TW201202842A - Radiation-sensitive resin composition and pattern forming method - Google Patents
Radiation-sensitive resin composition and pattern forming method Download PDFInfo
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- TW201202842A TW201202842A TW100110612A TW100110612A TW201202842A TW 201202842 A TW201202842 A TW 201202842A TW 100110612 A TW100110612 A TW 100110612A TW 100110612 A TW100110612 A TW 100110612A TW 201202842 A TW201202842 A TW 201202842A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
Abstract
Description
201202842 六、發明說明： 【發明所屬之技術領域】 本發明爲有關敏輻射線性樹脂組成物及使用其之有機 溶劑顯影圖型之形成方法，更詳細言之，爲相對於複數次 ' 之曝光，無須進行前置之曝光後燒焙或顯影等，而可以連 '續地進行隨後之曝光的曝光方法，特別是使用於以雙重曝 光所進行之圖型描繪（patterning )，亦適合使用於使用 水等之浸潤媒體所進行之浸潤式曝光製程的敏輻射線性樹 脂組成物及使用其之光阻圖型之形成方法。 【先前技術】 於代表積體電路元件製造之微細加工區域中，爲得到 更高之集積度時，最近則必須進展到可以對〇. 1 〇μηι以下層 級進行微細加工之微影蝕刻技術。今後將更要求更微細之 圖型的形成（例如，線寬爲45nm左右之微細光阻圖型）。 一般爲達成該形成微細圖型之手段，多使用將曝光裝置之 光源波長予以短波長化（ArF準分子雷射（波長193nm)) 或，增大透鏡之開口數（ΝΑ )等。但是，於光源波長之 短波長化時，則需使用新的高價曝光裝置。又，增大透鏡 之開口數（ΝΑ )，因解析度與焦點深度具有取捨（tradeoff) 關係， 故會產 生即使 提高解 析度時 ，其 焦點深 度會降 低之問題。 最近，已有提出可解決前述問題之微影蝕刻技術的報 告，即浸潤式曝光（液體浸漬微影蝕刻）法之方法。但是 -5- 201202842 ，浸潤式曝光法所得達到之曝光技術，亦僅止於45ηηι半間 距（half pitch) (hp)爲臨界點，故必須將技術開發至更 微細加工所必要之32nmhp世代。近年來，伴隨該些裝置之 複雜化、高密度化之要求，已有提出於重複描繪製程（DP )，或，重複曝光製程（DE)所得之疏線路圖型或獨立槽 型圖型中，以間隔半周期之方式重合，以進行32nm之線路 •與•空間（LS )之圖型描繪的技術（非專利文獻1 )。 上述DE，可對一層光阻塗膜進行至少2次之曝光以形成圖 型(patterning) 〇 具體例如，以形成有40nm之接觸孔（CH )作爲形成 圖型（patterning)之一例時，爲使用正型光阻組成物，例 如先前曝光40nm之第1個LS圖型，隨後再以對第1個LS爲 與LS圖型垂垂直交叉錯之方式進行第2次之曝光處理，即 可形成具有40ηηι之微細接觸孔。 此外，亦有顯影液使用酸系之有機溶劑的顯影製程（ 專利文獻1 )。使用有機溶劑之顯影製程，係指溶解對有 機溶劑爲未曝光之部份，而形成曝光部爲難溶之圖型的製 程。 〔先前技術文獻〕 〔專利文獻〕 〔專利文獻1〕曰本特許第3869306號 〔非專利文獻〕201202842 VI. Description of the Invention: [Technical Field] The present invention relates to a method for forming a linear composition of a radiation sensitive resin and an organic solvent developing pattern using the same, and more specifically, in comparison to a plurality of exposures, It is not necessary to perform pre-exposure baking, development or the like, and the exposure method for subsequent exposure can be continuously performed, in particular, for patterning by double exposure, and also for use of water. A method of forming a radiation-sensitive linear resin composition of an immersion exposure process by an infiltration medium and a method for forming a photoresist pattern using the same. [Prior Art] In order to obtain a higher degree of accumulation in a microfabricated region in which an integrated circuit component is manufactured, it has recently been advanced to a microlithography etching technique capable of microfabricating a layer below 〇.1 〇μηι. In the future, the formation of a finer pattern (for example, a fine photoresist pattern having a line width of about 45 nm) will be required. In general, in order to achieve the formation of the fine pattern, the wavelength of the light source of the exposure device is often shortened (ArF excimer laser (wavelength 193 nm)) or the number of openings of the lens (ΝΑ) is increased. However, when the wavelength of the light source is short-wavelength, a new high-priced exposure apparatus is required. Further, by increasing the number of apertures (ΝΑ) of the lens, since the resolution has a tradeoff relationship with the depth of focus, there is a problem that the depth of focus is lowered even when the degree of resolution is increased. Recently, a report of a lithography technique that solves the aforementioned problems, that is, a method of immersion exposure (liquid immersion lithography) has been proposed. However, -5-201202842, the exposure technique achieved by the immersion exposure method is only limited to the 45 ηη half pitch (hp), so the technology must be developed to the 32nmhp generation necessary for finer processing. In recent years, with the complication and high density requirements of these devices, it has been proposed in the repeated drawing process (DP), or the repeated exposure process (DE) to obtain the wiring pattern or the independent groove pattern. A technique of patterning a line and a space (LS) of 32 nm in a manner of overlapping half-cycles (Non-Patent Document 1). In the above DE, a photoresist coating film may be exposed to at least two times to form a pattern. Specifically, for example, when a 40 nm contact hole (CH) is formed as an example of patterning, it is used. The positive resist composition, for example, the first LS pattern previously exposed to 40 nm, and then subjected to the second exposure process in such a manner that the first LS is perpendicularly intersected with the LS pattern, thereby forming 40ηηι fine contact hole. Further, there is also a developing process using an acid-based organic solvent for the developer (Patent Document 1). The developing process using an organic solvent refers to a process of dissolving a portion in which the organic solvent is not exposed, and forming a pattern in which the exposed portion is insoluble. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent No. 3869306 [Non-Patent Document]
〔非專利文獻 1〕SPIE2006 Vol.6153 61531K 201202842 【發明內容】 〔發明所欲解決之問題〕 但是，前述數個提案的製程中，對於適合使 潤式曝光製程，且使用有機溶劑進行顯影之圖型 體材料之提案，仍爲尙未完備之現狀。 本發明，即是鑑於該些以往技術所具有之問 出者，而以提出於前述問題中，可使用於以有機 顯影之圖型描繪，且適合使用於浸潤式曝光製程 線性樹脂組成物。 〔解決問題之手段〕 本發明者們對於達成上述目的經過深入硏究 知樹脂成分於含有特定構成成分時，即可達成上 ，因而完成本發明。 即，本發明爲一種使用於以有機溶劑（X) 的光阻圖型之形成方法中所使用之敏輻射線性樹 ，其爲含有聚合物（A)，與敏輻射線性酸產生齊 與溶劑（C)，其特徵爲，上述聚合物（A)爲含 (1-1)至下述式（1-7)所選出之至少1個之重複 )之敏輻射線性樹脂組成物。 用該些浸 描繪的具 題點所提 溶劑進行 之敏輻射 結果，得 述之目的 進行顯影 脂組成物 11(B)， 有下述式 單位（a2 201202842 【化1】[Non-Patent Document 1] SPIE2006 Vol.6153 61531K 201202842 [Disclosure] [Problems to be Solved by the Invention] However, in the processes of the above-mentioned several proposals, the development is suitable for the wet exposure process and the development using an organic solvent. The proposal for the body material is still in the status quo. SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and can be used for drawing in an organic developing mode, and is suitable for use in an infiltrating exposure process linear resin composition. [Means for Solving the Problem] The inventors of the present invention have achieved in order to achieve the above object, and it is understood that the resin component can be obtained when a specific component is contained, and thus the present invention has been completed. That is, the present invention is a linear tree of a sensitive radiation used in a method for forming a photoresist pattern of an organic solvent (X), which comprises a polymer (A), which is conjugated with a linear solvent of a sensitive radiation ( C), characterized in that the polymer (A) is a radiation sensitive linear resin composition containing (1-1) to at least one selected from the following formula (1-7). The result of the sensitive radiation by the solvent extracted by the immersion is carried out for the purpose of developing the lipid composition 11(B), which has the following formula (a2 201202842 [Chemical 1]
(1-5) (1-6) (式（1-1)〜（1-7)中’ R1爲氫原子、甲基，或三氟甲 基；R2爲氫原子或碳數1〜4之取代或未取代之烷基；R3爲 氫原子或甲氧基；A爲單鍵、伸甲基 '碳數2〜10之直鏈狀 或支鏈狀之2價之烴基，或具有氧原子或硫原子之2價之連 結基；B爲氧原子或伸甲基；R4爲單鍵或2價之連結基；R5 爲具有環狀碳酸酯結構之1價之有機基；p爲2〜3之整數， m爲0或1 ’ η爲0或1 ;但’ η爲0時’ A不爲單鍵且b不爲伸 甲基）。 上述聚合物（A)，以再含有下述式（2-1)至式（2_ 4 )所選出之至少1個之重複單位（a3 )爲更佳。 -8 - 201202842(1-5) (1-6) (In the formula (1-1) to (1-7), 'R1 is a hydrogen atom, a methyl group, or a trifluoromethyl group; and R2 is a hydrogen atom or a carbon number of 1 to 4; a substituted or unsubstituted alkyl group; R 3 is a hydrogen atom or a methoxy group; A is a single bond, a methyl or a linear or branched divalent hydrocarbon group having a carbon number of 2 to 10, or an oxygen atom or a divalent linking group of a sulfur atom; B is an oxygen atom or a methyl group; R4 is a single bond or a divalent linking group; R5 is a monovalent organic group having a cyclic carbonate structure; p is 2 to 3 An integer, m is 0 or 1 'η is 0 or 1; but 'when η is 0' A is not a single bond and b is not a methyl group). The polymer (A) is more preferably a repeating unit (a3) further containing at least one selected from the following formulas (2-1) to (2-4). -8 - 201202842
(2-1)(2-1)
(式（2-1)〜（2-4)中，R6爲氫原子、三氟甲基，或碳 數1〜3之烷基；R7爲分別獨立之氫原子或羥基；R8爲碳數 1〜5之直鏈狀或支鏈狀之羥烷基；L爲可被碳數1〜5之烷 基所取代之碳數1〜5之直鏈狀或支鏈狀之2價之烴基；Μ爲 下述式（Ml)至式（Μ4)之任一所示之基；q爲1〜3之整 數）。 【化3】(In the formulae (2-1) to (2-4), R6 is a hydrogen atom, a trifluoromethyl group, or an alkyl group having 1 to 3 carbon atoms; R7 is an independently hydrogen atom or a hydroxyl group; and R8 is a carbon number of 1 a linear or branched hydroxyalkyl group of ～5; L is a linear or branched divalent hydrocarbon group having 1 to 5 carbon atoms which may be substituted by an alkyl group having 1 to 5 carbon atoms; It is a group represented by any one of the following formulas (M1) to (4); q is an integer of 1 to 3). [化3]
(M1 ) (M2) (M3) (M4) 上述聚合物（A)，以再含有下述式（3)所表示之重 複單位（a 1 )爲佳。 -9 - R1(M1) (M2) (M3) (M4) The above polymer (A) preferably contains a repeating unit (a 1 ) represented by the following formula (3). -9 - R1
201202842 【化4】 -f CH2—201202842 【化4】 -f CH2—
C —O / <5 X j (3) 0 、C — R9 R9 R9 (式（3)中，R1爲氫原子、甲基或三氟甲基；R9 獨立之碳數1〜4之直鏈狀或支鏈狀之烷基，或碳婁 之1價之脂環式烴基或其衍生物。但，任意2個之R9 鍵結，形成碳數4〜20之2價之脂環式烴基或其衍生！| 本發明爲包含，於具備有於基板上塗佈敏輻射 脂組成物以形成光阻層之光阻層形成步驟，與介由 以輻射線照射該光阻層之曝光步驟，與以有機溶齊 進行顯影之顯影步驟的光阻圖型之形成方法中，上 射線性樹脂組成物爲該該敏輻射線性樹脂組成物之 型之形成方法。 又，上述曝光步驟中，於曝光後，以持續進行 佳。 上述有機溶劑（X )，以由酮系溶劑、酯系溶 系溶劑、醯胺系溶劑、醚系溶劑及烴系溶劑所成群 出之至少1個之溶劑爲佳。 上述曝光步驟中，使用光遮罩形成線路•與. 型所進行之第1之曝光及第2之曝光，以使上述第1 圖型與上述第2之曝光圖型相互交叉者爲佳。 爲相互 ¥ 4 〜2 0 可相互 勿）° 線性樹 光遮罩 I ( X ) 述敏輻 光阻圖 曝光爲 劑、醇 中所選 空間圖 之曝光 -10- 201202842 〔發明之效果〕 使用本發明之敏輻射線性樹脂組成物之圖型之形成方 法，其經由曝光後，可使產生酸之曝光部形成極性變化， 及使其對於有機溶劑（X )形成難溶化，其結果，將可以 有機溶劑顯影容易且確實地形成圖型（Patterning)。 其中，極性變化係指作爲樹脂成分之聚合物（A )中 的酸解離性基產生解離，而使酸解離性基於解離前與後之 極性產生變化之意。 本發明之敏輻射線性樹脂組成物及使用其之光阻圖型 之形成方法，於使用DE進行圖型描繪中，無須使用DP等 第2光阻組成物，經由對光阻層進行複數次曝光處理時即 可形成接觸孔圖型，就控制之精度•產能等觀點，其較DP 更爲優良。又，浸潤式曝光製程中亦適合採用。 〔實施發明之形態〕 以下，將說明本發明之實施形態，但本發明並不受以 下之實施形態所限定。於不超出本發明之主旨之範圍，基 於該業者通常之知識，對以下之實施形態進行適當之變更 、加入改良等皆屬於本發明之範圍。 <光阻圖型之形成方法〉 本發明之光阻圖型之形成方法之一實施形態，將使用 圖面進行說明。又，本說明書中，「線路圖型」係指光阻 -11 - 201202842 圖型中，具有線路部分與空間部分的LS圖型。 (1 )於基板上形成光阻層之步驟 圖1爲，於基板1上形成光阻層2後之狀態例示之 模式圖。 基板1，並未有特定之內容，例如，可使用5夕晶 鋁所被覆之晶圓等以往公知之基板。又，爲引導出敏 線性樹脂組成物的最大潛在能力時，例如，可如特公 1 2452號公報或特開昭5 9-9344 8號公報等所揭示般， 使用之基板上形成有機系或無機系之抗反射膜。 光阻層2，可將敏輻射線性樹脂組成物塗佈於基 之方式形成。敏輻射線性樹脂組成物，爲後述本發明 輻射線性樹脂組成物。塗佈之方法，並未有特定之內 其可使用回轉塗佈、流動塗佈、滾筒塗佈等適當之塗 段進行。又，所形成之光阻層2之厚度並未有特別限 通常爲10〜lOOOnm，又以丨0〜500nm爲佳。 又，塗佈敏輻射線性樹脂組成物後，必要時，可 預燒焙（以下，亦稱爲「PB」）之方式使塗膜中之溶 發。PB之加熱條件，可由敏輻射線性樹脂組成物3之 組成作適當之選擇，通常爲30〜200°C左右，又以 15 0°C爲佳❶ 此外，爲防止環境雰圍中所含之鹼性雜質等之影 例如’可如特開平5- 1 88 598號公報等所揭示般，光阻 上設置保護膜。又，爲防止由光阻層流出酸產生劑等 截面 圓、 輻射 平6- 於所 板上 之敏 容， 佈手 定， 使用 劑揮 添加 50〜 響， 層上 ，例 -12- 201202842 如，可如特開2005 -3 523 84號公報等所揭示般，於光阻層 上設置浸潤用保護膜。又，亦可合倂使用前述技術。 (2 )曝光步驟 圖2所示般，使用敏輻射線性樹脂組成物，對於基板】 上形成光阻層2後所用之區域介由特定之LS圖型遮罩，任 意地介由水等浸潤液，而由平面圖之上方對曝光部3進行 曝光。 再如圖3所示般，隨後以對第丨之曝光部3爲交叉之方 式對第2之曝光部4由平面圖之上方進行曝光。第〗之曝光 部3與第2之曝光部4以垂直交叉者爲佳。經由垂直交叉， 可容易於曝光部3與曝光部4所圍之未曝光部5中，形成正 圓形之接觸孔圖型。又，經使用點狀圖型之遮罩，亦可經 由1次之曝光而形成接觸孔。又，曝光之際，可任意地介 由水或氟系惰性液體等之浸潤液。 曝光所使用之輻射線’可依敏轄射線性樹脂組成物所 含有之敏幅射線性酸產生劑（B)(以下，亦稱爲「酸產 生劑（B )」）之種類，由紫外線、遠紫外線、χ線、荷電 粒子線等作適當地選擇。其中又以ArF準分子雷射（波長 193nm)或KrF準分子雷射（波長248nm)所代表之遠紫外 線爲佳’就ArF準分子雷射（波長I93nm )而言，以遠紫外 線爲特佳。 曝光量等之曝光條件，可配合敏輻射線性樹脂組成物 之添加組成或添加劑之種類等作適當之選擇。 -13- 201202842 又，曝光後以進行加熱處理之燒焙（以下，亦稱 P E B」）處理爲佳。實施p E B處理時，可使敏輻射線 脂組成物中之酸解離性基或酸不穩定基的解離反應圓 進行。P EB之溫度條件，可配合敏輻射線性樹脂組成 添加組成作適當之選擇，通常爲3 0〜2 0 0 °C，又以 17〇°C爲佳。 (3 )顯影步驟 曝光步驟後，使用有機溶劑（X )進行顯影，於 上形成接觸孔圖型。 有機溶劑（X )之較佳例示，例如可使用酮系溶 酯系溶劑、醇系溶劑、醚系溶劑、醯胺系溶劑等極性 ，及烴系溶劑。 酮系溶劑例如，1-辛酮、2-辛酮、1-壬酮、2-壬 丙酮、4-庚酮、2-己酮、二異丁酮、環己酮、甲基環 、苯基丙酮、甲基乙基酮、甲基異丁酮等。 酯系溶劑例如，乙酸甲酯、乙酸丁酯、乙酸乙酯 酸異丙酯、乙酸戊酯、丙二醇單甲基醚乙酸酯、乙二 乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、二乙二醇 基醚乙酸酯、乙基-3-乙氧基丙酸酯、3-甲氧基丁基乙 、3-甲基-3-甲氧基丁基乙酸酯、甲酸甲酯、甲酸乙酯 酸丁酯、甲酸丙酯、乳酸乙酯、乳酸丁酯、乳酸丙酯〗 醇系溶劑例如，甲醇、乙醇、η-丙醇、異丙醇、 醇、sec -丁醇、tert -丁醇、異丁醇、η·己醇、η -庚醇 爲「 性樹 滑地 物之 50〜 基板 劑、 溶劑 酮、 己酮 、乙 醇單 單乙 酸酯 、甲 等。 η-丁 :乙 -14- 201202842 二醇、三乙二醇等之二醇系溶劑，或乙二醇 二醇單甲基醚、乙二醇、丙二醇、二乙二醇 乙二醇單乙基醚、甲氧基甲基丁醇等之二醇丨 醚系溶劑例如，上述二醇醚系溶劑以外 、四氫呋喃等。 醯胺系溶劑，例如N-甲基-2-吡咯啶酮 乙醯胺、N，N-二甲基甲醯胺等。 烴系溶劑例如，甲苯、二甲苯等之芳香 戊烷、己烷、辛烷、癸烷等之脂肪族烴系溶； 該些有機溶劑（X)之中，又以乙酸丁 酯、乙酸戊酯、甲基戊酮爲佳。上述之有機 可將複數混合亦可，或與上述以外之溶劑或 可。 (4)洗滌步驟 顯影後之洗滌.步驟，爲使用含有由烷系 劑、酯系溶劑、醇系溶劑、醯胺系溶劑及醚 之至少1種類之有機溶劑的洗滌液進行洗淨 爲，於顯影後，使用含有由酮系溶劑、酯系 劑、醯胺系溶劑所選出之至少1種類之有機 進行洗淨之步驟。更佳者爲，於負型顯影後 系溶劑或酯系溶劑之洗滌液進行洗淨之步驟 於負型顯影後，使用含有碳數6〜8之1價醇 洗淨之步驟。其中，負型顯影後之洗滌步驟 單甲基醚、丙 單甲基醚、三 魅系溶劑等。 ，例如二噁烷 、Ν ,Ν ·二甲基 族烴系溶劑， 剖。 酯、乙酸異丙 i溶劑（X )， 水混合使用亦 溶劑、酮系溶 系溶劑所選出 爲佳。較佳者 溶劑、醇系溶 溶劑的洗滌液 ，使用含有醇 。特佳者爲， 的洗漉液進行 所使用之碳數 -15- 201202842 6〜8之1價醇，例如直鏈狀、支鏈狀、環狀之1價醇等，具 體而言，例如，可使用1-己醇、1-庚醇、1-辛醇、2-己醇 、2-庚醇、2_辛醇、3_己醇、3-庚醇、3 -辛醇、4_辛醇、 苄醇等，較佳爲1-己醇、2-己醇、2-庚醇。 上述洗滌液之各成分，可將多數混合使用亦可，或與 上述以外之有機溶劑混合使用亦可。洗滌液中的含水率， 以1〇質量％以下爲佳，更佳爲5質量％以下，特佳爲3質量％ 以下。含水率爲1 0質量％以下時，可得到良好之顯影特性 〇 洗滌液中，可再適當添加界面活性劑使用。 本發明之光阻圖型之形成方法，如圖3所示般，以將 光阻圖型之線路部相互交叉之方式形成爲佳。相互交叉之 部分，爲使用有機溶劑（X)進行顯影而於基板上形成接 觸孔圖型。 <敏輻射線性樹脂組成物> 敏輻射線性樹脂組成物，爲受到經由曝光而由敏輻射 線性酸產生劑所產生之酸的作用，使存在於組成物中之酸 解離性蕋或酸不穩定基解離，生成羧基，其結果，可降低 曝光部對於有機溶劑（X)之溶解性，使未曝光部經由有 機溶劑（X )溶解、除去，而形成圖型。特別是適合形成 接觸孔圖型。以下，將對本發明之敏輻射線性樹脂組成物 進行說明。 當該敏輻射線性樹脂組成物爲含有，含有具有酸不穩 -16- 201202842 定基之重複單位的聚合物（A)，與酸產生劑（B) ’與溶 劑（C ) 〇 又，本說明書中所稱「酸不穩定基」與「酸解離性基 」，係指可經由酸而解離之基，並非特別指爲任何相異之 基。具有酸不穩定基或酸解離性基，而對有機溶劑（X ) 爲可溶之聚合物，爲經由酸之作用而使該酸不穩定基或酸 解離性基解離形成羧基，且對有機溶劑（X)爲不溶或難 溶之聚合物。 <聚合物（A ) > 聚合物（A)爲，含有上述式（1-1)至下述式（1-7 )所選出之至少1個之重複單位（a2 )。 (i )重複單位（a2 ) 重複單位（a2 )，爲使分別對應於下述式（1 a- 1 )〜 下述式（la-7 )所表示之單體進行聚合而得。 