TW201126268A

TW201126268A - Radiation-sensitive composition and method for forming resist pattern

Info

Publication number: TW201126268A
Application number: TW99141231A
Authority: TW
Inventors: Goji Wakamatsu; Yusuke Anno
Original assignee: Jsr Corp
Priority date: 2009-11-30
Filing date: 2010-11-29
Publication date: 2011-08-01
Also published as: JP5652404B2; WO2011065207A1; JPWO2011065207A1

Abstract

Disclosed is a radiation-sensitive composition that is used in step 1 of a method for forming a resist pattern that contains: (1) a step for forming a first resist pattern on a substrate using a first radiation-sensitive composition; (2) a step for insolubilizing the first resist pattern with respect to a second radiation-sensitive composition; and (3) a step for using the second radiation-sensitive composition to form a second resist pattern on the substrate whereupon the first resist pattern had been formed. The radiation-sensitive composition contains: (A) a polymer containing a repeating unit that has an acid labile group; (B) a polymer containing a repeating unit that has a fluorine atom, and a repeating unit that has a crosslinking group; (C) a radiation-sensitive acid generator; and (D) a solvent.

Description

201126268 六、發明說明：【發明所屬之技術領域】本發明係有關敏輻射線性組成物及光阻圖型之形成方法。更詳細而言係有關使用於雙重曝光（double-pa 11 e r n i n g ) 」，即使對於水等之液浸曝光製程也可不需另外形成上層膜而使用的敏輻射線性組成物及使用其之光阻圖型之形成方法。【先前技術】於製造積體電路元件所代表之微細加工領域中，爲了獲得更高的積集度（integration )，於最近需要可在 0· 1 Ομιη以下之等級進行微細加工之微影技術。今後將需要更微細之圖型形成（例如線寬爲4 5 nm左右之微細光阻圖型 )。用形成此種微細圖型的手段爲考慮曝光裝置之光源波長之短波長化（ArF準分子雷射（波長193nm))或增大透鏡之開口數（NA )等。然而，光源波長之短波長化時，需要新的高價曝光裝置。又，增大透鏡開口數（NA)時，由於解像度與焦點深度有互抵關係（trade off)，因此即使提高解像度，但會有焦點深度降低的問題。最近，可解決該等問題之微影技術已有液浸曝光（ Liquid Immersion Lithography)法。然而，液浸曝光法之曝光技術之進步也僅至45 nm半間距（hp )爲臨界，因而朝著需要更微細加工之3 2nmhp世代進行技術開發。近年，隨著利用形成微細圖型之微影技術之裝置的複雜化、高密度 -5- 201126268 化之要求，而提案雙重圖型化（DP)或雙重曝光（DE) 等之雙重曝光技術（例如參照非專利文獻1 )。此技術係使疏線圖型或孤立溝槽圖型偏移半週期重疊，可使 32nmLS進行圖型化" DP係指光阻層藉由曝光及顯像形成之第一光阻圖型上，另外形成光阻膜，藉由曝光及顯像形成第二光阻圖型的技術。DE係指使光阻層曝光後，未經顯像而對相同的光阻層連續進行第2次曝光，然後藉由顯像形成光阻圖型的技術。使3 2 nm L S圖型化之技術之一例，例如非專利文獻2中揭示有形成1: 1間距之32nm線。具體而言，首先形成1 : 3 間距之32nm線，藉由蝕刻加工Si02等之硬質光罩（以下稱爲「HM」）。然後’再於與第一層之光阻圖型偏移半週期的位置’同樣形成1 : 3間距之32iim線，藉由蝕刻再度進行HM加工。〔先行技術文獻〕〔非專利文獻〕201126268 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for forming a linear composition of a radiation and a pattern of a photoresist pattern. More specifically, it relates to a double-pa 11 erning which is a linear composition of a sensitive radiation which is used in an immersion exposure process for water or the like without using an additional upper film, and a photoresist pattern using the same. Forming method. [Prior Art] In the field of microfabrication represented by the manufacture of integrated circuit components, in order to obtain a higher integration degree, a lithography technique which can perform microfabrication at a level below 0·1 Ομηη has recently been required. In the future, a finer pattern formation will be required (for example, a fine photoresist pattern with a line width of about 45 nm). The means for forming such a fine pattern is to consider the short wavelength of the light source wavelength of the exposure device (ArF excimer laser (wavelength 193 nm)) or to increase the number of apertures (NA) of the lens. However, when the wavelength of the light source is shortened, a new high-priced exposure apparatus is required. Further, when the number of lens openings (NA) is increased, since the resolution is in a trade-off relationship with the depth of focus, even if the resolution is increased, there is a problem that the depth of focus is lowered. Recently, the lithography technique that solves these problems has been liquid immersion exposure (Liquid Immersion Lithography). However, advances in the exposure technique of liquid immersion exposure are only critical to the half-pitch (hp) of 45 nm, and thus the development of technology for the 32 nmhp generation requiring finer processing. In recent years, with the complication of high-density devices using the lithography technology that forms micro-patterns, and the requirement for high-density-5-201126268, double-exposure technologies such as double patterning (DP) or double exposure (DE) have been proposed ( For example, refer to Non-Patent Document 1). This technique allows the line-pattern or isolated groove pattern to be offset by a half-cycle overlap, which enables the 32 nm LS to be patterned. DP refers to the first photoresist pattern formed by exposure and development of the photoresist layer. In addition, a photoresist film is formed, and a second photoresist pattern is formed by exposure and development. The DE system refers to a technique in which the photoresist layer is exposed, the second photoresist is continuously exposed to the same photoresist layer without development, and then the photoresist pattern is formed by development. An example of a technique for patterning 32 2 L L S, for example, Non-Patent Document 2 discloses a 32 nm line which forms a 1:1 pitch. Specifically, a 32 nm line of 1:3 pitch is first formed, and a hard mask (hereinafter referred to as "HM") such as SiO 2 is processed by etching. Then, a 32iim line of 1:3 pitch is formed in the same manner as the position of the retardation pattern half period of the first layer, and HM processing is performed again by etching. [prior technical literature] [Non-patent literature]

