TWI305201B - Compound, polymer compound, positive resist composition, and method for forming resist pattern - Google Patents

Description

1305201 (1) 九、發明說明 【發明所屬之技術領域】 本發明爲有關新穎化合物、具有由該化合物所衍生之 結構單位的高分子化合物，使用該高分子化合物之正型光 阻組成物，及使用該光阻組成物的光阻圖型之形成方法。 【先前技術】 • 近年來，於半導體或液晶顯示元件之製造中，伴隨微 影蝕刻技術之進步而急遽邁向微細化。微細化之方法多將 一般之曝光光源短波長化之方式進行。具體而言，以往爲 使用以g線、i線爲代表之紫外線，但目前則導入KrF準 分子雷射（24 8nm )，並開始導入 ArF準分子雷射 (193nm )之階段。 前述KrF準分子雷射或ArF準分子雷射等光源所使 用之光阻，已被要求應具有可重現微細尺寸圖型之高解析 ^ 度’與對前述短波長光線具有高敏感度等特徵。而滿足前 述條件之光阻之一，已知例如含有經由酸之作用而可增大 鹼可溶性之基礎樹脂與，經由曝光而產生酸之酸產生劑之 增強化學型光阻組成物。 已知於使用KrF準分子雷射進行曝光之方法中，被提 議作爲適用光阻材料之增強化學性光阻組合物，一般而言 基礎樹脂爲使用，聚羥基苯乙烯系樹脂之羥基的一部份被 酸解離性溶解抑制基所保護者（例如參考專利文獻1 )。 又，酸解離性溶解抑制基，已知主要爲例如使用1 · 6 - (2) 1305201 乙氧乙基爲代表之鏈狀醚基或四氫呋喃基爲代表之環狀醚 基等之縮醛基，tert_丁基爲代表之三級烷基，tert-丁氧基 羰基爲代表之三級烷氧羰基等。 下述專利文獻2中，雖有揭示具有四環癸烷所衍生之 基與酸解離性溶解抑制基之支鏈的（甲基）丙烯酸酯、及 使用其作爲單體使用之聚合物，含有該聚合物與酸產生劑 之光阻組成物，但，並未記載本發明特定之酸解離性溶解 籲抑制基「-CH2-0-R3」。 [專利文獻1]特開平4-2 1 1 2 5 8號公報 [專利文獻2]特許第2 8 5 6 1 1 6號公報 【發明內容】 近年來，隨光阻圖型微細化之發展，已有尋求更高解 析度之傾向。又，以往正型光阻組成物所使用之酸產生劑 種類亦有受到限制等問題。即，使用三級烷基等酸解離性 ❿ 溶解抑制基時因未能充分解離，而會產生光型未能充分解 像等疑慮。因此，目前最常使用之酸產生劑多使用所產生 之酸強度較強之具有氟化烷基磺酸離子作爲陰離子部之鑰 鹽。 本發明即是爲解決前述問題所提出者，而以提出一種 可構成具有優良解析度以外，即使於使用所產生之酸強度 爲較弱的酸產生劑下也可得到良好圖型解析度之正型光阻 組成物’及製造該高分子化合物時所適用之化合物爲目 的’此外’含有該高分子化合物之正型光阻組成物，及使 -7- (3) 1305201 用該正型光阻組成物之光阻圖型之形成方法等皆屬本發明 之目的。 爲達上述目的，本發明係採用下述方法。 本發明提供下述式（I )所示化合物，</ RTI> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; A method of forming a photoresist pattern of the photoresist composition is used. [Prior Art] In recent years, in the manufacture of semiconductors or liquid crystal display devices, the progress of the lithography etching technology has been rushed toward miniaturization. The method of miniaturization is carried out in such a manner that the general exposure light source is shortened in wavelength. Specifically, conventionally, ultraviolet rays represented by g-line and i-line have been used. However, a KrF quasi-molecular laser (24 8 nm) has been introduced and a phase of ArF excimer laser (193 nm) has been introduced. The photoresist used in the above-mentioned KrF excimer laser or ArF excimer laser light source has been required to have a high resolution of a reproducible fine-size pattern and a high sensitivity to the aforementioned short-wavelength light. . One of the photoresists satisfying the above-mentioned conditions is, for example, a basal resin containing an alkali-soluble resin which acts by an action of an acid, and a reinforced chemical-type resist composition which generates an acid generator of an acid by exposure. It is known as a reinforced chemical resistive composition suitable for use as a photoresist material in a method of performing exposure using a KrF excimer laser. Generally, a base resin is used, and a hydroxyl group of a polyhydroxystyrene resin is used. The fraction is protected by an acid dissociable dissolution inhibiting group (for example, refer to Patent Document 1). Further, the acid-dissociable-dissolving group is mainly an acetal group such as a cyclic ether group represented by a chain ether group represented by 1-6-(2) 1305201 ethoxyethyl group or a cyclic ether group represented by a tetrahydrofuranyl group. The tert-butyl group is a tertiary alkyl group represented by tert-butoxycarbonyl group, and the tert-butoxycarbonyl group is represented by a tertiary alkoxycarbonyl group. In the following Patent Document 2, a (meth) acrylate having a branch derived from a tetracyclodecane group and an acid dissociable dissolution inhibiting group, and a polymer used as a monomer are disclosed. The photoresist composition of the polymer and the acid generator, however, the specific acid dissociable dissolution inhibiting group "-CH2-0-R3" of the present invention is not described. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 4-2 1 2 2 5 (Patent Document 2) Patent No. 2 8 5 6 1 1 6 (Invention) In recent years, with the development of the miniaturization of the photoresist pattern, There has been a tendency to seek higher resolution. Further, there have been problems in the types of acid generators used in conventional positive-type photoresist compositions. In other words, when an acid-dissociating ruthenium such as a tertiary alkyl group is used to dissolve the inhibitory group, the dissociation is not sufficiently dissociated, and there is a concern that the light type is not sufficiently resolved. Therefore, the acid generator which is most commonly used at present is often used as a key salt having a fluorinated alkylsulfonic acid ion as an anion portion. The present invention has been made to solve the above problems, and it is proposed that a good pattern resolution can be obtained in addition to an acid generator having a weak acidity even when used with excellent resolution. The type of photoresist composition and the compound suitable for the production of the polymer compound are intended to be 'in addition' a positive-type photoresist composition containing the polymer compound, and the positive-type photoresist of -7-(3) 1305201 is used. The method of forming the photoresist pattern of the composition and the like are all objects of the present invention. In order to achieve the above object, the present invention employs the following method. The present invention provides a compound represented by the following formula (I),

[式中，R1爲氫原子或低級烷基；R2爲碳原子數1至 1 5之烷基或脂肪族環式基，其可具有1種以上由醚鍵 結、羥基、羰基、酯基、與胺基所成群中所選出之取代 基；〜爲0或1至3之整數]。 又，本發明提供具有下述式（II )所示結構單位 (a 1 )之高分子化合物，[wherein R1 is a hydrogen atom or a lower alkyl group; R2 is an alkyl group having 1 to 15 carbon atoms or an aliphatic cyclic group, and may have one or more kinds of ether bonds, hydroxyl groups, carbonyl groups, ester groups, a substituent selected in a group with an amine group; ~ is 0 or an integer from 1 to 3. Further, the present invention provides a polymer compound having the structural unit (a 1 ) represented by the following formula (II),

(Π) -8- (4) 1305201 [式中，R1爲氫原子或低級烷基；R3爲碳原子數1 g 15之烷基或脂肪族環式基，其可具有1種以上由_鍵 結、羥基、羰基、酯基、與胺基所成群中所選出之取代 基；n2爲0或1至3之整數]。 又，本發明提供一種含有本發明之高分子化合物 (A1)，與經由曝光產生酸之酸產生劑成份（B)爲特徵 之正型光阻組成物。 又，本發明提供一種光阻圖型之形成方法，其爲包含 使用本發明之正型光阻組成物於基板上形成正型光阻膜， 並對該正型光阻膜進行選擇性曝光處理後，進行曝光後加 熱（PEB )處理，再施以顯影處理以形成光阻圖型爲特徵 之光阻圖型之形成方法。 又，本發明中，「結構單位」係指構成聚合物之單體 單位之意。又，「低級」係指碳原子數1至5之意。 本發明可得到一種具有優良解析度以外，即使於使用 所產生之酸強度爲較弱的酸產生劑下也可得到良好圖型解 析度之正型光阻組成物及使用該正型光阻組成物之光阻圖 型之形成方法。此外，亦可得到適用於製造正型光阻組成 物所使用之新穎高分子化合物與新穎化合物。 (化合物） 本發明之新穎化合物（以下亦稱爲化合物（a ))係 如上述式（I )所示者。 化合物（a )係如後所述般，爲可用於製造一種適合 -9- (5) 1305201 作爲正型光阻組成物之樹脂成份的本發明高分子化合物 (A 1 )之化合物。又，化合物（a )可含有作爲溶解抑制 劑之正型光阻組成物。 式（I)中，〜爲0至3之整數，ηι較佳爲1至2之 整數，更佳爲1。 \ 式（I )中，R1爲氫原子或低級烷基，低級烷基爲碳 原子數1至5之烷基，具體而言，例如甲基、乙基、丙 基、異丙基、η-丁基、異丁基、tert-丁基、戊基、異戊 基、新戊基等低級之直鏈狀或支鏈狀烷基等。 R1較佳爲氫原子或甲基。 R2爲碳原子數1至1 5之烷基或脂肪族環式基，其可 具有親水性取代基。前述烷基之具體例如甲基、乙基、丙 基、異丙基、η-丁基、異丁基、tert-丁基、戊基、異戊 基、新戊基等碳原子數1至5之直鏈狀或支鏈狀烷基等。 本發明所稱「脂肪族」，係指相對於芳香族之相對槪 念，即定義爲不具有芳香族性之基、化合物等之意。「脂 肪族環式基」係指不具有芳香族性之單環式基或多環式基 (脂環式基）之意，此時之「脂肪族環式基」並不僅限定 於由碳與氫所形成之基，但以烴基爲佳。又，「烴基」可 爲飽和或不飽和者皆可，一般又以飽和者爲佳。較佳者爲 多環式基（脂環式基）。 前述脂肪族環式基之具體例，例如由環己烷、環戊 烷、金剛烷、原菠烷、原菠烯、甲基原菠烷、乙基原菠 烷、甲基原菠烯、乙基原菠烯、異菠烷、三環癸烷、四環 -10- 1305201 ⑹ 十二烷等所衍生之1價基等。其中又以金剛烷基爲佳。 R2具有取代基之情形中，該取代基以由醚鍵結（-〇 -) '羥基、羰基、酯基與胺基所成群中所選出之1種以上 者爲佳。 其式（I )中，-c Η 2 - 0 - R2中較佳者例如下述化學式所 示者。(Π) -8- (4) 1305201 [wherein R1 is a hydrogen atom or a lower alkyl group; and R3 is an alkyl group having 1 g of 15 carbon atoms or an aliphatic cyclic group, which may have one or more kinds of _ bonds a substituent selected from the group consisting of a knot, a hydroxyl group, a carbonyl group, an ester group, and an amine group; n2 is 0 or an integer of 1 to 3]. Further, the present invention provides a positive-type photoresist composition comprising the polymer compound (A1) of the present invention and an acid generator component (B) which generates an acid by exposure. Moreover, the present invention provides a method for forming a photoresist pattern comprising forming a positive photoresist film on a substrate using the positive photoresist composition of the present invention, and selectively exposing the positive photoresist film. Thereafter, a post-exposure heating (PEB) treatment is performed, and then a development process is performed to form a photoresist pattern pattern characterized by a photoresist pattern. Further, in the present invention, "structural unit" means the unit constituting the monomer of the polymer. Further, "lower" means the number of carbon atoms of 1 to 5. The present invention can obtain a positive photoresist composition which has excellent resolution and can obtain good pattern resolution even under the use of an acid generator having a weak acid strength, and can be obtained by using the positive photoresist. The formation method of the photoresist pattern of the object. Further, novel polymer compounds and novel compounds suitable for use in the production of positive-type photoresist compositions can be obtained. (Compound) The novel compound of the present invention (hereinafter also referred to as the compound (a)) is as shown in the above formula (I). The compound (a) is a compound which can be used for producing a polymer compound (A 1 ) of the present invention which is suitable for the resin component of -9-(5) 1305201 as a positive-type photoresist composition, as described later. Further, the compound (a) may contain a positive resist composition as a dissolution inhibitor. In the formula (I), ~ is an integer of 0 to 3, and η is preferably an integer of 1 to 2, more preferably 1. In the formula (I), R1 is a hydrogen atom or a lower alkyl group, and the lower alkyl group is an alkyl group having 1 to 5 carbon atoms, specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a η- A lower linear or branched alkyl group such as a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group or a neopentyl group. R1 is preferably a hydrogen atom or a methyl group. R2 is an alkyl group having 1 to 15 carbon atoms or an aliphatic cyclic group which may have a hydrophilic substituent. Specific examples of the alkyl group such as methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. 1 to 5 A linear or branched alkyl group or the like. The term "aliphatic" as used in the present invention means a relative concept with respect to aromatics, that is, a meaning of a group or a compound having no aromaticity. The "aliphatic cyclic group" means a monocyclic group or a polycyclic group (alicyclic group) which does not have an aromatic meaning, and the "aliphatic ring group" at this time is not limited to carbon and The group formed by hydrogen, but preferably a hydrocarbon group. Further, the "hydrocarbon group" may be either saturated or unsaturated, and it is generally preferred to saturate. Preferred is a polycyclic group (alicyclic group). Specific examples of the above aliphatic cyclic group include, for example, cyclohexane, cyclopentane, adamantane, raw spinane, raw spinel, methylpyrrolidine, ethylpyrrolidine, methylpyrrolene, and B. A monovalent group derived from spinosa, isopinaline, tricyclodecane, tetracyclo-10-1305201 (6) dodecane or the like. Among them, adamantyl group is preferred. In the case where R2 has a substituent, the substituent is preferably one or more selected from the group consisting of an ether bond (-〇-) 'hydroxy group, a carbonyl group, an ester group and an amine group. Among the formula (I), preferred among -c Η 2 - 0 - R2 is, for example, the following chemical formula.