【化5】C —O / <5 X j (3) 0 , C — R9 R9 R9 (In the formula (3), R1 is a hydrogen atom, a methyl group or a trifluoromethyl group; and R9 is a linear chain having a carbon number of 1 to 4 independently. a monovalent alicyclic hydrocarbon group or a derivative thereof, wherein any two of R9 are bonded to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or Derived from the present invention| The present invention includes a step of forming a photoresist layer having a composition for coating a radiation sensitive grease on a substrate to form a photoresist layer, and an exposure step of irradiating the photoresist layer with radiation, In the method for forming a resist pattern of a developing step of developing by organic solvent, the upper ray resin composition is a method of forming the type of the sensitive radiation linear resin composition. Further, in the above exposure step, after the exposure Preferably, the organic solvent (X) is at least one solvent selected from the group consisting of a ketone solvent, an ester solvent, a guanamine solvent, an ether solvent, and a hydrocarbon solvent. In the exposure step, the first exposure and the second exposure performed by the line and the type are formed using a light mask to make the above 1 The pattern is the same as the above-mentioned second exposure pattern. It is better to mutually cross each other. For each other, ¥4 to 2 0 can not be each other.) Linear tree light mask I ( X ) The light-sensitive photoresist pattern is exposed to the agent and alcohol. Exposure of Selected Space Map - 201202842 [Effect of the Invention] The method for forming a pattern of the sensitive radiation linear resin composition of the present invention, after exposure, can cause a change in polarity of an exposed portion where acid is generated, and This forms an insoluble solubility in the organic solvent (X), and as a result, it is possible to develop an organic solvent easily and reliably to form a pattern. Here, the polarity change means that the acid dissociable group in the polymer (A) as a resin component is dissociated, and the acid dissociation is changed based on the polarity before and after the dissociation. The method for forming a sensitive radiation linear resin composition of the present invention and a photoresist pattern using the same, in the pattern drawing using DE, does not need to use a second photoresist composition such as DP, and performs multiple exposures on the photoresist layer. The contact hole pattern can be formed during processing, and it is superior to DP in terms of control accuracy and productivity. Also, it is suitable for use in the immersion exposure process. [Mode for Carrying Out the Invention] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. It is within the scope of the invention to make appropriate modifications, additions, and the like to the embodiments described below without departing from the scope of the invention. <Formation method of photoresist pattern> An embodiment of the method for forming a photoresist pattern of the present invention will be described using the drawings. In addition, in this specification, "line pattern" refers to the LS pattern of the line portion and the space portion in the pattern of the photoresist -11 - 201202842. (1) Step of Forming Photoresist Layer on Substrate Fig. 1 is a schematic view showing a state in which the photoresist layer 2 is formed on the substrate 1. The substrate 1 is not particularly limited. For example, a conventionally known substrate such as a wafer coated with a bismuth aluminum can be used. Further, in order to guide the maximum potential of the linear resin composition, for example, an organic system may be formed on the substrate to be used, as disclosed in Japanese Patent Publication No. Hei. No. 1 2452 or JP-A-59-9344 Inorganic anti-reflective film. The photoresist layer 2 can be formed by applying a radiation sensitive linear resin composition to a substrate. The radiation sensitive linear resin composition is a radiation linear resin composition of the present invention to be described later. The coating method is not particularly limited, and it can be carried out by using a suitable coating section such as rotary coating, flow coating, or roll coating. Further, the thickness of the photoresist layer 2 to be formed is not particularly limited to 10 to 100 nm, and is preferably 0 to 500 nm. Further, after the radiation sensitive linear resin composition is applied, if necessary, it can be preliminarily baked (hereinafter also referred to as "PB") to dissolve the coating film. The heating condition of PB can be appropriately selected from the composition of the sensitive radiation linear resin composition 3, usually about 30 to 200 ° C, and preferably 150 ° C. In addition, in order to prevent the alkalinity contained in the environmental atmosphere For example, a protective film can be provided on the photoresist as disclosed in Japanese Laid-Open Patent Publication No. Hei. In addition, in order to prevent the cross-section of the acid generator from flowing out of the photoresist layer, and to radiate the sensitization on the plate, the cloth is fixed, and the agent is added with 50~ ring, on the layer, for example, -12-201202842, A protective film for wetting is provided on the photoresist layer as disclosed in Japanese Laid-Open Patent Publication No. 2005-3 523 84. Moreover, the aforementioned techniques can also be used in combination. (2) Exposure step As shown in Fig. 2, the sensitive radiation linear resin composition is used, and the region used for forming the photoresist layer 2 on the substrate is masked by a specific LS pattern, optionally interposed with water or the like. The exposure portion 3 is exposed from above the plan view. Further, as shown in Fig. 3, the second exposure portion 4 is exposed from the upper side of the plan view by intersecting the exposure portions 3 of the second side. It is preferable that the exposure portion 3 of the first portion and the second exposure portion 4 intersect vertically. By the vertical crossing, it is possible to easily form a contact hole pattern of a perfect circle in the unexposed portion 5 surrounded by the exposure portion 3 and the exposure portion 4. Further, by using a mask of a dot pattern, a contact hole can be formed by exposure once. Further, at the time of exposure, a immersion liquid such as water or a fluorine-based inert liquid may be optionally used. The radiation used in the exposure may be based on the type of the sensitizing ray generating agent (B) (hereinafter, also referred to as "acid generator (B)") contained in the ray-sensitive resin composition. Far ultraviolet rays, sputum lines, charged particle lines, etc. are appropriately selected. Among them, the far-ultraviolet line represented by the ArF excimer laser (wavelength 193 nm) or the KrF excimer laser (wavelength 248 nm) is preferable. For the ArF excimer laser (wavelength I93 nm), the far ultraviolet line is particularly preferable. The exposure conditions such as the amount of exposure can be appropriately selected in accordance with the addition composition of the sensitive radiation linear resin composition or the kind of the additive. -13- 201202842 Further, it is preferable to perform baking (hereinafter, also referred to as P E B) after heat treatment after exposure. When the p E B treatment is carried out, the dissociation reaction of the acid dissociable group or the acid labile group in the radiation sensitive grease composition can be carried out. The temperature condition of P EB can be matched with the composition of the sensitive radiation linear resin to make a suitable choice, usually 30 to 200 ° C, and preferably 17 ° C. (3) Developing step After the exposure step, development was carried out using an organic solvent (X) to form a contact hole pattern thereon. For the preferred example of the organic solvent (X), for example, a polar group such as a ketone ester solvent, an alcohol solvent, an ether solvent or a guanamine solvent, or a hydrocarbon solvent can be used. Ketone solvents such as 1-octanone, 2-octanone, 1-nonanone, 2-anthraquinone, 4-heptanone, 2-hexanone, diisobutylketone, cyclohexanone, methyl ring, phenyl Acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like. The ester solvent is, for example, methyl acetate, butyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol acetate, diethylene glycol monobutyl Ether acetate, diethylene glycol ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutylethyl, 3-methyl-3-methoxybutylacetic acid Ester, methyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate. Alcohol solvents such as methanol, ethanol, η-propanol, isopropanol, alcohol, sec - Butanol, tert-butanol, isobutanol, η-hexanol, and η-heptanol are "50 to substrate agent, solvent ketone, ketone, ethanol monoacetate, and the like." Η-丁:乙-14- 201202842 diol solvent such as diol or triethylene glycol, or ethylene glycol diol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol ethylene glycol monoethyl The glycol oxime ether solvent such as ether or methoxymethylbutanol is, for example, the above glycol ether solvent, tetrahydrofuran or the like. A guanamine solvent such as N-methyl-2-pyrrolidone acetamide, N N-dimethylformamide, etc. The hydrocarbon solvent is, for example, an aromatic hydrocarbon such as toluene or xylene, or an aliphatic hydrocarbon such as hexane, octane or decane; and the organic solvent (X) Further, it is preferably butyl acetate, amyl acetate or methyl amyl ketone. The above organic may be mixed in plural or in a solvent other than the above. (4) Washing after development in a washing step. The washing liquid containing at least one type of organic solvent containing an alkylating agent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether is used, and after the development, the ketone solvent and the ester system are used. a step of washing at least one type of organic agent selected from the group consisting of a solvent and a guanamine solvent, and more preferably a step of washing the solvent or the ester solvent after the negative development, after the negative development. The step of washing with a monovalent alcohol having a carbon number of 6 to 8. wherein the washing step after the negative development is monomethyl ether, propyl monomethyl ether, tri-embedded solvent, etc., for example, dioxane, hydrazine, Ν · Dimethyl hydrocarbon solvent, section. Ester, isopropyl acetate (X), It is preferred to use a solvent or a ketone-based solvent for mixing water. A solvent or an alcohol-based solvent is preferably used in a washing liquid containing an alcohol. The most suitable one is a carbon-based -15- 201202842 A monovalent alcohol of 6 to 8 is, for example, a linear, branched or cyclic monovalent alcohol. Specifically, for example, 1-hexanol, 1-heptanol, 1-octanol, 2 can be used. -hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, benzyl alcohol, etc., preferably 1-hexanol, 2-hexanol 2. The heptanol may be used in combination with a plurality of components of the above-mentioned washing liquid, or may be used in combination with an organic solvent other than the above. The water content in the washing liquid is preferably 1% by mass or less. It is preferably 5% by mass or less, and particularly preferably 3% by mass or less. When the water content is 10% by mass or less, good development characteristics can be obtained. 界面 In the washing liquid, a surfactant can be added as appropriate. As shown in Fig. 3, the method for forming the photoresist pattern of the present invention is preferably formed such that the line portions of the photoresist pattern intersect each other. The portions intersecting each other form a contact hole pattern on the substrate by development using an organic solvent (X). <sensitive radiation linear resin composition> The sensitive radiation linear resin composition is an acid which is subjected to exposure by a linear acid generator generated by a sensitive radiation, so that the acid dissociated hydrazine or acid present in the composition does not The stable group dissociates to form a carboxyl group, and as a result, the solubility of the exposed portion in the organic solvent (X) can be lowered, and the unexposed portion can be dissolved and removed via the organic solvent (X) to form a pattern. In particular, it is suitable for forming a contact hole pattern. Hereinafter, the sensitive radiation linear resin composition of the present invention will be described. When the sensitive radiation linear resin composition is a polymer (A) containing a repeating unit having an acid labile-16-201202842 basis, and an acid generator (B) 'and a solvent (C), in this specification The term "acid-labile group" and "acid-dissociable group" means a group which can be dissociated by an acid, and does not specifically mean any difference. a polymer having an acid labile group or an acid dissociable group and a soluble organic solvent (X), which dissociates the acid labile group or the acid dissociable group to form a carboxyl group via an action of an acid, and is an organic solvent. (X) is an insoluble or poorly soluble polymer. <Polymer (A) > The polymer (A) is a repeating unit (a2) containing at least one selected from the above formula (1-1) to the following formula (1-7). (i) Repeating unit (a2) The repeating unit (a2) is obtained by polymerizing monomers respectively corresponding to the following formula (1 a-1) to the following formula (la-7). 【化5】
(1a-2) (1a-3) (1a-4) H2C 二 17- 201202842(1a-2) (1a-3) (1a-4) H2C II 17- 201202842
(1a-5) (1a-6) (1a-7) 式（la-1)〜式（la-7)中，R1、R2、R3、R4、R5、 A、B、p、m、n與式（1-1)〜式（1-7)中之該些內容具 有相同意義。 上述式（1-1)中之R2所表式之碳數1〜4之取代或未 取代之烷基，例如甲基、乙基、丙基、丁基，或該些之結 構異構物等。 上述式（1-2)及式（1-3)中之以A表示之具有氧原 子或硫原子之2價之連結基 '例如-Ra-O-Rb-'-Ra-CO-Rb-、-Ra-COO-Rb-，或-Ra-S-Rb-所表示之2價之基等。Ra及 Rb表示分別獨立之單鍵或碳數1〜10之烴基。上述2價之連 結基，例如下述式（A-1 )〜式（A-6 )所表示之基等。 【化6】(1a-5) (1a-6) (1a-7) In the formula (la-1) to the formula (la-7), R1, R2, R3, R4, R5, A, B, p, m, n and These contents in the formula (1-1) to the formula (1-7) have the same meaning. The substituted or unsubstituted alkyl group having a carbon number of 1 to 4 represented by R2 in the above formula (1-1), such as a methyl group, an ethyl group, a propyl group, a butyl group, or a structural isomer thereof . a divalent linking group represented by A in the above formula (1-2) and formula (1-3) having an oxygen atom or a sulfur atom, such as -Ra-O-Rb-'-Ra-CO-Rb-, -Ra-COO-Rb-, or a 2-valent group represented by -Ra-S-Rb-. Ra and Rb represent a single bond or a hydrocarbon group having 1 to 10 carbon atoms, respectively. The above-mentioned divalent linking group is, for example, a group represented by the following formula (A-1) to formula (A-6). 【化6】
(A-1)(A-1)
(A-2) -18- 201202842(A-2) -18- 201202842
(A-3) (A-4)(A-3) (A-4)
Ra1 0 I II Rb1 I I \ II CH j-C —0- (-CH (A-5)Ra1 0 I II Rb1 I I \ II CH j-C —0- (-CH (A-5)
Ra1 S Rb1 I , II ,l , chVc~Hch^- (A-6) 上述式（A-l)〜式（A-6)中，Ral及Rbl，表示互相 獨立之氫原子、甲基、乙基或丙基。又，q、r表示相互獨 立之0〜5之整數。但，1個之連結基中，9及1·不同爲0。 上述式（1-7 )中之R4所表示之2價之連結基，例如碳 數 1 〜10之烴基、-Rc-O-Rd-、-Rc-CO-Rd-、-Rc-COO-Rd-所表示之2價之基等。Rc及Rd分別獨立表示碳數1〜10之烴 基。又，Rc及Rd，可鍵結於主鏈側之氧原子，或R5。 上述式（1-7)中之R5’例如下述式（l-7a) 、（l-7b )所表示之基等。Ra1 S Rb1 I , II , l , chVc~Hch^- (A-6) In the above formula (Al) to formula (A-6), Ral and Rbl represent mutually independent hydrogen atoms, methyl groups, ethyl groups or Propyl. Further, q and r represent integers of 0 to 5 which are independent from each other. However, among the ones of the linkages, 9 and 1 are different from 0. a divalent linking group represented by R4 in the above formula (1-7), for example, a hydrocarbon group having 1 to 10 carbon atoms, -Rc-O-Rd-, -Rc-CO-Rd-, -Rc-COO-Rd - The base of the 2 price indicated. Rc and Rd each independently represent a hydrocarbon group having 1 to 10 carbon atoms. Further, Rc and Rd may be bonded to an oxygen atom on the side of the main chain or R5. R5' in the above formula (1-7) is, for example, a group represented by the following formulas (l-7a) and (l-7b).