〔非專利文獻 1〕SPIE2006 6 1 53 1 K 〔非專利文獻 2〕3rd International Symposium on Immersion Lithography PO-1 1 【發明內容】〔發明槪要〕但是如非專利文獻1及2有提案幾個製程，但是目前仍 201126268 未提案適合用於使用這種液浸曝光製程之雙重曝光製程之具體的材料。此外，提案的製程中，形成第一光阻圖型後，形成第二光阻圖型時，有時第一光阻圖型會變形，而有圖型形狀、尺寸之精度降低的問題。此外，將以第一敏輻射線性組成物所形成之第一光阻層、或以第二敏輻射線性組成物所形成之第二光阻層進行曝光時，通常爲了避免由光阻層溶離至液浸液中污染透鏡，而必須使用液浸用上層膜。但是形成液浸用上層膜時，因步驟數增加因而有產率降低等的問題。本發明係有鑑於這種以往技術的問題點而完成者，本發明之課題係在於提供使用於雙重曝光（double-patterning ) 」 ’即使對於水等之液浸曝光製程也可不需另外形成上層膜而使用的敏輻射線性組成物。本發明人等爲了解決上述課題而精心硏究結果，發現含有構成成分爲含有具有交聯基之重複單位及具有氟原子之重複單位的聚合物，可達成上述課題，遂完成本發明。換言之’依據本發明時，可提供以下所示之敏輻射線性組成物及光阻圖型之形成方法。〔1〕一種敏輻射線性組成物，其特徵係含有：於包含使用第一敏輻射線性組成物，在基板上形成第—光阻圖型的步驟（1 );使前述第一光阻圖型對於第二敏輻射線性組成物不溶化的步驟（2 );及使用前述第二敏輻射線性組成物’在形成有前述第一光阻圖型的基板上形成第二光阻圖型的步驟（3)之光阻圖型之形成方法之前述步驟 201126268 (1)所使用的下述（A)〜（D)成分， (A) 含有具有酸不安定基之重複單位的聚合物（以下也稱爲「聚合物（A)」）、 (B) 含有具有交聯基之重複單位及具有氟原子之重複單位的聚合物（以下也稱爲「聚合物（B)」）、 (C )敏輻射線性酸產生劑（以下也稱爲「酸產生劑（C ) J ) ' (D)溶劑。〔2〕如前述〔1〕項之敏輻射線性組成物，其中前述聚合物（B)相對於前述聚合物（A) 100質量份，含有 1~80質量份。〔3〕如前述〔1〕或〔2〕項之敏輻射線性組成物，其中前述交聯基爲熱硬化性之反應性基。〔4〕如前述〔1〕〜〔3〕項中任一項之敏輻射線性組成物，其中前述聚合物（B)爲含有下述一般式（1-1)表示之重複單位及下述一般式（1-2)表示之重複單位之至少任一表示的重複單位（1 )(以下也稱爲「重複單位（1 )j )， -8- 201126268 【化1 R1 ~(~CH2_c~-|—[Non-Patent Document 1] SPIE2006 6 1 53 1 K [Non-Patent Document 2] 3rd International Symposium on Immersion Lithography PO-1 1 [Summary of the Invention] However, there are several processes proposed in Non-Patent Documents 1 and 2. However, there are still no specific materials suitable for the double exposure process using this immersion exposure process. Further, in the proposed process, when the first photoresist pattern is formed and the second photoresist pattern is formed, the first photoresist pattern may be deformed, and the pattern shape and the dimensional accuracy may be lowered. In addition, when the first photoresist layer formed by the linear composition of the first sensitizing radiation or the second photoresist layer formed by the linear composition of the second sensitizing radiation is exposed, generally, in order to avoid elution from the photoresist layer to The liquid immersion liquid contaminates the lens, and the upper layer film must be used for liquid immersion. However, when the upper layer film for liquid immersion is formed, there is a problem that the yield is lowered due to an increase in the number of steps. The present invention has been made in view of the problems of the prior art, and the object of the present invention is to provide for double-patterning. "Even for liquid immersion exposure processes such as water, it is not necessary to additionally form an upper film. The linear composition of the sensitive radiation used. In order to solve the above problems, the inventors of the present invention have found that the above-mentioned problems can be attained by including a polymer containing a repeating unit having a crosslinking group and a repeating unit having a fluorine atom, and the present invention has been completed. In other words, according to the present invention, the method of forming the radiation sensitive linear composition and the photoresist pattern shown below can be provided. [1] A sensitive radiation linear composition, comprising: a step (1) of forming a first photoresist pattern on a substrate by using a linear composition of a first sensitive radiation; and making the first photoresist pattern a step (2) of insolubilizing the second sensitive radiation linear composition; and a step of forming a second photoresist pattern on the substrate on which the first photoresist pattern is formed using the second sensitive radiation linear composition The above-mentioned steps of the method for forming a photoresist pattern 201126268 (1), the following components (A) to (D), (A) a polymer containing a repeating unit having an acid labile group (hereinafter also referred to as "Polymer (A)"), (B) a polymer containing a repeating unit having a crosslinking group and a repeating unit having a fluorine atom (hereinafter also referred to as "polymer (B)"), (C) linearity of sensitivity radiation The acid generator (hereinafter also referred to as "acid generator (C) J)' (D) solvent. [2] The linear radiation sensitive composition according to the above [1], wherein the polymer (B) is polymerized relative to the foregoing (A) 100 parts by mass, containing 1 to 80 parts by mass. [3] as described above [1] or [2] The radiation-sensitive linear composition, wherein the crosslinking group is a thermo-curable reactive group. The radiation-sensitive linear composition according to any one of the above items [1] to [3] wherein the polymer ( B) is a repeating unit (1) represented by at least one of a repeating unit represented by the following general formula (1-1) and a repeating unit represented by the following general formula (1-2) (hereinafter also referred to as "repeating unit" (1)j ), -8- 201126268 [Chemical 1 R1 ~(~CH2_c~-|-

0 R10 R1

HN)=0 R3 (1-1)HN)=0 R3 (1-1)

R5 (1~2) R1係表示氫原子、甲中’ R2係表示亞甲基般式（2 )或（3 )表 R4係表示亞甲基或碳表示氫原子、甲基或 (前述一般式（1-1)及（1 ^ )中，基或三氟甲基，前述一般式（i i) 、伸乙基或伸丙基。R3係表午 ’丨、卜 j7|t ~~- 示之基團，前述一般式（κ,、^ Z )中，數2〜6之亞烷基（alkanediyl、 , )。R5 係乙基。η係表示0或1 ) 【化2】R5 (1~2) R1 represents a hydrogen atom, and 'R2' represents a methylene group. (2) or (3) Table R4 represents a methylene group or carbon represents a hydrogen atom, a methyl group or (the above general formula) (1-1) and (1 ^ ), a group or a trifluoromethyl group, the above general formula (ii), an extended ethyl group or a propyl group. The R3 system is a noon '丨, 卜 j7|t ~~- a group, in the above general formula (κ, , ^ Z ), an alkylene group of 2 to 6 (alkanediyl, , ). R5 is an ethyl group. The η system represents 0 or 1) [Chemical 2]

(前述一般式（2)及（3)中，複數之R6係相互獨立表示氫原子、甲基、乙基、或碳數3〜10之直鏈狀或支鏈狀之烷基）。〔5〕如前述〔1〕〜〔4〕項中任一項之敏輻射線性組 -9 - 201126268 成物，其中前述聚合物（B)爲含有下述一般式（4)表示之重複單位及下述一般式（5)表示之重複單位之至少任一表示之重複單位（2)，【化3】 R1(In the above general formulas (2) and (3), the plural R6 groups independently represent a hydrogen atom, a methyl group, an ethyl group, or a linear or branched alkyl group having a carbon number of 3 to 10). [5] The radiation sensitive linear group of any one of the above-mentioned items [1] to [4], wherein the polymer (B) is a repeating unit represented by the following general formula (4) and The repeating unit (2) representing at least one of the repeating units represented by the following general formula (5), [Chemical 3] R1

(前述一般式（4)中’ R1係表示氫原子、甲基或三氟甲基。R7係表示單鍵或碳數1〜2 0之直鏈狀、支鏈狀或環狀之飽和或不飽和之2價烴基。X係表示被氟原子取代之亞甲基或碳數2〜20之直鏈狀或支鏈狀之氟亞烷基。R8係表示氫原子或〗價有機基）【化4】 R1 外时⑸(In the above general formula (4), 'R1' represents a hydrogen atom, a methyl group or a trifluoromethyl group. R7 represents a single bond or a linear, branched or cyclic saturated or unsubstituted carbon number of 1 to 2 0. a saturated divalent hydrocarbon group. X represents a methylene group substituted by a fluorine atom or a linear or branched fluoroalkylene group having 2 to 20 carbon atoms. R8 represents a hydrogen atom or a valence organic group. 4] R1 outside time (5)

AA

I R9 (前述一般式（5)中，R1係表示氫原子、甲基或三氟甲基。A係表示具有單鍵、醚鍵、硫醚鍵、羰基、酯基、醯胺基、磺醯胺基、胺基甲酸酯基之2價有機基。R9係表示具有至少1個以上之氟原子之甲基、乙基、碳數3〜6之直鏈狀或支鏈狀之烷基、或碳數4〜20之1價脂環式烴基）。〔6〕如前述〔1〕〜〔5〕項中任一項之敏輻射線性組成物，其中前述聚合物（B)進一步含有具有酸不安定基 -10- 201126268 的重複單位。〔7〕如前述〔6〕項之敏輻射線性組成物’其中前述具有酸不安定基之重複單位爲下述一般式（6)表示之重複單位（3 )，【化5】 R1 -f-c—ch?4~I R9 (In the above general formula (5), R1 represents a hydrogen atom, a methyl group or a trifluoromethyl group. A represents a single bond, an ether bond, a thioether bond, a carbonyl group, an ester group, a decyl group, or a sulfonium group. a divalent organic group of an amino group or a urethane group, and R9 means a methyl group having at least one or more fluorine atoms, an ethyl group, a linear or branched alkyl group having 3 to 6 carbon atoms, Or a monovalent alicyclic hydrocarbon group having a carbon number of 4 to 20). [6] The radiation sensitive linear composition according to any one of [1] to [5] wherein the polymer (B) further contains a repeating unit having an acid labyrinth-10-201126268. [7] The linear composition of the sensitive radiation of the above [6] wherein the repeating unit having the acid unstable group is a repeating unit (3) represented by the following general formula (6), [Chemical 5] R1 - fc - Ch?4~

