-necked flask of 3 g of 2-butanone for 30 minutes. After flushing with nitrogen, the reaction kettle was stirred at 80 ° C, and the pre-prepared liquid was added dropwise using a dropping funnel for 3 hours. The start of the dropwise addition was taken as the polymerization start time, and 6 small reactions were carried out. After the completion of the polymerization, the water was cooled. The polymerization solution was cooled until the polymerization solution was transferred to a 2 L separatory funnel. Then, the polymerization solution was diluted with n-hexane, and 600 g of methanol was added thereto, and 30 g of distilled water was mixed therein, and the mixture was stirred and allowed to stand for 30 minutes. Then, when As a propylene glycol monomethyl ether acetate solution, the resin solution was classified into a polymer (the polymer) as follows, and the yield was 55%.

爲 Mw = 4300，Mw/Mn=l .46，13 C - Ν Μ P 分析的結 含量= 9.60原子％，由單體（M-l)及 & ( M-2)而 複單位之含有率係70 · 9:29.1 (莫耳％) 共聚物 合物當作聚合物（A-3 )。 [樹脂（B-1 )的合成] 將5 5 · 4 4克（5 0吴耳％ )則述單轉（μ 6 ) (40 莫耳 ％)單體（Μ-4)、及 1〇·99 兄〔1 0彦 體（Μ-5 )溶解於200克2-丁酮中，再投入5 Μ 2,2，-偶氮雙（2_甲基丙酸酯）以準備單體、溶彳夜， 及 14.17 酮中，再 )以準備 5〇〇mL 之 邊加熱到 述單體溶 時的聚合 3 0 °C以下 以1 5 0克 合後，投 回收下層 的固體成 此聚合物 果爲·第 來的各重 。以此聚 33.57 克 耳％ )單 克二甲基 以氮氣沖 -67 - 200839449 洗已投入有100克2-丁酮的500mL之三口燒瓶30分鐘。 氮氣沖洗後，邊攪拌反應釜邊加熱到80°C ’使用滴液漏斗 費3小時滴下事前準備的前述單體溶液。以滴下的開始當 作聚合開始時間，實施6小時的聚合反應。聚合結束後’ * 藉由水冷將聚合溶液冷卻到30°C以下，投入到2000克甲 ， 醇，過濾分離所析出的白色粉末。將所過濾分離的白色粉 末在400克的甲醇中以漿體狀洗淨兩次後，過濾分離，在 φ 50°C乾燥17小時，得到白色粉末的聚合物（72克，收率 7 2%)。 此聚合物爲 Mw=6400，Mw/Mn=1.67，13C-NMR 分析 的結果爲：氟含量=0原子％，由單體（M-6 ) 、( M-4 ) 及（Μ·5)而來的各重複單位之含有率係52.2:3 8.1:9.7 ( 莫耳％ )的共聚物。以此聚合物當作樹脂（B-1 )。 [樹脂（B-2)的合成] • 將47.54克（46莫耳％ )前述單體（M-6) 、12.53克 (15莫耳％)單體（M-1) 、39.93克（39莫耳％)單體 (M-7)溶解於200克2-丁酮中，再投入4.08克2,2，·偶 氮雙（異丁腈）以準備單體溶液。 另一方面，以氮氣沖洗已投入有1〇〇克2 -丁酮的 1000mL之三口燒瓶30分鐘。氮氣沖洗後，邊攪拌三口燒 瓶內的內容物邊加熱到80°C，使用滴液漏斗費3小時滴下 事前準備的前述單體溶液。以滴下的開始當作聚合開始時 間，實施6小時的聚合反應。聚合結束後，藉由水冷將聚 -68- 200839449 合溶液冷卻到30°C以下，投入到2000克甲醇，過濾分離 所析出的白色粉末。將所過濾分離的白色粉末在400克的 甲醇中以漿體狀洗淨兩次後，過濾分離，在50°C乾燥17 小時，得到白色粉末的聚合物（7 3克，收率7 3 % )。 此聚合物爲 Mw = 5700，Mw/Mn=1.7，13C-NMR 分析 的結果爲：氟含量=0原子％，由單體（M-6) 、( M-1 ) 及（M-7)而來的各重複單位之含有率係51·4:14·6:34·0( 莫耳％ )的共聚物。以此聚合物當作樹脂（Β _2 )。 [樹脂（Β - 3 )的合成] 將45.81克（40莫耳％)前述單體（Μ-6) 、34·68克 (40莫耳％)單體、6·71克（1〇莫耳％)單體（ Μ_9)溶解於200克2-丁酮中，再投入4.23克偶氮雙異丁 腈以準備單體溶液，以氮氣沖洗已投入有1 2.8 〇克（丨〇莫 耳％)前述單體（Μ-8)及100克2 -丁酮的lOOOmL之三 □燒瓶3 0分鐘。氮氣沖洗後，邊攪拌反應釜邊加熱到 8 0 °C ’使用滴液漏斗費3小時滴下事前準備的前述單體溶 '液。以滴下的開始當作聚合開始時間，實施6小時的聚合 反應。聚合結束後，藉由水冷將聚合溶液冷卻到3 0 °C以下 ’投入到2000克己烷，過濾分離所析出的白色粉末。 再者，使所過濾分離的白色粉末再溶解於300克2-丁醒中’再投入到2000克己烷，過濾分離所析出的白色 粉末。重複此再溶解、過濾分離作業3次後，在5(TC乾燥 17小時，得到白色粉末的聚合物（75克，收率75% )。 -69- 200839449 此聚合物爲 Mw= 6000，Mw/Mn=1.7，13C-NMR 分析 的結果爲：氟含量=〇原子％，由單體（M_6) 、( M-4 ) 、（M·9 )、及（M-8 )而來的各重複單位之含有率係 4 1·3:39·5:9·2··1〇·〇 (莫耳％ )的共聚物。以此聚合物當作 樹脂（Β-3)。 [樹脂（Β · 4 )的合成] 將4 3.48克（40莫耳％ )前述單體（μ-6 ) 、32.91克 (40旲耳％ )單體（Μ-4 ) 、1 1.46克（1 〇莫耳％ )單體 (Μ-7)溶解於200克2-丁酮中，再投入4.26克偶氮雙異 丁腈以準備單體溶液，以氮氣沖洗已投入有1 2 ·丨5克（1〇 旲耳°/。）刖述單體（Μ-8)及1〇〇克2-丁酮的100〇1111^之 二口燒瓶3 0分鐘。氮氣沖洗後，邊攪拌反應釜邊加熱到 8 0 °C，使用滴液漏斗費3小時滴下事前準備的前述單體溶 液。以滴下的開始當作聚合開始時間，實施6小時的聚合 反應。聚合結束後，藉由水冷將聚合溶液冷卻到3 〇它以下 ’投入到2000克甲醇，過濾分離所析出的白色粉末。將 所過濾分離的白色粉末在400克的甲醇中以漿體狀洗淨兩 次後，過濾分離，在5 0 °C乾燥1 7小時，得到白色粉末的 聚合物（7 6克，收率7 6 % )。 此聚合物爲]Vlw = 5 800，Μ\ν/Μη=1·6，13C-NMR 分析 的結果爲：氟含量=〇原子％，由單體（Μ - 6 ) 、 （ Μ - 4 ) 、（Μ_7 )及（Μ-8 )而來的各重複單位之含有率係 4ΐ·6:39·5:8·9:1〇·〇 (莫耳％ )的共聚物。以此聚合物當作 -70· 200839449 樹脂（B-4)。 <敏輻射線性樹脂組成物的調製> 以表1所示的比例來混合聚合物（A )、樹脂（B ) 、酸產生劑（C )、含氮化合物（D )及溶劑（E )，調製 實施例1〜6及比較例1〜2的各敏輻射線性樹脂組成物。 [表1] 聚合物(A) (份） 樹脂(B) (份） 酸產生劑(c) (份） 含氮化合物(D) (份） 溶劑〇E) (份） 實施例1 A-2(5) B-2(95) C-1(7.0) C-2(2.0) D-l(l.lO) E-i(1400) E-2(30) E-3(600) 實施例2 A-3(5) B-2(95) C-l(7.0) 02(2.0) D-l(l.lO) E-l(1400) E-2(30) E-3(600) 實施例3 A-2(5) B-l(95) C-3(6.5) C-4(2.0) D-l(l.lO) E-l(1400) E-2(30) E-3(600) 實施例4 A-3(5) B-l(95) 03(6.5) C-4(2.0) D-l(LlO) E-l(1400) E_2(30) E-3(600) 實施例5 A-2(3,5) B-3(96.5) C-l(7.0) C-2(2.0) 0-1(1.53) E-l(1400) E-2(30) E-3(600) 實施例6 A-2(3.5) B-4(96.5) C-l(7.0) C-2(2.0) D-1(1.44) E-l(1400) E-2(30) E-3(600) 比較例1 A-l(5) B-2(95) C-l(7.0) C-2(2.0) D-l(l.lO) E-l(1400) E-2(30) E-3(600) 比較例2 A-l(5) B-l(95) C-3(6.5) C-4(2.0) D-l(i.lO) E-l(1400) E-2(30) E-3(600) -71 - 200839449 再者，以下顯示表1中所示的酸產生劑（C)、含氮 化合物（D )及溶劑（E )之詳細。