Ο (1-7b) 【化7Ο (1-7b)
0丫0 Ο (1-7a) 式（l-7a)中，η,表示0〜2之整數。式〇-7b)中， n2〜n5，表示各自獨立之0〜2之整數。式（l-7a)及式（ • 19- 201202842 1 -7b )中，「*」表示鍵結於式（1 -7 )中之R4的鍵結鍵。 又，式（l-7a)及式（1-7b)所表示之基可具有取代基。 上述式（l-7a )或式（l-7b )所表示之較佳之基，例 如下述式（l-7aa)或（l-7bb)所表示之內容等。 【化8】0丫0 Ο (1-7a) In the formula (l-7a), η represents an integer of 0 to 2. In the formula 〇-7b), n2 to n5 represent integers of 0 to 2 which are each independent. In the formula (l-7a) and the formula ( • 19-201202842 1 -7b ), "*" indicates the bonding key of R4 bonded to the formula (1-7). Further, the group represented by the formula (l-7a) and the formula (1-7b) may have a substituent. Preferred groups represented by the above formula (l-7a) or formula (l-7b) are, for example, those represented by the following formula (l-7aa) or (l-7bb). 【化8】
式（l-7aa)及式（l-7bb)中，「*」表示鍵結於一般 式（1-7)中之R4的鍵結鍵。 重複單位（1-7)之具體例如，下述式所表示之內容 等。又，式（1-7-1)〜（1-7-22)中之 R1，與式（1-7) 中之R1具有相同之意義。 -20- 201202842In the formula (l-7aa) and the formula (l-7bb), "*" represents a bonding bond of R4 bonded to the general formula (1-7). Specific examples of the repeating unit (1-7) are, for example, the contents indicated by the following formulas. Further, R1 in the formula (1-7-1) to (1-7-22) has the same meaning as R1 in the formula (1-7). -20- 201202842
R1 -^-ch2 — c c=oR1 -^-ch2 — c c=o
R1R1
CH2 — C c=o / o \CH2 — C c=o / o \
CH〇 / ^ H2C \ ch2 / h2c \CH〇 / ^ H2C \ ch2 / h2c \
(1-7-4) (1-7-1) (1-7-2) (1-7-3 )(1-7-4) (1-7-1) (1-7-2) (1-7-3)
【化1 0】[化1 0]
-21 - 201202842-21 - 201202842
【化1 1】[1 1]
Ri -(-ch2—C^-j- c=o / o \ ch2 h2c-o-chRi -(-ch2—C^-j- c=o / o \ ch2 h2c-o-ch
(1-7-16) o CH2 — c c=o o(1-7-16) o CH2 — c c=o o
0 0 CH-CH30 0 CH-CH3
(1 - 7-21 ) (1-7-22) (1 - 7 - 20 ) 提供式（1 -7 )所表示之重複單位單體，例如可依 -22- 201202842(1 - 7-21) (1-7-22) (1 - 7 - 20 ) Provide the repeat unit monomer represented by formula (1 -7 ), for example, -22- 201202842
Tetrahedron Letters, Vo 1. 27， No. 3 2 p.3741(1986)、 Organic Letters, Vol. 4，Νο·15 p_2561(2002)等所記載之以 往公知之方法予以合成。 提供重複單位（a2 )之單體中，較佳之單體例如以下 之例示。 【化1 2】 Η3' H3C c=ch2 c=ch2 c=ch2 / / / o=c o=c 0=cTetrahedron Letters, Vo 1. 27, No. 3 2 p. 3741 (1986), Organic Letters, Vol. 4, Νο. 15 p_2561 (2002), etc., are synthesized by a known method. Among the monomers which provide the repeating unit (a2), preferred monomers are exemplified below. [1 2] Η3' H3C c=ch2 c=ch2 c=ch2 / / / o=c o=c 0=c
聚合物（A)，可僅含有1種重複單位（a2)者，或含 有2種以上者亦可。含有重複單位（a2)之比例’相對於 聚合物（A)所含之重複單位之合計lOOmol%，通常爲 80mol%以下’較佳爲2〇〜80mol%’更佳爲30〜70mol%。 重複單位（a2 )之含有比例於此範圍內時’就可顯著抑制 -23- 201202842 光微影蝕刻後淤渣發生之效果，及顯著之抑制圖型頂部消 失之效果等觀點，爲特別有效者。 (ii )重複單位（a3 ) 聚合物（A)以含有由上述式（2-1)至式（2-4)所 選出之至少1個之重複單位（a3)爲佳。聚合物（A)，因 含有重複單位（a3 )，故可提高曝光部之耐蝕刻性。 上述式（2-1 )〜（2-4 )中之R6所表示之碳數1〜3之 烷基，例如甲基、乙基、丙基等。 又，R8所表式之碳數1〜5之直鏈狀或支鏈狀之羥烷基 ’例如甲基、乙基、丙基、丁基、戊基，或該些之結構異 構物的氫原子被羥基所取代之基等。 又，L所表示之可被碳數1〜5之烷基所取代之碳數1〜 5之直鏈狀或支鏈狀之烴基，例如伸甲基、伸乙基、伸丙 基、伸丁基等。 又，Μ表示上述式（Ml)〜式（M4)之任一者所示 之基。又，並不論上述式（Ml)、式（M2)之鍵結方向 。例如’式（Μ 1 )中，氧原子鍵結於金剛烷之橋頭位置亦 可，與-ch2-鍵結亦可。 q表示1〜3之整數，特別是以q=1爲佳。 提供重複單位（a3 )之聚合性單體，例如下述式（2-a)〜（2-t)所表示之化合物等。又，本發明中，提供重 複單位（a3)之聚合性單體並不限定於該些之內容。 -24 - 201202842 【化1 4】 ch=ch2 o=c οThe polymer (A) may be contained in only one type of repeating unit (a2), or may be contained in two or more types. The ratio of the ratio of the repeating unit (a2) to the repeating unit contained in the polymer (A) is usually 100 mol% or less, preferably 2 Å to 80 mol%, more preferably 30 to 70 mol%. When the ratio of the repeating unit (a2) is within this range, it is possible to significantly suppress the effect of the occurrence of sludge after the photolithography etching, and the effect of suppressing the disappearance of the top of the pattern, which is particularly effective. . (ii) Repeating unit (a3) The polymer (A) preferably contains at least one repeating unit (a3) selected from the above formula (2-1) to formula (2-4). Since the polymer (A) contains a repeating unit (a3), the etching resistance of the exposed portion can be improved. The alkyl group having 1 to 3 carbon atoms represented by R6 in the above formula (2-1) to (2-4), for example, a methyl group, an ethyl group, a propyl group or the like. Further, a straight-chain or branched hydroxyalkyl group having a carbon number of 1 to 5 represented by R8, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a structural isomer thereof A group in which a hydrogen atom is replaced by a hydroxyl group or the like. Further, a linear or branched hydrocarbon group having 1 to 5 carbon atoms which may be substituted by an alkyl group having 1 to 5 carbon atoms represented by L, for example, a methyl group, an ethyl group, a propyl group, and a butyl group. Base. Further, Μ represents a group represented by any one of the above formulas (M1) to (M4). Further, regardless of the bonding direction of the above formula (M1) and formula (M2). For example, in the formula (Μ 1 ), the oxygen atom may be bonded to the bridgehead position of the adamantane, and may be bonded to the -ch2- bond. q represents an integer of 1 to 3, particularly preferably q=1. The polymerizable monomer of the repeating unit (a3) is provided, for example, a compound represented by the following formula (2-a) to (2-t). Further, in the present invention, the polymerizable monomer providing the repeating unit (a3) is not limited to the contents. -24 - 201202842 【化1 4】ch=ch2 o=c ο
OH (2-a)OH (2-a)
(2-c)(2-c)
ch3 h2c=c c = oCh3 h2c=c c = o
(2-d)(2-d)
-25- 201202842 【化1 6 h3c h3c H3C c = ch2 / c = ch2 / c = ch2 / =c o=c o=c \ \ \ 0 0 〇 / / / h2c h2c h2c \ \ \ c = o c = o c=o / 0 / 0 / 0-25- 201202842 【化1 6 h3c h3c H3C c = ch2 / c = ch2 / c = ch2 / =co=co=c \ \ \ 0 0 〇 / / / h2c h2c h2c \ \ \ c = oc = oc= o / 0 / 0 / 0
h3cH3c
(2-k)(2-k)
CH c=ch2 / ch3 o=c h2c 、 h2c=c \ \ 0 c = / / 、 〇 \ \ NH ch2 / / o = c / 3 h2c=c c = o 〇 o = cCH c=ch2 / ch3 o=c h2c , h2c=c \ \ 0 c = / / , 〇 \ \ NH ch2 / / o = c / 3 h2c=c c = o 〇 o = c
\ CH 2\ CH 2
【化1 7[Chemical 1 7
H2C = CH h2c=ch c=o c=o c=o hoh2cH2C = CH h2c=ch c=o c=o c=o hoh2c
00
ch2oh 2-0) (2-q) h2c=chCh2oh 2-0) (2-q) h2c=ch
26- 201202842 c=o H2O == c ch326- 201202842 c=o H2O == c ch3
ch3 ch3 H2C = C H〇C — C \ \ c=o / c = y / 0 / 0Ch3 ch3 H2C = C H〇C — C \ \ c=o / c = y / 0 / 0
ch2oh 2-r)Ch2oh 2-r)
^CH HOH2Cy VCH2OH (2-t) 聚合物（A)，可爲僅含有1種重複單位（a3)者，或 含有2種以上者亦可。重複單位（a3)之含有比例，相對 於聚合物（A )所含重複單位之合計1 OOmol%，通常爲 60mol%以下，較佳爲60〜5mol%，更佳爲50〜5mol%。重 複單位（a3)之含有比例爲該範圍內時，可提高曝光部之 耐蝕刻性。 (iii )重複單位（al ) 聚合物（A)，以含有含上述式（3)所表示之酸不穩 定基的重複單位（al)者爲佳。 上述式（3 )中之R9所表示之碳數1〜4之直鏈狀或支 鏈狀之烷基，例如甲基、乙基、η-丙基、i-丙基、n_丁基 、2 -甲基丙基、1-甲基丙基、t -丁基等。 又，碳數4〜20之1價之脂環式烴基或其衍生物，例如 ，原菠烷、三環癸烷、四環十二烷、金剛烷、環丁烷、環 戊烷、環己烷、環庚烷、環辛烷等之環烷類等所生成之脂 環族環所形成之基；該些脂環族環所形成之基，被例如甲 -27- 201202842 基、乙基、π -丙基、i -丙基、η -丁基、2 -甲基两基、ι_甲基 丙基、t-丁基等之碳數1〜4之直鏈狀、支鏈狀或環狀之烷 基所取代之基等。 此外，任意2個之R9相互鍵結形成碳數4〜2 0之2價之 脂環式烴基或其衍生物，例如由原菠烷、三環癸烷、四環 十二烷、金剛烷、環戊烷、環己烷等所生成之脂環族環所 形成之基；該些脂環族環所形成之基，例如，可被甲基、 乙基、η-丙基、i-丙基、η-丁基、2 -甲基丙基、1-甲基丙基 、t-丁基等碳數1〜4之直鏈狀或支鏈狀之烷基，或碳數3〜 1 〇之脂環式烴基所取代之基等。 式（3 )中，-C ( R9 ) 3所表示之基之較佳例示，如t-丁基、1-n- ( 1-乙基-1-甲基）丙基、1-n- ( 1,1-二甲基） 丙基、l-n-(l，l-二甲基）丁基、l-n-(l，l-二甲基）戊基 、1-(1，1-二乙基）丙基、〗-n-(l，l-二乙基）丁基、ΐ-η· (1，1-二乙基）戊基等之不具有脂環族環之基；1-(1-甲 基）環戊基、丨-(1-乙基）環戊基、1-(1-η-丙基）環戊 基、丙基）環戊基、1-(1-甲基）環己基、1-(1-乙基）環己基、l-(l-n-丙基）環己基、丙基）環 己基、1-(1-甲基-1·(2-原菠基））乙基、1-(1·甲基-1-(2-四環癸烷基））乙基、1-0-甲基-1-(1-金剛烷基） )乙基、2-(2-甲基）原菠基、2-(2-乙基）原菠基、2-(2-η-丙基）原菠基、2-(2-i-丙基）原菠基、2-(2-甲基 )四環十二烷基、2-(2-乙基）四環十二烷基、2-(2-n-丙基）四環十二烷基、2- (2-i-丙基）四環十二烷基、2- -28- 201202842 甲基-2 -金剛院基、2 -乙基-2 -金剛院基、2 _丙基-2 _金剛院 基等之具有脂環族環之基·，該些具有脂環族環之基，可被 例如，甲基、乙基、η -丙基、i -丙基、n_ 丁基、2_甲基丙 基、1-甲基丙基、t-丁基等碳數1〜10之直鏈狀或支鏈狀之 烷基、環戊基、環己基、環辛基等之碳數4〜20之環狀之 烷基所取代之基等。 提供重複單位（al)之單體中，又以（甲基）丙烯酸 2_甲基金剛垸基-2-基醋、（甲基）丙稀酸2 -乙基金剛院 基-2-基酯、（甲基）丙烯酸-2-甲基二環〔2.2.1〕庚-2-基 酯、（甲基）丙烯酸-2-乙基二環〔2.2.1〕庚-2-基酯、（ 甲基）丙烯酸1-(二環〔2.2.1〕庚-2-基）-1-甲基乙基酯 、（甲基）丙烯酸1-(金剛烷-1-基）-1-甲基乙基酯、（ 甲基）丙烯酸1-甲基-1-環戊基酯、（甲基）丙烯酸1-乙 基-1-環戊基酯 '(甲基）丙烯酸1-甲基-1-環己基酯、（ 甲基）丙烯酸1-乙基-1-環己基酯等。 提供重複單位（a 1 )之單體，較佳之單體例如以下之 例示。 【化1 8】^CH HOH2Cy VCH2OH (2-t) The polymer (A) may be one containing only one repeating unit (a3), or may be contained in two or more types. The content of the repeating unit (a3) is usually 10,000 mol%, usually 60 mol% or less, preferably 60 to 5 mol%, more preferably 50 to 5 mol%, based on the total of the repeating units contained in the polymer (A). When the content ratio of the repeating unit (a3) is within this range, the etching resistance of the exposed portion can be improved. (iii) The repeating unit (al) of the polymer (A) is preferably a repeating unit (al) containing the acid labile group represented by the above formula (3). a linear or branched alkyl group having 1 to 4 carbon atoms represented by R9 in the above formula (3), for example, methyl group, ethyl group, η-propyl group, i-propyl group, n-butyl group, 2-methylpropyl, 1-methylpropyl, t-butyl, and the like. Further, the alicyclic hydrocarbon group having a carbon number of 4 to 20 or a derivative thereof, for example, raw spinel, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane, cyclohexane a group formed by an alicyclic ring formed by a cycloalkane such as an alkane, a cycloheptane or a cyclooctane; and a group formed by the alicyclic ring, for example, a group of a -27-201202842, an ethyl group, a linear, branched or cyclic carbon number of 1 to 4 such as π-propyl, i-propyl, η-butyl, 2-methyldiyl, i-methylpropyl, t-butyl or the like a group substituted with an alkyl group. Further, any two of R9 are bonded to each other to form an alicyclic hydrocarbon group having a carbon number of 4 to 2, or a derivative thereof, for example, a raw spinach, a tricyclodecane, a tetracyclododecane, an adamantane, a group formed by an alicyclic ring formed by cyclopentane, cyclohexane or the like; a group formed by the alicyclic ring, for example, may be methyl, ethyl, η-propyl, i-propyl , a linear or branched alkyl group having a carbon number of 1 to 4, such as η-butyl, 2-methylpropyl, 1-methylpropyl or t-butyl, or a carbon number of 3 to 1 〇 a group substituted with an alicyclic hydrocarbon group or the like. In the formula (3), preferred examples of the group represented by -C(R9)3, such as t-butyl, 1-n-(1-ethyl-1-methyl)propyl, 1-n- ( 1,1-dimethyl)propyl, ln-(l,l-dimethyl)butyl, ln-(l,l-dimethyl)pentyl, 1-(1,1-diethyl) a group having no alicyclic ring such as propyl, 〖-n-(l,l-diethyl)butyl, ΐ-η·(1,1-diethyl)pentyl; 1-(1- Methyl)cyclopentyl, 丨-(1-ethyl)cyclopentyl, 1-(1-η-propyl)cyclopentyl, propyl)cyclopentyl, 1-(1-methyl)cyclohexyl , 1-(1-ethyl)cyclohexyl, 1-(ln-propyl)cyclohexyl, propyl)cyclohexyl, 1-(1-methyl-1·(2-indolyl))ethyl, 1-(1·methyl-1-(2-tetracyclodecyl))ethyl, 1-0-methyl-1-(1-adamantyl))ethyl, 2-(2-methyl ) raw spinach, 2-(2-ethyl) raw spiny base, 2-(2-η-propyl) proto-spinyl, 2-(2-i-propyl) pro-spinyl, 2-(2- Methyl)tetracyclododecyl, 2-(2-ethyl)tetracyclododecyl, 2-(2-n-propyl)tetracyclododecyl, 2-(2-i-propyl Base) tetracyclododecyl, 2- -28- 201202842 methyl-2 - diamond base, 2-ethyl-2 - 金刚院a group having an alicyclic ring, such as a methyl group, an ethyl group, an η-propyl group, an i-propyl group, or a group having an alicyclic ring group. a linear or branched alkyl group having a carbon number of 1 to 10, such as a base, n-butyl group, 2-methyl group, 1-methylpropyl group, t-butyl group, a cyclopentyl group, a cyclohexyl group, or a ring A group substituted with a cyclic alkyl group having 4 to 20 carbon atoms such as an octyl group. Providing a repeating unit (al) of a monomer, followed by (meth)acrylic acid 2-methylglycosyl-2-yl vinegar, (meth)acrylic acid 2-ethyl galenyl-2-yl ester , (meth)acrylic acid-2-methylbicyclo[2.2.1]hept-2-yl ester, (meth)acrylic acid-2-ethylbicyclo[2.2.1]heptan-2-yl ester, ( 1-(bicyclo[2.2.1]hept-2-yl)-1-methylethyl methacrylate, 1-(adamantan-1-yl)-1-methylethyl (meth)acrylate Base ester, 1-methyl-1-cyclopentyl (meth)acrylate, 1-ethyl-1-cyclopentyl (meth)acrylate '1-methyl-1-cyclo(meth)acrylate Hexyl ester, 1-ethyl-1-cyclohexyl (meth)acrylate, and the like. A monomer of repeating unit (a 1 ) is provided, and preferred monomers are exemplified below. [化1 8]
C = CH2 •29 201202842C = CH2 • 29 201202842
聚合物（A)，可僅含1種重複單位（al)所得者，或 含有2種以上者亦可。重複單位（al)之含有比例’相對 於聚合物（A)所含之重複單位之合計lOOmol%，較佳爲 2 0 ~ 9 0 m ο 1 % '更佳爲 20 〜80mol%，最佳爲 20 〜70mol%。 重複單位（al )之含有比例爲該範圍內之情形，就就兼具 確保塗佈後之撥水性，與對PEB後之顯影液的接觸角之提 升等觀點爲特別有效者。 (iv )其他重複單位 聚合物（A)可再含有1種以上重複單位（al)、重複 單位（a2 )及重複單位（a3 )以外之重複單位（以下，亦 稱爲「其他重複單位」）。 其他重複單位，例如，式（4 )所表示之重複單位（ 以下’亦稱爲「重複單位（以）」）、式（5 )所表示之 重複單位（以下’亦稱爲「重複單位（aS)」）、式（b. 2-1 )所表示之重複單位（b-2-丨）、式（b-2-2 )所表示之 重複單位（b-2-2)、該些以外之其他重複單位（a6)等。 -30- (4) 201202842 【化1 9】 R10The polymer (A) may be contained in only one type of repeating unit (al), or may be contained in two or more types. The content ratio of the repeating unit (al) is 100% by mole based on the total of the repeating units contained in the polymer (A), preferably 20 to 90 m ο 1 % 'more preferably 20 to 80 mol%, most preferably 20 to 70 mol%. When the content ratio of the repeating unit (al) is within this range, it is particularly effective in that the water repellency after coating is ensured and the contact angle with the developer after PEB is increased. (iv) The other repeating unit polymer (A) may further contain one or more repeating units (al), repeating units (a2), and repeating units other than the repeating unit (a3) (hereinafter, also referred to as "other repeating units") . Other repeating units, for example, the repeating unit represented by the formula (4) (hereinafter referred to as "repetitive unit (by)"), and the repeating unit represented by the formula (5) (hereinafter referred to as "repetitive unit (aS) )"), the repeating unit (b-2-丨) represented by the formula (b. 2-1), the repeating unit (b-2-2) represented by the formula (b-2-2), and the other Other repeating units (a6) and so on. -30- (4) 201202842 【化1 9】 R10