/ (前述一般式（6)中，RM系表示氫原子、甲基或三氟甲基。R1()係相互獨立表示甲基、乙基、碳數3〜4之直鏈狀或支鏈狀之烷基、或碳數4〜20之1價脂環式烴基。但是任2個 R1C)相互結合與各自結合之碳原子一同形成碳數4〜20之2價脂環式烴基，剩餘之R1()可表示甲基、乙基、碳數3〜4之直鏈狀或支鏈狀之烷基、或碳數4〜2 0之1價脂環式烴基）。〔8〕如前述〔2〕〜〔7〕項中任一項之敏輻射線性組成物，其中前述聚合物（A)爲不含具有交聯基之重複單位。〔9〕如前述〔4〕〜〔8〕項中任一項之敏輻射線性組成物，其中前述重複單位（1)之含有比例爲相對於前述聚合物（B)所含之重複單位之合計i〇〇mol%，含有 1 〜3 0 m ο 1 % 〇〔1 〇〕如前述〔5〕〜〔9〕項中任一項之敏輻射線性 -11 - 201126268 組成物’其中前述重複單位（2 )之含有比例爲相對於前述聚合物（B)所含之重複單位之合計100m〇1%，含有 1 〜7 0mol %。〔11〕一種光阻圖型之形成方法，其特徵係包含：使用如前述〔1〕~〔 1 0〕項中任一項之敏輻射線性組成物’在基板上形成第一光阻圖型的步驟（1 ):使前述第一光阻圖型對於第二敏輻射線性組成物不溶化的步驟（2 );及使用前述第二敏輻射線性組成物，在形成有前述第一光阻圖型的基板上形成第二光阻圖型的步驟（3 )。〔1 2〕如前述〔1 1〕項之光阻圖型之形成方法，其中前述第一光阻圖型具有線部分及間距部分，前述第二光阻圖型具有線部分及間距部分，使前述第一光阻圖型之前述線部分與前述第二光阻圖型之前述線部分相互交錯的方式，形成前述第二光阻圖型。〔1 3〕如前述〔1 1〕項之光阻圖型之形成方法，其中前述第一光阻圖型具有線部分及間距部分，前述第二光阻圖型具有線部分及間距部分，使前述第一光阻圖型之前述線部分與前述第二光阻圖型之前述線部分平行的方式，形成前述第二光阻圖型。〔14〕如前述〔11〕〜〔13〕項中任一項之光阻圖型之形成方法，其中前述步驟（1 )爲將前述敏輻射線性組成物塗佈於前述基板上，形成第一光阻層，經加熱後，使前述第一光阻層在最表面，進行曝光處理形成前述第一光 -12· 201126268 阻圖型的步驟。〔1 5〕如前述〔1〕〜〔1 4〕項中任一項之光阻形成方法，其中前述步驟（3)爲將則述第—敏輪組成物塗佈於形成有前述第一光阻圖型之基板上，二光阻層，經加熱後，使前述第二光阻層在最表面曝光處理形成前述第二光阻圖型的步驟。本發明之敏輻射線性組成物係具有使用於雙重 d 〇 u b 1 e - p a 11 e r n i n g )」，即使對於水等之液浸曝光可不需另外形成上層膜的效果。依據本發明之光阻圖型之形成方法時，雙重曝中，形成第二光阻圖型用之曝光時，第一光阻圖型敏輻射線性組成物爲不溶化，因此，可保持第一光之形狀、尺寸的狀態，形成第二光阻圖型。即，可一光阻圖型之線寬變動。此外，本發明之光阻圖型方法也具有可用於液浸曝光製程的效果。〔實施發明之形態〕以下說明本發明之實施之形態，但是本發明不下之實施形態者。在不超脫本發明之實質內容的範依據熟悉該項技藝者之通常知識，對於以下之實施行適度變更、改良等者，也包括本發明之範圍內。 I.光阻圖型之形成方法：本發明之光阻圖型形成方法爲包含步驟（1 ) 圖型之射線性形成第，進行曝光（製程也光製程對第二阻圖型抑制第之形成限於以圍內，形態進 -13- 201126268 之方法。使用圖面說明包含步驟（1)〜（3)之本發明之光阻圖型之形成方'法之一實施形態。又，本說明書中，所謂「線圖型」係指光阻圖型具有線部分與間距部分之線與空間（line-and-space)圖型（以下也稱爲「LS」）。 1·步驟（1 ): 圖1 A〜D係表示本發明之光阻圖型之形成方法中之步驟（1 )之一例的模式圖，步驟（1 )係使用第一敏輻射線性組成物，於基板上形成第一光阻圖型的步驟。其中較佳爲將第一敏輻射線性組成物塗佈於基板上，經加熱形成第一光阻層後，使該光阻層在最表面，未經由形成上層膜之步驟等其他步驟，而進行曝光處理後，形成第一光阻圖型的步驟。此乃是因爲可節省形成上層膜所使用之材料及減少步驟數、提高產量的緣故。更具體而言。首先如圖1 A所示，使用第一敏輻射線性組成物’於基板1上形成第一光阻層2。接著，如圖1B所示，依特定圖型之光罩4及透鏡6的順序配置於所用的區域，且任意地使用水等之液浸液3，藉由輻射線之照射（圖之箭頭）進行曝光。藉此，如圖1C所示，在第一光阻層2上形成鹼顯像部5。然後，藉由顯像，如圖1 D所示，在基板1 上形成具有線部分12a及間距部分12b之第一光阻圖型12 ( 1 L3 S :相對於1線爲3線份之空間）。 (1 )第一光阻層之形成： -14- 201126268 第一光阻層可藉由在基板上塗佈第一敏輻射線性組成物而形成。塗佈方法並無特別限制，可藉由例如旋轉塗佈、流延塗佈、輥塗佈等適當的塗佈方法來塗佈。另外，所形成之第一光阻層之厚度並無特別限制。通常爲 10 〜lOOOnm，較佳爲 10~500nm。另外，塗佈第一敏輻射線性組成物後，必要時可藉由預烘烤（以下稱爲「PB ( pre-bake)」）使塗膜中之溶劑揮發。PB之加熱條件係依據第一敏輻射線性組成物之調配組成適當選擇。通常爲30〜200 °C左右，較佳爲50〜1 5 0°C。 (i )第一敏輻射線性組成物：第一敏輻射線性組成物爲後述之本發明的敏輻射線性組成物。 (ii )基板：基板並無特別限制，可使用例如矽晶圓、以鋁被覆之晶圓等以往習知的基板。另外，爲了發揮第一敏輻射線性組成物之最大的潛在能力，可在使用的基板上形成有機系或無機系之抗反射膜（參照例如特公平6-12452號公報或特開昭59-93448號公報）。 (2)曝光：如圖1 B所示’依特定圖型之光罩4及透鏡6的順序配置於第一光阻層2之所用區域，藉輻射線照射進行曝光。藉此如圖1 C所示，在第一光阻層2上形成鹼顯像部5。曝光時，可任意使用水或氟系惰性液體等的液浸液3。 -15- 201126268 曝光所使用之輻射線係配合第一敏輻射線性組成物中所含有之酸產生劑（C)的種類，可適當選自可見光、紫外線、遠紫外線、X射線、帶電粒子束等。其中較佳爲以 ArF準分子雷射（波長〗93nm )或KrF準分子雷射（波長 2 4 8 n m )所代表之遠紫外線，特佳爲a r F準分子雷射（波長 193nm)之遠紫外線。又’曝光量等之曝光條件係配合第一敏輻射線性組成物之調配組成或添加劑之種類等來適當選擇。此外，曝光後進行加熱處理（以下稱爲「PEB ( Post-Exposure Bake ) 」）較佳。藉由進行 PEB ，可順暢的進行第一敏輻射線性組成物中之酸不安定基之解離反應。PEB 之加熱條件係依據第一敏輻射線性組成物之調配組成來適當選擇。通常爲30〜200°C，較佳爲50〜170°C。 (3)第一光阻圖型之形成：第一光阻層以顯像液進行顯像，使鹼顯像部溶解。藉此形成如圖1D所示之具有線部分12a及間距部分12b之第一光阻圖型1 2。又’以顯像液顯像後，通常以水洗淨、乾燥〇顯像方法無特別限定，可使用以往公知的方法。其中，較佳爲使用攪拌式、LD噴嘴式、GP噴嘴式等進行顯像〇顯像液之較佳例，例如有溶解有氫氧化鈉、氫氧化鉀、四甲基氫氧化錢等之鹼性化合物之至少一種的鹼性水溶 -16- 201126268 液。鹼性水溶液之濃度通常爲1 〇質量％以下。若鹼性水溶液之濃度超過1 0質量％時，非曝光部也可能溶解於顯像液中。此外，鹼性水溶液之濃度的下限値係因使用之化合物而異。但是通常爲0.5質量％以上。本說明書中之「鹼不溶性或鹼難溶性」係指在形成光阻圖型時所進行之鹼顯像條件下，僅由聚合物所形成之被膜之初期膜厚的50%以上在顯像後殘存的性質。又，鹼性水溶液中可添加有機溶劑。例如有丙酮、甲基乙酮等酮類；甲醇、乙醇等醇類；四氫呋喃、二噁烷等醚類；乙酸乙酯、乙酸正丁酯、乙酸異戊酯等酯類；甲苯、二甲苯等芳香族烴類；及酚、丙酮基丙酮、二甲基甲醯胺等。此等有機溶劑可單獨1種或混合2種以上使用。有機溶劑之使用比例係相對於鹼性水溶液1 00體積份，較佳爲1 00體積份以下。有機溶劑之使用比例超過1 00體積份時，有時顯像性降低，曝光部之顯像殘餘變多。顯像液中可再添加適量的界面活性劑等。在此，體積係在25 °c 所測定的體積。 2 ·步驟（2 ): 圖2係本發明之光阻圖型之形成方法中，表示步驟（2 )之一例的模式圖。如圖2所示，對於步驟（1 )形成的第一光阻圖型，藉由120°C以上（較佳爲140°C以上）的溫度之加熱（以下以稱爲「PDB( Post-Development Bake)」 -17- 201126268 )及/或輻射（較佳爲300nm以下的波長）照射（圖之箭頭 )’使第一光阻圖型形成對第二敏輻射線性組成物爲不溶化的第一光阻圖型22。換言之，第一光阻圖型22係對於加熱（步驟（3 )之PB、PEB )或輻射線照射（步驟（3 )之曝光）爲惰性化。輻射線照射條件例如有以形成第一光阻圖型用之最佳曝光量之2〜20倍的曝光量照射輻射線的條件。另外，加熱條件例如有比形成第一光阻圖型時之P E B溫度更高的溫度條件下進行加熱的條件。此外，輻射線照射所使用的燈，可使用例如Ar2燈、KrCl燈、Kr2燈、XeCl燈、Xe2燈（以上爲牛尾電機公司製）等的燈。此等惰性化方法可謹進行 —種，也可進行兩種以上。又，本說明書中，「對光爲惰性」係指即使照射輻射線等而曝光，敏輻射線性組樹脂組成物也不會從不溶於鹼性水溶液者，變成可溶者。換言之，第一光阻圖型2 2即使曝光也不會變成鹼可溶性者。此外，「對熱爲惰性」係指藉由使用第二敏輻射線性組成物形成第二光阻圖型時之加熱，不會產生分解、熔融等之變形。換言之，圖型形狀不會因加熱而消失。 3.步驟（3 ): 步驟（3 )係使用第二敏輻射線性組成物，在形成有第一光阻圖型的基板上形成第二光阻圖型的步驟。其中，較佳爲將第二敏輻射線性組成物塗佈於形成有第一光阻圖 -18- 201126268 型之基板上，經加熱形成第二光阻層後，與步驟（1 )同樣，使該光阻層爲最表面，未進行形成上層膜之步驟等之其他的步驟，而進行曝光處理，形成第二光阻圖型的步驟。此乃是可節省形成上層膜而使用的材料或刪減步驟數，提高產量的緣故。更具體而言，首先，如圖3A所示，使用第二敏輻射線性組成物在形成有第一光阻圖型22的基板1上形成第二光阻層32。接著，如圖3B所示，將所定圖型之光罩4及透鏡6 依序配置於第二光阻層3 2，任意使用水等之液浸液3 3，藉由輻射線照射（圖3B之箭頭）進行曝光。藉此，如圖3C所示，在第二光阻層3 2上形成鹼顯像部3 5。最後藉由顯像，如圖3D所示，在形成有第一光阻圖型22之基板1上形成第二光阻圖型（第二線部分42a)。 (1 )第二光阻層之形成：第二光阻層係可將第二敏輻射線性組成物塗佈於形成有第一光阻圖型之基板上來形成。塗佈的方法無特別限定。可藉由例如旋轉塗佈、流延塗佈、輥塗佈等之適當的塗佈方法進行。第二光阻層之厚度無特別限定。通常爲 10〜lOOOnm，較佳爲 10~500nm。此外，塗佈第二敏輻射線性組成物後，必要時，可藉由P B使塗膜中之溶劑揮發。此p b的加熱條件係依據第二敏輻射線性組成物之調配組成來適當選擇。通常爲 30~200°C程度，較佳爲50〜150°C。 • 19 _ 201126268 關於第二敏輻射線性組成物係如後述。而第一敏輻射線性組成物與第二敏輻射線性組成物所含有的溶劑爲相同的溶劑或可爲不同的溶劑。此乃是因爲進行步驟（2 )，使第一光阻圖型對於熱或光爲惰性化，對於第二敏輻射線性組成物爲不溶化。因此，可部與第一光阻圖型混合而形成第二光阻層的緣故。 (2 )曝光：接著，此步驟（3)係如圖3B所示，將所定圖型之光罩4及透鏡6依序配置於形成有第二光阻層32的基板1上，藉由輻射線照射進行曝光。藉此如圖3 C所示，在第二光阻層32上形成鹼顯像部35。此外，曝光時，可任意使用水或氟系惰性液體等的液浸液33。可以步驟（1)所述的曝光條件進行曝光。 (3 )顯像：曝光後，藉由顯像如圖3 D所示，在形成有第一光阻圖型22的基板1上形成第二光阻圖型（第二線部分42a)。可以步驟（1 )所述的顯像方法進行顯像方法。如此’如步驟（1 ) ~ ( 3 )藉由雙重曝光，在基板上可形成第一光阻圖型及第二光阻圖型交互排列之1L1S (線部分與間距部分之寬的比爲1: 1)的光阻圖型。此外，藉由雙重曝光可形成例如圖4所示之光阻圖型 (接觸孔圖型1 5 )。此光阻圖型係使以步驟（3 )所形成 -20- 201126268 之第二光阻圖型42的第二線部分42a與第一光阻圖型22之第一線部分22a直交的方式，形成於第一光阻圖型22之第 —線部22a上。再藉由雙重曝光也可形成例如圖6所示之光阻圖型（接觸孔圖型1 5 )。此光阻圖型係將以步驟（3 )所形成的第二光阻圖型42形成於第一光阻圖型22之空間部22b。此外，此光阻圖型係形成藉由第一光阻圖型2 2之第一線部分 22a與第二光阻圖型42之第二線部42a區分的格子狀。藉由使用本發明之光阻圖型之形成方法，即雙重曝光可形成更微細的線圖型、或更微細的接觸孔（以下藉由本發明之光阻圖型之形成方法（雙重曝光）而得的光阻圖型 (線圖型或接觸孔圖型）也稱爲「DP圖型」）。本發明之光阻圖型之形成方法係如圖4〜圖6所示，使第一光阻圖型22之線部22a與第二光阻圖型42之線部42a直交的方式’在第一光阻圖型22上形成第二光阻圖型42較佳〇形成如上述之接觸孔圖型時的光阻圖型係線部分及間距部分之寬均爲40〜100nm ( 1L1S)者較佳，40~65nm ( 1L1S)者更佳，40〜50nm(lLlS)者更佳。 II.敏輻射線性組成物：敏輻射線性組成物係藉由曝光自敏輻射線性酸產生劑產生之酸的作用，使存在於組成物中之酸不安定基解離產生殘基。結果曝光部分對於鹼顯像液之溶解性升高，被驗 5 -21 - 201126268 顯像液溶解、去除，可形成光阻圖型者。換線性組成物係含有因酸的作用成爲鹼可溶性之難溶性的聚合物、敏輻射線性酸產生劑、及溶。以下另外記載形成第一光阻層時所使用之本射線性組成物之第一敏輻射線性組成物與形成時所使用的第二敏輻射線性組成物。 1.第一敏輻射線性組成物：第一敏輻射線性組成物係含有聚合物（A (B )、酸產生劑（C) 、（D)溶劑者。其中光阻圖型後，藉由300nm以下波長之輻射線照: 由l4〇°C以上加熱，使第一光阻圖型對光或熱者較佳。此第一光阻圖型係具有對於第二敏輻物之耐性。因此，第二光阻圖型形成時，不會存者。本說明書中所謂「酸不安定基」係指藉由團，並非特別不同的基團。不溶或難溶於具有之鹼顯像液的聚合物係藉由酸之作用解離成爲爲可溶於鹼顯像液的聚合物。 (1 )聚合物（A)：聚合物（A)係含有具有（A)酸不安定位者，不含有具有交聯基之重複單位者較佳。線性組成物係含有聚合物（A )，可形成藉由之，敏輻射鹼不溶性或劑的組成物發明之敏輻第二光阻層 )、聚合物 *形成第一时，及/或藉形成惰性化射線性組成受傷害而殘酸解離的基酸不安定基羧基，而成基之重複單第一敏輻射酸之作用， -22- 201126268 對鹼顯像液產生溶解的第一光阻層。而具有交單位係在「（ 2 )聚合物（B )」中敘述。聚合物（A )之較佳例’例如有含有前述重 )與選自一般式（7-1)〜（7-5)及式（7·6)所少一個內酯構造的重複單位、或—般式（8)表單位（以下也稱爲「重複單位（4)」）。