又，只要沒有特別的 記載，則表中的「份」係以質量爲基準。 [酸產生劑（C )] (C-1 ):三苯基毓九氟正丁烷磺酸鹽 . (C-2) :1-(4-正丁氧基萘基）四氫噻吩鐵全氟正 φ 丁烷磺酸鹽 (C-3 ):三苯基毓 2-(雙環[2.2.1]庚-2，-基）-1，1，2,2-四氟乙烷磺酸鹽 (C-4 ) : 1- ( 4-正丁氧基萘基）四氫噻吩鐵2-(雙 環[2.2.1]庚-2’-基）-1，1，2,2-四氟乙烷磺酸鹽 [含氮化合物（D)] (D-l ) :N-第三丁氧羰基一 4一羥基哌啶 [溶劑（E)] (E-1 ):丙二醇單甲基醚醋酸酯 (E-2) : γ-丁內酯 (Ε-3 ):環己酮 <敏_射線性樹脂組成物的評價> 對實施例1〜6及比較例1〜2的各敏輻射線性樹脂組 成物，如以下地進行下述[1 ]〜[6]的各種評價。表2中顯 -72- 200839449 示此等的評價結果。 各評價方法係如以下。 π]溶出量的測定 如第1圖所示地，於預先在CLEAN TRACK ACT8 ( 東京電子株式會社製）中進行HMDS (六甲基二矽氮烷） 1 1處理（100 °C，60秒）的8吋矽晶圓1上之中心部上， 載置中央部經挖空爲直徑11.3cm的圓形之矽橡膠片2( KUREHA ELASTOMER公司製，厚度：1.0mm，形狀：單 邊30 cm的正方形）。接著，於矽橡膠中央部之挖空部， 使用1 OmL的無刻度吸管，注滿1 OmL的超純水3。 之後，預先藉由CLEAN TRACK ACT8形成膜厚77nm 的下層抗反射膜（「ARC29A」，BULWER科學公司製） 41，接著藉由前述CLEAN TRACK ACT8，將表1之光阻 組成物旋塗在前述下層抗反射膜4 1上，於表2的條件下 進行烘烤而形成膜厚205nm的光阻膜42，將形有該光阻 膜的矽晶圓4，以光阻塗膜面與前述超純水3成接觸的方 式配合，且以超純水3不從矽橡膠2漏出的方式，載置在 前述矽橡膠片2上。 然後，將該狀態照原樣地保持1 〇秒。之後，移除前 述8吋矽晶圓4，以玻璃注射器來回收超純水3，以其當 作分析用樣品。再者，實驗結束後的超純水之回收率爲 95%以上。 接著，使用LC-MS (液體層析質量分析計，LC部： AGILENT 公司製 SERIES1100、MS 部·· Perseptive Biosystems， -73- 200839449Mw = 4300, Mw / Mn = 1.46, 13 C - Ν Μ P analysis of the knot content = 9.60 atomic %, the monomer (Ml) and & (M-2) and the unit of the content of 70 · 9:29.1 (mol%) The copolymer was used as the polymer (A-3). [Synthesis of Resin (B-1)] 5 5 · 4 4 g (50 μM of %) is described as a single (μ 6 ) (40 mol %) monomer (Μ-4), and 1〇· 99 brother [1 0 body (Μ-5) dissolved in 200 g of 2-butanone, and then 5 Μ 2,2,-azobis(2-methylpropionate) to prepare monomers, solvent In the night, and in the 14.17 ketone, and further, when the preparation is 5 〇〇mL, the polymerization is carried out at a temperature of 30 ° C or less at a temperature of 30 ° C, and then the lower layer of the solid is added to the polymer. · The first weight. In this way, 33.57 g of the monogram of dimethyl group was purged with nitrogen -67 - 200839449 A 500 mL three-necked flask having 100 g of 2-butanone was washed for 30 minutes. After the nitrogen purge, the mixture was heated to 80 ° C while stirring the reaction vessel. The previously prepared monomer solution was dropped using a dropping funnel for 3 hours. The polymerization reaction was carried out for 6 hours at the start of the polymerization as the polymerization start time. After the completion of the polymerization, the polymerization solution was cooled to 30 ° C or lower by water cooling, and 2000 g of methyl alcohol and alcohol were charged, and the precipitated white powder was separated by filtration. The white powder which was separated by filtration was washed twice in 400 g of methanol, and separated by filtration, and dried at φ 50 ° C for 17 hours to obtain a white powder polymer (72 g, yield 72%). ). The polymer had Mw = 6400 and Mw / Mn = 1.67. The result of 13C-NMR analysis was: fluorine content = 0 atom%, from monomers (M-6), (M-4) and (Μ·5). The content of each repeating unit is 52.2:3 8.1:9.7 (mole %) of the copolymer. This polymer was used as the resin (B-1). [Synthesis of Resin (B-2)] • 47.54 g (46 mol%) of the above monomer (M-6), 12.53 g (15 mol%) of monomer (M-1), 39.93 g (39 mo The monomer (M-7) was dissolved in 200 g of 2-butanone, and then 4.08 g of 2,2,-azobis(isobutyronitrile) was added to prepare a monomer solution. On the other hand, a 1000 mL three-necked flask to which 1 g of 2-butanone had been charged was flushed with nitrogen for 30 minutes. After the nitrogen purge, the contents of the three-piece flask were stirred while heating to 80 ° C, and the previously prepared monomer solution was dropped using a dropping funnel for 3 hours. The polymerization reaction was carried out for 6 hours at the start of the polymerization as the start of the polymerization. After the completion of the polymerization, the poly-68-200839449 solution was cooled to 30 ° C or lower by water cooling, and 2000 g of methanol was charged, and the precipitated white powder was separated by filtration. The white powder which was separated by filtration was washed twice in 400 g of methanol, and separated by