式（4)中’ R1Q爲’氫原子、甲基或三氟甲基；γ爲 ’單鍵或碳數1〜3之2價之有機基；w爲，碳數7〜20之取 代或未取代之多環型脂環式烴基；但，上述多環型脂環式 烴基具有取代基之情形，取代基爲碳數1〜1〇之直鏈狀或 支鏈狀之烷基、碳數4〜20之環狀之烷基、羥基、氰基、 碳數1〜10之羥烷基、羧基，或酮基； 【化2 0 R11 -{CH2 —C + (5) c=o / ο \ R12 / C — CF〇 /\ f3c oh 式（5)中，R11爲氫原子、碳數1〜4之烷基、三氟甲 基或羥基甲基；R12爲2價之有機基； 式（4 )中，W所表示之碳數7〜20之取代或未取代之 多環型脂環式烴基，例如，下述式所示之二環〔2·2·1〕庚 烷（4a)、二環〔2.2.2〕辛烷（4b) '三環〔5.2·1·02’6〕 癸烷（4c)、四環〔6.2.1.13,6.02,7〕十二烷（4d)、三環 -31 - 201202842 〔3.3.1.13’7〕癸烷（4e)等之環烷類所生成之烴基等。 【化2 1】In the formula (4), 'R1Q is a hydrogen atom, a methyl group or a trifluoromethyl group; γ is a 'single bond or a divalent organic group having a carbon number of 1 to 3; w is a substitution or not having a carbon number of 7 to 20; a polycyclic alicyclic hydrocarbon group substituted; however, in the case where the above polycyclic alicyclic hydrocarbon group has a substituent, the substituent is a linear or branched alkyl group having a carbon number of 1 to 1 Å, and a carbon number of 4 a cyclic alkyl group of ～20, a hydroxyl group, a cyano group, a hydroxyalkyl group having a carbon number of 1 to 10, a carboxyl group, or a ketone group; [Chemical 2 0 R11 -{CH2 - C + (5) c=o / ο \ R12 / C — CF〇/\ f3c oh In the formula (5), R11 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group or a hydroxymethyl group; and R12 is a divalent organic group; In the above, a substituted or unsubstituted polycyclic alicyclic hydrocarbon group having 7 to 20 carbon atoms represented by W, for example, a bicyclo[2·2·1]heptane (4a) represented by the following formula, Ring [2.2.2] Octane (4b) 'Tricyclo[5.2·1·02'6] decane (4c), tetracyclo[6.2.1.13, 6.02,7]dodecane (4d), tricyclic- 31 - 201202842 [3.3.1.13'7] Hydrocarbyl group formed by naphthenes such as decane (4e). [Chem. 2 1]
"CO (4a) (4b) (4c) (4d) (4e) 上述環烷類所生成之烴基可具有取代基之情形，取代 基例如可爲，甲基、乙基、η-丙基、i-丙基、η-丁基、2-甲基丙基、1-甲基丙基、t-丁基等碳數1〜10之直鏈狀或支 鏈狀之烷基，環戊基、環己基、環辛基等碳數4〜20之環 狀之烷基等。又，取代基並不限定於該些之烷基，亦可爲 羥基、氛基、碳數1〜10之羥烷基、羧基、酮基。 式（5)中，R11所表示之碳數1〜4之烷基，例如，甲 基、乙基、η-丙基、i-丙基、η-丁基、2-甲基丙基、1-甲基 丙基、t-丁基等。 式（5 )中，R12所表示之2價之有機基，以2價之烴基 爲佳。又，亦可爲烷二醇基、伸烷酯基等。2價之有機基 ’具體而言，例如，伸甲基、伸乙基、1，3 -伸丙基或1，2 -伸丙基等之伸丙基、伸四甲基、伸五甲基、伸六甲基、伸 七甲基、伸八甲基、伸九甲基、伸十甲基、伸十一甲基、 伸十二甲基、伸十三甲基、伸十四甲基、伸十五甲基、伸 十六甲基、伸十七甲基、伸十八甲基、伸十九甲基、伸二 十烷基、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-i，4-伸丁基、2-甲基-1，4-伸丁基、亞 乙基、亞丙基、2-亞丙基等之鏈狀烴基；1,3-環伸丁基等 -32- 201202842 之環伸丁基、1，3-環伸戊基等之環伸戊基、I4,環伸己基 等之環伸己基，1，5 -環伸辛基等之環伸辛基等之碳數3〜10 之環伸院基等單環式烴環基；】，伸原疲基或2,5 -伸原疲 基等之伸原菠基、1，5 -伸金剛院基或2，6 -伸金剛院基等伸 金剛院基等之2〜4環式之碳數4〜30之環烴基等父聯環式 烴環基等。其中又以包含2，5 -伸原菠基之烴基、丨，2 -伸乙 基、伸丙基爲佳。 又，R 12爲包含2價之脂肪族環式烴環基之情形’以於 雙三氟甲基-羥基-甲基（-C(CF：j) 2〇H) ’與2價之脂肪 族環式烴基之間配置作爲調距器之碳數1〜4之伸院基爲佳 【化2 2】"CO (4a) (4b) (4c) (4d) (4e) In the case where the hydrocarbon group formed by the above cycloalkane may have a substituent, the substituent may be, for example, methyl, ethyl, η-propyl, a linear or branched alkyl group having 1 to 10 carbon atoms such as i-propyl, η-butyl, 2-methylpropyl, 1-methylpropyl or t-butyl, cyclopentyl, a cycloalkyl group having a carbon number of 4 to 20, such as a cyclohexyl group or a cyclooctyl group. Further, the substituent is not limited to the alkyl group, and may be a hydroxyl group, an aryl group, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group or a ketone group. In the formula (5), the alkyl group having 1 to 4 carbon atoms represented by R11, for example, methyl, ethyl, η-propyl, i-propyl, η-butyl, 2-methylpropyl, 1 -methylpropyl, t-butyl and the like. In the formula (5), the divalent organic group represented by R12 is preferably a divalent hydrocarbon group. Further, it may be an alkylene glycol group or an alkylene ester group. The divalent organic group 'specifically, for example, a methyl group, an ethyl group, a 1,3 -propyl group or a 1,2-propyl group, etc., a propyl group, a tetramethyl group, a pentamethyl group , hexamethyl, hexamethylene, octamethyl, hexamethylene, hexamethyl, undopentenyl, tenth methyl, thirteen methyl, tetramethyl, Extending fifteen methyl, stretching hexadecylmethyl, stretching heptamethyl, stretching octamethyl, stretching nine methyl, extending eicosyl, 1-methyl-1,3-propanyl, 2 -methyl-1,3-propanyl, 2-methyl-1,2-propanyl, 1-methyl-i,4-tert-butyl, 2-methyl-1,4-butylene a chain hydrocarbon group such as an ethylene group, a propylene group or a 2-propylene group; a ring of a butyl group such as a 1,3-cyclobutylene group such as -32-201202842; a ring of a 1,3-cyclopentyl group; a monocyclic hydrocarbon ring group such as a cyclopentyl group, an I4 ring, a cyclohexyl group or the like, a 1,5-cyclodextylene group or the like, and a ring-like octyl group having a carbon number of 3 to 10; , extension 2 or 5 - extension of the original base of the base, 1,5 - extension of the gold base, or 2,6 - extension of the gold base, etc. a hydrocarbon group having a carbon number of 4 to 30, etc. Linked cyclic hydrocarbon ring group. Further, it is preferably a hydrocarbon group containing a 2,5-extended starting base, an anthracene, a 2-ethylidene group, and a propyl group. Further, R 12 is a case of containing a divalent aliphatic cyclic hydrocarbon ring group 'for bistrifluoromethyl-hydroxy-methyl (-C(CF:j) 2〇H)' and a divalent aliphatic group It is better to arrange the ring-type hydrocarbon group as the pitcher with the carbon number of 1~4. [Chemical 2 2]
(b-2-1 ) (b-2-2) 重複單位（a6)例如，具有不飽和羧酸之有橋式烴骨 架的含有羧基之酯類；不具有有橋式烴骨架之（甲基）丙 烯酸酯類；不具有不飽和羧酸之有橋式烴骨架的含有羧基 之酯類；具有有橋式烴骨架之多官能性單體：不具有有橋 式烴骨架之多官能性單體等聚合性不飽和鍵結經開裂所得 之單位等。其中又以具有有橋式烴骨架之（甲基）丙烯酸 -33- 201202842 酯類的聚合性不飽和鍵結經開裂後之重複單位等爲佳。又 ，聚合物（A)，可爲僅含有1種重複單位（a4)〜（a6) 、（b-2-l )或（b-2-2 )之單位，或爲含有2種以上之單位 亦可。 上述提供其他重複單位之單體，較佳之單體例如以下 之例示。 【化2 3】 CH3 Η h2c=c h2c=c c=o c=o / /(b-2-1) (b-2-2) repeating unit (a6), for example, a carboxyl group-containing ester having a bridged hydrocarbon skeleton of an unsaturated carboxylic acid; and having no bridged hydrocarbon skeleton (methyl) Acrylates; carboxyl group-containing esters having a bridged hydrocarbon skeleton having no unsaturated carboxylic acid; polyfunctional monomers having a bridged hydrocarbon skeleton: polyfunctional monomers having no bridged hydrocarbon skeleton The unit obtained by the polymerization of the unsaturated unsaturated bond or the like. Among them, a polymerizable unsaturated bond having a bridged hydrocarbon skeleton of (meth)acrylic acid-33-201202842 ester is preferably a repeating unit after cracking or the like. Further, the polymer (A) may be a unit containing only one type of repeating unit (a4) to (a6), (b-2-l) or (b-2-2), or a unit containing two or more kinds. Also. The above-mentioned monomers which provide other repeating units are preferred, and the preferred monomers are exemplified below. [Chemical 2 3] CH3 Η h2c=c h2c=c c=o c=o / /
o o 【化2 4】o o 【化2 4】
h3c h3C\ h3c、 H3C\ c=ch2 / c=ch2 / c = ch2 C = CH； 0 = c \ o = c \ o = c \ o = c 0 / 〇 / 0 \ 0 h5c2- CH p \ / h3c-ch 、 / ( h2c: CHo / ㈠ ch2 0 = c F \ F3C-八 HN 〇 0 / HO CF3 h2c 1 X H3c 二 c f \ /C、 0 cf3 H3c ch3 f3c I cf3 OH -34- 201202842 h3c h3c c=ch2 /C = CH: o=c 0 = C \ \ 0 0 / / H5C2 —CH f V / h2c C3F7 o^c F \ OH h3c、 h3c C = CH5 / o = c \ c: / o=c \ 0 / h2c \ \ 0 / h2c HN CH, C = 0 ,CH,H3c h3C\ h3c, H3C\ c=ch2 / c=ch2 / c = ch2 C = CH; 0 = c \ o = c \ o = c \ o = c 0 / 〇 / 0 \ 0 h5c2- CH p \ / H3c-ch, / ( h2c: CHo / (a) ch2 0 = c F \ F3C- eight HN 〇 0 / HO CF3 h2c 1 X H3c two cf \ /C, 0 cf3 H3c ch3 f3c I cf3 OH -34- 201202842 h3c h3c c=ch2 /C = CH: o=c 0 = C \ \ 0 0 / / H5C2 —CH f V / h2c C3F7 o^c F \ OH h3c, h3c C = CH5 / o = c \ c: / o= c \ 0 / h2c \ \ 0 / h2c HN CH, C = 0 , CH,
H3CH3C
0 = C \ c=ch2 / h3c \ c=ch2 / o / h2c \ CH / \ h2c-o h3c o=c \ o H2Cwc2H5 h2< >h2、〇/ h3c c=ch2 \ c=ch2 o=c \ o / HC / \ f3c cf3 o=c o h2c \ CF, HN O CH3 N = C 、C2H50 = C \ c=ch2 / h3c \ c=ch2 / o / h2c \ CH / \ h2c-o h3c o=c \ o H2Cwc2H5 h2<>h2/〇/ h3c c=ch2 \ c=ch2 o=c \ o / HC / \ f3c cf3 o=co h2c \ CF, HN O CH3 N = C , C2H5
〔聚合物（A)之製造方法；I 聚合物（A ) ’例如，將提供前述各重複單位之聚合 性不飽和單體，使用過氫化物類、二烷基過氧化物類、二 醯基過氧化物類、偶氮化合物等自由基聚合起始劑，必要 時，可於鏈移轉劑之存在下，於適當之溶劑中進行聚合之 方式予以製造。 聚合所使用之溶劑，例如，η-戊烷、η-己烷、η-庚烷 、η-辛烷、η-壬烷、η-癸烷等之.院類；環己烷、環庚烷、 環辛烷、十氫·萘、原菠烷等之環烷類：苯、甲苯、二甲苯 、乙基苯、異丙苯等之芳香族烴類；氯丁烷、溴己烷、二 氯乙烷、六甲基二溴化物、氯苯等之鹵化烴類：乙酸乙酯 、乙酸η-丁酯、乙酸i-丁酯、丙酸甲酯等之飽和羧酸酯類 -35- 201202842 :丙酮' 2-丁酮、4-甲基-2-戊酮、2-庚酮等之酮類；四氫 呋喃、二甲氧基乙烷、二乙氧基乙烷等之醚類等。又，該 些溶劑可單獨使用1種，或將2種以上混合使用亦可。 〔聚合物（A )之物性値〕 聚合物（A)之凝膠滲透色層分析（GPC)之聚苯乙 烯換算的重量平均分子量（以下，亦稱爲「Mw」）並未 有特別限定，其以分別爲1，〇〇〇〜1 00,000爲佳，以1，〇〇〇〜 30,000爲較佳，以1，000〜20,000爲更佳。Mw未達1，〇〇〇時 ，會有降低光阻層之耐熱性的疑慮。又，超過1 0 〇 , 〇 〇 〇時 ，會有造成鹼顯影部之顯影性降低之疑慮。 又，各聚合物之Mw，與各聚合物之凝膠滲透色層分 析（GPC )之聚苯乙烯換算的數平均分子量（以下，亦稱 爲「Μη」）之比（Mw/Mn)，通常分別爲1〜5，又以1 〜3爲佳" 聚合物（A)中，會有包含製造時所使用之單體所生 成之低分子量成分之情形。該低分子量成分之含有比例， 相對於各聚合物100質量％ (固形分換算），較佳爲0.1質 量％以下，更佳爲0.07質量％以下，更佳爲0.05質量％以下 。低分子量成分之含有比例爲〇· 1質量％以下時，於浸潤式 曝光時，可降低對所接觸之水等浸潤液的溶出物之量。又 ，存放光阻時，於光阻中極少會產生異物，於塗佈光阻時 ，也可降低塗佈斑之發生，而可充分抑制光阻圖型形成時 缺陷之發生。 -36- 201202842 又，本說明書中，「低分子量成分」係指Mw爲500以 下之成分，具體而言，例如，單體、二聚物、三聚物、低 聚物等。低分子量成分，例如，可經由水洗、溶液萃取等 化學性精製法，或該些化學性精製法與臨界過濾、離心分 離等物理性精製法組合等方式予以去除。又，分析爲使用 、高速液體色層分析器（HPLC)進行。 此外，聚合物（A)以鹵素、金屬等雜質越少越好。 降低雜質時’可更改善所形成之光阻層的感度、解析度、 製程安定性、圖型形狀等。 聚合物（A)之精製法，例如，可使用水洗、溶液萃 取等化學性精製法，或該些化學性精製法與臨界過濾、離 心分離等物理性精製法之組合等。 <酸產生劑（B ) > 酸產生劑（B )，例如鑰鹽化合物、含鹵素之化合物 、重氮酮化合物、颯化合物、磺酸化合物等。 酸產生劑（B)，以下述式（6)所表示之化合物爲佳 【化2 5】 R13[Method for Producing Polymer (A); I Polymer (A) ' For example, a polymerizable unsaturated monomer of each of the above repeating units is provided, and a perhydride, a dialkyl peroxide, a dimercapto group is used. A radical polymerization initiator such as a peroxide or an azo compound can be produced by, if necessary, polymerization in a suitable solvent in the presence of a chain transfer agent. a solvent used for the polymerization, for example, η-pentane, η-hexane, η-heptane, η-octane, η-decane, η-decane, etc.; hexane, cycloheptane And naphthenes such as cyclooctane, decahydronaphthalene, and raw spinel: aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumene; chlorobutane, bromohexane, and dichloro Halogenated hydrocarbons such as ethane, hexamethyldibromide, chlorobenzene, etc.: saturated carboxylic acid esters such as ethyl acetate, η-butyl acetate, i-butyl acetate, methyl propionate, etc. -35 - 201202842 : a ketone such as acetone '2-butanone, 4-methyl-2-pentanone or 2-heptanone; an ether such as tetrahydrofuran, dimethoxyethane or diethoxyethane. Further, these solvents may be used alone or in combination of two or more. [The physical properties of the polymer (A)] The polystyrene-equivalent weight average molecular weight (hereinafter also referred to as "Mw") of the gel permeation chromatography (GPC) of the polymer (A) is not particularly limited. Preferably, it is 1, 〇〇〇~1 00,000, preferably 1, 〇〇〇 to 30,000, and more preferably 1,000 to 20,000. When the Mw is less than 1, there is a concern that the heat resistance of the photoresist layer is lowered. Further, when it exceeds 10 〇 and 〇 〇 , there is a fear that the developability of the alkali developing unit is lowered. Further, the ratio of the Mw of each polymer to the polystyrene-equivalent number average molecular weight (hereinafter also referred to as "Μη") of the gel permeation chromatography (GPC) of each polymer is usually It is preferably 1 to 5, and preferably 1 to 3, and the polymer (A) may contain a low molecular weight component formed by a monomer used in the production. The content ratio of the low molecular weight component is preferably 0.1% by mass or less, more preferably 0.07% by mass or less, even more preferably 0.05% by mass or less based on 100% by mass of the polymer (calculated as solid content). When the content ratio of the low molecular weight component is 〇·1 mass% or less, the amount of the eluted material of the infiltrating liquid such as water to be contacted can be reduced during the immersion exposure. Further, when the photoresist is stored, foreign matter is rarely generated in the photoresist, and when the photoresist is applied, the occurrence of the coating spot can be reduced, and the occurrence of defects in the formation of the photoresist pattern can be sufficiently suppressed. In the present specification, the "low molecular weight component" means a component having a Mw of 500 or less, and specific examples thereof include a monomer, a dimer, a trimer, and an oligomer. The low molecular weight component can be removed, for example, by a chemical purification method such as water washing or solution extraction, or by combining these chemical purification methods with a physical purification method such as critical filtration or centrifugal separation. Further, the analysis was carried out using a high-speed liquid chromatography analyzer (HPLC). Further, the polymer (A) is preferably as small as impurities such as halogen or metal. When the impurity is reduced, the sensitivity, resolution, process stability, pattern shape, and the like of the formed photoresist layer can be further improved. For the purification method of the polymer (A), for example, a chemical purification method such as water washing or solution extraction, or a combination of the chemical purification methods, a physical purification method such as critical filtration or centrifugation, or the like can be used. <Acid Generator (B) > The acid generator (B), for example, a key salt compound, a halogen-containing compound, a diazoketone compound, an anthracene compound, a sulfonic acid compound, or the like. The acid generator (B) is preferably a compound represented by the following formula (6).