-11 - (7) 1305201 本發明之化合物（a ) ’例如可由下述式（III )所示 具有羧基之（〇：-低級烷基）丙烯酸之衍生物，與鹵化甲 基醚化合物反應，將前述丙烯酸衍生物之羧基上的氫原子 取代爲「-CH^O-R2」所示之基之方式製得。-11 - (7) 1305201 The compound (a) of the present invention ' can be reacted with a halogenated methyl ether compound by, for example, a derivative of a (?:lower alkyl)acrylic acid having a carboxyl group represented by the following formula (III); The hydrogen atom on the carboxyl group of the acrylic acid derivative is substituted with a group represented by "-CH^O-R2".

(瓜) [R1與係與前述式（I)之內容相同] 前述鹵化甲基醚化合物’可使用含有氯、溴等鹵素原 子之醇化合物依公知之方法合成。例如將氯甲基醚化合物 依下示反應式所示公知方法合成。即，於醇化合物上加入 對甲醛，並對該醇化合物，吹入2.0至3.0當量之氯化氫 氣體，於鹽酸酸性下之4 0至1 〇 〇 °C下進行反應。反應結 束後，將產物減壓蒸餾即製得標的物之氯甲基醚化合物。 於下述反應式中，R2係對應於式（1)所示化合物中之R2 內容。 (CH2〇)n +H0-R2 G hCH2 -〇一R2 (高分子化合物） 結構單位（a 1 ) 本發明之高分子化合物（以下亦稱爲高分子化合物 -12- (8) 1305201 (A 1 ))係以上述式（11 )所示結構單位（a 1 )爲必要之 結構單位。 高分子化合物（A I )爲適合作爲正型光阻組成物之 樹脂成份者。 該結構單位（a 1 )，係由本發明之化合物（a )之乙 烯性雙鍵經開裂所形成之結構單位。 式（II)中，R1係與前述式（I)中之R1爲相同之內 容。n2與前述式（I)中之ηι爲相同之內容。R3與前述式 (I)中之R2爲相同之內容。 高分子化合物（A 1 )用於正型光阻組成物時’結構 單位（al)之取代基「-CH2-0-R3」係作爲酸解離性溶解 抑制基使用。其爲縮醛基形式之酸解離性溶解抑制基（-R-0-R’ ；烷氧烷基），例如與三級烷基形式之酸解離性溶 解抑制基相比較時，其具有更易受酸之作用而解離之傾 向。因此，於酸產生劑所產生之酸爲較弱酸時（如後述二 偶氮甲烷系酸產生劑或肟磺酸系酸產生劑或陰離子不具有 莰烷磺酸之鑰鹽等），也可以使酸解離性溶解抑制基充分 產生解離。 結構單位（a2 ) 高分子化合物（A1 )中，除結構單位（a ])以外，可 再含有具內酯之單環或多環式基之（α-低級烷基）丙烯 酸酯所衍生之結構單位（a2 ) ° 其中，「（ α-低級烷基）丙烯酸酯」係指丙烯酸酯 與α -低級烷基丙烯酸酯中任一者或二者之意。又， -13- (9) (9)1305201 「（ α -低級烷基）丙烯酸酯所衍生之結構單位」係指 (α -低級烷基）丙烯酸酯之乙烯性雙鍵經開裂所構成之 結構單位之意。 結構單位（a2 )中，α -位取代基之低級烷基，例如 與前述式（I )與式（Π )中之R1的低級烷基爲相同之內 容。 結構單位（a2)之含內酯之單環或多環式基，於使用 於本發明之高分子化合物形成光阻膜之情形時，因可提高 光阻膜與基板之密著性，故可有效提高與顯影液之親和 性，。 此時之內酯環爲含有- O-C(O)-結構之一個環之意’ 並將其以第一個環單位進行計數。因此，此時，僅爲內酯 環之情形爲單環式基，若尙具有其他環結構時，無論其結 構爲何，皆稱爲多環式基。 結構單位（a2 )只要同時具有前述內酯結構「-0-C (〇 )-」與環式基時’則無特別限定而可任意使用。具體 而言’含內酯之單環式基例如由丁內酯去除1個氫原 子之基，又，含內酯環之多環式基，例如由具有內酯環之 二環鏈烷、三環鏈烷、四環鏈烷中去除I個氫原子所得之 基等。特別是由含有具下述結構式（IV )、或結構式 (V)之含內酯三環鏈烷中去除1個氫原子所得之基’就 工業上容易取得等觀點而言爲較佳。 -14 - (10) 1305201(Melon) [R1 is the same as the above formula (I)] The above-mentioned halogenated methyl ether compound ' can be synthesized by a known method using an alcohol compound containing a halogen atom such as chlorine or bromine. For example, a chloromethyl ether compound is synthesized by a known method shown by the following reaction formula. Namely, a para-formaldehyde is added to the alcohol compound, and the alcohol compound is blown with 2.0 to 3.0 equivalents of hydrogen chloride gas, and the reaction is carried out under the acidity of hydrochloric acid at 40 to 1 Torr. After the reaction is completed, the product is distilled under reduced pressure to obtain the chloromethyl ether compound of the title compound. In the following reaction formula, R2 corresponds to the R2 content in the compound represented by the formula (1). (CH2〇)n +H0-R2 G hCH2 -〇-R2 (polymer compound) structural unit (a 1 ) The polymer compound of the present invention (hereinafter also referred to as polymer compound-12-(8) 1305201 (A 1 )) The structural unit (a 1 ) represented by the above formula (11) is a necessary structural unit. The polymer compound (A I ) is a resin component suitable as a positive photoresist composition. The structural unit (a 1 ) is a structural unit formed by the cleavage of the ethylenic double bond of the compound (a) of the present invention. In the formula (II), R1 is the same as R1 in the above formula (I). N2 is the same as ηι in the above formula (I). R3 is the same as R2 in the above formula (I). When the polymer compound (A 1 ) is used in the positive resist composition, the substituent "-CH2-0-R3" in the structural unit (al) is used as an acid dissociable dissolution inhibiting group. It is an acid dissociable dissolution inhibiting group (-R-0-R'; alkoxyalkyl group) in the form of an acetal group, which is more susceptible when compared with, for example, an acid dissociable dissolution inhibiting group of a tertiary alkyl form. The tendency to dissociate by the action of acid. Therefore, when the acid generated by the acid generator is a weak acid (such as a diazomethane acid generator or an oxime sulfonic acid generator or an anion having a key salt of decanesulfonic acid described later), it may be The acid dissociable dissolution inhibiting group sufficiently produces dissociation. Structural unit (a2) A structure derived from (α-lower alkyl) acrylate having a monocyclic or polycyclic group having a lactone, in addition to the structural unit (a), in the polymer compound (A1) Unit (a2) ° wherein "(α-lower alkyl) acrylate" means either or both of an acrylate and an α-lower alkyl acrylate. Further, -13- (9) (9)1305201 "Structural unit derived from (α-lower alkyl) acrylate" means a structure in which an ethylenic double bond of (α-lower alkyl) acrylate is cracked. The meaning of the unit. In the structural unit (a2), the lower alkyl group of the α-position substituent is, for example, the same as the lower alkyl group of R1 in the above formula (I) and formula (Π). The monocyclic or polycyclic group containing a lactone of the structural unit (a2) can improve the adhesion between the photoresist film and the substrate when the polymer compound of the present invention is used to form a photoresist film. Effectively improve the affinity with the developer. The lactone ring at this time is intended to contain a ring of the -O-C(O)- structure and is counted in the first ring unit. Therefore, in this case, the case of only the lactone ring is a monocyclic group, and if the ring has other ring structures, regardless of the structure, it is called a polycyclic group. The structural unit (a2) is not particularly limited as long as it has the above-mentioned lactone structure "-0-C (〇)-" and a cyclic group, and can be used arbitrarily. Specifically, the monocyclic group containing a lactone is, for example, a group in which one hydrogen atom is removed from butyrolactone, and a polycyclic group having a lactone ring, for example, a bicycloalkane having a lactone ring, and three A group obtained by removing one hydrogen atom from a cycloalkane or a tetracycloalkane. In particular, it is preferred from the viewpoint that it is industrially easy to obtain a base obtained by removing one hydrogen atom from a lactone-containing tricyclic alkane having the following structural formula (IV) or structural formula (V). -14 - (10) 1305201

結構單位（a2 )之例，如含有具內酯之單環烷基或三 環烷基之（甲基）丙烯酸酯所衍生之結構單位等。 本發明中，「（甲基）丙烯酸」係指甲基丙烯酸與丙 烯酸之任一者或二者之意。 結構單位（a2 )之例，更具體而言，例如下述式 (a2-l)至（a2-5)所示之結構單位等。 又，下述式（a2-l )至（a2-5 )中之 R’係與前述式 (I)與式（II)中之R1爲相同之內容。 -15- 1305201Examples of the structural unit (a2) include a structural unit derived from a (meth) acrylate having a monocyclic alkyl group or a tricycloalkyl group having a lactone. In the present invention, "(meth)acrylic acid" means either or both of methacrylic acid and acrylic acid. The structural unit (a2) is more specifically, for example, a structural unit represented by the following formulas (a2-l) to (a2-5). Further, R' in the following formulae (a2-l) to (a2-5) is the same as R1 in the above formula (I) and formula (II). -15- 1305201

(式中，R’爲氫原子或低級烷基）(wherein R' is a hydrogen atom or a lower alkyl group)

(a2 - 2) (式中，R'爲氫原子或低級烷基）(a2 - 2) (wherein R' is a hydrogen atom or a lower alkyl group)

(式中，R’之內容與前述內容相同’ r4、R5各自獨立 -16- (12) 1305201(wherein, the content of R' is the same as the above - ' r4, R5 are independent -16- (12) 1305201

爲氫原子或低級烷基）Is a hydrogen atom or a lower alkyl group)