filtration, and dried at 50 ° C for 17 hours to obtain a white powder polymer (73 g, yield 73%). ). The polymer had Mw = 5700 and Mw/Mn = 1.7. The result of 13C-NMR analysis was: fluorine content = 0 atom%, from monomers (M-6), (M-1) and (M-7). The content of each repeating unit is a copolymer of 51.4:14·6:34·0 (mol%). This polymer was used as a resin (Β _2 ). [Synthesis of Resin (Β - 3 )] 45.81 g (40 mol%) of the aforementioned monomer (Μ-6), 34.68 g (40 mol%) of monomer, and 6.71 g (1 mol) %) Monomer (Μ_9) was dissolved in 200 g of 2-butanone, and then 4.23 g of azobisisobutyronitrile was added to prepare a monomer solution, which was flushed with nitrogen to have a concentration of 12.8 g (% by mol) The above monomer (Μ-8) and 100 g of 2-butanone in a 1000 mL three-necked flask were allowed to stand for 30 minutes. After flushing with nitrogen, the mixture was heated to 80 ° C while stirring the reaction vessel. The previously prepared monomer solution was dropped using a dropping funnel for 3 hours. The polymerization reaction was carried out for 6 hours by taking the start of the dropping as the polymerization start time. After the completion of the polymerization, the polymerization solution was cooled to 30 ° C or lower by water cooling to 2000 g of hexane, and the precipitated white powder was separated by filtration. Further, the white powder which was separated by filtration was redissolved in 300 g of 2-butyl oxime and then poured into 2000 g of hexane, and the precipitated white powder was separated by filtration. This redissolution and filtration separation operation were repeated three times, and then dried at 5 (TC for 17 hours to obtain a white powder of a polymer (75 g, yield: 75%). -69-200839449 This polymer was Mw = 6000, Mw/ Mn = 1.7, and the result of 13C-NMR analysis was: fluorine content = 〇 atomic %, each repeating unit derived from monomers (M_6), (M-4), (M·9), and (M-8) The content is a copolymer of 4 1·3:39·5:9·2··1〇·〇 (mole %). This polymer is used as a resin (Β-3). [Resin (Β · 4 Synthesis] 4 3.48 g (40 mol%) of the aforementioned monomer (μ-6), 32.91 g (40 旲 ear%) of monomer (Μ-4), 1 1.46 g (1 〇 mol%) The body (Μ-7) was dissolved in 200 g of 2-butanone, and then 4.26 g of azobisisobutyronitrile was added to prepare a monomer solution, which was charged with 1 2 · 丨 5 g (1 〇旲 ear). /.) The monomer (Μ-8) and 1 gram of 2-butanone in a 100〇1111^ two-necked flask for 30 minutes. After flushing with nitrogen, the mixture was heated to 80 °C while stirring the reaction vessel. The aforementioned monomer solution prepared beforehand was dropped using a dropping funnel for 3 hours, and the start of the dropping was used as the polymerization start. The polymerization was carried out for 6 hours. After the completion of the polymerization, the polymerization solution was cooled to 3 Torr by water cooling, and the mixture was poured into 2000 g of methanol, and the precipitated white powder was separated by filtration. The white powder which was separated by filtration was 400 g. After washing twice in a slurry, the mixture was separated by filtration, and dried at 50 ° C for 17 hours to obtain a white powder of a polymer (76 g, yield: 6%). = 5 800, Μ\ν/Μη=1·6, the result of 13C-NMR analysis is: fluorine content = 〇 atomic %, from monomers (Μ - 6 ) , ( Μ - 4 ) , (Μ_7 ) and (Μ -8 ) The content of each repeating unit is a copolymer of 4ΐ·6:39·5:8·9:1〇·〇(mole %). The polymer is used as the -70· 200839449 resin ( B-4) <Preparation of Sensitive Radiation Linear Resin Composition> The polymer (A), the resin (B), the acid generator (C), and the nitrogen-containing compound (D) were mixed at a ratio shown in Table 1. And the solvent (E), each of the radiation sensitive linear resin compositions of Examples 1 to 6 and Comparative Examples 1 to 2 was prepared. [Table 1] Polymer (A) (part) Resin (B) (part) Acid generator ( c) (parts) Nitrogen compound (D) (part) Solvent 〇E) (part) Example 1 A-2(5) B-2(95) C-1(7.0) C-2(2.0) Dl(l.lO) Ei( 1400) E-2(30) E-3(600) Example 2 A-3(5) B-2(95) Cl(7.0) 