【化6】/ (In the above general formula (6), RM represents a hydrogen atom, a methyl group or a trifluoromethyl group. R1() independently represents a methyl group, an ethyl group, and a linear or branched chain of 3 to 4 carbon atoms. An alkyl group or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. However, any two R1C) are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms together with the carbon atom to be bonded thereto, and the remaining R1 () may represent a methyl group, an ethyl group, a linear or branched alkyl group having 3 to 4 carbon atoms, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms). [8] The radiation sensitive linear composition according to any one of [2] to [7] wherein the polymer (A) is a repeating unit having no crosslinking group. [9] The radiation sensitive linear composition according to any one of [4] to [8] wherein the content of the repeating unit (1) is a total of the repeating units contained in the polymer (B). I 〇〇 mol%, containing 1 to 3 0 m ο 1 % 〇 [1 〇] The sensitive radiation linear -11 - 201126268 of any one of the above [5] to [9], wherein the aforementioned repeating unit 2) The content ratio is 100 m〇1% based on the total of the repeating units contained in the polymer (B), and contains 1 to 70 mol%. [11] A method for forming a photoresist pattern, comprising: forming a first photoresist pattern on a substrate by using the sensitive radiation linear composition of any one of the above [1] to [10] Step (1): the step (2) of inactivating the first photoresist pattern for the second sensitivity radiation linear composition; and using the second second radiation linear composition to form the first photoresist pattern The step (3) of forming the second photoresist pattern on the substrate. [2] The method for forming a photoresist pattern according to the above [1 1], wherein the first photoresist pattern has a line portion and a pitch portion, and the second photoresist pattern has a line portion and a pitch portion, such that The second photoresist pattern is formed in such a manner that the line portion of the first photoresist pattern and the line portion of the second photoresist pattern are interdigitated with each other. [13] The method for forming a photoresist pattern according to the above [1 1], wherein the first photoresist pattern has a line portion and a pitch portion, and the second photoresist pattern has a line portion and a pitch portion, such that The second photoresist pattern is formed in such a manner that the line portion of the first photoresist pattern is parallel to the line portion of the second photoresist pattern. [14] The method for forming a photoresist pattern according to any one of [11] to [13] wherein the step (1) is to apply the linear radiation sensitive composition to the substrate to form a first After the photoresist layer is heated, the first photoresist layer is exposed on the outermost surface to perform the step of forming the first light -12·201126268 resistance pattern. The method for forming a photoresist according to any one of the above-mentioned items, wherein the step (3) is to apply the first-sensitive wheel composition to the first light. On the resistive type substrate, after the two photoresist layers are heated, the second photoresist layer is exposed to the outermost surface to form the second photoresist pattern. The sensitive radiation linear composition of the present invention has a double d 〇 u b 1 e - p a 11 e r n i n g )", and the effect of additionally forming an upper film is not required even for immersion exposure of water or the like. According to the method for forming a photoresist pattern of the present invention, in the double exposure, when the exposure for the second photoresist pattern is formed, the linear composition of the first photoresist pattern-sensitive radiation is insolubilized, and therefore, the first light can be maintained. The shape and size state form a second photoresist pattern. That is, the line width of a photoresist pattern can be varied. Further, the photoresist pattern method of the present invention also has an effect that can be used in a liquid immersion exposure process. [Mode for Carrying Out the Invention] The embodiment of the present invention will be described below, but the embodiment of the present invention is not limited. The general knowledge of the skilled artisan will be apparent to those skilled in the art without departing from the spirit and scope of the invention, and modifications and improvements may be made within the scope of the invention. I. Method for Forming Photoresist Pattern: The method for forming a photoresist pattern of the present invention comprises the step of forming a ray in the step (1), and performing exposure (the process is also formed by the photo process to suppress the second pattern). It is limited to the method of the method of forming a pattern of the photoresist pattern of the present invention comprising the steps (1) to (3). The term "line pattern" refers to a line-and-space pattern (hereinafter also referred to as "LS") having a line portion and a pitch portion of a photoresist pattern. 1·Step (1): 1A to D are schematic diagrams showing an example of the step (1) in the method for forming a photoresist pattern of the present invention, and the step (1) is to form a first photoresist on the substrate by using the first sensitive radiation linear composition. The step of patterning, wherein preferably, the first sensitive radiation linear composition is coated on the substrate, and after heating to form the first photoresist layer, the photoresist layer is on the outermost surface, and the step of forming the upper layer film is not performed. Other steps, after performing exposure processing, forming a first photoresist pattern This is because the material used for forming the upper film can be saved, the number of steps can be reduced, and the yield can be increased. More specifically, first, as shown in FIG. 1A, the first sensitive radiation linear composition is used on the substrate 1 The first photoresist layer 2 is formed thereon. Next, as shown in FIG. 1B, the mask 4 and the lens 6 of a specific pattern are arranged in the order of use, and the liquid immersion liquid 3 of water or the like is arbitrarily used. The irradiation of the radiation (arrow of the figure) is performed. Thereby, as shown in Fig. 1C, the alkali developing portion 5 is formed on the first photoresist layer 2. Then, by development, as shown in Fig. 1D, A first photoresist pattern 12 having a line portion 12a and a pitch portion 12b is formed on the substrate 1 (1 L3 S: a space of 3 lines with respect to the 1 line). (1) Formation of the first photoresist layer: 14- 201126268 The first photoresist layer can be formed by coating a linear composition of the first radiation radiation on the substrate. The coating method is not particularly limited and can be, for example, spin coating, cast coating, roll coating. The coating is applied by a suitable coating method, and the thickness of the formed first photoresist layer is not particularly limited. 10 to 100om, preferably 10 to 500 nm. Further, after applying the first sensitive radiation linear composition, it may be pre-baked (hereinafter referred to as "PB (pre-bake)") in the coating film if necessary. The solvent is volatilized. The heating condition of PB is appropriately selected according to the composition of the first sensitive radiation linear composition, and is usually about 30 to 200 ° C, preferably 50 to 150 ° C. (i) First sensitive radiation linearity Composition: The first sensitive radiation linear composition is a linear radiation sensitive composition of the present invention to be described later. (ii) Substrate: The substrate is not particularly limited, and conventional wafers such as tantalum wafers and aluminum-coated wafers can be used. The substrate. In addition, in order to exert the maximum potential of the first sensitive radiation linear composition, an organic or inorganic antireflection film can be formed on the substrate to be used (see, for example, Japanese Patent Publication No. 6-12452 or JP-A-59-93448) Bulletin). (2) Exposure: As shown in Fig. 1B, the mask 4 and the lens 6 of the specific pattern are arranged in the order of