(式中’ K之內容與前述內容相同） 式（a2-3 )中，114與R5各自獨立爲氫原子或低級烷 ® 基’就考量工業上容易取得等觀點而言，以使用氫原子爲 佳。 R’之低級烷基可爲直鏈狀或支鏈狀烷基皆可，又以碳 原子數1至5之烷基爲佳，例如甲基、乙基、丙基、異丙 基' η-丁基、異丁基 '戊基、異戊基、新戊基等。 又，前述式（a2-])至（a2-5 )所示結構單位中，於 作爲光阻組成物使用時。就提昇抑制、減低近接效果等觀 點而言’以內酯骨架上ct碳上具有酯鍵結之式（a2-1 )所 示（甲基）丙烯酸之r-丁內酯，即7-丁內酯之（甲基） -17- (13) 1305201 丙燦酸酯所衍生之結構單位爲佳。 又’式（a2-l ) 、 （ a2-2 )所示（甲基）丙烯酸之原 疲院內醋’即原菠烷內酯之（甲基）丙烯酸酯所衍生之結 構單位’於用於光阻組成物使用時，可使所製得之光阻圖 型形狀’例如矩形性更佳等而爲較佳。特別是式（a2_2 ) 所示結構單位顯示出極高之效果，而爲更佳。 高分子化合物（A1 )中，結構單位（a2 )，可單獨使 用1種’或將相互不同之2種以上組合使用亦可。高分子 化合物（A1 )骨架中於導入相互不同之2種以上之內酯 骨架時’可提高對光阻膜之基板的密著性或對鹼顯影液之 親和性及蝕刻耐性等，而爲更佳。 更佳之組合爲，將單環式之內酯與多環式之內酯組合 使用爲宜。 相對於構成高分子化合物（A 1 )之全體結構單位而 言，結構單位（a 1 )之比例，以含有1 0莫耳％時，可得 到本發明之效果而爲更佳。相對於構成高分子化合物 (A 1 )之全體結構單位而言，結構單位（a 1 )之較佳比例 爲10至80莫耳％ ，更佳爲20至70莫耳％ 。 高分子化合物（A 1 )爲具有結構單位（a 1 )與結構單 位（a2 )之共聚物時，相對於構成高分子化合物（A 1 )之 全體結構單位而言，結構單位（a 1 )之比例爲1 0至8 0莫 耳％ ，結構單位（a 2 )之比例爲2 0至9 0莫耳％爲更佳。 結構單位（a2 )之比例於上述範圍內時，以含有結構單位 (a2 )結果而可得到充分之效果。更佳爲，結構單位 -18- (14) (14)1305201 (a 1 )之比例爲20至70莫耳％ ’結構單位（a2 )之比例 爲30至80莫耳％ 。 又，高分子化合物（A1)中’於未損及本發明效果 之範圍時，結構單位（a 1 ) 、（ a2 )以外，可再含有其他 結構單位。 其他結構單位 其他結構單位例如下述結構單位（a3 )等。 結構單位（a3 )爲由含有具極性基之脂肪族烴基之 (甲基）丙烯酸酯所衍生之結構單位。含有前述結構單位 時’可提升高分子化合物（A 1 )之親水性，增強與顯影 液之親和性，提高曝光部之鹼溶解性，進而可提升解析 度。 極性基，例如羥基、氰基（CN基）等，特別是以羥 基爲佳。 脂肪族烴基，例如碳原子數1至10之直鏈狀或支鏈 狀烴基（伸烷基）或，多環式之脂肪族烴基（多環式基） 等。前述多環式基，例如可由ArF準分子雷射用之光阻組 成物用樹脂中，由多數提案之內容中作適當選擇使用。 其中又以含有具羥基、氰基或羧基之脂肪族多環式 基’且爲由（甲基）丙烯酸酯所衍生之結構單位爲更佳。 該多環式基’例如二環鏈烷、三環鏈烷、四環鏈烷中去除 1個氫原子之基等，具體而言，例如由金剛烷、原菠烷、 異疲烷、二環癸烷、四環十二烷等去除1個以上氫原子所 -19- (15) 1305201 得之基等。前述之多環式基，例如可由ArF準分子雷射用 之光阻組成物用聚合物（樹脂成份）中，由多數提案之內 容中作適當選擇使用。前述多環式基之中，例如以金剛烷 基、原菠烷基、四環十二烷基較適合工業上使用。(In the formula, the content of 'K is the same as the above-mentioned content.) In the formula (a2-3), 114 and R5 are each independently a hydrogen atom or a lower alkyl group, and the use of a hydrogen atom is considered from the viewpoint of easy industrial availability. good. The lower alkyl group of R' may be a linear or branched alkyl group, and preferably an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl 'η- Butyl, isobutyl 'pentyl, isopentyl, neopentyl and the like. Further, in the structural unit represented by the above formulas (a2) to (a2-5), when used as a photoresist composition. From the viewpoints of enhancing inhibition and reducing the proximity effect, 'r-butyrolactone of (meth)acrylic acid represented by formula (a2-1) having an ester bond on the ct carbon in the lactone skeleton, that is, 7-butyrolactone The structural unit derived from (methyl)-17-(13) 1305201 propionate is preferred. Further, the structural unit derived from the (meth) acrylate of the original (meth) acrylate, which is represented by the formula (a2-l) and (a2-2), is the structural unit derived from the (meth) acrylate of the original spinane lactone. When the resist composition is used, it is preferable that the obtained resist pattern shape 'for example, a rectangular shape is better. In particular, the structural unit shown by the formula (a2_2) exhibits an extremely high effect, and is more preferable. In the polymer compound (A1), the structural unit (a2) may be used singly or in combination of two or more kinds different from each other. When introducing two or more kinds of lactone skeletons different from each other in the polymer compound (A1) skeleton, the adhesion to the substrate of the photoresist film, the affinity to the alkali developing solution, and the etching resistance can be improved. good. More preferably, a combination of a monocyclic lactone and a polycyclic lactone is preferred. The ratio of the structural unit (a 1 ) to the entire structural unit constituting the polymer compound (A 1 ) is preferably 10% by mol, and the effect of the present invention can be more preferably obtained. The preferred ratio of the structural unit (a 1 ) is from 10 to 80 mol%, more preferably from 20 to 70 mol%, based on the entire structural unit constituting the polymer compound (A 1 ). When the polymer compound (A 1 ) is a copolymer having a structural unit (a 1 ) and a structural unit (a2), the structural unit (a 1 ) is relative to the entire structural unit constituting the polymer compound (A 1 ). The ratio is from 10 to 80% by mole, and the ratio of the structural unit (a 2 ) is from 20 to 90% by mole. When the ratio of the structural unit (a2) is within the above range, a sufficient effect can be obtained by containing the structural unit (a2). More preferably, the structural unit -18-(14) (14)1305201 (a 1 ) is 20 to 70 mol% ‘the structural unit (a2) ratio is 30 to 80 mol%. Further, when the polymer compound (A1) does not impair the effects of the present invention, other structural units may be contained in addition to the structural units (a 1 ) and ( a2 ). Other structural units Other structural units are, for example, the following structural unit (a3). The structural unit (a3) is a structural unit derived from a (meth) acrylate having an aliphatic hydrocarbon group having a polar group. When the above structural unit is contained, the hydrophilicity of the polymer compound (A 1 ) can be enhanced, the affinity with the developer can be enhanced, the alkali solubility of the exposed portion can be improved, and the resolution can be improved. The polar group is, for example, a hydroxyl group, a cyano group (CN group) or the like, and particularly preferably a hydroxyl group. The aliphatic hydrocarbon group is, for example, a linear or branched hydrocarbon group having 1 to 10 carbon atoms (alkylene group) or a polycyclic aliphatic hydrocarbon group (polycyclic group). The polycyclic group may be, for example, a resin for a photoresist composition for use in an ArF excimer laser, and is appropriately selected from the contents of most proposals. Further, it is more preferably a structural unit containing an aliphatic polycyclic group having a hydroxyl group, a cyano group or a carboxyl group and derived from a (meth) acrylate. The polycyclic group 'for example, a dicycloalkane, a tricycloalkane, a tetracyclic alkane, a group in which one hydrogen atom is removed, and the like, specifically, for example, adamantane, raw spinel, iso-, or bi-cyclohexane The decane, tetracyclododecane, etc. are removed by removing one or more hydrogen atoms, -19-(15) 1305201. The above polycyclic group may be, for example, a polymer (resin component) for a photoresist composition for use in an ArF excimer laser, and is appropriately selected from the contents of most proposals. Among the above polycyclic groups, for example, an adamantyl group, a raw spintenyl group or a tetracyclododecyl group is suitable for industrial use.

結構單位（a3 )中’含有極性基之脂肪族烴基中之烴 基爲碳原子數1至10之直鏈狀或支鏈狀之烴基時，以由 (甲基）丙烯酸之羥基乙基酯所衍生之結構單位爲佳，該 烴基爲多環式基時，例如以下述式（a3-I ) 、（ a3_2 )所 示結構單位爲佳。In the structural unit (a3), when the hydrocarbon group in the aliphatic hydrocarbon group having a polar group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, it is derived from a hydroxyethyl (meth)acrylate. The structural unit is preferable, and when the hydrocarbon group is a polycyclic group, for example, a structural unit represented by the following formulas (a3-I) and (a3_2) is preferred.

(a3-i)(a3-i)

(式中’ R|之內容與前述內容相同，^爲丨至3之整 數） 即’該式中’以η爲1，羥基爲鍵結於金剛烷基之3 位者爲佳。 -20- (16) 1305201(The content of 'R| in the formula is the same as the above, and ^ is an integer from 丨 to 3). That is, in the formula, η is 1 and the hydroxyl group is bonded to 3 of the adamantyl group. -20- (16) 1305201

(式中’ R'之內容與前述內容相同，k爲1 . 數）。 其中又k爲1者爲佳。其可以異構物之形式 基鍵結於原菠烷基之4位或5位之化合物的混合 結構單位（a 3 )非爲（A 1 )成份之必要成份 有於（A )成份之中時，以對構成（a )成份之 單位的合計，爲含有5至5 0莫耳％ ，更佳爲含 40莫耳％爲宜。於下限値以上時具有良好之ί (線路邊緣粗糙）效果，於上限値以下時，可保 結構單位之平衡，而防止光阻圖型型狀之劣化。 又，高分子化合物（A1 )成份中，可再含 於前述結構單位（a 1 )至（a3 )之其他結構單位 即爲不含有酸解離性溶解抑制基、不含內酯官能 基之結構單位。例如含酸不解離性之脂肪族多環 由（甲基）丙烯酸酯所衍生之結構單位等爲佳。 結構單位用於正型光阻組成物使用時，可使獨立 半圖型（相對於線寬爲1時，空間寬爲1.2至2 至3之整 存在（氰 物）。 ，若其含 全部結構 有1 0至 是昇 LER 持與其他 有未分類 (a4 )， 基、極性 式基，且 使用前述 圖型至倍 之線路與 -21 - (17) 1305201 空間圖型）具有優良解析度而爲較佳。 該多環式基例如與則述結構單iu ( a3 )中所例示之內 谷爲相问之基’其可由作爲ArF準分子雷射用材料之以往 已知之多數內容中作適當選擇使用。 特別是以三環癸基、金剛烷基、四環十二: 出之至少1種’以工業上容易取得而爲較佳。 特別是以下述式（a4-l ) 、（ a4-3 )爲佳。(The content of ' R ' in the formula is the same as the above, k is 1. number). Among them, k is one. a mixed structural unit (a 3 ) which may be bonded to a 4- or 5-position of a raw spinel group in the form of an isomer, and is not a component of the (A 1 ) component. The total of the units constituting the component (a) is preferably from 5 to 50% by mole, more preferably 40% by mole. It has a good ί (line edge roughness) effect above the lower limit ,. When it is below the upper limit ,, it can maintain the balance of the structural unit and prevent the deterioration of the resist pattern. Further, among the components of the polymer compound (A1), other structural units which may be further contained in the structural units (a1) to (a3) are structural units which do not contain an acid dissociable dissolution inhibiting group and which do not contain a lactone functional group. . For example, an aliphatic polycyclic ring containing an acid-non-dissociable property is preferably a structural unit derived from (meth) acrylate. When the structural unit is used for the positive-type photoresist composition, it can be used as an independent half-pattern (when the line width is 1, the space width is 1.2 to 2 to 3 (cyano). If it contains all structures There are 10 to liters of LER holding and other unclassified (a4), base, polar base, and using the above-mentioned pattern to double the line and -21 - (17) 1305201 spatial pattern) with excellent resolution Preferably. The polycyclic group is, for example, a base which is the same as the inner valley exemplified in the structure single iu (a3 ), which can be appropriately selected from the conventionally known contents of the ArF excimer laser material. In particular, it is preferred that at least one of tricyclodecyl, adamantyl and tetracycline is industrially easy to obtain. In particular, the following formulae (a4-l) and (a4-3) are preferred.

(式中’ R'之內容與前述內容相同） -22- (18) 1305201(where the content of 'R' is the same as above) -22- (18) 1305201

〇A〇 (a4-3)〇A〇 (a4-3)