-37- (6) 201202842 上述式（6)中，R13表示氫原子、氟原子、經基、碳 數1〜ίο之直鏈狀或支鏈狀之烷基、碳數1〜1〇之直鏈狀或 支鏈狀之烷氧基，或碳數2〜11之直鏈狀或支鏈狀之烷氧 羰基。又，R14表示碳數1〜1〇之直鏈狀或支鏈狀之烷基、 碳數1〜10之直鏈狀或支鏈狀之烷氧基，或碳數1〜10之直 鏈狀、支鏈狀或環狀之烷磺醯基。又，R15表示相互獨立 之碳數1〜10之直鏈狀或支鏈狀之烷基、苯基，或萘基。2 個之R15可相互鍵結形成包含硫陽離子之碳數2〜10之2價 之基。但，上述苯基、萘基，及碳數2〜10之2價之基可具 有取代基。k表示0〜2之整數，r表示0〜10之整數（較佳 爲0〜2之整數）。X_表示下述式（7-1)〜（7-4)所表示 之陰離子。 【化2 6 ΟII . R16—CtF2t —S = 0IIο ο1β II _ R16 —S = 〇IIο Ο-37- (6) 201202842 In the above formula (6), R13 represents a hydrogen atom, a fluorine atom, a meridine, a linear or branched alkyl group having a carbon number of 1 to ίο, and a carbon number of 1 to 1 〇. a chain or branched alkoxy group or a linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms. Further, R14 represents a linear or branched alkyl group having 1 to 1 carbon atom, a linear or branched alkoxy group having 1 to 10 carbon atoms, or a linear chain having 1 to 10 carbon atoms. a branched or cyclic alkanesulfonyl group. Further, R15 represents a linear or branched alkyl group, a phenyl group or a naphthyl group having 1 to 10 carbon atoms which are independent of each other. Two of R15 may be bonded to each other to form a divalent group having a carbon number of 2 to 10 including a sulfur cation. However, the above phenyl group, naphthyl group, and a valence group having a carbon number of 2 to 10 may have a substituent. k represents an integer of 0 to 2, and r represents an integer of 0 to 10 (preferably an integer of 0 to 2). X_ represents an anion represented by the following formulas (7-1) to (7-4). [6 2 ΟII . R16—CtF2t —S = 0IIο ο1β II _ R16 —S = 〇IIο Ο
S ΝS Ν
S Ο R17 R17 Οο (7-1 ) (7-2) R (7-3) 17 #4—II 0 ο^δ\ R17 (7-4) 式（7-1)及（7-2)中，R16表示氟原子或可被取代之 碳數1〜12之烴基。式（7-1)中，t表示1〜10之整數。式 (7-3)及（7-4)中’ Ri7爲相互獨立之被氟原子所取代之 碳數1〜10之直鏈狀或支鏈狀之烷基。又，2個R17可相互 鍵結形成被氟原子所取代之碳數2〜10之2價之有機基。又 ，氟原子所取代之碳數2〜10之2價之有機基亦可具有氟原 子以外之取代基。 -38- 201202842 酸產生劑（B)，可單獨含有1種上述式（6)所表示 之酸產生劑，或上述例示之酸產生劑’或含有2種以上亦 可° 酸產生劑（B )之使用比例，相對於敏輻射線性樹脂 組成物100質量％，爲20質量％以下’較佳爲1〜15質量％。 又，使用其他酸產生劑之情形，其使用比例，相對於 酸產生劑（B) 100質量％，通常爲80質量％以下，較佳爲 60質量％以下。 <溶劑（C ) > 溶劑（C)，例如，2-丁酮、2-戊酮、3-甲基-2-丁酮 、2-己酮、4-甲基-2-戊酮、3-甲基-2-戊酮、3,3-二甲基-2-丁酮、2-庚酮、2-辛酮等之直鏈狀或支鏈狀之酮類；環戊 酮、3-甲基環戊酮、環己酮、2-甲基環己酮、2,6-二甲基 環己酮、異佛爾酮等之環狀之酮類；丙二醇單甲基醚乙酸 酯、丙二醇單乙基醚乙酸酯、丙二醇單-η-丙基醚乙酸酯、 丙二醇單-i-丙基醚乙酸酯、丙二醇單-η-丁基醚乙酸酯、 丙二醇單-i-丁基醚乙酸酯 '丙二醇單-sec-丁基醚乙酸酯、 丙二醇單-t-丁基醚乙酸酯等之丙二醇單烷基醚乙酸酯類； 2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基丙酸η-丙酯、 2-羥基丙酸i-丙酯、2-羥基丙酸η-丁酯、2-羥基丙酸i-丁酯 、2-羥基丙酸sec-丁酯、2-羥基丙酸t-丁酯等之2-羥基丙酸 烷酯類；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 -乙氧基丙酸乙酯等之3 -烷氧丙酸烷酯類以 -39- 201202842 外，例如 η-丙基醇、i-丙基醇、η-丁基醇、t-丁基醇、環己醇、 乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單-η·丙基醚、 乙二醇單- η-丁基醚、二乙二醇二甲基醚、二乙二醇二乙基 醚、二乙二醇二-η-丙基醚、二乙二醇二-η-丁基醚、乙二 醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單-η-丙基醚乙酸酯、丙二醇單甲基醚、丙二醇單乙基醚、丙二 醇單-η-丙基醚、甲苯、二甲苯、2-羥基-2·甲基丙酸乙酯 、乙氧基乙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基酪酸甲 酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、 3-甲基-3-甲氧基丁基丙酸酯、3-甲基-3-甲氧基丁基丁酸 酯、乙酸乙基、乙酸η-丙酯、乙酸η-丁酯、乙醯乙酸甲酯 、乙醯乙酸乙酯、丙酮酸甲酯、丙酮酸乙酯' Ν-甲基吡咯 啶酮、Ν，Ν-二甲基甲醯胺、Ν，Ν-二甲基乙醯胺、苄基乙基 醚、二-η-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 '苄醇、乙酸苄酯、苯甲 酸乙酯、草酸二乙酯、馬來酸二乙酯、γ-丁內酯、碳酸乙 烯、碳酸丙烯等。 其中又以直鏈狀或支鏈狀之酮類、環狀之酮類、丙二 醇單烷基醚乙酸酯類、2-羥基丙酸烷基類、3-烷氧丙酸烷 基類、γ_丁內酯等爲佳。 敏輻射線性樹脂組成物，可單獨含有1種溶劑（C )， 或含有2種以上亦可。 溶劑（C )之使用量，相對於敏輻射線性樹脂組成物 -40- 201202842 之全固形分濃度，通常爲形成1〜50質量％之量，較佳爲形 成1〜25質量％之量。 <添加劑> 敏輻射線性樹脂組成物，必要時，可再含有酸擴散控 制劑（D )、脂環族添加劑、界面活性劑、增感劑、含氟 原子之聚合物（以下’亦稱爲聚合物（F))等各種添加 劑。 (i )酸擴散控制劑（D )： 酸擴散控制劑，爲具有可控制因曝光使酸產生劑（B )所產生之酸擴散於光阻層中之擴散現象，而抑制非曝光 區域中所不欲之化學反應之作用的成分。含有該些酸擴散 控制劑時，可提高敏輻射線性樹脂組成物之存放安定性。 又，作爲光阻時，除可使解析度再向上提升的同時，也可 抑制由曝光至曝光後之加熱處理之間因存放時間（PED ) 之改變所造成之光阻圖型之線寬變化，而可得到具有極優 良製程安定性之組成物。 酸擴散控制劑，例如，胺化合物、含醯胺基之化合物 、脲化合物、含氮雜環化合物等。 (胺化合物） 單（環）烷基胺類；二（環）烷基胺類；三（環）烷 基胺類；取代烷基之苯胺或其衍生物；乙烯二胺、 -41 - 201202842 Ν,Ν,Ν'Ν1-四甲基乙烯二胺、伸四甲基 、4,4’-二胺基二苯基甲烷、4,4·-二胺基 胺基二苯甲酮、4,4’-二胺基二苯基胺、 基）丙烷、2-(3-胺基苯基）-2-(4-胺 (4-胺基苯基）-2- ( 3^羥基苯基）丙燒 )-2- ( 4-羥基苯基）丙烷、1，4-雙（1-甲基乙基）苯、1，3-雙（1-(4-胺基苯: 苯、雙（2-二甲基胺基乙基）醚、雙（ )醚、1- ( 2-羥基乙基）-2-咪唑啶酉 1^，：^>^,：^'-四（2-羥基丙基）乙烯二胺 甲基二乙烯三胺等。 (含醯胺基之化合物） 含醯胺基之化合物中之較佳例示， 吡咯嗪等之含N-t-丁氧羰基之胺基化合 胺、N-甲基甲醯胺、N，N-二甲基甲醯胺 乙醯胺、N，N-二甲基乙醯胺、丙醯胺、 、N-甲基吡咯啶酮、N-乙醯基-1-金剛 酸三（2-羥基乙基）等。 (脲化合物） 脲化合物之較佳例示，例如脲、甲 脲、1，3-二甲基脲、1,1，3,3-四甲基脲、 η - 丁基硫服等。 二胺、六甲基二胺 二苯基醚、4,4’-二 2,2-雙（4-胺基苯 基苯基）丙烷、2-:、2- ( 4-胺基苯基 (4-胺基苯基）-1-_ ) -1-甲基乙基） 2-二乙基胺基乙基 同、2-羥基喹啉、 、N,N，N，，N"，N"-五 例如N-t-丁氧羰基 物以外，例如甲醯 、乙醯胺、N -甲基 苯醯胺、吡咯啶酮 烷基胺、異三聚氰 基脲、1，1 -二甲基 1，3-二苯基脲 '三_ -42- 201202842 (含氮雜環化合物） 含氮雜環化合物之較佳例示，例如咪唑類；吡啶類； 六氫吡啶類以外’例如吡嗪、吡唑、嗒嗪、喹唑啉、嘌呤 、吡咯嗪、哌啶、哌啶乙醇、3 -哌啶基-1，2 -丙烷二醇、嗎 啉、4 -甲基嗎啉、1 - ( 4 -嗎啉基）乙醇、4 -乙醯基嗎啉、 3- ( N-嗎啉基）-1,2-丙烷二醇、1,4_二甲基六氫吡啶、 1,4-重氮二環〔2.2.2〕辛烷等。 又，酸擴散控制劑，除前述酸擴散控制劑以外，可使 用經由曝光而感光’產生鹼之光崩壊性驗。 (光崩壞性鹼） 光崩壞性鹼之一例如，經由曝光而分解而失去酸擴散 控制性之鑰鹽化合物。該些鎗鹽化合物之具體例如，式（ 8)所表示之毓鹽化合物或，式（9)所表示之碘鎩鹽化合 物等。 【化2 7】S Ο R17 R17 Οο (7-1 ) (7-2) R (7-3) 17 #4—II 0 ο^δ\ R17 (7-4) In equations (7-1) and (7-2) R16 represents a fluorine atom or a hydrocarbon group having 1 to 12 carbon atoms which may be substituted. In the formula (7-1), t represents an integer of 1 to 10. In the formulae (7-3) and (7-4), ' Ri7 is a linear or branched alkyl group having 1 to 10 carbon atoms which is substituted by a fluorine atom. Further, two R17 groups may be bonded to each other to form a divalent organic group having 2 to 10 carbon atoms which is substituted by a fluorine atom. Further, the organic group having a carbon number of 2 to 10, which is substituted by a fluorine atom, may have a substituent other than a fluorine atom. -38-201202842 The acid generator (B) may contain one kind of the acid generator represented by the above formula (6) or the above-mentioned acid generator or may contain two or more kinds of acid generators (B). The use ratio is 20% by mass or less with respect to 100% by mass of the sensitive radiation linear resin composition, preferably from 1 to 15% by mass. In the case of using another acid generator, the use ratio thereof is usually 80% by mass or less, preferably 60% by mass or less based on 100% by mass of the acid generator (B). <Solvent (C) > Solvent (C), for example, 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, a linear or branched ketone such as 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-heptanone or 2-octanone; cyclopentanone, 3 a cyclic ketone such as methylcyclopentanone, cyclohexanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone or isophorone; propylene glycol monomethyl ether acetate , propylene glycol monoethyl ether acetate, propylene glycol mono-η-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-η-butyl ether acetate, propylene glycol mono-i a propylene glycol monoalkyl ether acetate such as butyl ether acetate propylene glycol mono-sec-butyl ether acetate or propylene glycol mono-t-butyl ether acetate; methyl 2-hydroxypropionate, Ethyl 2-hydroxypropionate, η-propyl 2-hydroxypropionate, i-propyl 2-hydroxypropionate, η-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, 2- 2-hydroxypropionic acid alkyl esters such as hydroxy-propionic acid sec-butyl ester and 2-hydroxypropionic acid t-butyl ester; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, 3-B The alkyl 3-propoxypropionate such as ethyl propyl propionate is other than -39-201202842, such as η-propyl alcohol, i-propyl alcohol, η-butyl alcohol, t-butyl alcohol, cyclohexane Alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-η·propyl ether, ethylene glycol mono-η-butyl ether, diethylene glycol dimethyl ether, two Ethylene glycol diethyl ether, diethylene glycol di-η-propyl ether, diethylene glycol di-η-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, ethylene glycol mono-η-propyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-η-propyl ether, toluene, xylene, 2-hydroxy-2· Ethyl methacrylate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methyl Oxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, η-propyl acetate, Η-butyl acetate, methyl acetate, ethyl acetate, methyl pyruvate, ethyl pyruvate 'Ν-methylpyrrolidone, hydrazine, hydrazine-dimethyl Mercaptoamine, hydrazine, hydrazine-dimethylacetamide, benzyl ethyl ether, di-η-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, hexanoic acid, Caprylic acid, 1-octanol, 1-nonanol 'benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and the like. Among them, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, 2-hydroxypropionic acid alkyls, 3-alkoxypropionic acid alkyls, γ_ Butyrolactone and the like are preferred. The sensitive radiation linear resin composition may contain one type of solvent (C) alone or two or more types. The amount of the solvent (C) to be used is usually from 1 to 50% by mass, preferably from 1 to 25% by mass, based on the total solid content of the radiation sensitive linear resin composition of -40 to 201202842. <Additive> The sensitive radiation linear resin composition may further contain an acid diffusion controlling agent (D), an alicyclic additive, a surfactant, a sensitizer, a fluorine atom-containing polymer (hereinafter also referred to as 'also known as It is various additives such as polymer (F)). (i) Acid diffusion controlling agent (D): an acid diffusion controlling agent having a diffusion phenomenon capable of controlling diffusion of an acid generated by the acid generating agent (B) into the photoresist layer by exposure, thereby suppressing a non-exposed area An ingredient that does not interfere with the chemical reaction. When the acid diffusion controlling agent is contained, the storage stability of the sensitive radiation linear resin composition can be improved. Moreover, as the photoresist, in addition to the resolution can be increased upward, the line width variation of the photoresist pattern caused by the change of the storage time (PED) between the exposure and the exposure after the exposure can be suppressed. A composition having excellent process stability can be obtained. The acid diffusion controlling agent is, for example, an amine compound, a guanamine-containing compound, a urea compound, a nitrogen-containing heterocyclic compound or the like. (amine compound) mono(cyclo)alkylamines; di(cyclo)alkylamines; tri(cyclo)alkylamines; substituted alkyl anilines or derivatives thereof; ethylenediamine, -41 - 201202842 Ν ,Ν,Ν'Ν1-tetramethylethylenediamine, tetramethyl, 4,4'-diaminodiphenylmethane, 4,4·-diaminoaminobenzophenone, 4,4 '-Diaminodiphenylamine, yl)propane, 2-(3-aminophenyl)-2-(4-amine(4-aminophenyl)-2-(3^hydroxyphenyl)propane Burning)-2-(4-hydroxyphenyl)propane, 1,4-bis(1-methylethyl)benzene, 1,3-bis(1-(4-aminobenzene: benzene, bis(2-) Dimethylaminoethyl)ether, bis()ether, 1-(2-hydroxyethyl)-2-imidazolidinium 1^,:^>^,:^'-tetrakis(2-hydroxypropyl Ethylenediaminemethyldiethylenetriamine, etc. (Compound containing amidino group) Preferred examples of the amine group-containing compound, Nt-butoxycarbonyl group-containing amine compound of pyrrolazine or the like, N- Methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, acetamide, N-methylpyrrolidone, N-ethenyl- 1-adanic acid tris(2-hydroxyethyl), etc. (Urea compound) Preferred examples of the urea compound are, for example, urea, methyl urea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, η-butylsulfate, etc. , hexamethyldiamine diphenyl ether, 4,4'-di 2,2-bis(4-aminophenylphenyl)propane, 2-:, 2-(4-aminophenyl) Aminophenyl)-1-()-1-methylethyl) 2-diethylaminoethyl, 2-hydroxyquinoline, N, N, N,, N", N"-five For example, other than Nt-butoxycarbonyl, such as formazan, acetamide, N-methylbenzamide, pyrrolidone alkylamine, isocyanatourea, 1,1-dimethyl1,3- Diphenylurea 'Tris-42-201202842 (nitrogen-containing heterocyclic compound) Preferred examples of nitrogen-containing heterocyclic compounds, such as imidazoles; pyridines; other than hexahydropyridines, such as pyrazine, pyrazole, pyridazine , quinazoline, hydrazine, pyrrole, piperidine, piperidine ethanol, 3-piperidinyl-1,2-propanediol, morpholine, 4-methylmorpholine, 1-(4-morpholinyl) Ethanol, 4-ethylhydrazinomorpholine, 3-(N-morpholinyl)-1,2-propanediol, 1,4-dimethylhexahydropyridine, 1,4-diazobicyclo[2.2. 2] octane, etc. Further, the acid diffusion controlling agent may be used in addition to the acid diffusion controlling agent, and may be used to detect light-induced photocracking by exposure. (Photocracking base) One of photocracking bases For example, a key salt compound which decomposes by exposure and loses acid diffusion controllability. Specific examples of the gun salt compound include an onium salt compound represented by the formula (8) or an iodonium salt compound represented by the formula (9). . [化 2 7]