02(2.0) Dl(l.lO) El(1400) E-2 (30) E-3 (600) Example 3 A-2(5) Bl(95) C-3(6.5) C-4(2.0) Dl(l.lO) El(1400) E-2(30) E-3 (600) Example 4 A-3(5) Bl(95) 03(6.5) C-4(2.0) Dl(LlO) El(1400) E_2(30) E-3(600) Example 5 A-2(3,5) B-3(96.5) Cl(7.0) C-2(2.0) 0-1(1.53) El(1400) E-2(30) E-3(600) Example 6 A -2(3.5) B-4(96.5) Cl(7.0) C-2(2.0) D-1(1.44) El(1400) E-2(30) E-3(600) Comparative Example 1 Al(5) B-2(95) Cl(7.0) C-2(2.0) Dl(l.lO) El(1400) E-2(30) E-3(600) Comparative Example 2 Al(5) Bl(95) C -3 (6.5) C-4 (2.0) Dl (i.lO) El (1400) E-2 (30) E-3 (600) -71 - 200839449 Furthermore, the acid generation shown in Table 1 is shown below. Details of the agent (C), the nitrogen-containing compound (D), and the solvent (E). Further, unless otherwise stated, the "parts" in the table are based on mass. [Acid generator (C)] (C-1): triphenylsulfonium nonafluoro-n-butanesulfonate. (C-2): 1-(4-n-butoxynaphthyl)tetrahydrothiophene iron Fluorine-n-butane sulfonate (C-3): triphenylsulfonium 2-(bicyclo[2.2.1]hept-2,-yl)-1,1,2,2-tetrafluoroethane sulfonate (C-4) : 1-(4-n-butoxynaphthyl)tetrahydrothiophene iron 2-(bicyclo[2.2.1]hept-2'-yl)-1,1,2,2-tetrafluoroethane Alkane sulfonate [nitrogen-containing compound (D)] (Dl): N-tert-butoxycarbonyl-4-hydroxyl piperidine [solvent (E)] (E-1): propylene glycol monomethyl ether acetate (E -2) : γ-butyrolactone (Ε-3): cyclohexanone <Evaluation of composition of sensitive ray-ray resin> Composition of each sensitive radiation linear resin of Examples 1 to 6 and Comparative Examples 1 and 2 The following evaluations of [1] to [6] were carried out as follows. Table 2 shows the evaluation results of -72- 200839449. Each evaluation method is as follows. As shown in Fig. 1, HMDS (hexamethyldioxane) 1 1 treatment (100 ° C, 60 seconds) was carried out in CLEAN TRACK ACT8 (manufactured by Tokyo Electronics Co., Ltd.) as shown in Fig. 1 On the center of the 8 吋矽 wafer 1, a circular enamel rubber sheet 2 having a diameter of 11.3 cm was hollowed out at the center (KUREHA ELASTOMER, thickness: 1.0 mm, shape: 30 cm on one side) square). Next, in the hollowed out portion of the center of the rubber, 1 OmL of ultra-pure water 3 was filled with a 10 mL unscaled pipette. Thereafter, a lower anti-reflection film ("ARC29A", manufactured by BULWER Scientific Co., Ltd.) 41 having a film thickness of 77 nm was formed in advance by CLEAN TRACK ACT8, and then the photoresist composition of Table 1 was spin-coated on the lower layer by the aforementioned CLEAN TRACK ACT8. The anti-reflection film 41 is baked under the conditions of Table 2 to form a photoresist film 42 having a film thickness of 205 nm, and the germanium wafer 4 having the photoresist film is formed, and the photoresist film surface and the above-mentioned ultrapure The water is placed in contact with each other, and the ultrapure water 3 is placed on the ruthenium rubber sheet 2 so as not to leak from the ruthenium rubber 2. Then, the state is maintained as it is for 1 second. Thereafter, the above-mentioned 8 wafer 4 was removed, and ultrapure water 3 was recovered by a glass syringe to be used as a sample for analysis. Furthermore, the recovery rate of ultrapure water after the end of the experiment was 95% or more. Next, LC-MS (Liquid Chromatography Mass Spectrometer, LC Department: SERIES 1100 manufactured by AGILENT, MS Department, Perseptive Biosystems, -73- 200839449)

Inc.公司製Mariner)，藉由下述的測定條件來測定前述 所得之超純水中的光酸產生劑之陰離子部的尖峰強度。於 該情況下，以前述測定條件來測定光酸產生劑的1 ppb、 lOppb、lOOppb水溶液之各尖峰強度，製作校正曲線，使 用此校正曲線從前述尖峰強度來算出溶出量。又，同樣地 ，以前述測定條件來測定酸擴散控制劑的lppb、lOppb、 lOOppb水溶液之各尖峰強度，製作校正曲線，使用此校 正曲線從前述尖峰強度來算出酸擴散控制劑的溶出量。溶 出量爲 5.0xl(T12mol/cm2/sec以上時係「不良」，以下時 係「良好」。 (管柱條件） 使用管柱：「CAPCELL PAK MG」，資生堂株式會社 製，1支 流量：0.2mL/分鐘 流出溶劑：於水/甲醇（3/7 )加有0.1質量％的草酸 %Inc., manufactured by Inc., Inc., the peak intensity of the anion portion of the photoacid generator in the ultrapure water obtained above was measured by the following measurement conditions. In this case, the peak intensities of the 1 ppb, 10 ppb, and 100 ppb aqueous solutions of the photoacid generator were measured under the above-described measurement conditions to prepare a calibration curve, and the amount of elution was calculated from the peak intensity using the calibration curve. Further, similarly, the peak intensities of the lppb, lOppb, and 100 ppb aqueous solutions of the acid diffusion controlling agent were measured under the above-described measurement conditions to prepare a calibration curve, and the elution amount of the acid diffusion controlling agent was calculated from the peak intensity using the calibration curve. The amount of elution is 5.0xl ("T12mol/cm2/sec or more" is "poor", and the following is "good". (column condition) Use column: "CAPCELL PAK MG", manufactured by Shiseido Co., Ltd., 1 flow: 0.2 5%/min effluent solvent: 0.1% by mass of oxalic acid added to water/methanol (3/7)

測定溫度：35°C U]動態接觸角（前進接觸角及後退接觸角）的測定 前進接觸角及後退接觸角的測定係使用KRUS公司製 的「D S A -1 0」’形成各敏輻射線性樹脂組成物的光阻膜 ’於製作在表2的條件下烘烤所作成的基板（晶圓）後， 迅速在室溫：23°C、濕度·· 45%、常壓的環境下，如下述 地測定。 (Ο調整晶圓台位置。 -74- 200839449 (2)將晶圓固定在台上。 (3 )將水注入到針。 (4 )微調整針的位置。 (5 )從針排出水，在晶圓上形成25 pL的水滴。 (6 )從水滴中暫時拔出針。 (7 )再度將針降低到前述（4 )所調整的位置° (8-1 )由針以lOpL/min的速度吸引水滴90秒°同 時測定每秒的後退接觸角（計9 0次）。 (8-2 )由針以lOpL/min的速度注入水滴90秒。同 時測定每秒的前進接觸角（計9 0次）。 (9 )由各接觸角穩定的時間點，分別對計20點的各 接觸角（前進接觸角及後退接觸角）算出平均値’胃# @ 進接觸角及後退接觸角。 [3]感度 作爲基板，使用表面上形成有膜厚77nm的下層抗反 射膜（「ARC29A」，BULWER科學公司製）的12吋矽晶 圓。再者，該抗反射膜的形成係使用「CLEAN TRACK ACT12」（東京電子株式會社製）。 接著，藉由前述CLEAN TRACK ACT 12，將表1之光 阻組成物旋塗在前述基板上，於表2的條件下進行烘烤（ PB )而形成膜厚120nm的光阻膜。對此光阻膜，藉由 ArF準分子雷射浸潤式曝光裝置（「ASML AT 1 25 0i」， ASML 製），以 ΝΑ = 0·85、σ 0 / σ 1 = 0 · 9 6 / 0.7 6、偶極（ Dipole )，通過光罩圖型進行曝光。此時，在光阻上面與 -75- 200839449 浸潤式曝光機透鏡之間，使用純水當作浸潤溶 於表2所示的條件下進行PEB後，藉由2.38 氧化四甲銨水溶液，在2 3 °C顯像6 0秒，進行 ，形成正型的光阻圖型。此時，將以1對1的 寬6 5nm的線與間隙圖型（1L1S )之曝光量當 曝光量，以此最合適的曝光量當作感度。再者 使用掃描型電子顯微鏡（「S-93 80」，株式會 技公司製）。 [4] 焦點深度（DOF ) 與前述[3]同樣地，形成線寬65nm的線與 1 L 1 S )。此時之以1對1的線寬形成前述線與 曝光量，即表2所示之感度（最合適的曝光量 度性能（DOF性能），係藉由掃描型電子顯 93 80」，株式會社日立高科技公司製）來測定 [5] 圖型的截面形狀 與前述[3 ]同樣地，藉由株式會社日立高 「S-4800」來觀察如第2圖所示般之基板5上 6 5nm之線與間隙圖型（1L1S )之截面形狀， 型 6的中間之線寬 Lb、膜的上部之線 〇.9$La/Lb€ 1.1的範圍內係爲「良好」，於範 不良」。 [6] 缺陷性能（水印缺陷及氣泡缺陷的各產生數 作爲基板，使用表面上形成有膜厚77nm 射膜（「ARC29A」，BULWER科學公司製）白 劑。然後， 質量％的氫 水洗、乾燥 線寬形成線 作最合適的 ，此測長係 社日立高科 間隙圖型（ 間隙圖型的 )的焦點深 微鏡（「 S- 科技公司製 形成的線寬 測定光阻圖 寬 La，於 圍外係爲「 :之測定） 的下層抗反 勺1 2吋矽晶 -76- 200839449 圓。再者，該抗反射膜的形成係使用「CLEAN TRACK ACT12」（東京電子株式會社製）。 接著，藉由前述CLEAN TRACK ACT12，將表1之光 阻組成物旋塗在前述基板上，於表2的條件下進行烘烤（ PB )而形成膜厚150nm的光阻膜。對此光阻膜，藉由 ArF準分子雷射浸潤式曝光裝置（「ASML AT 1 250i」， ASML 製），以 ΝΑ = 0·85、σ0/σ1=0·96/0.76、環形（ Annular)，通過光罩圖型進行曝光。此時，在光阻上面 與浸潤式曝光機透鏡之間，使用純水當作浸潤溶劑。然後 ，於表2所示的條件下進行PEB後，藉由2.38質量％的 氫氧化四甲銨水溶液，在23 °C顯像60秒，進行水洗、乾 燥，形成正型的光阻圖型。此時，將以1對1的線寬形成 線寬lOOiim的線與間隙圖型（1L1S )之曝光量當作最合 適的曝光量，以此最合適的曝光量當作感度。再者，此測 長係使用掃描型電子顯微鏡（「S-9380」，株式會社日立 高科技公司製）。 然後，使用KLA-Tencor公司製的「KLA23 5 1」來測 定線寬lOOnm的線與間隙圖型（1L1S )上之缺陷數。再 者，使用掃描型電子顯微鏡（「S-9 3 80」，株式會社日立 高科技公司製）來觀察「KLA23 5 1」所測定的缺陷，區分 爲預料從ArF準分子雷射浸潤式曝光而來的水印缺陷（ water-mark缺陷）與氣泡缺陷，測定各缺陷數。再者，第 3圖顯示典型的水印缺陷，第4圖顯示典型的氣泡缺陷。 -77- 200839449Measurement temperature: 35° CU] Measurement of dynamic contact angle (advance contact angle and receding contact angle) The measurement of the advancing contact angle and the receding contact angle was carried out by using "DSA -10" manufactured by KRUS Co., Ltd. to form a linear composition of each sensitive radiation. After the substrate (wafer) prepared by baking under the conditions of Table 2, the photoresist film of the object is rapidly exposed to room temperature: 23 ° C, humidity · 45%, atmospheric pressure, as follows. Determination. (Ο Adjust the position of the wafer table. -74- 200839449 (2) Fix the wafer on the stage. (3) Inject water into the needle. (4) Finely adjust the position of the needle. (5) Drain the water from the needle. 