(式中，R'之內容與前述內容相同） 前述結構單位（a4 ) 非爲（A )成份之 若其含有於（A )成份之中時，以對構成（A ) 部結構單位的合計，結構單位（a4 )爲含有1 \ % ，更佳爲含有10至20莫耳％爲宜。以其具窄 圖型至倍半圖型之解析度更向上提昇而爲較佳。 又，前述（al)單位以外’可再與具有公矢 φ 性基之（甲基）丙烯酸酯所衍生之結構單位徒 佳。 局分子化合物（A1)之質量平均分子量（ 色層分析法（GPC )之苯乙烯換算質量平均分号 同）並未有特別限定’於作爲正型光阻組成物信 2000至50000爲佳，更佳爲5000至4〇〇〇〇。 本發明之高分子化合物（A 1 )，例如可狀 位之單體，例如使用偶氮二異丁腈（AIBN )等 合起始劑依公知之自由基聚合等聚合反應而製辑 要成份， 成份之全 莫耳 可使獨立 之酸解離 合使用爲 凝膠滲透 量，以下 用時，以 各結橇單 自由基聚 -23- (19) 1305201 (正型光阻組成物） 本發明之正型光阻組成物，爲含有（A)具有酸解離 性溶解抑制基且可經由酸之作用而增大鹼可溶性之樹脂成 份，與（B )酸產生劑成份者，其中該樹脂成份（A )爲 使用本發明之高分子化合物（A 1 )。 前述正型光阻組成物中，於經由曝光使（B )酸產生 劑成份產生酸時，因該酸之作用使酸解離性溶解抑制基解 • 離，而增大樹脂成份（A )全體之鹼可溶性。 因此，於光阻圖型之形成方法中，介由光阻圖型進行 曝光時，或曝光以外再進行曝光後加熱（PEB )處理時， 於曝光部中可增大鹼可溶性，故經由鹼顯影處理而可形成 正型光阻圖型。 本發明之正型光阻組成物，爲含有高分子化合物 (A 1 )與，經由曝光產生酸之酸產生劑成份（B)爲必要 成份者。該樹脂成份（A )，除高分子化合物（A1 )以 0 外，可再適當添加聚羥基苯乙烯樹脂、（甲基）丙烯酸樹 脂等之可用於正型光阻組成物之其他樹脂成份，爲達到本 發明之效果，正型光阻組成物中所含之樹脂成份（A ) 中，高分子化合物（A1 )以80質量％以上爲佳，以90 質量％以上爲更佳，以1 00質量％爲最佳。 正型光阻組成物中，樹脂成份（A )之比例，可配合 目的之光阻膜厚度作適當之調製。 酸產生劑成份（B )(以下亦簡稱（B )成份） 本發明之正型光阻組成物中所使用之酸產生劑成份 -24- (20) (20)1305201 (B )，可由公知之經曝光或經放射線照射產生酸之化合 物中作適當之選擇使用。前述酸產生劑，目前爲止例如碘 鎗鹽或銃鹽等鑰鹽系酸產生劑，肟磺酸酯系酸產生劑、雙 烷基或雙芳基磺醯基二偶氮甲烷類、聚（雙磺醯基）二偶 氮甲烷類、二偶氮甲烷硝基苄磺酸酯類等二偶氮甲烷系酸 產生劑、亞胺基磺酸酯系酸產生劑、二硕類系酸產生劑等 多種已知化合物。 鑰鹽系酸產生劑之具體例如，二苯基碘鑰之三氟甲烷 磺酸酯或九氟丁烷磺酸酯、雙（4-tert-丁基苯基）碘鑰之 二氣甲院擴酸醋或九氣丁院磺酸醋、三苯基疏之三氟甲院 磺酸酯、其七氟丙烷磺酸酯或其九氟丁烷磺酸酯、三（4_ 甲基苯基）錡之三氟甲烷磺酸酯、其七氟丙烷磺酸酯或其 九氟丁烷磺酸酯、二甲基（4-羥基萘基）锍之三氟甲烷磺 酸酯、其七氟丙烷磺酸酯或其九氟丁烷磺酸酯、單苯基二 甲基銃之三氟甲烷磺酸酯、其七氟丙烷磺酸酯或其九氟丁 院磺酸酯、一苯基單甲基疏之二氟甲垸磺酸酯、其七氟丙 烷磺酸酯或其九氟丁烷磺酸酯、（4-甲基苯基）二苯基硫 之三氟甲烷磺酸酯、其七氟丙烷磺酸酯或其九氟丁烷磺酸 酯、（4 -甲氧基苯基）二苯基毓之三氟甲烷磺酸酯、其七 氟丙烷磺酸酯或其九氟丁烷磺酸酯、三（4-tert-丁基）銃 之三氟甲烷磺酸酯'其七氟丙烷磺酸酯或其九氟丁烷磺酸 酯等。 前述鍚鹽系酸產生劑中，可使用酸強度較弱，陰離子 部具有莰烷磺酸離子之陰離子的鑰鹽。具體而言，例如下 -25- (21) 1305201 述化學式（B - 1 )所示化合物等。(In the formula, the content of R' is the same as the above). The structural unit (a4) is not the component (A), but if it is contained in the component (A), the total of the structural units of the component (A) is The structural unit (a4) is preferably 1% by weight, more preferably 10% to 20% by mole. It is better to increase the resolution from a narrow pattern to a half-width pattern. Further, it is preferable that the structural unit other than the above (al) unit can be further derived from a (meth) acrylate having a φ group. The mass average molecular weight of the molecular compound (A1) (the same as the styrene-converted mass averaged number of the color layer analysis method (GPC)) is not particularly limited as the positive resistive composition is preferably from 2,000 to 50,000. Good for 5000 to 4 baht. The polymer compound (A1) of the present invention, for example, a monomer capable of being in a form, is prepared by a polymerization reaction such as radical polymerization using a combined initiator such as azobisisobutyronitrile (AIBN). The total mole of the component can be used as a gel permeation amount for the independent acid dissociation, and the following is a single-radical poly-labeled -23-(19) 1305201 (positive-type photoresist composition). A photoresist composition comprising (A) a resin component having an acid dissociable dissolution inhibiting group and capable of increasing alkali solubility via an action of an acid, and a (B) acid generator component, wherein the resin component (A) The polymer compound (A 1 ) of the present invention is used. In the positive-type photoresist composition, when an acid is generated by the (B) acid generator component by exposure, the acid dissociable dissolution inhibiting group is decomposed by the action of the acid, and the resin component (A) is increased. Alkali soluble. Therefore, in the formation method of the photoresist pattern, when the exposure is performed by the resist pattern or the post-exposure heating (PEB) treatment is performed after the exposure, the alkali solubility can be increased in the exposed portion, so that the alkali is developed. Processing can form a positive photoresist pattern. The positive resist composition of the present invention is a component containing a polymer compound (A 1 ) and an acid generator component (B) which generates an acid by exposure. In addition to the polymer compound (A1), the resin component (A) may be further added with other resin components such as polyhydroxystyrene resin or (meth)acrylic resin which can be used for the positive resist composition. In the resin component (A) contained in the positive resist composition, the polymer compound (A1) is preferably 80% by mass or more, more preferably 90% by mass or more, and more preferably 100% by mass. % is the best. In the positive resist composition, the ratio of the resin component (A) can be appropriately adjusted in accordance with the thickness of the target photoresist film. Acid generator component (B) (hereinafter also referred to as (B) component) The acid generator component -24(20)(20)1305201 (B) used in the positive photoresist composition of the present invention can be known. The compound which is exposed to light or irradiated with radiation to produce an acid is suitably used. The acid generator is, for example, a key salt generator such as an iodine salt or a phosphonium salt, an oxime sulfonate acid generator, a dialkyl or bisarylsulfonyldiazomethane, or a poly (double) Diazomethane acid generators such as sulfonyl)diazomethanes and diazomethane nitrobenzylsulfonates, iminosulfonate acid generators, and two acid generators A variety of known compounds. Specific examples of the key salt acid generator include, for example, diphenyl iodine trifluoromethane sulfonate or nonafluorobutane sulfonate, and bis (4-tert-butylphenyl) iodine Sour vinegar or nine gas butyl sulfonate, triphenyl sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tris(4-methylphenyl) oxime Fluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, dimethyl(4-hydroxynaphthyl)phosphonium trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane Alkane sulfonate, triphenylmethanesulfonate of monophenyldimethylhydrazine, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, monophenylmonomethyldifluoromethanesulfonate , heptafluoropropane sulfonate or nonafluorobutane sulfonate, (4-methylphenyl) diphenyl sulfide trifluoromethane sulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate , (4-methoxyphenyl)diphenylphosphonium trifluoromethanesulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tris(4-tert-butyl)phosphonium trifluoride Methanesulfonate Its heptafluoropropane sulfonate or its nonafluorobutane sulfonate. Among the above-mentioned sulfonium-based acid generators, a key salt having a weak acid strength and an anion having an anion of a decanesulfonic acid ion can be used. Specifically, for example, a compound represented by the chemical formula (B-1) described below is -25-(21) 1305201.

肟磺酸酯系酸產生劑之具體例如〇： - ( p-甲苯磺醯氧 亞胺基）-苄基氰化物（cyanide) 、ο: - ( ρ-氯基苯磺醯氧 亞胺基）-苄基氰化物、α - ( 4-硝基苯磺醯氧亞胺基）-苄 基氰化物、α-(4-硝基-2-三氟甲基苯磺醯氧亞胺基）-苄 基氰化物、α-(苯磺醯氧亞胺基）-4-氯基苄基氰化物、 α -(苯磺醯氧亞胺基）-2,4-二氯基苄基氰化物、〇:-(苯 φ 磺醯氧亞胺基）-2,6-二氯基苄基氰化物、〇:-(苯磺醯氧 亞胺基）-4-甲氧基苄基氰化物、α-(2-氯基苯磺醯氧亞 胺基）_4_甲氧基苄基氰化物、α -(苯磺醯氧亞胺基）-噻 嗯-2-基乙腈、α - ( 4-十二烷基苯磺醯氧亞胺基）-苄基氰 化物、α -[( ρ-甲苯磺醯氧亞胺基）-4-甲氧基苯基]乙 腈、α -[(十二烷基苯磺醯氧亞胺基）-4-甲氧基苯基]乙 腈、α -(對甲苯磺醯氧亞胺基）-4-噻嗯基氰化物、α -(甲基磺醯氧亞胺基）-1-環戊烯基乙腈、α-(甲基磺醯 氧亞胺基）-1-環己烯基乙腈、α-(甲基磺醯氧亞胺基）-1 -環庚烯基乙腈、α -(甲基磺醯氧亞胺基）-1 -環辛烯基 -26- (22) 1305201 乙腈、α -(三氟甲基磺醯氧亞胺基）-1 -環戊烯基乙腈' α-(三氟甲基磺醯氧亞胺基）-]-環己烯基乙腈、α-(乙 基磺醯氧亞胺基）-乙基乙腈、ct-(丙基磺醯氧亞胺 基）-丙基乙腈、環己基磺醯氧亞胺基）-環戊基乙 腈、α -(環己基磺醯氧亞胺基）-環己基乙腈、α -(環 己基磺醯氧亞胺基）-1-環戊烯基乙腈、α-(乙基磺醯氧 亞胺基）-I-環戊烯基乙腈、異丙基磺醯氧亞胺基）-Φ 1-環戊烯基乙腈、α-(η-丁基磺醯氧亞胺基）-卜環戊烯 基乙腈、α -(乙基磺醯氧亞胺基）-1 -環己烯基乙腈、α -(異丙基磺醯氧亞胺基）-1-環己烯基乙腈、α-(η-丁基 磺醯氧亞胺基）-1 -環己烯基乙腈、《 ·(甲基磺醯氧亞胺 基）-苯基乙腈、α -(甲基磺醯氧亞胺基）-ρ_甲氧基苯基 乙腈、〇:-(三氟甲基磺醯氧亞胺基）-苯基乙腈、α-(三氟甲基磺醯氧亞胺基）-Ρ-甲氧基苯基乙腈、α -(乙 基磺醯氧亞胺基）-Ρ -甲氧基苯基乙腈、α -(丙基磺醯氧 ^ 亞胺基）-Ρ-甲基苯基乙腈、0：-(甲基磺醯氧亞胺基）·Ρ-溴基苯基乙腈等。其中又以α -(甲基磺醯氧亞胺基）-Ρ-甲氧基苯基乙腈爲較佳。 前述二偶氮甲烷系酸產生劑中，雙烷基或雙芳基磺醯 基二偶氮甲烷類之具體例，如雙（異丙基磺醯基）二偶氮 甲烷、雙（Ρ-甲苯磺醯基）二偶氮甲烷 '雙（1J -二甲基 乙基磺醯基）二偶氮甲烷、雙（環己基磺醯基）二偶氮甲 烷、雙（2,4 -二甲基苯基磺醯基）二偶氮甲烷等。 又，聚（雙磺醯基）二偶氮甲烷類例如具有下示結構 -27- (23) 1305201 之1，3 -雙（苯基磺醯基二偶氮甲基磺醯基）丙烷（化合物 A，分解點135°C ) 、1,4-雙（苯基磺醯基二偶氮甲基磺醯 基）丁烷（化合物B，分解點147°C ) 、1，6-雙（苯基磺 醯基二偶氮甲基磺醯基）己烷（化合物C，熔點1 3 2°C、 分解點145 °C )、1,10-雙（苯基磺醯基二偶氮甲基磺醯 基）癸烷（化合物D，分解點147°C ) 、1,2-雙（環己基 磺醯基二偶氮甲基磺醯基）乙烷（化合物E，分解點14 9 ® °C ) 、：l , 3 -雙（環己基磺醯基二偶氮甲基磺醯基）丙烷 (化合物F，分解點1 5 3 °C ) 、1,6 -雙（環己基磺醯基二 偶氮甲基磺醯基）己烷（化合物G，熔點109°C、分解點 122 °C ) 、1，10-雙（環己基磺醯基二偶氮甲基磺醯基）癸 烷（化合物Η，分解點1 16t )等。Specific examples of the oxime sulfonate-based acid generator include -: -( p-toluenesulfonyloxyimido)-benzyl cyanide (cyanide), ο: - ( ρ-chlorophenylsulfonyloxyimino) -benzyl cyanide, α-(4-nitrobenzenesulfonyloxyimino)-benzyl cyanide, α-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimido)- Benzyl cyanide, α-(phenylsulfonyloxyimido)-4-chlorobenzyl cyanide, α-(phenylsulfonyloxyimino)-2,4-dichlorobenzyl cyanide, 〇:-(Benzene φ sulfonate oxyimino)-2,6-dichlorobenzyl cyanide, hydrazine: -(phenylsulfonyloxyimino)-4-methoxybenzyl cyanide, α -(2-Chlorophenylsulfonyloxyimino)_4_methoxybenzyl cyanide, α-(phenylsulfonyloxyimino)-thien-2-ylacetonitrile, α - (4-10 Dialkylbenzenesulfonyloxyimido)-benzyl cyanide, α-[(ρ-toluenesulfonyloxyimido)-4-methoxyphenyl]acetonitrile, α-[(dodecyl) Phenylsulfonyloxyimido)-4-methoxyphenyl]acetonitrile, α-(p-toluenesulfonyloxyimino)-4-thiol cyanide, α-(methylsulfonyloxyimine 1,-1-cyclopentenylacetonitrile, α-(methylsulfonate Oxyimido)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimido)-1 -cycloheptenylacetonitrile, α-(methylsulfonyloxyimino)-1 Cyclooctenyl-26-(22) 1305201 acetonitrile, α-(trifluoromethylsulfonyloxyimido)-1 -cyclopentenylacetonitrile 'α-(trifluoromethylsulfonyloxyimino) -]-cyclohexenylacetonitrile, α-(ethylsulfonyloxyimino)-ethylacetonitrile, ct-(propylsulfonyloxyimino)-propylacetonitrile, cyclohexylsulfonyloxyimine -cyclopentylacetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclohexylacetonitrile, α-(cyclohexylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(B Alkylsulfonyloxyimido)-I-cyclopentenylacetonitrile, isopropylsulfonyloxyimido)-Φ 1-cyclopentenylacetonitrile, α-(η-butylsulfonyloxyimido )-bucyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1 -cyclohexenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclohexenyl Acetonitrile, α-(η-butylsulfonyloxyimido)-1 -cyclohexenylacetonitrile, "(methylsulfonyloxyimino)-phenylacetonitrile, α-(methylsulfonate) Imino)-ρ_methoxy Phenylacetonitrile, hydrazine: -(trifluoromethylsulfonyloxyimino)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimido)-fluorene-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino)-fluorene-methoxyphenylacetonitrile, α-(propylsulfonyloxy)imino-indole-methylphenylacetonitrile, 0:-(methylsulfonate Ominoimido)·Ρ-bromophenylacetonitrile and the like. Among them, α-(methylsulfonyloxyimido)-fluorene-methoxyphenylacetonitrile is preferred. Among the above-mentioned diazomethane acid generators, specific examples of the dialkyl or bisarylsulfonyldiazomethanes, such as bis(isopropylsulfonyl)diazomethane and bis(indole-toluene) Sulfhydryl)diazomethane 'bis(1J-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylbenzene Sulfosyl) diazomethane and the like. Further, poly(bissulfonyl)diazomethanes have, for example, 1,3-bis(phenylsulfonyldisazomethylsulfonyl)propane (compound) having the structure -27-(23) 1305201 shown below. A, decomposition point 135 ° C), 1,4-bis(phenylsulfonyldiazomethylsulfonyl)butane (Compound B, decomposition point 147 ° C), 1,6-bis (phenyl Sulfonyldiazomethylsulfonyl)hexane (Compound C, melting point 1 3 2 ° C, decomposition point 145 ° C), 1,10-bis(phenylsulfonyldiazomethylsulfonate) Base) decane (Compound D, decomposition point 147 ° C), 1,2-bis(cyclohexylsulfonyldiazomethylsulfonyl)ethane (Compound E, decomposition point 14 9 ® °C), :l , 3 - bis(cyclohexylsulfonyldiazomethylsulfonyl)propane (Compound F, decomposition point 1 5 3 °C), 1,6-bis(cyclohexylsulfonyldiazo) Sulfosyl)hexane (compound G, melting point 109 ° C, decomposition point 122 ° C), 1,10-bis(cyclohexylsulfonyldiazomethylsulfonyl)decane (compound, decomposition) Point 1 16t) and so on.