(8)(8)
R2>C R22 (9) 式（8 )中之R18〜R: 及式（9 )中之R21〜R22表示 -43- 201202842 相互獨立之氫原子、烷基、烷氧基、羥基，或鹵素原子。 又，式（8)及式（9)中，Z-爲 OH·、R23-C00-、R23_ S〇T(其中，R23表示烷基、芳基，或烷芳基），或式（1〇 )所表示之陰離子。 【化2 8】R2>C R22 (9) R18 to R in the formula (8): and R21 to R22 in the formula (9) represent -43 to 201202842 mutually independent hydrogen atoms, alkyl groups, alkoxy groups, hydroxyl groups, or halogen atoms . Further, in the formulae (8) and (9), Z- is OH·, R23-C00-, R23_S〇T (wherein R23 represents an alkyl group, an aryl group or an alkylaryl group), or a formula (1〇) ) the anion represented. [化2 8]
式（10)中，R24表示，可被氟原子所取代或未取代 之碳數1〜12之直鏈狀或支鏈狀之烷基，或碳數ι〜12之直 鏈狀或支鏈狀之烷氧基，η表示0〜2之整數。 又，該些酸擴散控制劑，可單獨使用1種，或將2種以 上混合使用亦可。 酸擴散控制劑之含量，相對於聚合物（Α) 1〇〇質量份 ，以0_001〜15質量份爲佳，以0.01〜10質量份爲較佳，以 0.05〜5質量份爲更佳。含量超過15質量份時，作爲光阻 時會有感度降低之情形。又，未達〇.〇〇 1質量份時，依製 造條件之不同，作爲光阻時會有圖型形狀或尺寸忠實度降 低之情形。 (ii)脂環族添加劑： 脂環族添加劑爲具有可改善耐乾蝕刻性、圖型形狀、 與基板之黏著性等之作用的成分。 脂環族添加劑，例如，1 -金剛烷羧酸、2 -金剛烷酮、 -44 - 201202842 i-金剛烷羧酸t-丁酯、1-金剛烷羧酸t-丁氧羰基甲酯 剛烷羧酸α-丁內酯、1,3-金剛烷二羧酸二-t-丁酯、 烷乙酸t-丁酯、1-金剛烷乙酸t-丁氧羰基甲酯、1，3-二乙酸二-t-丁酯、2,5-二甲基-2,5-二（金剛烷基羰 )己烷等之金剛烷衍生物類；去氧膽酸t-丁酯、去 t-丁氧羰基甲酯、去氧膽酸2-乙氧基乙酯、去氧膽 己基氧乙酯、去氧膽酸3-酮基環己酯、去氧膽酸四 、去氧膽酸甲基戊酸內醋（Meval〇nolactone)等之 酸酯類；膽石酸（Lithocholic acid ) t-丁酯 '膽石 氧羰基甲酯、膽石酸2-乙氧基乙酯、膽石酸2-環己 酯、膽石酸3-酮基環己酯、膽石酸四氫吡喃、膽石 戊酸內酯等之膽石酸酯類；3-(2-羥基-2,2-雙（三 )乙基）四環〔6.2_1.13’6.〇2’7〕十二烷等。又，該 環族添加劑，可單獨使用1種，或將2種以上混合使 (iii)界面活性劑： 界面活性劑爲具有改良塗佈性、線性、顯影性 用的成分。 界面活性劑，例如，聚氧乙烯月桂醚、聚氧乙 醚、聚氧乙烯油醚、聚氧乙烯η-辛基苯醚、聚氧乙 基苯醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸 離子系界面活性劑以外’例如以下商品名之ΚΡ3 41 化學工業公司製）、POLY FLOW No.75、同No.95 ( 、1-金 1 -金剛 金剛烷 基氧基 氧膽酸 酸2-環 氫卩比喃 去氧膽 酸t-丁 基氧乙 酸甲基 氟甲基 些之脂 用亦可 等之作 烯硬脂 烯η-壬 酯等非 (信越 以上， -45- 201202842 共榮公司化學公司製）、FTOP EF301、同EF303、同 EF352(以上，托克製品公司製）、美格氟F171、同F173 (以上，大日本塗料化學工業公司製）、氟樂拉FC43 0、 同F C 4 3 1 (以上，住友3 Μ公司製）、朝日A G 7 1 0、沙氟隆 S-382、同 SC-101、同 SC-102、同 SC-103、同 SC-104、同 SC-105、同SC-106C以上，旭硝子公司製）等。又，該些 界面活性劑可單獨使用1種，或將2種以上混合使用亦可。 (iv )增感劑： 增感劑爲，具有可吸收輻射線之能量，並將該能量傳 達至酸產生劑（B)，並以其增加酸之生成量作用者，添 加於敏輻射線性樹脂組成物時，具有提升感度之效果。 增感劑例如，咔唑類、苯乙酮類、二苯甲酮類、萘類 、酣類、二乙醯、洋紅（Eosin)、玫瑰紅（Rose bengal ) '芘類、蒽類、酚噻嗪類等。又，該些增感劑可單獨使 用1種，或將2種以上混合使用》 (v)含氟原子之聚合物（F) 敏輻射線性樹脂組成物，於含有含氟原子之聚合物（ F)時，於形成光阻膜之際，基於膜中含氟原子之聚合物 的撥油性特徵，具有使其分布偏處於光阻膜表面附近之局 部化傾向，而可抑制浸潤式曝光時中之酸產生劑或酸擴散 控制劑等溶出於浸潤媒體。 上述含氟聚合物（F)，只要具有氟原子時，則無特 -46- 201202842 別之限定’又以含氟原子之比率（質量。/。）較〔A〕聚合 物爲高者爲佳。含氟原子之比率較〔A〕聚合物爲高時， 可更提高上述局部化之程度，而可提高所得光阻被膜之撥 水性及溶出抑制性等特性。 (v i )其他添加劑： 敏輻射線性樹脂組成物，可含有前述添加劑以外之添 加劑（以下，亦稱爲「其他添加劑」）。其他添加劑，例 如鹼可溶性樹脂 '具有酸解離性保護基之低分子的鹼溶解 性控制劑、抗暈劑、保存安定劑、消泡劑等。又，於含有 染料或顏料時’可使曝光部之潛像形成可視化，而緩和曝 光時之光暈的影響。此外，含有黏著助劑時，可改善與基 板之黏著性。 敏輻射線性樹脂組成物，爲將上述各構成成分溶解於 溶劑（C )後’再使用例如孔徑〇 · 2 μιη左右之過濾器，經由 過爐方式製作塗佈液，而可塗佈於基板上。 【實施方式】 〔實施例〕 二乂下’本發明將以實施例爲基礎作具體之說明，但本 發明並不受限於該些實施例。又，實施例、比較例中之「 份J及「％」’於無特別規定下係爲質量基準。又，各種 %'丨生丨直之 '測定方法，及各種特性之評估方法係如以下所示 -47- 201202842 〔重量平均分子量（Mw)及數平均分子量（Mn)〕； 使用東曹公司製GPC管柱（G2000HXL2管、 G3 000HXL1管、G4000HXL1管），流量：、溶 出溶劑：四氫呋喃、管柱溫度：4 0。(：之分析條件，以凝膠 滲透色層分析（GPC) ’使用單分散聚苯乙烯爲標準進行 測定。 〔13C-NMR分析〕： 各聚合物之13c-nmr分析爲使用日本電子公司製「J Ν Μ - E X 2 7 0」進行測定。 〔圖型評估〕： 將形成有單一圖型（以下，亦稱爲s Ε )及以D Ε所形 成之接觸孔圖型後之評估用基板，使用掃描型電子顯微鏡 (曰立計測器公司製，CG-4000)進行觀察，光阻圖型產 生損失或附著雜物之情形評估爲「不良」，孔洞沒有掩埋 •沒有淤渣下，解析至底部而形成接觸孔圖型之情形評估 爲「良好」。 〔蝕刻程度評估〕： 對形成接觸孔圖型後之評估用基板，使用簡易蝕刻裝 置進行觀察，蝕刻後之殘膜率相對於當初膜厚爲60%以下 者評估爲「不良」，60%以上良好之情形評估爲「良好」 -48- 201202842 以下，將說明聚合物（A )之製作方法。又，製作聚 合物（A )所使用之單體（M-1 )〜單體（M-26 )係如以 下所示。單體（M-1 )〜單體（M-26 )中，提供重複單位 (al)之單體爲單體（M-1)〜單體（M-5)，提供重複單 位（a2)之單體爲單體（M-7)〜單體（M-13)，提供重 複單位（a3)之單體爲單體（M-14)〜單體（M-23)，提 供其他重複單位之單體爲單體（M-6 )及單體（M-24 )〜 單體（M-26 )。 【化2 9】In the formula (10), R24 represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted or unsubstituted by a fluorine atom, or a linear or branched chain having a carbon number of 1-4 The alkoxy group, η represents an integer of 0 to 2. Further, the acid diffusion controlling agents may be used singly or in combination of two or more. The content of the acid diffusion controlling agent is preferably 0-001 to 15 parts by mass, more preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per part by mass of the polymer (?). When the content exceeds 15 parts by mass, the sensitivity may be lowered as a photoresist. Further, when it is less than 1 part by mass, depending on the manufacturing conditions, there may be a case where the pattern shape or the dimensional fidelity is lowered as a photoresist. (ii) Alicyclic additive: The alicyclic additive is a component having an effect of improving dry etching resistance, pattern shape, adhesion to a substrate, and the like. Alicyclic additives, for example, 1-adamantanecarboxylic acid, 2-adamantanone, -44 - 201202842 i-adamantanecarboxylic acid t-butyl ester, 1-adamantanecarboxylic acid t-butoxycarbonyl methyl esterane A-butyrolactone carboxylic acid, di-t-butyl 1,3-adamantane dicarboxylate, t-butyl methacrylate, t-butoxycarbonyl methyl ester of 1-adamantane acetate, 1,3-diacetic acid Adamantane derivatives such as di-t-butyl ester, 2,5-dimethyl-2,5-di(adamantylcarbonyl)hexane; t-butyl deoxycholate, de-butoxy Carbonyl methyl ester, 2-ethoxyethyl deoxycholate, deoxycholyloxyethyl ester, 3-ketocyclohexyl deoxycholate, deoxycholic acid tetradeoxycholic acid methylvalerate Acid vinegar (Meval 〇 nolactone) and other acid esters; Lithocholic acid t-butyl ester 'cholesteryl oxycarbonyl methyl ester, cholic acid 2-ethoxyethyl ester, cholinate 2-cyclohexyl Ester, cholinate, 3-ketocyclohexyl ester, tetrahydropyran, cholinate, etc.; 3-(2-hydroxy-2,2-bis(III) Ethyl) tetracyclo[6.2_1.13'6.〇2'7]dodecane and the like. Further, the cycloaddite additive may be used singly or in combination of two or more kinds thereof. (iii) Surfactant: The surfactant is a component having improved coatability, linearity, and developability. Surfactant, for example, polyoxyethylene lauryl ether, polyoxyethyl ether, polyoxyethylene ether, polyoxyethylene η-octyl phenyl ether, polyoxyethyl phenyl ether, polyethylene glycol dilaurate, polyethylene Other than the diol distearate ion-based surfactant, for example, the following product name: ΚΡ3 41 Chemical Industry Co., Ltd., POLY FLOW No. 75, and the same No. 95 (, 1-gold 1 -adamantine alkoxy oxygen The bile acid 2-ring hydroquinone is more than the t-butyl oxyacetic acid methyl fluoromethyl carboxydeoxycholate, and can also be used as the stearyl η- oxime ester, etc. (Shin-Etsu, above -45 - 201202842 Co., Ltd.), FTOP EF301, EF303, EF352 (above, Toke Products Co., Ltd.), Megfried F171, F173 (above, manufactured by Dainippon Coating Chemical Industry Co., Ltd.), Fluorella FC43 0, same as FC 4 3 1 (above, Sumitomo 3 Μ company), Asahi AG 7 10, Shaflon S-382, same SC-101, same SC-102, same SC-103, same SC-104 , with the same SC-105, the same as SC-106C, Asahi Glass Co., Ltd.). Further, these surfactants may be used alone or in combination of two or more. (iv) sensitizer: A sensitizer is a linear resin that absorbs radiation and transmits the energy to the acid generator (B) and increases the amount of acid generated by it. When the composition is used, it has the effect of lifting sensitivity. Sensitizers, for example, oxazoles, acetophenones, benzophenones, naphthalenes, anthraquinones, acetophenones, eosin, rose bengal 'steroids, anthraquinones, phenolthiophenes Ethyls and the like. Further, these sensitizers may be used singly or in combination of two or more kinds thereof. (v) fluorine atom-containing polymer (F) radiation sensitive linear resin composition in a fluorine atom-containing polymer (F When the photoresist film is formed, the oil-repellent property of the polymer based on the fluorine atom in the film has a localization tendency to make the distribution biased near the surface of the photoresist film, and can suppress the exposure during the immersion exposure. An acid generator or an acid diffusion controlling agent or the like is dissolved in the infiltration medium. When the fluorine-containing polymer (F) has a fluorine atom, it is not particularly limited to -46 to 201202842, and it is preferable that the ratio of the fluorine atom (mass / /) is higher than that of the polymer [A]. . When the ratio of the fluorine-containing atom is higher than that of the [A] polymer, the degree of localization can be further improved, and characteristics such as water repellency and dissolution inhibition of the obtained photoresist film can be improved. (v i ) Other additives: The sensitive radiation linear resin composition may contain an additive other than the above additives (hereinafter also referred to as "other additives"). Other additives, such as an alkali-soluble resin, a low molecular alkali solubility control agent having an acid dissociable protecting group, an antihalation agent, a storage stabilizer, an antifoaming agent, and the like. Further, when a dye or a pigment is contained, the latent image of the exposed portion can be visualized to mitigate the influence of halation during exposure. In addition, when it contains an adhesion aid, it can improve the adhesion to the substrate. The radiation-sensitive linear resin composition is prepared by dissolving the above-mentioned respective components in the solvent (C) and then using a filter having a pore diameter of about 2 μm, and preparing a coating liquid by a furnace method to coat the substrate. . [Embodiment] [Embodiment] The present invention will be specifically described based on the embodiments, but the present invention is not limited to the embodiments. Further, in the examples and comparative examples, "part J and "%"" are based on the quality standard unless otherwise specified. In addition, various methods for measuring the '% of the sputum' and the evaluation methods of various characteristics are as follows -47 - 201202842 [weight average molecular weight (Mw) and number average molecular weight (Mn)]; GPC made by Tosoh Corporation Pipe column (G2000HXL2 pipe, G3 000HXL1 pipe, G4000HXL1 pipe), flow rate: dissolution solvent: tetrahydrofuran, column temperature: 40. (The analysis conditions were determined by gel permeation chromatography (GPC)' using monodisperse polystyrene as a standard. [13C-NMR analysis]: 13c-nmr analysis of each polymer was performed by Nippon Electronics Co., Ltd. J Ν Μ - EX 2 7 0" is measured. [Graph evaluation]: An evaluation substrate in which a single pattern (hereinafter, also referred to as s Ε ) and a contact hole pattern formed by D 形成 is formed, Using a scanning electron microscope (manufactured by Sigma Instruments Co., Ltd., CG-4000), the loss of the photoresist pattern or the attachment of impurities was evaluated as "poor", the holes were not buried, and the bottom was not resolved, and the bottom was resolved to the bottom. The case where the contact hole pattern was formed was evaluated as "good." [Evaluation of etching degree]: The evaluation substrate after forming the contact hole pattern was observed using a simple etching apparatus, and the residual film ratio after etching was relative to the original film thickness. 60% or less is evaluated as "poor", and 60% or more is evaluated as "good" -48-201202842 Hereinafter, the production method of the polymer (A) will be explained. Further, the polymer (A) is used. Monomer (M The monomer (M-26) is as follows. In the monomer (M-1) to the monomer (M-26), the monomer which provides the repeat unit (al) is a monomer (M-1). ~ monomer (M-5), the monomer providing repeat unit (a2) is monomer (M-7) ~ monomer (M-13), and the monomer providing repeat unit (a3) is monomer (M -14) ~ monomer (M-23), the monomers providing other repeating units are monomer (M-6) and monomer (M-24) ~ monomer (M-26).