the region of the first photoresist layer 2, and exposure is performed by radiation. As a result, as shown in Fig. 1C, the alkali developing portion 5 is formed on the first photoresist layer 2. At the time of exposure, a liquid immersion liquid 3 such as water or a fluorine-based inert liquid can be used arbitrarily. -15- 201126268 The radiation used in the exposure is matched with the type of the acid generator (C) contained in the linear composition of the first sensitive radiation, and may be appropriately selected from the group consisting of visible light, ultraviolet light, far ultraviolet light, X-ray, charged particle beam, and the like. . Preferably, it is a far-ultraviolet light represented by an ArF excimer laser (wavelength: 93 nm) or a KrF excimer laser (wavelength of 248 nm), and particularly a far ultraviolet ray of an ar F excimer laser (wavelength: 193 nm). . Further, the exposure conditions such as the amount of exposure are appropriately selected in accordance with the composition of the first sensitive radiation linear composition, the type of the additive, and the like. Further, it is preferable to carry out heat treatment after exposure (hereinafter referred to as "PEB (Post-Exposure Bake)"). By performing PEB, the dissociation reaction of the acid labile group in the linear composition of the first sensitive radiation can be smoothly performed. The heating conditions of the PEB are appropriately selected depending on the blending composition of the first sensitive radiation linear composition. It is usually 30 to 200 ° C, preferably 50 to 170 ° C. (3) Formation of the first photoresist pattern: The first photoresist layer is developed with a developing liquid to dissolve the alkali developing portion. Thereby, the first photoresist pattern 12 having the line portion 12a and the pitch portion 12b as shown in Fig. 1D is formed. Further, after developing with a developing liquid, it is usually washed with water and dried. The method of developing the image is not particularly limited, and a conventionally known method can be used. Among them, preferred examples of the development of a developing photographic liquid using a stirring type, an LD nozzle type, a GP nozzle type, and the like are, for example, a base in which sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide or the like is dissolved. An alkaline water-soluble-16-201126268 solution of at least one of the compounds. The concentration of the alkaline aqueous solution is usually 1% by mass or less. If the concentration of the alkaline aqueous solution exceeds 10% by mass, the non-exposed portion may be dissolved in the developing solution. Further, the lower limit of the concentration of the alkaline aqueous solution varies depending on the compound to be used. However, it is usually 0.5% by mass or more. In the present specification, "alkali-insoluble or alkali-insoluble" refers to 50% or more of the initial film thickness of the film formed only of the polymer under the alkali development conditions which are formed when the photoresist pattern is formed, after development. The nature of the surviving. Further, an organic solvent may be added to the alkaline aqueous solution. Examples include ketones such as acetone and methyl ethyl ketone; alcohols such as methanol and ethanol; ethers such as tetrahydrofuran and dioxane; and esters such as ethyl acetate, n-butyl acetate and isoamyl acetate; toluene, xylene, etc. Aromatic hydrocarbons; and phenol, acetone acetone, dimethylformamide, and the like. These organic solvents may be used alone or in combination of two or more. The use ratio of the organic solvent is 100 parts by volume, preferably 100 parts by volume or less, based on the alkaline aqueous solution. When the ratio of use of the organic solvent exceeds 100 parts by volume, the developability may be lowered, and the development residual of the exposed portion may be increased. An appropriate amount of surfactant or the like may be added to the developing solution. Here, the volume is the volume measured at 25 °c. 2. Step (2): Fig. 2 is a schematic view showing an example of the step (2) in the method for forming a photoresist pattern of the present invention. As shown in FIG. 2, the first photoresist pattern formed in the step (1) is heated by a temperature of 120 ° C or higher (preferably 140 ° C or higher) (hereinafter referred to as "PDB (Post-Development). Bake)" -17- 201126268) and/or radiation (preferably wavelength below 300 nm) illumination (arrow of the figure)' causes the first photoresist pattern to form a first light that is insoluble to the second sensitive radiation linear composition Resistance pattern 22. In other words, the first photoresist pattern 22 is inert to heating (PB, PEB in step (3)) or radiation (exposure in step (3)). The radiation irradiation condition is, for example, a condition in which the radiation is irradiated with an exposure amount of 2 to 20 times the optimum exposure amount for forming the first photoresist pattern. Further, the heating conditions are, for example, conditions in which heating is performed at a temperature higher than the P E B temperature at the time of forming the first photoresist pattern. Further, for the lamp used for the radiation irradiation, for example, an Ar2 lamp, a KrCl lamp, a Kr2 lamp, a XeCl lamp, or a Xe2 lamp (manufactured by Oxtail Electric Co., Ltd.) or the like can be used. These inertization methods may be carried out in one type or in two or more. In the present specification, the term "inert to light" means that the radiation-sensitive linear group resin composition does not become soluble in an alkali aqueous solution even when exposed to radiation or the like. In other words, the first photoresist pattern 2 2 does not become alkali-soluble even if it is exposed. Further, "inert to heat" means heating by forming a second photoresist pattern by using the linear composition of the second sensitive radiation, and deformation such as decomposition, melting, or the like is not caused. In other words, the shape of the pattern does not disappear due to heating. 3. Step (3): Step (3) is a step of forming a second photoresist pattern on the substrate on which the first photoresist pattern is formed using the second sensitive radiation linear composition. Preferably, the second sensitive radiation linear composition is applied onto the substrate on which the first photoresist pattern -18-201126268 is formed, and after heating to form the second photoresist layer, similarly to the step (1), The photoresist layer is the outermost surface, and the other steps such as the step of forming the upper layer film are not performed, and the exposure processing is performed to form the second photoresist pattern. This is because the material used to form the upper film can be saved or the number of steps can be reduced to increase the yield. More specifically, first, as shown in Fig. 3A, a second photoresist layer 32 is formed on the substrate 1 on which the first photoresist pattern 22 is formed, using the second radiation sensitive linear composition. Next, as shown in FIG. 3B, the mask 4 and the lens 6 of the predetermined pattern are sequentially disposed on the second photoresist layer 32, and the liquid immersion liquid 3 of water or the like is used arbitrarily, and irradiated by radiation (FIG. 