-28- (24)1305201 o=s=oonsno OHSHO onsno N2&quot;cn2=cn2=c—n2&quot;c—---- o=s=o o=s=o onsno onsno 物rJ 物/ j 物/ 物 化 化化化 N=c - OHSHO - 3 H2)c 2 Hc 2 Hc H2c o=s=o onsMO OHSno Y- on SH o on snn o on sn o OHM SH o 一 _ I I N = c N=c N=c-28- (24)1305201 o=s=oonsno OHSHO onsno N2&quot;cn2=cn2=c-n2&quot;c—---- o=s=oo=s=o onsno onsno object rJ object / j object / materialization N=c - OHSHO - 3 H2)c 2 Hc 2 Hc H2c o=s=o onsMO OHSno Y- on SH o on snn o on sn o OHM SH o I_ IIN = c N=c N=c

E 物 合 化E materialization

onsno onsno N2=c—n2=c-1 1 onsno OHSno /i H2)c n2c G 物 合 化 onsnoOnsno onsno N2=c-n2=c-1 1 onsno OHSno /i H2)c n2c G complex onsno

n2c /IV _ OHSHO o=s-=o OHSno o=s=o N2HC—N2=c~n2=c— I - i onsno onsno onsnoN2c /IV _ OHSHO o=s-=o OHSno o=s=o N2HC—N2=c~n2=c— I - i onsno onsno onsno

i 合 化 OHSHO 1 0 H2)1c /—\ 1 OHSHO 2 -nhc -onsnoi 合化 OHSHO 1 0 H2)1c /—\ 1 OHSHO 2 -nhc -onsno

-29- (25) 1305201 (B )成份，可單獨使用前述1種酸產生劑’或將2 種以上組合使用亦可。 (B)成份之含量，對含有前述高分子化合物（A1) 之樹脂成份（A)成份100質量份爲使用0.5至30質量 份，較佳爲使用1至1 〇質量份爲宜。於下限値以上時， 可充分形成圖型，於上限値以下時，可得到均勻之溶液， 且可防止保存安定性降低。 含氮有機化合物（c )(以下亦簡稱（C )成份） 本發明之正型光阻組成物中，必要時，可再添加含氮 有機化合物（C )。增強化學性光阻組合物中添加含氮有 機化合物作爲酸擴散阻礙劑因已屬公知之技術，於本發明 中，亦可添加前述公知之含氮有機化合物。前述含氮有機 化合物，例如胺或銨鹽等。 前述胺例如二乙基胺、二丙基胺、二丁基胺、二戊基 胺等脂肪族二級胺，三甲基胺、三乙基胺、三丙基胺、三 丁基胺、三戊基胺、Ν,Ν-二甲基丙基胺、N-乙基-N-甲基 丁基胺、三己基胺、三庚基胺、三辛基胺、三癸基胺、 三-十二烷基胺等脂肪族三級胺（三烷基胺，又，上述與 氮鍵結之3個院基可爲相同或不同），Ν,Ν -二甲基單乙醇 胺、三異丙醇胺、Ν，Ν -二乙基單乙醇胺、三乙醇胺、三丁 醇胺等三級烷醇胺，Ν,Ν-二甲基苯胺、Ν，Ν-二乙基苯胺、 Ν -乙基-Ν -甲基苯胺、Ν,Ν -二甲基甲苯胺、Ν -甲基二苯基 胺、Ν·乙基二苯基胺、三苯基胺等芳香族三級胺等。 前述敍鹽，例如錢離子、四甲基鞍離子、四乙基銨離 -30- (26) 1305201 子、四丙基銨離子、四丁基錢離子、四戊基錢離子等四級 烷基銨離子與乳酸等具有羥基之有機羧酸之離子所形成之 鹽等。 其中又以三乙醇胺、三異丙醇胺、三丁醇胺等低級之 三級烷醇胺，三己基胺、三庚基胺、三辛基胺、三癸基 胺、三-十二烷基胺、三-十四烷基胺等碳原子數6以上1 5 以下之三烷基胺具有優良的降低微細光阻圖型之冠狀部份 的膜衰減效果，而爲較佳。 前述含氮有機化合物（C)，對含有前述高分子化合 物（A1)之樹脂成份（A)成份100質量份而言，一般爲 使用0.0 1至5質量份之範圍。於此範圍內時，具有可抑 制因曝光所產生之酸的擴散效果，故可得到較佳之圖型形 狀改善效果。 酸成份（D)(以下亦稱爲（D)成份） 又，本發明中，爲防止添加前述（C)成份所造成之 感度劣化等目的，可再添加任意之（D)成份，其爲含有 有機羧酸或磷之含氧酸或其衍生物者。 前述有機羧酸，例如丙二酸、檸檬酸、蘋果酸、琥珀 酸、苯甲酸、水楊酸等爲佳。 前述磷之含氧酸或其衍生物，例如磷酸、磷酸二-η-丁酯、磷酸二苯酯等磷酸或其酯等衍生物，膦酸 (Phosphonic acid) ' 膦酸二甲酯、膦酸-二-η-丁酯、苯 基膦酸、膦酸二苯酯、膦酸二苄酯等膦酸及其酯等瞵酸衍 生物’次膦酸（Phosphinic acid )'苯基次膦酸等次膦酸 -31 - (27) 1305201 及其酯等次膦酸衍生物，其中又以膦酸爲佳。 (D )成份，對含有前述高分子化合物（A 1 )之樹脂 成份（A)成份100質量份而言，一般爲使用〇_〇1至5.0 質量份之範圍。 有機溶劑 本發明之正型光阻組成物，爲將含有前述高分子化合 ® 物（A 1 )之樹脂成份（A )、前述酸產生劑成份（B )、 與含氮有機化合物（C )、及必要時所添加之任意成份均 勻的溶解於有機溶劑之方式以製得。 有機溶劑只要可溶解所使用之各成份而形成均勻之溶 液即可，例如可使用由以往作爲增強化學性光阻溶劑之公 知溶劑中，適當的選擇1種或2種以上使用。 前述有機溶劑，例如r - 丁內酯、丙酮、甲基乙基 酮、環己酮、甲基異戊酮、2-庚酮等酮類或，乙二醇、乙 ® 二醇單乙酸酯、二乙二醇、二乙二醇單乙酸酯、丙二醇、 丙二醇單乙酸酯'二丙二醇、或二丙二醇單乙酸酯之單甲 基醚、單乙基醚、單丙基醚、單丁基醚或單苯基醚等多元 醇類及其衍生物，或二噁烷等環式醚類或乳酸甲酯、乳酸 乙酯（EL)、乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酮酸 甲酯、丙酮酸乙酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯等 酯類。前述有機溶劑可單獨使用，或以2種以上之混合溶 劑形式使用亦可。其中，丙二醇單甲基醚乙酸酯 (PGMEA )與極性溶劑之添加比例，於考慮PGMEA與極 -32- (28) (28)1305201 性溶劑之相溶性等作適當之決定即可，較佳爲1 : 9至 9: 1，更佳爲2: δ至8: 2之範圍。 更具體而言，極性溶劑爲使用乳酸乙酯（EL )時， PGMEA : EL之質量比較佳爲2 : 8至8 : 2，更佳爲3 : 7 至7 : 3。又’有機溶劑中，其他例如使用由PGMEΑ與 EL中選出至少1種與r -丁內酯所得混合溶劑爲佳。此 時’較佳之混合比例以前者與後者之質量比爲7〇 : 3〇至 95 : 5。（ E )成份之使用量並未有特別限定，一般可於可 塗佈於基板等之濃度，塗膜厚度等作適當的選擇設定，有 機溶劑之使用量一般以光阻組成物中之固體成份濃度達2 至20質量％ ’較佳爲5至15質量％之範圍。 其他成份 本發明之光阻組成物，可再適度添加需要增加混合性 之添加劑’例如公知之溶解抑制劑、改良光阻膜性能所添 加之加成性樹脂，提昇塗覆性之界面活性劑、可塑劑、安 定劑、著色劑、光暈防止劑等。 又’本發明之化合物（a )可以溶解抑制劑形式含於 正型光阻組成物中。正型光阻組成物中，該化合物（a ) 於曝光前具有抑制溶解於鹼顯影液之作用，曝光製程後經 由去保護處理後而產生鹼溶解性。經具有前述化合物，可 防止光阻圖型之圖型膜偏移，而可提供高解析度之微細圖 型。 以往之增強化學型光阻中，常爲提昇解析度而增加酸 -33- (29) (29)1305201 解離性溶解抑制基之導入率，但常會產生具有缺陷之比例 提高等問題。又，以往雖廣泛使用三級烷基作爲酸解離性 溶解抑制基，但仍會產生所使用之酸產生劑之種類受到限 制等問題。即，若不使用可產生較強酸強度之酸產生劑， 例如陰離子部具有氟化烷基磺酸離子之鑰鹽時，該酸解離 性溶解抑制基（三級烷基）則因未能充分解離而未能得到 良好之解析度。換言之，使用所產生之酸強度較弱之酸產 生劑時，其感度將不充分。 相對於此，本發明之正型光阻組成物於不需提高酸解 離性溶解抑制基之導入率下，即可提高解析度，而得到良 好之感度。又，也可實現降低線路邊緣粗糙（LER )、顯 影缺陷等目標。 此推測應爲高分子化合物（A1 )之結構單位（al )具 有經由酸之作用而容易產生解離之酸解離性溶解抑制基所 得到之效果。即，高分子化合物（A 1 )之結構單位（a 1 ) 中之酸解離性溶解抑制基’爲經由酸之作用而容易產生解 離之基，故可提高曝光部之鹼溶解性，即使酸產生劑所產 生之酸爲較弱時’也可使酸解離性溶解抑制基充分解離。 又，也可使用之酸產生劑之選擇性更爲廣泛。 又，使用二偶氮甲烷系酸產生劑等非離子性酸產生劑 亦可得到充分之解析度。因此，特別是曝光時透鏡與光阻 層之間充滿折射率較空氣之折射率爲大之溶劑的浸漬曝光 製程等，基於溶劑之污染問題等而多使用非離子性之酸產 生劑爲較佳之方法中’亦適合使用本發明之正型光阻組成 -34 - (30) 1305201-29- (25) 1305201 (B) The above-mentioned one type of acid generator may be used singly or in combination of two or more. The content of the component (B) is preferably 0.5 to 30 parts by mass, preferably 1 to 1 part by mass, per 100 parts by mass of the resin component (A) containing the polymer compound (A1). When the lower limit is 値 or more, the pattern can be sufficiently formed. When the upper limit is 値 or less, a uniform solution can be obtained, and the preservation stability can be prevented from being lowered. Nitrogen-containing organic compound (c) (hereinafter also referred to as (C) component) In the positive resist composition of the present invention, if necessary, a nitrogen-containing organic compound (C) may be further added. It is a well-known technique to add a nitrogen-containing organic compound as an acid diffusion inhibitor to the chemically-resistant photoresist composition, and the above-mentioned known nitrogen-containing organic compound may be added in the present invention. The aforementioned nitrogen-containing organic compound, such as an amine or an ammonium salt or the like. The above amines are aliphatic secondary amines such as diethylamine, dipropylamine, dibutylamine, dipentylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, three Amylamine, hydrazine, hydrazine-dimethylpropylamine, N-ethyl-N-methylbutylamine, trihexylamine, triheptylamine, trioctylamine, tridecylamine, tri-ten An aliphatic tertiary amine such as a dialkylamine (trialkylamine, further, the above three bases bonded to nitrogen may be the same or different), hydrazine, hydrazine-dimethyl monoethanolamine, triisopropanolamine , hydrazine, hydrazine - a tertiary alkanolamine such as diethyl monoethanolamine, triethanolamine or tributylolamine, hydrazine, hydrazine-dimethylaniline, hydrazine, hydrazine-diethylaniline, hydrazine-ethyl-hydrazine An aromatic tertiary amine such as methylaniline, hydrazine, hydrazine-dimethyltoluidine, hydrazine-methyldiphenylamine, hydrazine-ethyldiphenylamine or triphenylamine. The foregoing salt, for example, a tetraalkyl group such as a money ion, a tetramethyl saddle ion, a tetraethylammonium -30-(26) 1305201, a tetrapropylammonium ion, a tetrabutyl ketone, a tetrapentyl ketone or the like A salt formed by an ion of an organic carboxylic acid having a hydroxyl group such as an ammonium ion or a lactic acid. Among them, lower tertiary alkanolamines such as triethanolamine, triisopropanolamine, and tributylolamine, trihexylamine, triheptylamine, trioctylamine, tridecylamine, tri-dodecyl group A trialkylamine having 6 or more and 15 or less carbon atoms such as an amine or tri-tetradecylamine has an excellent film attenuating effect for lowering the crown portion of the fine photoresist pattern, and is preferable. The nitrogen-containing organic compound (C) is generally used in an amount of from 0.01 to 5 parts by mass per 100 parts by mass of the resin component (A) component containing the polymer compound (A1). When it is in this range, it has a effect of suppressing the diffusion of the acid generated by the exposure, so that a better shape-improving effect can be obtained. Acid component (D) (hereinafter also referred to as component (D)) In the present invention, in order to prevent deterioration of sensitivity caused by the addition of the component (C), any component (D) may be further added. An organic carboxylic acid or a phosphorus oxyacid or a derivative thereof. The above organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid or the like is preferred. The phosphorus oxyacid or its derivative, such as phosphoric acid, di-n-butyl phosphate, diphenyl phosphate or the like, or a derivative thereof, Phosphonic acid dimethyl phosphonate, phosphonic acid Phosphonic acid derivatives such as di-n-butyl ester, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate and the like, and phthalic acid derivatives such as phosphinic acid, phenylphosphinic acid, etc. Phosphonic acid-31 - (27) 1305201 and its esters and other phosphinic acid derivatives, of which phosphonic acid is preferred. The component (D) is generally in the range of 〇_〇1 to 5.0 parts by mass based on 100 parts by mass of the resin component (A) component containing the polymer compound (A1). Organic solvent The positive resist composition of the present invention is a resin component (A) containing the polymer compound (A 1 ), the acid generator component (B), and a nitrogen-containing organic compound (C). And any component added as necessary is uniformly dissolved in an organic solvent to obtain. The organic solvent may be used as it is, for example, one or two or more kinds of the above-mentioned solvents can be used. The aforementioned organic solvent, for example, a ketone such as r - butyrolactone, acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone or 2-heptanone or ethylene glycol or ethylene glycol monoacetate , diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate 'dipropylene glycol, or dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, single Polyols such as butyl ether or monophenyl ether and derivatives thereof, or cyclic ethers such as dioxane or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, An ester such as methyl pyruvate, ethyl pyruvate, methyl methoxypropionate or ethyl ethoxypropionate. The above organic solvent may be used singly or in the form of a mixture of two or more kinds of solvents. The ratio of the addition of propylene glycol monomethyl ether acetate (PGMEA) to the polar solvent may be appropriately determined by considering the compatibility of PGMEA with the polar-32-(28)(28)1305201 solvent. It is from 1:9 to 9:1, more preferably from 2: δ to 8:2. More specifically, when the polar solvent is ethyl lactate (EL), the mass of PGMEA : EL is preferably from 2:8 to 8:2, more preferably from 3:7 to 7:3. Further, in the organic solvent, for example, a mixed solvent obtained by selecting at least one of p-butyrolactone from PGME and EL is preferably used. At this time, the ratio of the former to the latter is 7 〇 : 3 〇 to 95 : 5. The amount of the component (E) is not particularly limited. Generally, the concentration can be applied to a substrate or the like, and the thickness of the coating film can be appropriately selected. The amount of the organic solvent used is generally a solid component in the photoresist composition. The concentration is from 2 to 20% by mass 'preferably in the range of from 5 to 15% by mass. Other Ingredients The photoresist composition of the present invention may be further suitably added with an additive which requires an increase in miscibility, such as a known dissolution inhibitor, an addition resin added to improve the performance of the photoresist film, a surfactant which enhances coating properties, A plasticizer, a stabilizer, a coloring agent, a halo preventing agent, and the like. Further, the compound (a) of the present invention can be contained in the positive resist composition in the form of a dissolution inhibitor. In the positive resist composition, the compound (a) has an effect of inhibiting dissolution in an alkali developing solution before exposure, and is subjected to deprotection treatment to cause alkali solubility after the exposure process. By having the foregoing compound, the pattern film of the photoresist pattern can be prevented from shifting, and a fine pattern of high resolution can be provided. In the conventional enhanced chemical resist, the introduction rate of the acid-33-(29)(29)1305201 dissociative dissolution inhibiting group is often increased to improve the resolution, but the problem of an increase in the proportion of defects is often caused. Further, conventionally, a tertiary alkyl group has been widely used as an acid dissociable dissolution inhibiting group, but there has been a problem that the type of the acid generator to be used is limited. That is, if an acid generator which produces a strong acid strength is not used, for example, when the anion portion has a sulfonate alkylsulfonate ion key, the acid dissociable dissolution inhibiting group (trialkyl group) is not sufficiently dissociated. And failed to get a good resolution. In other words, when an acid generator having a weak acid strength is used, the sensitivity is insufficient. On the other hand, in the positive-type resist composition of the present invention, the resolution can be improved without increasing the introduction rate of the acid-dissociable dissolution inhibiting group, and a good sensitivity can be obtained. In addition, it is also possible to achieve the goal of reducing line edge roughness (LER) and development defects. This is supposed to be an effect obtained by the structural unit (al) of the polymer compound (A1) having an acid dissociable dissolution inhibiting group which is easily dissociated by the action of an acid. In other words, the acid dissociable dissolution inhibiting group ' in the structural unit (a 1 ) of the polymer compound (A 1 ) is a group which is easily dissociated by the action of an acid, so that the alkali solubility of the exposed portion can be improved even if an acid is produced. When the acid produced by the agent is weak, the acid dissociable dissolution inhibiting group can also be sufficiently dissociated. Further, the acid generator which can also be used is more selective. Further, a sufficient resolution can be obtained by using a nonionic acid generator such as a diazomethane acid generator. Therefore, in particular, an immersion exposure process in which a lens and a photoresist layer are filled with a solvent having a refractive index higher than that of air at the time of exposure, etc., and a nonionic acid generator is preferably used based on a solvent contamination problem or the like. In the method, it is also suitable to use the positive photoresist composition of the present invention -34 - (30) 1305201