-49 - 201202842 CH, CH,-49 - 201202842 CH, CH,
H2C = C ch3 CHa h2c = c C = 0H2C = C ch3 CHa h2c = c C = 0
H2C = C c=o c=oH2C = C c=o c=o
(M-11 c=o h2c=c \ n h3c(M-11 c=o h2c=c \ n h3c
0 \ ch2 / c=o \ o 0, (Μ·12) 【化3 0】0 \ ch2 / c=o \ o 0, (Μ·12) [化3 0]
H3C \ c = ch2 h3c \ c=ch2 H3c o = c c=ch2 / ch3 h2c = c o=c o=c c=oH3C \ c = ch2 h3c \ c=ch2 H3c o = c c=ch2 / ch3 h2c = c o=c o=c c=o
h3c \H3c \
h3c \ 〇H3c \ 〇
CH, / h3c c=ch2 c = ch2 C = CH, h2c = c o = c o=c o=c c = o o o o h2c h2c c=o c=o h2c \CH, / h3c c=ch2 c = ch2 C = CH, h2c = c o = c o=c o=c c = o o o o h2c h2c c=o c=o h2c \
o \o \
(M-19)(M-19)
0 = C0 = C
NHNH
CH 2 hoh2c (M-21 ) 50- 201202842CH 2 hoh2c (M-21) 50- 201202842
\ ch2oh (M- 22 ) (M- 23 ) 【化3 1】 H3C\ \ C — CH2 h3c c = / ch2 1 o=c c=ch2 / c o=c \ 0 / \ 0 H2C o=c \ 0 / h3c-ch ch2 / /CH2 HN h2c \ cf3 F3C —c / \ h3c、 \ c = o HO CF3 y-N； VN 1 ch3 (M - 24 ) (M - 25 ) (M - 26 ) 〔聚合例 1〕 聚合 物（A -1 )之製 '、出 is 首先 > 準備 將單體（M-l 1 )50mol%、單體（ M-3 ) 1 5 m ο 1 %、 單 體（ M - 2 ) 3 5 m 01 % 、及聚合起始劑（二 甲基- 2,2’-偶氮 二 異丁 酸酯（MAIB ) )溶解於l〇〇g甲基乙基 酮 所得之單 體 溶液 。以製造混合時之單體的合計量爲 5〇g 〇 又，各單 體 之me >1%爲表示相對: 於單體全量之mol% ’聚 合 起始劑之 使 用比 例，相對於單體 丨與聚合起始劑之合計量 ， 設定爲5mol%。 -51 - 201202842 又，於具備有溫度計及滴下漏斗之500mL之三口燒瓶 中，加入甲基乙基酮50g’進行30分鐘之氮氣吹入。隨後 ，於燒瓶內使用磁攪拌子進行攪拌，並加熱至80。(：。其次 ，將所準備之單體溶液使用滴下漏斗以3小時時間滴入於 燒瓶內。滴下結束後，進行3小時熟成後，冷卻至3 〇 -c以 下以製得聚合物溶液。隨後，將聚合物溶液投入1 0 00g之 甲醇中進行混合。其次，實施吸引過濾。隨後，回收粉體 ’再度投入2 0 0 g之甲醇中’經洗淨、過濾。再次進行此洗 淨處理，將回收之粉體於60°c下減壓乾燥。所得聚合物作 爲聚合物（A-1) 。該聚合物（A-l)之Mw爲6,200，Mw/ Μη爲1 .5，13 C-NMR分析結果，得知爲各單體所生成之各 重複單位之含有率（M-3) / (M-2) / ( (Μ-11) =14.6 /35.9/49.5 (mol%)之共聚合物。 〔聚合例2〜21〕聚合物（A-2)〜（A-16)、聚合物（F-1 )〜（F-5 )之製造 對聚合物（A-2)〜（A-16)及聚合物（F-1)〜（F-5)，除使用表1所示種類及添加量之單體以外，其他皆依 聚合例1相同方法進行製造。又，表2爲記載各聚合物之 13C-NMR所測得之各單體所生成之各重複單位的含有率、 Mw、及 Mw/Mno 52- 201202842 【表1】 聚合例 聚合物 生成(al)之單體 生成(a2)之單體 生成(a3)之單體 其他單體 mm 添加量 (mol%) 種類 添加量 (mol%) mm 添加量 (mol%) 種類 添加量 (mol%) 1 A-1 M-2 35 M-11 50 - - - - M-3 15 2 A-2 M-2 60 M-8 20 - - M-6 20 3 A-3 M-4 25 M-13 50 M-21 10 - - M-5 15 4 A-4 M-2 35 M-8 30 M-14 15 M-6 20 5 A-5 M-3 25 M-7 25 M-19 15 - - M-8 35 6 A-6 M-4 35 M-8 10 M-18 15 M-6 40 7 A-7 M-3 35 M-8 40 M-17 10 - - M-20 15 8 A-8 M-4 40 M-12 40 M-14 20 - - 9 A-9 M-3 35 M-9 20 M-15 15 M-6 30 10 A-10 M-4 25 M-10 50 M-21 15 - - M-5 10 11 A-11 M-4 . 25 M-11 50 M-23 15 - - M-5 10 12 A-12 M-3 20 M-8 50 M-21 15 - - M-5 15 13 A-13 M-4 30 M-12 40 M-16 20 - - M-5 10 14 A-14 M-1 30 M-8 48 M-22 20 M-25 2 15 A-15 M-4 40 M-8 30 M-14 20 - - M-5 10 16 A-16 M-3 60 - - M-15 40 - - 17 F-1 M-2 70 - - - - M-26 30 18 F-2 - - - - M-14 50 M-24 30 M-26 20 19 F-3 - - - - M-21 40 ‘24 20 M-26 40 20 F-4 M-2 30 - - M-15 30 M-26 40 21 F-5 - - - - M-14 40 M-24 20 M-26 40 -53- 201202842 【表2】 聚合例 聚合物 生成(al)之單體 生成(a2)之單體 生成(a3)之單體 其他單體 Mw 種類 添加fl (mol%) 種類 添加il (mol%) 種類 添加 (mol%) 種類 添加量 (mol%) 1 A-1 M-2 35.9 M-11 49.5 - - - - 6200 M-3 14.6 2 A-2 M-2 60,5 M-8 18.5 - M-6 21 6800 3 A-3 Μ-4 24.5 M-13 52.5 M-21 9.8 - - 6100 Μ-5 13.2 4 A-4 Μ-2 35.8 M-8 28 M-14 15.2 M*6 21 6300 5 A-5 Μ-3 25.5 M-7 25.5 M-19 14.2 - - 6500 M-8 34.8 6 A-6 Μ-4 34.5 M-8 9 M-18 15.2 M-6 41.3 6700 7 A-7 Μ-3 34.8 M-8 4U M-17 8.9 - - 6800 M-20 15.2 8 A-8 Μ-4 38,8 M-12 41.6 M-14 19.6 - - 6000 9 A-9 Μ-3 34.5 M-9 20.5 M-15 14.5 M-6 30.5 5900 10 A-10 Μ-4 25.1 M-10 51.2 M-21 14.7 - - 6300 υτ 9 11 A-11 μ-4 25.3 M-11 51 M-23 14,3 - - 6400 9‘4 12 A-12 Μ-3 20.5 M-8 50.2 M-21 15.1 - - 6000 Μ-5 14.2 13 A-13 Μ-4 29 M-12 41.3 M-16 18.7 - -♦ 6800 Μ-5 11 14 A-14 Μ-1 30.3 M-8 48.3 M-22 19.6 M-25 1.8 6500 15 A-15 Μ-4 40.8 M**8 30.3 M-14 19.8 - - 6200 Μ-5 9.1 16 A-16 Μ-3 59.5 - M-15 40.5 - - 5500 17 F-1 Μ-2 70.5 - - 墨 - M-26 29.5 4800 18 F_2 - - - - M-14 50.2 M-24 29.5 5500 20.3 19 F*3 - - - - M-21 40.2 M~24 20.3 5700 M-26 39*5 20 F-4 Μ-2 30.2 - - M-15 29.8 M-26 40 5900 21 F-5 - - - - M-14 39.6 M-24 19.6 5800 Μ-2έ 40.8 〔實施例1〕敏輻射線性樹脂組成物之製造 添加聚合物（A)之聚合物（A-1) 100份、酸產生劑 (B)之酸產生劑（B-1)(三苯基锍九氟-η-丁烷磺酸酯 )7.5份、含氮化合物（D )之酸擴散抑制劑（D-l ) ( Ν- t-丁氧羰基吡咯嗪）0.94份、聚合物（F)之聚合物（F-2 )5份、及溶劑（C)之溶劑（C-1)(丙二醇單甲基醚乙 -54- 201202842 酸酯）1287份及溶劑（C-2)(環己酮）551份，將各成分 混合以形成均勻溶液。隨後，使用孔徑200nm之膜過濾器 進行過濾結果，製得敏輻射線性樹脂組成物。 〔實施例2〜1 6及比較例1〕 除使用表3所記載之添加配方以外，其他皆依實施例1 相同方法製造各敏輻射線性樹脂組成物。 【表3】 敏輻射線 性樹脂 組成物 聚合 Ι^Ι(Α) 聚合物(F) 酸產生劑(B) 溶劑 (C) 酸擴散控制劑(D) 麵 使用量 (份） 種類 使用量 (份） 種類 使用量 (份） mm 使用量 (份） 種類 使用量 (份） 種類 使用量 (份） 實施例1 I A-1 100 F~2 5 β-1 7.5 €·Ι 1287 ¢-2 551 0-1 0.94 實施例2 2 A*2 !00 F-*3 5 B-1 7.5 C-1 1267 C-2 551 0.94 實施例3 3 A~3 100 F—4 5 Β-1 7.5 C-1 1287 C-2 551 CM 0.94 實施例4 4 Α·4 100 S β** 1 7.5 C-1 126? 0*2 551 D-l 0.94 實施*5 5 Α-5 !00 F-1 5 β崎Ί 7.5 <Μ 1237 C-2 551 D-1 0.94 實施例6 6 Λ*6 too F—1 S 8—1 7.5 C-I 1237 C-2 551 D-1 ΜΑ 實施例7 7 Α-7 100 F-2 5 B—*1 7.5 C-1 1287 C-2 $51 D-l 0.94 實施例8 8 Α-8 too F-5 S 8—1 7.S C-I 1287 G-2 551 D-1 0.94 實施例9 9 Α-9 IO0 F-3 5 Θ—Ι 7.5 C-1 1287 C-2 551 0-1 0.94 實施例10 10 ΑΗΟ too F-4 5 Β-1 7*5 C-I i287 C-2 551 » - 實施例11 11 Α·" 100 F-4 δ 8-1 ?.δ C-I mi C-2 551 D-l ad4 實施例12 12 Α_12 too F-3 5 Β-1 7.5 CH 1287 C'2 551 D-1 0.94 實施例13 13 Α-13 100 F—4 5 Β-1 7.5 C·*! 1237 C-2 551 D-1 a94 實施例” 14 Α-14 100 F-2 5 Β-1 7.5 <Μ *287 C-2 55) D-1 0.94 實施例J 15 A-1S too F-»5 5 8»1 7.5 C-1 1287 C-2 551 D-1 0.34 實施例16 16 Α-8 too F-l 5 8-1 7.5 C-J 1267 C-2 551 D-T 0.94 比較例1 17 Α·1β 100 F—2 5 C-1 7.5 (Μ 1287 C-2 551 D-1 0.94 又，表1所使用之酸產生劑、溶劑、及酸擴散控制劑 之種類係如以下所示。 酸產生劑（B-1):三苯基锍九氟-η-丁烷磺酸酯 溶劑（C -1 ):丙二醇單甲基醚乙酸酯 溶劑（C - 2 ):環己酮 酸擴散控制劑（D-l ) : N-t-丁氧羰基吡咯嗪 -55- 201202842 〔實施例1 7〕光阻圖型之形成 將下層抗反射膜（商品名「ARC66」、普瓦科技公司 製）使用商品名「Lithius Pro-i」（東京電子公司製）旋 轉塗佈器塗佈於12英吋矽晶圓上之後’進行PB ( 205 °C、 60秒）後以形成膜厚77nm之塗膜。 使用商品名「CLEAN TRACK ACT12」旋轉塗佈器旋 轉塗佈實施例1所製造之敏輻射線性組成物（1 )，進行PB (130°C、60秒）處理後，進行冷卻（23°C、30秒）以形成 膜厚90nm之光阻層。使用所形成之光阻層，形成以下之 DE圖型、SE圖型，並進行各種評估。 〔DE圖型〕： 使用ArF浸潤式曝光裝置（商品名「S61 0C」、NIKON 公司製），於NA: 1.30、Dipole之光學條件下，介由48nm 線路/96nm間距（48nmlL/lS)之圖型形成用遮罩進行曝 光。隨後，以對先前之曝光爲垂直交叉之方式，介由48nm 線路/96nm間距（48nmlL/lS)之圖型形成用遮罩進行 曝光。 於商品名「Lithius Pro-i」之熱壓板上進行peb ( 125°C、60秒）’冷卻（23°C、30秒）後，使用顯影杯之 GP噴嘴，將乙酸丁酯作爲顯影液進行攪拌顯影（1 〇秒間） ，並使用4 -甲基-2-戊醇洗滌》於2000rpm、15秒鐘振動下 進行旋轉乾燥結果，製得形成有48nm通孔/ 96nm間距之 -56- 201202842 接觸孔圖型的評估用基板。 該評估用基板之DE圖型之評估及蝕刻程度之評估爲「 良好」。 〔SE圖型〕： 使用ArF浸潤式曝光裝置（商品名「S610C」、NIKON 公司製），於NA: 1.30、交叉桿之光學條件下，介由 48nm點狀/9 6nm間距（遮罩偏向（bias )爲+ 15nm，實際 上爲於遮罩上形成25 2nm點狀/3 84nm間距之形狀）的圖型 形成用遮罩進行曝光。 於商品名「Lithius Pr〇-i」之熱壓板上進行PEB ( 125°C、60秒），經冷卻（23 °C、30秒）後，以顯影杯之 GP噴嘴，將乙酸丁酯作爲顯影液進行攪拌顯影（3 0秒間） ’使用4-甲基-2-戊醇進行洗滌。2000 rpm、15秒鐘振動下 進行旋轉乾燥結果，製得形成有48nm通孔/ 96nm間距之 接觸孔圖型的評估用基板。 該評估用基板之SE圖型之評估及蝕刻程度之評估爲「 良好」。 〔實施例1 8〜3 2、比較例2〕 除表4所記載之內容以外，其他皆依實施例1 7相同方 法製得各評估用基板。所得之各評估用基板之評估結果合 倂記載於表4。 -57- 201202842 【表4】 敏輻射 線性組 成物 光阻膜之ΡΒ 條件 雙重曝光後 之PEB條件 顯影液之洗滌溶劑種類 DEH型 之評估 SE圖型之 評估 蝕刻程度 之評估 溫度 (°C ) 時間 (秒） 酿 (°C ) 時間 (秒） 顯影液 洗滌液 ϋ施例π 130 60 125 60 乙酸丁酯 4-甲基-2-戊醇 良好 良好 良好 Η施例18 2 130 60 115 60 乙酸異戊酯 1-己醇 良好 良好 良好 贲施例19 3 125 60 110 60 乙酸丁酯 異丙醇 良好 良好 良好 0施例20 4 120 60 115 60 甲基異丁酮 1-己醇 良好 良好 良好 麵例21 5 125 60 105 60 乙酸丁酯 4·甲基-2-戊醇 良好 良好 良好 Κ施例22 6 120 60 100 60 二異戊醚 4-甲基-2-戊醇 良好 良好 良好 Η施例23 7 120 60 100 60 乙酸丁酯 1-己醇 良好 良好 良好 Η施例24 8 125 60 110 60 乙酸丁酯 4-甲基-2-戊醇 良好 良好 良好 0施例25 9 130 60 105 60 乙酸異戊酯 4-甲基-2-戊醇 良好 良好 良好 Η施例26 10 120 60 100 60 乙酸異戊酯 4-甲基-2-戊醇 良好 良好 良好 ΪΓ施例27 11 120 60 110 60 乙酸丁酯 甲醇 良好 良好 良好 Η施例28 12 110 60 115 60 乙酸丁酯 I-己醇 良好 良好 良好 Κ施例29 13 120 60 110 60 乙酸丁酯 4-甲基-2-戊醇 良好 良好 良好 ΪΪ施例30 14 115 60 110 60 乙酸異戊酯 1-己醇 良好 良好 良好 S施例31 15 110 60 110 60 乙酸丁酯 4-甲基-2-戊醇 良好 良好 良好 0施例32 16 110 60 100 60 乙酸異戊酯 1·己醇 良好 良好 良好 比較例2 17 100 60 90 60 乙酸丁酯 4-甲基-2-戊醇 良好 不良 不良 由表4之結果得知，使用本發明之敏輻射線組成物之 光阻圖型之形成方法，可形成S E、D E皆爲良好之圖型， 且顯示出良好之耐蝕刻性，故可形成超過波長界限之圖型 。又，使用比較例1之敏輻射線性組成物之比較例2，於SE 、DP圖型之評估皆爲「不良」。 〔產業上之利用性〕 使用本發明之感輻射線組成物的光阻圖型之形成方法 -58- 201202842 ，可經濟地形成超過波長界限之良好圖型，故本發明之敏 輻射線性組成物及圖型之形成方法，極適合使用於今後更 加微細化之以積體電路元件之製造爲代表之微細加工技術 領域。 【圖式簡單說明】 〔圖1〕本發明之光阻圖型之形成方法步驟中，於基 板上形成光阻層之後的狀態例示之截面模式圖。 〔圖2〕本發明之光阻圖型之形成方法步驟中，由上 部觀察光阻層進行第1次曝光狀態的例示之模式圖。 〔圖3〕本發明之光阻圖型之形成方法步驟中，由上 部觀察光阻層進行第2次曝光狀態的例示之模式圖。 【主要元件符號說明】 1 :基板 2 :光阻層 3 :第1之曝光部 4 :第2之曝光部 5 :未曝光部 -59-\ ch2oh (M- 22 ) (M- 23 ) [3 3] H3C\ \ C — CH2 h3c c = / ch2 1 o=cc=ch2 / co=c \ 0 / \ 0 H2C o=c \ 0 / H3c-ch ch2 / /CH2 HN h2c \ cf3 F3C —c / \ h3c, \ c = o HO CF3 yN; VN 1 ch3 (M - 24 ) (M - 25 ) (M - 26 ) [Polymer 1] Polymerization The preparation of the substance (A-1), the first is > preparation of monomer (Ml 1 ) 50 mol%, monomer (M-3) 15 m ο 1 %, monomer (M - 2 ) 3 5 m 01 % and a polymerization initiator (dimethyl-2,2'-azobisisobutyrate (MAIB)) were dissolved in 1 g of methyl ethyl ketone to obtain a monomer solution. The total amount of the monomers in the production of the mixture is 5 〇g 〇, and the me > 1% of each monomer means the relative: the mol% of the total amount of the monomer 'the ratio of the polymerization initiator to the monomer The total amount of hydrazine and the polymerization initiator was set to 5 mol%. -51 - 201202842 Further, in a 500 mL three-necked flask equipped with a thermometer and a dropping funnel, methyl ethyl ketone 50 g' was added and nitrogen gas was blown in for 30 minutes. Subsequently, stirring was carried out in a flask using a magnetic stir bar and heated to 80. (:. Next, the prepared monomer solution was dropped into the flask over a period of 3 hours using a dropping funnel. After the completion of the dropwise addition, the mixture was aged for 3 hours, and then cooled to 3 〇-c or less to prepare a polymer solution. The polymer solution was poured into methanol of 100 00 g for mixing. Next, suction filtration was carried out. Subsequently, the recovered powder was re-introduced into methanol of 200 g, washed and filtered, and washed again. The recovered powder was dried under reduced pressure at 60 ° C. The obtained polymer was used as the polymer (A-1). The Mw of the polymer (Al) was 6,200, Mw / Μη was 1.5, 13 C-NMR analysis As a result, a copolymer of a content (M-3) / (M-2) / ((Μ-11) = 14.6 / 35.9 / 49.5 (mol%) of each repeating unit which was produced for each monomer was obtained. [Polymerization Examples 2 to 21] Production of Polymers (A-2) to (A-16) and Polymers (F-1) to (F-5) to Polymers (A-2) to (A-16) And the polymers (F-1) to (F-5) were produced in the same manner as in the polymerization example 1 except that the monomers of the types and addition amounts shown in Table 1 were used. Further, Table 2 shows the respective polymers. Measured by 13C-NMR The content rate of each repeating unit produced by each monomer, Mw, and Mw/Mno 52-201202842 [Table 1] Polymerization Example Polymer Formation (al) Monomer Formation (a2) Monomer Formation (a3) Monomer monomer Other addition amount (mol%) Type addition amount (mol%) mm Addition amount (mol%) Type addition amount (mol%) 1 A-1 M-2 35 M-11 50 - - - - M -3 15 2 A-2 M-2 60 M-8 20 - - M-6 20 3 A-3 M-4 25 M-13 50 M-21 10 - - M-5 15 4 A-4 M-2 35 M-8 30 M-14 15 M-6 20 5 A-5 M-3 25 M-7 25 M-19 15 - - M-8 35 6 A-6 M-4 35 M-8 10 M-18 15 M-6 40 7 A-7 M-3 35 M-8 40 M-17 10 - - M-20 15 8 A-8 M-4 40 M-12 40 M-14 20 - - 9 A-9 M -3 35 M-9 20 M-15 15 M-6 30 10 A-10 M-4 25 M-10 50 M-21 15 - - M-5 10 11 A-11 M-4 . 