3B). The arrow) is exposed. Thereby, as shown in Fig. 3C, the alkali developing portion 35 is formed on the second photoresist layer 32. Finally, by developing, as shown in Fig. 3D, a second photoresist pattern (second line portion 42a) is formed on the substrate 1 on which the first photoresist pattern 22 is formed. (1) Formation of a second photoresist layer: The second photoresist layer can be formed by applying a second sensitive radiation linear composition onto a substrate on which a first photoresist pattern is formed. The method of coating is not particularly limited. This can be carried out by an appropriate coating method such as spin coating, cast coating, roll coating or the like. The thickness of the second photoresist layer is not particularly limited. It is usually 10 to 100 nm, preferably 10 to 500 nm. Further, after the second sensitive radiation linear composition is applied, if necessary, the solvent in the coating film can be volatilized by P B . The heating condition of this p b is appropriately selected depending on the compounding composition of the second sensitive radiation linear composition. It is usually from 30 to 200 ° C, preferably from 50 to 150 ° C. • 19 _ 201126268 The second sensitive radiation linear composition system will be described later. The first sensitive radiation linear composition is the same solvent as the solvent contained in the second sensitive radiation linear composition or may be a different solvent. This is because step (2) is carried out so that the first photoresist pattern is inert to heat or light, and is insolubilized for the second sensitive radiation composition. Therefore, the second photoresist layer can be formed by mixing with the first photoresist pattern. (2) Exposure: Next, in step (3), as shown in FIG. 3B, the mask 4 and the lens 6 of the predetermined pattern are sequentially disposed on the substrate 1 on which the second photoresist layer 32 is formed, by radiation. Line illumination is performed for exposure. Thereby, the alkali developing portion 35 is formed on the second photoresist layer 32 as shown in Fig. 3C. Further, at the time of exposure, a liquid immersion liquid 33 such as water or a fluorine-based inert liquid can be used arbitrarily. The exposure can be performed under the exposure conditions described in the step (1). (3) Development: After exposure, a second photoresist pattern (second line portion 42a) is formed on the substrate 1 on which the first photoresist pattern 22 is formed by development as shown in Fig. 3D. The development method can be carried out by the development method described in the step (1). Thus, as in steps (1) to (3), 1L1S (the ratio of the width of the line portion to the pitch portion) of the first photoresist pattern and the second photoresist pattern can be formed on the substrate by double exposure. : 1) Photoresist pattern. Further, a resist pattern (contact hole pattern 15) as shown in Fig. 4 can be formed by double exposure. The photoresist pattern is such that the second line portion 42a of the second photoresist pattern 42 formed by the step (3) is orthogonal to the first line portion 22a of the first photoresist pattern 22, It is formed on the first line portion 22a of the first photoresist pattern 22. Further, for example, a photoresist pattern (contact hole pattern 15) shown in Fig. 6 can be formed by double exposure. This resist pattern is formed in the space portion 22b of the first photoresist pattern 22 by the second photoresist pattern 42 formed in the step (3). Further, the photoresist pattern is formed in a lattice shape which is distinguished by the first line portion 22a of the first photoresist pattern 22 and the second line portion 42a of the second photoresist pattern 42. By using the formation method of the photoresist pattern of the present invention, that is, double exposure, a finer line pattern or a finer contact hole can be formed (hereinafter, by the formation method of the photoresist pattern of the present invention (double exposure)) The resulting photoresist pattern (line pattern or contact hole pattern) is also called "DP pattern"). The method for forming the photoresist pattern of the present invention is as shown in FIG. 4 to FIG. 6, and the line portion 22a of the first photoresist pattern 22 is orthogonal to the line portion 42a of the second photoresist pattern 42. Preferably, the second photoresist pattern 42 is formed on a photoresist pattern 22, and the photoresist pattern portion and the pitch portion are 40 to 100 nm (1L1S) when the contact hole pattern is formed as described above. Good, 40~65nm (1L1S) is better, 40~50nm (lLlS) is better. II. Sensitive Radiation Linear Composition: The linear composition of the sensitive radiation is obtained by exposing the acid generated by the self-sensitive radiation linear acid generator to dissociate the acid labile group present in the composition to generate a residue. As a result, the solubility of the exposed portion to the alkali imaging solution was increased, and it was examined that the imaging solution was dissolved and removed, and a photoresist pattern could be formed. The linear composition contains a poorly soluble polymer which is alkali-soluble due to the action of an acid, a radiation sensitive linear acid generator, and a solution. The first sensitive radiation linear composition of the radiation composition used in forming the first photoresist layer and the second radiation radiation linear composition used in the formation are additionally described below. 1. First Sensitive Radiation Linear Composition: The first sensitive radiation linear composition contains a polymer (A (B ), an acid generator (C), (D) solvent. After the photoresist pattern, by 300 nm Radiation of the following wavelengths: heating above l4 〇 ° C, making the first photoresist pattern better for light or heat. This first photoresist pattern has resistance to the second sensitive emitter. When the second photoresist pattern is formed, it does not exist. The term "acid-unstable group" as used in the present specification means a group which is not particularly different by a group. It is insoluble or poorly soluble in the polymerization of an alkali-developing liquid. The system is dissociated by the action of an acid to become a polymer soluble in an alkali developing solution. (1) Polymer (A): The polymer (A) contains a (A) acid uneasy position, and does not contain a cross. Preferably, the repeating unit of the unit is a linear composition comprising a polymer (A), which can be formed by a composition of a sensitive radiation-insoluble or agent-inducing composition of the second photoresist layer, and a polymer* formation. At the first time, and/or by the formation of an inerting ray-based composition, the acid-depleted base acid is unstable. Carboxyl group, repeating single group, first sensitive radiation, acid action, -22- 201126268 The first photoresist layer which dissolves in the alkali imaging solution. The unit of intersection is described in "(2) Polymer (B)". The preferred example of the polymer (A) is, for example, a repeating unit containing the above-mentioned weight and one of the lactone structures selected from the general formulae (7-1) to (7-5) and (7·6), or The general formula (8) table unit (hereinafter also referred to as "repetition unit (4)"). 【化6】