此外’本發明之正型光阻組成物中，結構單位（a 1 ) 之R3導入親水性基之情形及/或含有結構單位（a2 )時， 可提高對光阻圖型之基板的密著性，經由提高對鹼顯影液 之親和性而可得到降低顯影缺陷之效果。 本發明之正型光阻組成物極適合用於使用微影蝕刻對 半導體基板進行圖型描繪等製程。特別是於波長3 00nm ® 以下之光源，其中又以使用KrF、ArF、F2準分子雷射所 進行之微細圖型描繪等，皆可達成優良之解析性。其中又 以使用ArF準分子雷射之效果最佳。此外，對於電子線亦 屬有效。 (光阻圖型之形成方法） 以下，將對本發明之光阻圖型之形成方法作一說明。 即，首先於矽晶圓等基板上，將本發明之正型光阻組 成物使用旋轉塗佈機等進行塗覆後，進行預燒培。隨後使 用曝光裝置等，介由特定光罩圖型對正型光阻組成物之塗 膜進行選擇性曝光後，再進行PEB (曝光後加熱）。其次 使用鹼顯影液進行顯影處理後，再經由洗滌處理，將基板 上之顯影液與該顯影液所溶解之光阻組成物洗除後再予乾 燥。 前述步驟，可依一般公知方法進行。操作條件等，依 所使用之正型光阻組成物之組成內容與特性而作適當之設 定即可。 -35- (31) 1305201 又’曝光步驟所使用之光源並例如可使用波長3 00nm 以下之遠紫外線，具體而言例如可使用KrF準分子雷射、 ArF準分子雷射、F2準分子雷射、EUV (極紫外線）等、 電子線、軟X射線、X射線等。又，特別是以KrF準分 子雷射、ArF準分子雷射、ρ2準分子雷射爲更佳。 又’必要時’可於上述鹼顯影後再含有後燒培步驟亦 可’於基板與光阻組成物之塗佈層之間，可設置有機系或 Φ 無機系反射防止膜亦可。 預燒培之加熱溫度與曝光後加熱（PEB )之加熱溫 度’一般爲90 °C以上’爲形成具有良好矩形性之光阻圖 型時’特別是以分別爲9 0至1 4 0 °C、較佳爲9 0至1 3 0 °C 爲佳。又’於此溫度範圍時，具有可抑制微橋接現象之效 果。 【實施方式】 (合成例1 ) 本發明之化合物（a )之一例，如合成下述化學式 (1 )所示化合物1。 將29g之9-甲基丙烯醯基四環十二烷-4-羧酸溶解於 300mL四氫呋喃中，再加入I2.1g之三乙基胺。於室溫下 攪拌後，滴入溶解有9.5g之氯甲基乙基醚之四氫呋喃 1 OOmL，於室溫下攪拌1 2小時後，將析出之鹽濾除。由 所得濾液中濾除溶劑，使其溶解於200mL乙酸乙酯後， 再使用1 OOmL純水進行3次洗淨處理，將溶劑餾除後得 -36- (32) 1305201 無色油狀物（化合物1 )。所得化合物1使用紅外線吸收 圖譜（IR )、質子核磁共振圖譜（W-NMR )測定結果係 如下所示。 IR(cm—]) : 3049、 2957(C-H 伸縮）、1717 (C = 〇 伸縮）、1637 ( C = C 伸縮） i—NMRCCDCh、內部標準：四甲基矽烷）ppm: 1.05〜2‘70 (m、2 1 Η ) 、3.64 〜3.75 (m、2H ) ' 4.55~4.62Further, in the positive resist composition of the present invention, when R3 of the structural unit (a1) is introduced into the hydrophilic group and/or the structural unit (a2) is contained, the adhesion to the substrate of the resist pattern can be improved. The effect of reducing development defects can be obtained by improving the affinity for the alkali developing solution. The positive-type photoresist composition of the present invention is extremely suitable for use in a process of patterning a semiconductor substrate using photolithography. In particular, light sources with a wavelength of 300 nm or less, and fine pattern drawing using KrF, ArF, and F2 excimer lasers, can achieve excellent resolution. Among them, the use of ArF excimer lasers is the best. In addition, it is also valid for electronic wires. (Method of Forming Photoresist Pattern) Hereinafter, a method of forming a photoresist pattern of the present invention will be described. That is, first, the positive resist composition of the present invention is coated on a substrate such as a tantalum wafer using a spin coater or the like, and then pre-fired. Subsequently, an exposure apparatus or the like is used to selectively expose the coating film of the positive resist composition by a specific mask pattern, and then PEB (post-exposure heating) is performed. Next, after developing treatment using an alkali developing solution, the developing solution on the substrate and the photoresist composition dissolved in the developing solution are washed by a washing treatment, and then dried. The foregoing steps can be carried out in accordance with generally known methods. The operating conditions and the like may be appropriately set depending on the composition and characteristics of the positive resist composition used. -35- (31) 1305201 Further, the light source used in the exposure step can be, for example, a far ultraviolet ray having a wavelength of 300 00 nm or less. Specifically, for example, a KrF excimer laser, an ArF excimer laser, or an F2 excimer laser can be used. , EUV (extreme ultraviolet), etc., electronic lines, soft X-rays, X-rays, etc. Further, it is particularly preferable that a KrF quasi-molecular laser, an ArF excimer laser, and a ρ2 excimer laser are used. Further, if necessary, an organic or Φ inorganic antireflection film may be provided between the substrate and the coating layer of the photoresist composition after the alkali development. The heating temperature of the pre-firing and the heating temperature after exposure (PEB) 'generally 90 °C or more' is to form a photoresist pattern with good squareness', especially at 90 to 140 °C respectively. Preferably, it is preferably 90 to 130 ° C. Also in this temperature range, there is an effect of suppressing the microbridge phenomenon. [Examples] (Synthesis Example 1) An example of the compound (a) of the present invention is the synthesis of the compound 1 represented by the following chemical formula (1). 29 g of 9-methylpropenyltetracyclododecane-4-carboxylic acid was dissolved in 300 mL of tetrahydrofuran, and then 12.1 g of triethylamine was added. After stirring at room temperature, 100 mL of tetrahydrofuran in which 9.5 g of chloromethylethyl ether was dissolved was added dropwise thereto, and the mixture was stirred at room temperature for 12 hours, and then the precipitated salt was filtered. The solvent was filtered off from the obtained filtrate, dissolved in 200 mL of ethyl acetate, and then washed three times with 100 mL of pure water, and the solvent was distilled off to obtain -36-(32) 1305201 colorless oil (compound) 1 ). The results of the measurement of the obtained Compound 1 using an infrared absorption spectrum (IR) and a proton nuclear magnetic resonance spectrum (W-NMR) are shown below. IR(cm—]) : 3049, 2957 (CH stretching), 1717 (C = 〇 stretching), 1637 (C = C stretching) i-NMRCCDCh, internal standard: tetramethyl decane) ppm: 1.05~2'70 ( m, 2 1 Η ), 3.64 ～3.75 (m, 2H ) ' 4.55~4.62