25 pL of water droplets are formed on the wafer. (6) The needle is temporarily pulled out from the water droplets. (7) The needle is again lowered to the position adjusted by the above (4) ° (8-1) by the needle at a speed of 10 pL/min. The water droplets were attracted for 90 seconds. The receding contact angle per second was measured at the same time (90 times). (8-2) The water droplets were injected by the needle at a rate of 10 pL/min for 90 seconds. The advancing contact angle per second was measured at the same time. (9) From the time points at which the contact angles are stabilized, the average contact angles (advance contact angle and receding contact angle) of 20 points are calculated to calculate the average contact angle and the receding contact angle. Sensitivity As a substrate, a 12-inch wafer having a lower-layer anti-reflection film ("ARC29A", manufactured by BULWER Scientific Co., Ltd.) having a film thickness of 77 nm was formed on the surface. Further, the anti-reflection film was formed using "CLEAN TRACK ACT12". (manufactured by Tokyo Electronics Co., Ltd.) Next, the photoresist composition of Table 1 was spin-coated on the above basis by the aforementioned CLEAN TRACK ACT 12. Then, baking (PB) was performed under the conditions of Table 2 to form a photoresist film having a film thickness of 120 nm, and the photoresist film was subjected to an ArF excimer laser immersion exposure apparatus ("ASML AT 1 25 0i"). ASML system, with ΝΑ = 0·85, σ 0 / σ 1 = 0 · 9 6 / 0.7 6, dipole (Dipole), exposure through the reticle pattern. At this time, above the photoresist with -75- 200839449 Between the lenses of the immersion exposure machine, using pure water as the wetting and dissolving in the conditions shown in Table 2, PEB, and then developing the solution of tetramethylammonium chloride at 2.38 for 60 seconds at 2 3 °C. A positive resist pattern is formed. At this time, the exposure amount of the line and gap pattern (1L1S) of 1 to 1 width and 6 5 nm is used as the exposure amount, and the optimum exposure amount is used as the sensitivity. A scanning electron microscope ("S-93 80", manufactured by Ltd.) was used. [4] Depth of focus (DOF) A line having a line width of 65 nm and 1 L 1 S ) were formed in the same manner as in the above [3]. At this time, the line and the exposure amount are formed by a line width of one to one, that is, the sensitivity shown in Table 2 (the most suitable exposure measurement performance (DOF performance) is obtained by scanning type electronic display 93 80", Hitachi Co., Ltd. In the same way as the above [3], the cross-sectional shape of the [5] pattern is observed on the substrate 5 as shown in Fig. 2 by the Hitachi High "S-4800". The cross-sectional shape of the line and gap pattern (1L1S), the line width Lb in the middle of the pattern 6, and the line 〇.9$La/Lb € 1.1 in the upper part of the film are "good" and are inferior. [6] Defective performance (the number of occurrences of watermark defects and bubble defects is used as a substrate, and a film having a film thickness of 77 nm ("ARC29A", manufactured by BULWER Scientific Co., Ltd.) is formed on the surface. Then, the mass% of hydrogen is washed and dried. The line width forming line is the most suitable. This measuring length is a deep micromirror of the Hitachi High-Tech gap pattern (gap pattern type) ("S-Technology company's line width measuring resist pattern width La, in the circumference In the case of the "anti-reflection film, the "CLEAN TRACK ACT12" (manufactured by Tokyo Electronics Co., Ltd.) is used for the formation of the anti-reflection film. The photoresist composition of Table 1 was spin-coated on the substrate by the above CLEAN TRACK ACT12, and baked (PB) under the conditions of Table 2 to form a photoresist film having a film thickness of 150 nm. Through the ArF excimer laser immersion exposure apparatus ("ASML AT 1 250i", ASML system), through reticle pattern with ΝΑ = 0·85, σ0/σ1=0·96/0.76, ring ( Annular) Exposure. At this time, on the photoresist and the infiltrating exposure machine Pure water was used as a wetting solvent between the mirrors. Then, PEB was carried out under the conditions shown in Table 2, and then washed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 60 seconds. Drying and forming a positive resist pattern. At this time, the line-width lOOiim line-and-gap pattern (1L1S) with a line width of 1 to 1 is used as the most appropriate exposure amount. A suitable amount of exposure