(般式（7-1 )中，R11係表示氫原子或碳數取代之院基杳。ρ係表示丨〜3之整數。—般式（ 5)中，R12係表示氫原子或甲氧基。—般式^ 7'3 )中，八係表示單鍵或亞甲基。m係表示0或 )及（7-5)中，B係表示氧原子或亞甲基基之重複 I單位（3 成群之至示之重複(In the general formula (7-1), R11 represents a hydrogen atom or a substituted carbon group. The ρ system represents an integer of 丨~3. In the general formula (5), R12 represents a hydrogen atom or a methoxy group. In the general formula ^7'3), the octasystem represents a single bond or a methylene group. The m system represents 0 or ) and (7-5), and the B system represents a repeating I unit of an oxygen atom or a methylene group (3 groups are repeated as shown

0 (7-6) 〜4之可被，-4)及（卜2)及（。一般式0 (7-6) ~4 can be, -4) and (b 2) and (.. general

(8) 般式（8)中，Rl係表示氫原子甲基或三氟甲基。 -23- 201126268 R係表示單鍵或2價連結基。RCe係表示具有環狀碳酸酯構造之1價有機基。） —般式（8)中，Rc。例如有下述—般式（cc_u或（ Cc-2 )表示之基團。【化8】(8) In the general formula (8), R1 represents a hydrogen atom methyl group or a trifluoromethyl group. -23- 201126268 R represents a single bond or a divalent linking group. RCe means a monovalent organic group having a cyclic carbonate structure. ) - In the general formula (8), Rc. For example, there is a group represented by the following general formula (cc_u or (Cc-2). [Chemical 8]