(m、1H ) ' 5.20-5.3 8 ( m、2H ) 、5.48〜5.51 ( m、 1 Η ) 、6.02-6.08 ( m ' 1 Η )(m, 1H ) ' 5.20-5.3 8 ( m, 2H ) , 5.48~5.51 ( m, 1 Η ), 6.02-6.08 ( m ' 1 Η )

CH〇 〇CH〇 〇

0 0 [合成例2] 本發明之化合物（a )之一例，如合成下述化學式 (2 )所示化合物2。 於上述合成例1中之「29g之9-甲基丙烯醯基四環十 二烷-4-羧酸」以「27_6g之9-丙烯醯基四環十二烷-4·羧 @ J替代以外，其他皆依相同方法製得無色油狀物（化合 物2 )。所得化合物2使用紅外線吸收圖譜（IR )、質子 核磁共振圖譜（W-NMR)測定結果係如下所示。 IR(cm_1) : 3049、2958 (C— Η 伸縮）、1722 (C = 〇 伸縮）、1635 ( C = C 伸縮） 'Η - NMR ( CDC13 )、內部標準：四甲基矽烷） PPm ： 1.05-2.70 ( m、18H) 、3.65〜3.73 ( m、2H)、 -37- 13052010 [Synthesis Example 2] An example of the compound (a) of the present invention is the synthesis of the compound 2 represented by the following chemical formula (2). In the above Synthesis Example 1, "29 g of 9-methylpropenyltetracyclododecane-4-carboxylic acid" was replaced by "27_6 g of 9-propenylfluorenyltetracyclododecane-4·carboxy@J A colorless oil (Compound 2) was obtained by the same method. The obtained Compound 2 was analyzed by infrared absorption spectrum (IR) and proton nuclear magnetic resonance (W-NMR) as follows. IR (cm_1) : 3049 , 2958 (C-Η telescopic), 1722 (C = 〇 telescopic), 1635 (C = C telescopic) 'Η - NMR (CDC13), internal standard: tetramethyl decane) PPm : 1.05-2.70 (m, 18H) , 3.65~3.73 (m, 2H), -37- 1305201

7 5 〜5 . 8 0 、1H ) (合成例3 ) 本發明之化合物（a )之一例’如合成下述 (3 )所示化合物3。 將14g之9-甲基丙烯醯基四環十二烷-4-羧酵 300mL四氫呋喃中，再加入5.6g之三乙基胺。东 攪拌後，滴入溶解有10.7g之4-氧代-2-金剛烷基 醚之四氫呋喃100mL，於室溫下攪拌12小時後， 之鹽濾除。由所得濾液中濾除溶劑，使其溶解於 乙酸乙酯後，再使用10 OmL純水進行3次洗淨虔 溶劑餾除後得無色油狀物（化合物3)。所得化合 用紅外線吸收圖譜（IR )、質子核磁共振圖I N M R )測定結果係如下所示。 IR ( cm一 *) : 3049、 2938 ( C_H 伸縮） (C = 0 伸縮）、1 63 6 ( C = C 伸縮） NMR(CDC13、內部標準：四甲基矽烷： 1.05 〜2.80( m、30H) ' 4·15~4.25 (m、1H) 、4· (m、1Η) 5.25 〜5.38 (m、2Η) ' 5.48-5.52 ( m ' 6.0~6.02(m、1H) 化學式 :溶解於 ‘室溫下 :氯甲基 將析出 2 0 0 m L :理，將 物3使 I ( 'H- 、1717 ppm : 56〜4.62 1 Η )、 -38- (34) 13052017 5 to 5 . 8 0 , 1H ) (Synthesis Example 3) An example of the compound (a) of the present invention is as follows. A compound 3 represented by the following (3) is synthesized. 14 g of 9-methylpropenyltetracyclododecane-4-carboxyl fermentation in 300 mL of tetrahydrofuran was further added with 5.6 g of triethylamine. After stirring in the east, 100 mL of tetrahydrofuran in which 10.7 g of 4-oxo-2-adamantyl ether was dissolved was added dropwise thereto, and the mixture was stirred at room temperature for 12 hours, and then filtered. The solvent was filtered off from the obtained filtrate, and the mixture was dissolved in ethyl acetate, and then washed three times with 10 mL of purified water. The solvent was distilled off to give a colorless oil (comp. 3). The results of the measurement using the infrared absorption spectrum (IR) and the proton nuclear magnetic resonance spectrum I N M R were as follows. IR ( cm a*) : 3049, 2938 ( C_H stretching) (C = 0 stretching), 1 63 6 ( C = C stretching) NMR (CDC13, internal standard: tetramethyl decane: 1.05 to 2.80 (m, 30H) ' 4·15~4.25 (m, 1H), 4· (m, 1Η) 5.25 to 5.38 (m, 2Η) ' 5.48-5.52 ( m ' 6.0~6.02 (m, 1H) Chemical formula: dissolved at 'room temperature : chloromethyl will precipitate 2 0 m L : rationally, give 3 to I ( 'H- , 1717 ppm : 56~4.62 1 Η ), -38- (34) 1305201

(合成例4 ) 本發明之化合物（a )之一例，如合成下述化學式 φ ( 4 )所示化合物4。 將14g之9-甲基丙烯醯基四環十二烷-4-羧酸溶解於 3 00mL四氫呋喃中’再加入5_6g之三乙基胺。於室溫下 攪拌後，滴入溶解有9.9 g之氯甲氧環己烷之四氫呋喃 10 OmL，於室溫下攪拌12小時後，將析出之鹽濾除。由 所得濾液中濾除溶劑，使其溶解於200mL乙酸乙酯後， 再使用lOOmL純水進行3次洗淨處理，將溶劑餾除後得 無色油狀物（化合物4)。所得化合物4使用紅外線吸收 φ 圖譜（ΠΟ 、質子核磁共振圖譜（W-NMR )測定結果係 如下所示。 IR ( cm - 1 ) : 3049、2936 (C— Η 伸縮）、1717 (C = 〇 伸縮）、1637 ( C = C 伸縮） ^—NMRCCDCh、內部標準··四甲基砂院）ppm: 1.05〜2.70 ( m、28H ) 、3·50~3·6225 ( m、1Η )、 4.58-4.62 ( m ' 1H) ' 5.2 5-5.3 8 ( m &gt; 2H) ' 5.48-5.52 (m、]H) 、6.0〜6.02(m、1H) -39- (35) 1305201(Synthesis Example 4) An example of the compound (a) of the present invention is a compound 4 represented by the following chemical formula φ ( 4 ). 14 g of 9-methylpropenyltetracyclododecane-4-carboxylic acid was dissolved in 300 mL of tetrahydrofuran and 5-6 g of triethylamine was further added. After stirring at room temperature, 10 mL of tetrahydrofuran in which 9.9 g of chloromethoxycyclohexane was dissolved was added dropwise thereto, and the mixture was stirred at room temperature for 12 hours, and then the precipitated salt was filtered. The solvent was filtered off from the obtained filtrate, and the mixture was dissolved in ethyl acetate (200 mL), and then washed three times with 100 mL of purified water, and the solvent was distilled off to obtain a colorless oil (Comp. 4). The obtained compound 4 was measured by the infrared absorption φ spectrum (ΠΟ, proton nuclear magnetic resonance spectrum (W-NMR). The results are as follows. IR ( cm - 1 ) : 3049, 2936 (C - 伸缩 expansion), 1717 (C = 〇 expansion) ), 1637 ( C = C telescopic) ^ - NMRCCDCh, internal standard · tetramethyl sand court) ppm: 1.05~2.70 (m, 28H), 3·50~3·6225 (m, 1Η), 4.58-4.62 ( m ' 1H) ' 5.2 5-5.3 8 ( m &gt; 2H) ' 5.48-5.52 (m,]H) , 6.0~6.02 (m, 1H) -39- (35) 1305201

(合成例5) 本發明之高分子化合物（A 1 )之一例，如合成下述 • 化學式（6 )所示高分子化合物1。 將6_8g之上述合成例1所得之化合物1，與3.0g之 下述化學式（5)所示化合物溶解於5 OmL四氫呋喃中， 再加入0.30g之偶氮二異丁腈。經6小時迴流後，將反應 溶液滴入1公升η -庚烷中。 將析出之高分子化合物濾出，減壓乾燥後得白色之粉 體（高分子化合物1)。該高分子化合物1之分子量 (Mw)爲312〇〇。又，使用碳13(質量數13的碳之意， ® 以下相同）核磁共振圖譜（13 C -N M R )測定結果，得知化 學式（6)中之組成比（m: η)爲0.29: 0.71。(Synthesis Example 5) As an example of the polymer compound (A 1 ) of the present invention, the polymer compound 1 represented by the following chemical formula (6) is synthesized. 6 to 8 g of the compound 1 obtained in the above Synthesis Example 1 and 3.0 g of the compound of the following chemical formula (5) were dissolved in 50 mL of tetrahydrofuran, and 0.30 g of azobisisobutyronitrile was further added. After refluxing for 6 hours, the reaction solution was dropped into 1 liter of η-heptane. The precipitated polymer compound was filtered off and dried under reduced pressure to give a white powder (polymer compound 1). The polymer compound 1 had a molecular weight (Mw) of 312 Å. Further, using a nuclear magnetic resonance spectrum (13 C - N M R ) measurement result of carbon 13 (the mass of carbon 13 and the following is the same), it was found that the composition ratio (m: η) in the chemical formula (6) was 0.29: 0.71.

0 -40- (36) 13052010 -40- (36) 1305201

• ( (合成例6) 本發明之高分子化合物（A1)之一例，如合成下述 化學式（7 )所示高分子化合物2。 將7.1 g之上述合成例2所得之化合物2，與3.0 g之 上述化學式（5 )所示化合物溶解於5〇mL四氫呋喃中， 再加入0.3 2g之偶氮二異丁腈。經6小時迴流後，將反應 Φ 溶液滴入1公升η-庚烷中。 將析出之高分子化合物濾出，減壓乾燥後得白色之粉 體（高分子化合物 2)。該高分子化合物 2之分子量 (Mw )爲1 3 8 00。又，使用碳13核磁共振圖譜（13C-N M R )測定結果，得知化學式（7 )中之組成比（m ·· η ) 爲 0.33 : 0_67。 -41 - (37) 1305201(Synthesis Example 6) As an example of the polymer compound (A1) of the present invention, the polymer compound 2 represented by the following chemical formula (7) is synthesized. 7.1 g of the compound 2 obtained in the above Synthesis Example 2, and 3.0 g The compound of the above formula (5) was dissolved in 5 mL of tetrahydrofuran, and then 0.32 g of azobisisobutyronitrile was added. After refluxing for 6 hours, the reaction Φ solution was dropped into 1 liter of η-heptane. The precipitated polymer compound was filtered off and dried under reduced pressure to give a white powder (polymer compound 2). The molecular weight (Mw) of the polymer compound 2 was 1 3 8000. Further, a carbon 13 nuclear magnetic resonance spectrum (13C) was used. -NMR), it was found that the composition ratio (m ·· η ) in the chemical formula (7) was 0.33 : 0_67. -41 - (37) 1305201