is used as the sensitivity. In addition, this measurement system uses a scanning electron microscope ("S-9380", manufactured by Hitachi High-Tech Co., Ltd.). Then, "KLA23 5 1" manufactured by KLA-Tencor Co., Ltd. is used. The number of defects on the line and the gap pattern (1L1S) with a line width of 100 nm was measured. Further, a scanning electron microscope ("S-9 3 80", manufactured by Hitachi High-Technologies Co., Ltd.) was used to observe "KLA23 5 1 The measured defects are classified into watermark defects (water-mark defects) and bubble defects expected from laser exposure by ArF excimer laser irradiation, and the number of defects is measured. Furthermore, Fig. 3 shows a typical watermark defect. Figure 4 shows a typical bubble defect. -77- 200839 449

S m <N (N (N (N (Ν m (N DU 征 氣泡 缺陷數 o 〇 〇 〇 〇 Ο m r—^ 〇 ^-H ▼«H 到芨 Ife Ife & & 醒給 遞 涵 4¾ {1¾ #( 赋 m, sB o o … o o o ο ο CO o in 峡 感度 (mJ/cm2) m CN cn (N (N yn CN 〇\ (N 00 (Ν m CN 騣^ (N oo 卜 5¾ w (N OO νή oo (N OO § g 00 00 C 銷w VO 寸 卜 VO r- Τ—Η oo o r^H 00 fe 溶出量 & ife -0¾ -1¾ 賊 〇£( § U-H C/5 CO PQ ^ VO VO Ό i〇 VO v〇 g \ P 1—H P Τ"Ή P ο m 〇〇 m Ρ Ο Η Ρ S P i—H P s ψ 'A i-Η t-H ι—Η r-H i 占 占 占 VO i〇 v〇 i〇 頰 P u^l i-H 1 < P r"H P o P o 1—1 Ρ ο Τ-Η 〇〇 r—Η r—Η P t-H T—^ P o T-H 匡 (N m 寸 匡 匡 ν〇 匡 (N ㈣ 辑 辑 ㈣ ㈣ ㈣ 鎰 鎰 IK |i( IK IK {_ JJ J-Λ J-J J-Λ -78- 200839449 根據表2，使用本發明的敏輻射線性樹脂組成物時， 可確認對浸潤式曝光時所接觸的水等之浸潤介質的溶出物 之量少，一般的光阻性能（感度、焦點深度、圖型形狀） 優異，且具有大幅減少預料從ArF準分子雷射浸潤式曝光 而來的氣泡缺陷之效果。再者，使用本發明的樹脂組成物 時，確認可給予高的後退接觸角，亦可抑制預料從ArF準 分子雷射g潤式曝光而來的氣泡缺陷。 根據上述，可知本發明的樹脂組成物能在浸潤式曝光 中合適地操作，茲認爲在今後的微細化微影中，可合適地 操作。 【圖式簡單說明】 第1圖係說明溶出量的測定用樣品的製作方法之示意 圖。 第2圖係顯示線與間隙圖型的截面形狀之圖。 .第3圖係顯示典型的水印缺陷之圖。 第4圖係顯示典型的氣泡缺陷之圖。 【主要元件符號說明】S m <N (N (N (N (N ( Ν m (N DU 气泡 气泡 o o r r r r r r r r - - - - - - - - - - - fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe fe 43 43 43 43 43 43 43 43 43 {13⁄4 #( 赋 m, sB oo ... ooo ο ο CO o in gorge sensitivity (mJ/cm2) m CN cn (N (N yn CN 〇\ (N 00 (Ν m CN 騣^ (N oo 卜 53⁄4 w ( N OO νή oo (N OO § g 00 00 C pin w VO inch VO r- Τ-Η oo or^H 00 fe Dissolution & ife -03⁄4 -13⁄4 thief 〇 £ ( § UH C/5 CO PQ ^ VO VO Ό i〇VO v〇g \ P 1—HP Τ"Ή P ο m 〇〇m Ρ Ο Η Ρ SP i—HP s ψ 'A i-Η tH ι—Η rH i Occupy VO i〇 V〇i〇 cheek P u^l iH 1 < P r"HP o P o 1—1 Ρ ο Τ-Η 〇〇r—Η r—Η P tH T—^ P o TH 匡 (N m inch 匡匡ν〇匡(N (4) Collection (4) (4) (4) 镒镒IK |i( IK IK {_ JJ J-Λ JJ J-Λ -78- 200839449 According to Table 2, when using the radiation sensitive linear resin composition of the present invention, Can confirm the pair The amount of eluted matter of the immersion medium such as water contacted during the wet exposure is small, and the general photoresist performance (sensitivity, depth of focus, pattern shape) is excellent, and the exposure is greatly reduced from the ArF excimer laser immersion exposure. Further, when the resin composition of the present invention is used, it is confirmed that a high receding contact angle can be imparted, and it is possible to suppress bubble defects which are expected to be exposed from the ArF excimer laser. As described above, it is understood that the resin composition of the present invention can be suitably handled in the immersion exposure, and it is considered that it can be suitably operated in the future fine lithography. [Simplified description of the drawings] Fig. 1 illustrates the amount of dissolution. A schematic diagram of a method for producing a sample for measurement. Figure 2 is a diagram showing the cross-sectional shape of the line and gap patterns. Figure 3 shows a diagram of a typical watermark defect. Figure 4 is a diagram showing typical bubble defects. [Main component symbol description]

1 :砍晶圓 21 : HMDS 2 :矽橡膠片 3 ··超純水 4 :矽晶圓 -79- 200839449 4 1 :抗反射膜 42 :光阻膜 5 :基板 6 :圖型1 : chopped wafer 21 : HMDS 2 : 矽 rubber sheet 3 · · ultrapure water 4 : 矽 wafer -79- 200839449 4 1 : anti-reflection film 42 : photoresist film 5 : substrate 6 : pattern

Claims (1)