25 M-11 50 M-23 15 - - M-5 10 12 A-12 M-3 20 M-8 50 M-21 15 - - M-5 15 13 A-13 M-4 30 M-12 40 M-16 20 - - M-5 10 14 A-14 M-1 30 M-8 48 M-22 20 M-25 2 15 A-15 M-4 40 M-8 30 M-14 20 - - M-5 10 16 A-16 M-3 60 - - M-15 40 - - 17 F-1 M-2 70 - - - - M-26 30 18 F-2 - - - - M-14 50 M-24 30 M-26 20 19 F -3 - - - - M-21 40 '24 20 M-26 40 20 F-4 M-2 30 - - M-15 30 M-26 40 21 F-5 - - - - M-14 40 M-24 20 M-26 40 -53- 201202842 Table 2] Polymerization example Polymer formation (al) Monomer formation (a2) Monomer formation (a3) Monomer Other monomer Mw Species added fl (mol%) Species added il (mol%) Species added (mol %) Type of addition (mol%) 1 A-1 M-2 35.9 M-11 49.5 - - - - 6200 M-3 14.6 2 A-2 M-2 60,5 M-8 18.5 - M-6 21 6800 3 A-3 Μ-4 24.5 M-13 52.5 M-21 9.8 - - 6100 Μ-5 13.2 4 A-4 Μ-2 35.8 M-8 28 M-14 15.2 M*6 21 6300 5 A-5 Μ- 3 25.5 M-7 25.5 M-19 14.2 - - 6500 M-8 34.8 6 A-6 Μ-4 34.5 M-8 9 M-18 15.2 M-6 41.3 6700 7 A-7 Μ-3 34.8 M-8 4U M-17 8.9 - - 6800 M-20 15.2 8 A-8 Μ-4 38,8 M-12 41.6 M-14 19.6 - - 6000 9 A-9 Μ-3 34.5 M-9 20.5 M-15 14.5 M- 6 30.5 5900 10 A-10 Μ-4 25.1 M-10 51.2 M-21 14.7 - - 6300 υτ 9 11 A-11 μ-4 25.3 M-11 51 M-23 14,3 - - 6400 9'4 12 A -12 Μ-3 20.5 M-8 50.2 M-21 15.1 - - 6000 Μ-5 14.2 13 A-13 Μ-4 29 M-12 41.3 M-16 18.7 - -♦ 6800 Μ-5 11 14 A-14 Μ -1 30.3 M-8 48.3 M-22 19.6 M-25 1.8 6500 15 A-15 Μ-4 40.8 M**8 30.3 M-14 19.8 - - 6200 Μ-5 9.1 16 A-16 Μ-3 59.5 - M-15 40.5 - - 5500 17 F-1 Μ-2 70.5 - - Ink - M-26 29.5 4800 18 F_2 - - - - M-14 50.2 M-24 29.5 5500 20.3 19 F*3 - - - - M-21 40.2 M~24 20.3 5700 M-26 39*5 20 F-4 Μ-2 30.2 - - M-15 29.8 M-26 40 5900 21 F-5 - - - - M-14 39.6 M-24 19.6 5800 Μ-2έ 40.8 [Example 1 Manufacture of sensitive radiation linear resin composition 100 parts of polymer (A-1) added with polymer (A), acid generator (B-1) of acid generator (B) (triphenylsulfonium nonafluoro-η -butane sulfonate) 7.5 parts, acid diffusion inhibitor (Dl) of nitrogen-containing compound (D) (Ν-t-butoxycarbonylpyrazine) 0.94 parts, polymer of polymer (F) (F-2 5 parts, and solvent (C-1) solvent (C-1) (propylene glycol monomethyl ether B-54-201202842 acid ester) 1287 parts and solvent (C-2) (cyclohexanone) 551 parts, each component Mix to form a homogeneous solution. Subsequently, filtration results were carried out using a membrane filter having a pore size of 200 nm to prepare a radiation sensitive linear resin composition. [Examples 2 to 16 and Comparative Example 1] Each of the radiation sensitive linear resin compositions was produced in the same manner as in Example 1 except that the additive formulations described in Table 3 were used. [Table 3] Sensitive radiation linear resin composition polymerization Ι^Ι(Α) Polymer (F) Acid generator (B) Solvent (C) Acid diffusion control agent (D) Surface usage (parts) Type of use (parts) ) Type of use (parts) mm Usage (parts) Type of use (parts) Type of use (parts) Example 1 I A-1 100 F~2 5 β-1 7.5 €·Ι 1287 ¢-2 551 0 -1 0.94 Example 2 2 A*2 !00 F-*3 5 B-1 7.5 C-1 1267 C-2 551 0.94 Example 3 3 A~3 100 F-4 4 Β-1 7.5 C-1 1287 C-2 551 CM 0.94 Example 4 4 Α·4 100 S β** 1 7.5 C-1 126? 0*2 551 Dl 0.94 Implementation*5 5 Α-5 !00 F-1 5 β Rugged 7.5 < Μ 1237 C-2 551 D-1 0.94 Example 6 6 Λ*6 too F-1 S 8-1 7.5 CI 1237 C-2 551 D-1 实施 Example 7 7 Α-7 100 F-2 5 B— *1 7.5 C-1 1287 C-2 $51 Dl 0.94 Example 8 8 Α-8 too F-5 S 8-1 7.S CI 1287 G-2 551 D-1 0.94 Example 9 9 Α-9 IO0 F -3 5 Θ—Ι 7.5 C-1 1287 C-2 551 0-1 0.94 Example 10 10 ΑΗΟ too F-4 5 Β-1 7*5 CI i287 C-2 551 » - Example 11 11 Α·" 100 F-4 δ 8-1 ?.δ CI mi C-2 551 Dl ad4 Example 12 12 Α_12 too F-3 5 Β-1 7.5 CH 1287 C'2 551 D-1 0.94 Example 13 13 Α-13 100 F—4 5 Β-1 7.5 C·*! 1237 C-2 551 D-1 A94 Example" 14 Α-14 100 F-2 5 Β-1 7.5 <Μ *287 C-2 55) D-1 0.94 Example J 15 A-1S too F-»5 5 8»1 7.5 C- 1 1287 C-2 551 D-1 0.34 Example 16 16 Α-8 too Fl 5 8-1 7.5 CJ 1267 C-2 551 DT 0.94 Comparative Example 1 17 Α·1β 100 F—2 5 C-1 7.5 (Μ 1287 C-2 551 D-1 0.94 Further, the types of the acid generator, the solvent, and the acid diffusion controlling agent used in Table 1 are as follows. Acid generator (B-1): triphenylsulfonium nonafluoro-η-butanesulfonate solvent (C-1): propylene glycol monomethyl ether acetate solvent (C-2): cyclohexanone acid diffusion Control agent (Dl): Nt-butoxycarbonylpyrazine-55-201202842 [Example 1 7] Formation of a photoresist pattern The underlying anti-reflection film (trade name "ARC66", manufactured by Pohwa Technology Co., Ltd.) was used. "Lithius Pro-i" (manufactured by Tokyo Electronics Co., Ltd.) was applied to a 12-inch wafer after a spin coater, and PB (205 ° C, 60 seconds) was applied to form a coating film having a film thickness of 77 nm. The photosensitive radiation linear composition (1) produced in Example 1 was spin-coated using a product name "CLEAN TRACK ACT12" rotary applicator, and subjected to PB (130 ° C, 60 seconds) treatment, followed by cooling (23 ° C, 30 seconds) to form a photoresist layer having a film thickness of 90 nm. Using the formed photoresist layer, the following DE pattern, SE pattern was formed, and various evaluations were performed. [DE pattern]: An ArF immersion exposure apparatus (trade name "S61 0C", manufactured by NIKON Co., Ltd.) was used under the optical conditions of NA: 1.30 and Dipole, via a line of 48 nm line/96 nm pitch (48 nmL/lS). The pattern is formed by exposure with a mask. Subsequently, the mask was formed by exposure of a pattern of 48 nm line/96 nm pitch (48 nmL/L) in a manner of vertical crossing of the previous exposure. After performing peb (125 ° C, 60 seconds) 'cooling (23 ° C, 30 seconds) on a hot plate of the trade name "Lithius Pro-i", butyl acetate was used as a developing solution using a GP nozzle of a developing cup. The mixture was subjected to agitation and development (within 1 〇 second) and spin-dried at 2000 rpm for 15 seconds using a 4-methyl-2-pentanol wash to obtain a 48 nm through hole/96 nm pitch-56-201202842. The substrate for evaluation of the contact hole pattern. The evaluation of the DE pattern of the evaluation substrate and the evaluation of the etching degree were "good". [SE pattern]: Using an ArF immersion exposure apparatus (trade name "S610C", manufactured by NIKON Co., Ltd.), under the optical condition of NA: 1.30, crossbar, via 48 nm dot/96 nm pitch (mask bias ( The pattern of the bias is +15 nm, which is actually a shape of a 25 2 nm dot/3 84 nm pitch formed on the mask, and is exposed by a mask. After PEB (125 ° C, 60 seconds) on a hot platen of the trade name "Lithius Pr〇-i", after cooling (23 ° C, 30 seconds), butyl acetate was used as a GP nozzle of the developing cup. The developing solution was stirred and developed (between 30 seconds) 'washing with 4-methyl-2-pentanol. The results of spin drying were carried out under vibration at 2000 rpm for 15 seconds to obtain a substrate for evaluation having a contact hole pattern of 48 nm via hole/96 nm pitch. The evaluation of the SE pattern of the evaluation substrate and the evaluation of the etching degree were "good". [Examples 1 to 8 and 2, Comparative Example 2] Each of the evaluation substrates was obtained in the same manner as in Example 1 except for the contents described in Table 4. The evaluation results of the obtained evaluation substrates are shown in Table 4. -57- 201202842 [Table 4] Sensitive radiation linear composition photoresist film ΡΒ Conditional PEB condition after double exposure Developer solvent type DEH type evaluation SE pattern evaluation Etching degree evaluation temperature (°C) time (seconds) Brewing (°C) Time (seconds) Developer Wash Solution π 130 60 125 60 Butyl acetate 4-methyl-2-pentanol Good and good Η Example 18 2 130 60 115 60 Acetic acid Amyl ester 1-hexanol is good and good. Example 19 3 125 60 110 60 Butyl acetate isopropanol Good good Good 0 Example 20 4 120 60 115 60 Methyl isobutyl ketone 1-hexanol Good good good surface 21 5 125 60 105 60 Butyl acetate 4·methyl-2-pentanol Good and good Κ Example 22 6 120 60 100 60 Diisoamyl ether 4-methyl-2-pentanol Good and good Η Example 23 7 120 60 100 60 Butyl acetate 1-hexanol Good and good Η Example 24 8 125 60 110 60 Butyl acetate 4-methyl-2-pentanol Good good good 0 Example 25 9 130 60 105 60 Acetic acid Amyl 4-methyl-2-pentanol is good and good. Example 26 10 120 60 100 60 Acetic acid Amyl 4-methyl-2-pentanol was good and good. Example 27 11 120 60 110 60 Butyl acetate methanol was good and good. Example 28 12 110 60 115 60 Butyl acetate I-hexanol was good and good. Example 29 13 120 60 110 60 Butyl acetate 4-methyl-2-pentanol is good and good. Example 30 14 115 60 110 60 Isoamyl acetate 1-hexanol Good good Good S Example 31 15 110 60 110 60 Butyl acetate 4-methyl-2-pentanol Good good Good 0 Example 32 16 110 60 100 60 Isoamyl acetate 1 · hexanol Good good Good Comparative Example 2 17 100 60 90 60 Butyl acetate 4- Methyl-2-pentanol is a good defect. It is known from the results of Table 4 that the formation pattern of the photoresist pattern of the sensitive radiation composition of the present invention can form a good pattern of SE and DE, and display A good etch resistance is obtained, so that a pattern exceeding the wavelength limit can be formed. Further, in Comparative Example 2 using the linear composition of the sensitive radiation of Comparative Example 1, the evaluation of both the SE and DP patterns was "poor". [Industrial Applicability] The use of the method for forming a photoresist pattern of the radiation-sensitive composition of the present invention -58-201202842 can economically form a good pattern exceeding the wavelength limit, so that the sensitive radiation linear composition of the present invention The method of forming the pattern is very suitable for use in the field of microfabrication technology represented by the manufacture of integrated circuit components, which is more compact in the future. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A cross-sectional schematic view showing a state in which a photoresist layer is formed on a substrate in the step of forming a photoresist pattern of the present invention. Fig. 2 is a schematic view showing an example of the first exposure state in which the photoresist layer is observed from the upper portion in the step of forming the photoresist pattern of the present invention. Fig. 3 is a schematic view showing an example of a second exposure state in which the photoresist layer is observed from the upper portion in the step of forming the photoresist pattern of the present invention. [Description of main component symbols] 1 : Substrate 2 : Photoresist layer 3 : First exposure section 4 : 2nd exposure section 5 : Unexposed section - 59-
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| CN104508563A (en) * | 2012-08-30 | 2015-04-08 | 富士胶片株式会社 | Pattern forming method, and electronic device producing method and electronic device each using the same |
| CN105980347A (en) * | 2014-02-14 | 2016-09-28 | 三菱瓦斯化学株式会社 | Method for producing novel alicyclic ester compound, novel alicyclic ester compound, (meth)acrylic copolymer produced by polymerizing said compound, and photosensitive resin composition using said copolymer |
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| JP2012230236A (en) * | 2011-04-26 | 2012-11-22 | Tokyo Ohka Kogyo Co Ltd | Resist composition and method for forming resist pattern |
| JP5707359B2 (en) | 2011-05-30 | 2015-04-30 | 富士フイルム株式会社 | Pattern forming method, actinic ray-sensitive or radiation-sensitive resin composition, resist film, method for producing electronic device, and electronic device |
| JP6121122B2 (en) * | 2011-10-13 | 2017-04-26 | 住友化学株式会社 | Compound, resin, resist composition, and method for producing resist pattern |
| US8790867B2 (en) * | 2011-11-03 | 2014-07-29 | Rohm And Haas Electronic Materials Llc | Methods of forming photolithographic patterns by negative tone development |
| JP6136562B2 (en) * | 2012-05-18 | 2017-05-31 | 住友化学株式会社 | Resin, resist composition and method for producing resist pattern |
| WO2014017144A1 (en) * | 2012-07-27 | 2014-01-30 | Jsr株式会社 | Method for forming negative resist pattern and photoresist composition |
| JP6167016B2 (en) | 2013-10-31 | 2017-07-19 | 富士フイルム株式会社 | Laminate, organic semiconductor manufacturing kit and organic semiconductor manufacturing resist composition |
| KR101904793B1 (en) | 2014-09-02 | 2018-10-05 | 후지필름 가부시키가이샤 | Pattern forming method, method for manufacturing electronic device, and electronic device |
| JP6872530B2 (en) * | 2016-03-31 | 2021-05-19 | 東京応化工業株式会社 | Resist composition and resist pattern forming method |
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| CN104508563A (en) * | 2012-08-30 | 2015-04-08 | 富士胶片株式会社 | Pattern forming method, and electronic device producing method and electronic device each using the same |
| CN105980347A (en) * | 2014-02-14 | 2016-09-28 | 三菱瓦斯化学株式会社 | Method for producing novel alicyclic ester compound, novel alicyclic ester compound, (meth)acrylic copolymer produced by polymerizing said compound, and photosensitive resin composition using said copolymer |
| US9994513B2 (en) | 2014-02-14 | 2018-06-12 | Mitsubishi Gas Chemical, Inc. | Method for producing novel ali cyclic ester compound, novel alicyclic ester compound, (meth)acrylic copolymer produced by polymerizing said compound, and photosensitive resin composition using said copolymer |
| TWI650310B (en) * | 2014-02-14 | 2019-02-11 | 日商三菱瓦斯化學股份有限公司 | A method for producing a novel alicyclic ester compound, a novel alicyclic ester compound, a (meth) acrylate copolymer obtained by polymerizing the compound, and a photosensitive resin composition containing the copolymer |
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