Ο • ( (合成例7 ) 本發明之高分子化合物（A 1 )之一例，如合成前述 化學式（6 )所示高分子化合物3。 將6.0g之上述合成例1所得之化合物1，與2.0g之 上述化學式（5 )所示化合物溶解於50mL四氫呋喃中， 再加入0.24g之偶氮二異丁腈。經6小時迴流後，將反應 ^ 溶液滴入1公升η-庚烷中。 將析出之高分子化合物濾出，減壓乾燥後得白色之粉 體（高分子化合物3 )。該高分子化合物 3之分子量 (Mw )爲1 3 900。又，使用碳13核磁共振圖譜（13C-NMR )測定結果，得知化學式（6 )中之組成比（m : η ) 爲 0.59 : 0.41 。 (比較合成例1 ) 比較例爲合成下述化學式（9 )所示高分子化合物 4 〇 -42- (38) 1305201 將9_9g之下述化學式（8)所示化合物（2-甲基-2-金 剛烷基甲基丙烯酸酯），與6.0g之上述化學式（5)所示 化合物溶解於1 40mL四氫呋喃中，再加入〇.63g之偶氮異 丁腈。經1 2小時迴流後’將反應溶液滴入2公升η -庚烷 中〇 將析出之高分子化合物濾出，減壓乾燥後得白色之粉 體（高分子化合物_4)。該高分子化合物4之分子量 (Mw)爲8700。又’使用碳13核磁共振圖譜（13C-NMR )測定結果，得知化學式（9 )中之組成比（m : n ) 爲 0.41 : 0.59 。(Synthesis Example 7) An example of the polymer compound (A 1 ) of the present invention is a polymer compound 3 represented by the above chemical formula (6). 6.0 g of the compound 1 obtained in the above Synthesis Example 1 and 2.0 are used. The compound of the above formula (5) of g was dissolved in 50 mL of tetrahydrofuran, and then 0.24 g of azobisisobutyronitrile was added. After refluxing for 6 hours, the reaction solution was dropped into 1 liter of η-heptane. The polymer compound was filtered off and dried under reduced pressure to give a white powder (polymer compound 3). The molecular weight (Mw) of the polymer compound 3 was 1 3 900. Further, a carbon 13 nuclear magnetic resonance spectrum (13C-NMR) was used. As a result of the measurement, it was found that the composition ratio (m : η ) in the chemical formula (6) was 0.59 : 0.41. (Comparative Synthesis Example 1) The comparative example was a synthesis of the polymer compound 4 〇-42- represented by the following chemical formula (9). (38) 1305201 9-9 g of the compound of the following formula (8) (2-methyl-2-adamantyl methacrylate), and 6.0 g of the compound of the above formula (5) are dissolved in 140 mL of tetrahydrofuran. In addition, 63.63g of azoisobutyronitrile was added. After refluxing for 12 hours, 'will The polymer compound which precipitated was filtered out by dropping 2 liters of η-heptane into the solution, and dried under reduced pressure to obtain a white powder (polymer compound 4). The molecular weight (Mw) of the polymer compound 4 was 8,700. Further, using the carbon 13 nuclear magnetic resonance spectrum (13C-NMR), it was found that the composition ratio (m : n ) in the chemical formula (9) was 0.41 : 0.59 .

(8) (9) 實施例1 將有機系反射防止膜組成物「ARC-29」（商品名， 百利科學公司製），以旋轉塗佈器塗佈於矽晶圓上，再於· 熱壓板上進行205 °C、60秒間之燒培乾燥，形成膜厚度 77nm之有機系反射防止膜。 隨後，將具有後述表1組成內容之正型光阻組成物使 用旋轉塗佈器塗佈於上述有機反射防止膜上，並於熱壓板 -43- (39) 1305201 上進行1 1 〇°C、90秒間之預燒培（PAB )，經乾燥處理結 果，形成膜厚2 5 0nm之光阻膜。 隨後，使用ArF曝光裝置NSR-S302 (理光公司製， NA (開口數）=0.60，2/3輪帶），將 ArF準分子雷射 (1 9 3 nm )介由光罩圖型進行選擇性照射。 隨後，於1 1 、90秒間之條件下進行PEB處理， 再使用23 °C、2.38質量％四甲基銨氫氧化物水溶液進行 Φ 6 0秒之浸漬顯影，其後再經6 0秒水洗、乾燥，以形成光 阻圖型。(8) (9) Example 1 An organic anti-reflection film composition "ARC-29" (trade name, manufactured by Gabriel Scientific Co., Ltd.) was applied onto a tantalum wafer by a spin coater, and then heated. The platen was dried by baking at 205 ° C for 60 seconds to form an organic anti-reflection film having a film thickness of 77 nm. Subsequently, a positive-type resist composition having the composition of Table 1 described later was applied onto the above-mentioned organic anti-reflection film using a spin coater, and subjected to 1 1 〇 ° C on a hot plate-43-(39) 1305201. The pre-baked culture (PAB) in 90 seconds was dried to form a photoresist film having a film thickness of 250 nm. Subsequently, using an ArF exposure apparatus NSR-S302 (manufactured by Ricoh Co., Ltd., NA (number of openings) = 0.60, 2/3 wheel belt), the ArF excimer laser (1 3 3 nm) was selectively selected by the mask pattern. Irradiation. Subsequently, PEB treatment was carried out under conditions of 1 1 and 90 seconds, and immersion development was carried out for Φ 60 seconds using an aqueous solution of 23 ° C and 2.38 mass % tetramethylammonium hydroxide, followed by washing with water for 60 seconds. Dry to form a photoresist pattern.

其特性之評估係如表2所示。又，實施例2中’， PAB/PEB 爲 120°C /120°C。比較例 1 中，PAB/PEB 爲 120 °C /120°C 下表1所示酸產生劑之化合物（B-1)爲前述化學式 (B -1 )所示之化合物。 [表1] (A麵旨 (B)酸產生劑 (D)含氮有機化合物 有機溶劑 實施例1 高分子化合物1 TPS-PFBS 三乙醇胺 PGMEA (100質量份） (3質量份） (0.35質量份） (2350質量份） 實施例2 高分子化合物2 化合物(B-1) 三乙醇胺 PGMEA (]00質量份） (4.7質量份） (0.35質量份） (2350質量份） 比較例1 高分子化合物4 化合物(B—1) 三乙醇胺 PGMEA (100質量份） (4.7質量份） (0.35質量份） (2350質量份） TPS-PFBS :三苯基銃九氟丁烷磺酸酯 -44 - 1305201 (40) [表2] 解析度 感度 (L/S ) (mJ/cm2 ) 實施例1 1 1 Onm 24 實施例2 1 3 Onm 41 比較例1 未解像 — (感度） 對形成1 3 Onm的線路與空間爲1 : 1之曝光時間作爲 感度（EOP )，並以mJ/cm2 (能量）單位進行測定。 (解析度） 上述EOP之臨界解析度爲使用SEM照片進行硏判。 由上述結果得知，含有本發明高分子化合物之一例的 高分子化合物1、2之正型光阻組成物，無論所使用酸產 生劑之種類爲何，皆可以高解析度對光阻圖型進行解像。 又，酸產生劑使用所產生之酸強度較TPS-PFBS爲弱 之上述化學式（B-1 )的化合物之比較例1的正型光阻組 成物，其光阻圖型並未能解像。 如上所述般，本發明之新穎化合物與新穎高分子化合 物，即使使用所產生之酸強度較弱之酸產生劑時，亦可形 成具有優良解析度之光阻圖型，故極適合產業上使用。 -45-The evaluation of its characteristics is shown in Table 2. Further, in Example 2, PAB/PEB was 120 ° C / 120 ° C. In Comparative Example 1, the PAB/PEB was 120 °C / 120 °C. The compound (B-1) of the acid generator shown in the following Table 1 was a compound represented by the above chemical formula (B-1). (A) (B) Acid generator (D) Nitrogen-containing organic compound organic solvent Example 1 Polymer compound 1 TPS-PFBS Triethanolamine PGMEA (100 parts by mass) (3 parts by mass) (0.35 parts by mass) (2350 parts by mass) Example 2 Polymer compound 2 Compound (B-1) Triethanolamine PGMEA (] 00 parts by mass) (4.7 parts by mass) (0.35 parts by mass) (2350 parts by mass) Comparative Example 1 Polymer compound 4 Compound (B-1) Triethanolamine PGMEA (100 parts by mass) (4.7 parts by mass) (0.35 parts by mass) (2350 parts by mass) TPS-PFBS: Triphenylsulfonium nonafluorobutanesulfonate-44 - 1305201 (40 [Table 2] Resolution sensitivity (L/S) (mJ/cm2) Example 1 1 1 Onm 24 Example 2 1 3 Onm 41 Comparative Example 1 Unresolved - (sensitivity) For forming a line of 1 3 Onm The exposure time with a space of 1:1 is used as the sensitivity (EOP) and is measured in units of mJ/cm2 (energy). (Resolution) The critical resolution of the above EOP is determined using an SEM photograph. A positive-type photoresist composition containing the polymer compounds 1 and 2 as an example of the polymer compound of the present invention, regardless of Regarding the type of the acid generator, the photoresist pattern can be resolved with high resolution. Further, the acid generator is a compound of the above chemical formula (B-1) which is weaker than TPS-PFBS. The positive-type photoresist composition of Comparative Example 1 has a photoresist pattern which is not resolved. As described above, the novel compound of the present invention and the novel polymer compound are produced by using an acid having a weak acid strength. When the agent is used, it can form a photoresist pattern with excellent resolution, so it is very suitable for industrial use. -45-

Claims (1)

1305201 ⑴ 十、申請專利範圍 1. 一種下述式（I)所示化合物，1305201 (1) X. Patent application scope 1. A compound of the following formula (I), (式中，R1爲氫原子或低級烷基；R2爲 至15之烷基或脂肪族環式基，其可具有1種 結、羥基、羰基、酯基、與胺基所成群中所 基；111爲〇或1至3之整數）。 2. —種高分子化合物，其爲具有下述式 結構單位（al)之高分子化合物， (I) g原子數1 乂上由醚鍵 丨出之取代 (II)所示(wherein R1 is a hydrogen atom or a lower alkyl group; R2 is an alkyl group of 15 or an aliphatic cyclic group, which may have one type of a group, a hydroxyl group, a carbonyl group, an ester group, and a group in the group of an amine group. ; 111 is 〇 or an integer from 1 to 3.) 2. A polymer compound which is a polymer compound having the following structural unit (al), (I) a number of g atoms of 1 乂 substituted by an ether bond (II) (Π) (式中，R1爲氫原子或低級烷基；R3爲 至1 5之烷基或脂肪族環式基，其可具有1種 結、羥基、羰基、酯基、與胺基所成群中所 原子數！ 上由醚鍵 出之取代 -46 - (2) 1305201 基；n2爲0或1至3之整數）。 3 .如申i靑專利範圍桌2項之闻分子化合物，其中前 述結構單位（a 1 )之比例爲1 〇莫耳％以上。 4.如申請專利範圍第2項之高分子化合物，其尙含 有具內酯之單環或多環式基之（低級烷基）丙烯酸酯 所衍生之結構單位（a2 )。 5 ·如申請專利範圍第4項之高分子化合物，其中前 Φ 述結構單位（a 1 )之比例爲1 0至8 0莫耳％ ，前述結構單 位（a2 )之比例爲20至90莫耳％ 。 6-如申請專利範圍第2項之高分子化合物，其質量 平均分子量爲2000至50000。 7. —種正型光阻組成物，其爲含有申請專利範圍第 2項之高分子化合物（A1)，與經由曝光產生酸之酸產生 劑成份（B )。 8 ·如申請專利範圍第7項之正型光阻組成物，其中 ^ 前述酸產生劑成份（B)爲含有1種以上由二偶氮甲烷系 酸產生劑與鎗鹽系酸產生劑所成群中所選出者。 9.如申請專利範圍第7項之正型光阻組成物，其尙 含有含氮有機化合物（C)。 1 〇· —種光阻圖型之形成方法，其爲包含使用申請專 利範圍第7項之正型光阻組成物於基板上形成正型光阻 膜’並對該正型光阻膜進行選擇性曝光處理後，進行曝光 後加熱（PEB )處理，再施以顯影處理以形成光阻圖型之 方法。 -47-(Π) (wherein R1 is a hydrogen atom or a lower alkyl group; R3 is an alkyl group of 15 or an aliphatic cyclic group, which may have one type of a group, a hydroxyl group, a carbonyl group, an ester group, and an amine group. The number of atoms in the group! The substitution by the ether bond -46 - (2) 1305201 base; n2 is 0 or an integer from 1 to 3). 3. The molecular compound of the second item of the patent range table, wherein the ratio of the aforementioned structural unit (a 1 ) is 1% or more. 4. The polymer compound of claim 2, wherein the oxime comprises a structural unit (a2) derived from a monocyclic or polycyclic (lower alkyl) acrylate having a lactone. 5. The polymer compound according to item 4 of the patent application, wherein the ratio of the structural unit (a 1 ) of the former Φ is 10 to 80 mol%, and the ratio of the structural unit (a2) is 20 to 90 m. %. 6- The polymer compound of the second aspect of the patent application has a mass average molecular weight of from 2,000 to 50,000. A positive-type resist composition comprising the polymer compound (A1) of the second aspect of the patent application and an acid generator component (B) which generates an acid by exposure. 8. The positive-type resist composition according to item 7 of the patent application, wherein the acid generator component (B) contains one or more kinds of a diazomethane-based acid generator and a gun salt-based acid generator. The selected one in the group. 9. The positive-type photoresist composition according to item 7 of the patent application, wherein the ruthenium contains a nitrogen-containing organic compound (C). 1 〇 · A method for forming a photoresist pattern, which comprises forming a positive photoresist film on a substrate using a positive photoresist composition of claim 7 and selecting the positive photoresist film After the exposure treatment, a post-exposure heating (PEB) treatment is performed, followed by a development treatment to form a photoresist pattern. -47-