200839449 十、申請專利範圍 1 ·一種浸潤式曝光用敏輻射線性樹脂組成物，其含有 含氟化烷基，氟含量爲3原子％以上，且藉由酸的作用成 爲鹼可溶性的聚合物（A )，及藉由酸的作用成爲鹼可溶 ' 性，且氟含量爲低於3原子％的樹脂（B )，以及敏輻射 . 線性酸產生劑（C )，其特徵爲將該浸潤式曝光用敏輻射 線性樹脂組成物塗佈在基板上而形成的光阻膜，對於水的 φ 前進接觸角係95度以下。 2.如申請專利範圍第1項之浸潤式曝光用敏輻射線性 樹脂組成物，其中該樹脂（B )含有含內酯構造的重複單 位、及含藉由酸的作用成爲鹼可溶性之骨架的重複單位。 3 ·如申請專利範圍第1或2項之浸潤式曝光用敏輻射 線性樹脂組成物，其中該聚合物（A )含有含下述通式（ 1 )所示的重複單位、及含藉由酸的作用成爲鹼可溶性之 骨架的重複單位， φ [化 1] R1 十卜 CH2+ (1) • ^ ， [通式（1)中，Rl表示氫、甲基或三氟甲基，A表示單鍵 、亞甲基、碳數2〜6的伸烷基、氧原子、硫原子、羰氧 基、氧羰基、醯胺基、磺酸胺基或胺甲酸酯基；r2表示 含有至少一個以上的氟原子之碳數1〜6的直鏈狀或支鏈 狀的烷基、或碳數4〜20的1價脂環式烴基或其衍生物] -81 - 200839449 4 ·如申請專利範圍第1至3項中任一項之浸潤式曝光 用敏輻射線性樹脂組成物，其中用於給予該通式（1 )所 示重複單位的單體係從2,2,2-三氟乙基（甲基）丙烯酸酯 、2-(1，1，1，3,3,3-六氟）丙基（甲基）丙烯酸酯、1-( 2,2,3,3,4,4,5,5-八氟）己基（甲基）丙烯酸酯、1-( 2,2,3,3,4,4,4-七氟）五（甲基）丙烯酸酯及全氟環己基（ 甲基）丙烯酸酯中所選出的至少一種。 5.如申請專利範圍第1至4項中任一項之浸潤式曝光 用敏輻射線性樹脂組成物，其中以該聚合物（A )及前述 樹脂（B )的合計爲100質量％時，該聚合物（A)的含量 係0.1質量％以上。 6 . —種光阻圖型之形成方法，其特徵爲具備： (1 )使用如申請專利範圍第1至5項中任一項之浸 潤式曝光用敏輻射線性樹脂組成物’在基板上形成光阻膜 的步驟， (2 )經由浸潤介質且通過具有指定圖型的光罩，對 該光阻膜照射輻射線，進行曝光的步驟’及 (3 )將經曝光的光阻膜顯像，形成光阻圖型的步驟 -82- 200839449 無 ·· 明 說 單 無簡 為符 圖件 表元 代之 定圖 :指表 圖案代 表本本 代 定一二 指 /IV Γν 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無 -4-200839449 X. Patent Application No. 1 · A linear radiation resin composition for immersion exposure containing a fluorine-containing alkyl group, having a fluorine content of 3 atom% or more, and an alkali-soluble polymer by the action of an acid (A And a resin (B) having a fluorine content of less than 3 atomic % by means of an acid, and a sensitive acid. A linear acid generator (C) characterized by exposing the immersion The photoresist film formed by coating the substrate with a sensitive radiation linear resin composition has a φ advancing contact angle of 95 degrees or less with respect to water. 2. The sensitized radiation linear resin composition for immersion exposure according to the first aspect of the invention, wherein the resin (B) contains a repeating unit having a lactone structure, and a repeat having a skeleton which becomes alkali-soluble by the action of an acid unit. 3. The sensitive radiation linear resin composition for immersion exposure according to claim 1 or 2, wherein the polymer (A) contains a repeating unit represented by the following formula (1), and a by-acid The action becomes the repeating unit of the skeleton of alkali solubility, φ [Chemical 1] R1 Xb CH2+ (1) • ^ , [In the formula (1), R1 represents hydrogen, methyl or trifluoromethyl, and A represents a single bond. a methylene group, an alkylene group having 2 to 6 carbon atoms, an oxygen atom, a sulfur atom, a carbonyloxy group, an oxycarbonyl group, a decylamino group, an sulfonic acid amine group or a urethane group; and r2 represents at least one or more a linear or branched alkyl group having 1 to 6 carbon atoms of a fluorine atom or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof - 81 - 200839449 4 · Patent Application No. 1 The sensitized radiation linear resin composition for immersion exposure according to any one of the items 3, wherein the single system for giving the repeating unit represented by the formula (1) is from 2,2,2-trifluoroethyl (A) Acrylate, 2-(1,1,1,3,3,3-hexafluoro)propyl (meth) acrylate, 1-( 2,2,3,3,4,4,5,5 -octafluoro)hexyl (meth) acrylate, 1 At least one selected from the group consisting of -( 2,2,3,3,4,4,4-heptafluoro)penta(meth)acrylate and perfluorocyclohexyl (meth)acrylate. 5. The sensitized radiation linear resin composition for immersion exposure according to any one of claims 1 to 4, wherein when the total of the polymer (A) and the resin (B) is 100% by mass, The content of the polymer (A) is 0.1% by mass or more. A method for forming a photoresist pattern, comprising: (1) forming a linear radiation-sensitive resin composition for immersion exposure according to any one of claims 1 to 5 on the substrate. a step of a photoresist film, (2) a step of exposing the photoresist film by irradiating the dielectric film through a mask having a specified pattern, irradiating the photoresist film, and (3) developing the exposed photoresist film, Steps for forming a photoresist pattern-82- 200839449 No.··························································· Please reveal the chemical formula that best shows the characteristics of the invention: none -4-