(Cc-1) (Cc-2) (―般式（Ce-1)中’ nci係表示〇~2之整數。一般式（ Cc-2)中’ nc2~nc5係分別獨立表示〇〜2之整數。一般式（ Cc-1 )及一般式（Cc-2 )中’ 「*」係表示與一般式（8 ) 中之Rei結合之連結鍵。此外，一般式（Cc-1 )及（Cc·2 )表示之基團可具有取代基。） (i )重複單位（3 ): 前述一般式（6)中，以R1Q表示之基團中，碳數3〜4 之直鏈狀或支鏈狀之烷基例如有η -丙基、i -丙基、η -丁基 ' 2-甲基丙基、1-甲基丙基、t-丁基等。另外，碳數4〜20之一價脂環式烴基，例如有來自降莰烷、三環癸烷、四環十二烷、金剛烷或環丁烷、環戊烷、環己烷、環庚烷、環辛烷等環烷類等之脂環族環所構成的 -24- 201126268 基團；將此等脂環族環所構成之基團以例如甲基、乙基、正丙基、異丙基、正丁基、2_甲基丙基、丨_甲基丙基、第二丁基等之碳數3〜4之直鏈狀或支鏈狀之烷基取代的基團等。再者’任二個R1G相互結合所形成之碳數4〜20之2價脂環式烴基例如有來自降莰烷、三環癸烷、四環十二烷、金剛院、環戊烷、環己烷等脂環族環所構成之基團；此等由脂環族環所構成之基團以例如甲基、乙基、正丙基、異丙基、正丁基、2-甲基丙基、1-甲基丙基、第三丁基等之碳數3〜4之直鏈狀或支鏈狀之烷基取代的基團等。一般式（6)中，以-C ( R1C) 3表示之基團的較佳例有第三丁基、l-n-(l，l-二甲基）丙基、l-(i，i-二乙基）丙基等之不具有脂環族環之基團；丨-(1_甲基）環戊基、！_ (1-乙基）環戊基、1-(1-甲基）環己基、1-(1-乙基）環己基、1-(1-甲基-1-(2-降莰基））乙基、1-(1-甲基-1-(2 -四環癸基））乙基、1-(1-甲基-1-(1-金剛烷基） )乙基、2-(2 -甲基）降莰基、2-(2 -乙基）降莰基、2-(2-n-丙基）降莰基、2-(2-甲基）四環癸基、2·(2_乙基）四環癸基、2-(2-甲基）金剛烷基、2-(2-乙基）金剛烷基等具有脂環族環之基團；此等具有脂環族環之基團以例如甲基、乙基、正丙基、異丙基、正丁基、2 -甲基丙基、1-甲基丙基、第三丁基等碳數3〜10之直鏈狀或支鏈狀烷基、環戊基、環己基、環辛基等碳數4~2 0之環狀烷基取代的基團等。 -25- 201126268 此等中，特佳爲（甲基）丙烯酸2-甲基金剛烷-2-基酯、（甲基）丙烯酸2-乙基金剛烷-2-基酯、（甲基）丙烯酸-2-甲基雙環〔2.2.1〕庚-2-基酯、（甲基）丙烯酸-2-乙基雙環〔2.2.1〕庚-2-基酯、（甲基）丙烯酸-1-(雙環〔 2·2·1〕庚-2-基）-1-甲基乙酯、（甲基）丙烯酸1-(金剛烷-1-基彡-丨-甲基乙酯、（甲基）丙烯酸丨·甲基-丨_環戊酯、（甲基）丙烯酸1-乙基-1-環戊酯、（甲基）丙烯酸1-甲基-1-環己酯、（甲基）丙烯酸-1-乙基-1-環己酯等。聚合物（Α)可爲僅含有1種或2種以上之重複單位（3 )者。重複單位（3 )之含有比例係相對於聚合物（A )所含有之重複單位之合計lOOmol%，較佳爲20〜90mol%，更佳爲20〜80mol%，更佳爲20~70mol%。重複單位（3 )之含有比例爲此範圍內時，從同時兼具塗佈後對於顯像液之溶解性之控制與形成第二光阻圖型時對曝光之耐性的觀點，特別有用。 (ii)重複單位（4): —般式（7-1)中，以R11表示之基團中，碳數1~4之可被取代之烷基，例如有甲基、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。提供一般式（8)表示之重複單位的單體，可藉由例如 Tetrahedron Letters，Vol.27，No.32 p.374 1 ( 1 986 )、 Organic Letters，Vol.4，Νο·15 ρ·2561 ( 2002)等所記載之以往公知的方法合成。 -26- 201126268 一般式（8 )表示之重複單位之特佳例，例如有一般式（8-1) ~(8-22)表示之重複單位。一般式（8-1)〜（ 8-22)中之R1係與一般式（8)中之R1相同意義。【化9】(Cc-1) (Cc-2) (In the general formula (Ce-1), the nci system represents an integer of 〇~2. In the general formula (Cc-2), 'nc2~nc5 are independent representations of 〇~2 Integer. In the general formula (Cc-1) and the general formula (Cc-2), ''*'' indicates a linkage bond with Rei in the general formula (8). In addition, the general formula (Cc-1) and (Cc) 2) The group represented may have a substituent.) (i) Repeating unit (3): In the above general formula (6), a linear or branched chain having 3 to 4 carbon atoms among the groups represented by R1Q Examples of the alkyl group include η-propyl group, i-propyl group, η-butyl '2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like. In addition, the carbon number 4 to 20 one-valent alicyclic hydrocarbon group, for example, is derived from norbornane, tricyclodecane, tetracyclododecane, adamantane or cyclobutane, cyclopentane, cyclohexane, cycloheptane a group of -24 to 201126268 which is composed of an alicyclic ring such as a cycloalkane such as an alkane or a cyclooctane; and a group consisting of such an alicyclic ring is, for example, a methyl group, an ethyl group, a n-propyl group or a different group. a linear or branched alkyl-substituted group having 3 to 4 carbon atoms such as a propyl group, a n-butyl group, a 2-methyl group, a fluorene-methyl group or a second butyl group. Further, the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms formed by combining any two R1Gs may be, for example, derived from norbornane, tricyclodecane, tetracyclododecane, diamond, cyclopentane or ring. a group consisting of an alicyclic ring such as hexane; such a group consisting of an alicyclic ring such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropane a linear or branched alkyl-substituted group having a carbon number of 3 to 4 such as a 1-methylpropyl group or a tributyl group. In the general formula (6), preferred examples of the group represented by -C(R1C) 3 are a third butyl group, an ln-(l,1-dimethyl)propyl group, and a 1-(i,i-di) group. a group other than an alicyclic ring such as ethyl)propyl; 丨-(1-methyl)cyclopentyl, _ (1-ethyl)cyclopentyl, 1-(1-methyl)cyclohexyl, 1-(1-ethyl)cyclohexyl, 1-(1-methyl-1-(2-norbornyl) Ethyl, 1-(1-methyl-1-(2-tetracycloindenyl))ethyl, 1-(1-methyl-1-(1-adamantyl))ethyl, 2-( 2-methyl)norbornyl, 2-(2-ethyl)norbornyl, 2-(2-n-propyl)norbornyl, 2-(2-methyl)tetracyclodecyl, 2· a group having an alicyclic ring such as a (2-ethyl)tetracyclononyl group, a 2-(2-methyl)adamantyl group or a 2-(2-ethyl)adamantyl group; these have an alicyclic group The group of the ring has a carbon number of 3 to 10 such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl or t-butyl. a group substituted with a cyclic alkyl group having 4 to 20 carbon atoms such as a chain or branched alkyl group, a cyclopentyl group, a cyclohexyl group or a cyclooctyl group. -25- 201126268 Among these, 2-methyladamantan-2-yl (meth)acrylate, 2-ethyladamantan-2-yl (meth)acrylate, (meth)acrylic acid -2-methylbicyclo[2.2.1]heptan-2-yl, 2-ethylbicyclo[2.2.1]hept-2-yl (meth)acrylate, (meth)acrylic acid-1-( Bicyclo[2·2·1]hept-2-yl)-1-methylethyl ester, 1-(adamantan-1-ylindole-indole-methyl ethyl ester, (meth)acrylic acid)丨·Methyl-丨-cyclopentyl ester, 1-ethyl-1-cyclopentyl (meth)acrylate, 1-methyl-1-cyclohexyl (meth)acrylate, (meth)acrylic acid-1 -ethyl-1-cyclohexyl ester, etc. The polymer (Α) may be one or more repeating units (3). The repeating unit (3) is contained in a ratio relative to the polymer (A). The total of the repeating units contained is 100% by mole, preferably 20 to 90% by mole, more preferably 20 to 80% by mole, still more preferably 20 to 70% by mole. When the ratio of the repeating unit (3) is within this range, Both the control of the solubility of the developing solution after coating and the resistance to exposure when forming the second photoresist pattern The viewpoint is particularly useful. (ii) Repeating unit (4): In the group represented by R11 in the general formula (7-1), an alkyl group having 1 to 4 carbon atoms which may be substituted, for example, a methyl group, Ethyl, η-propyl, i-propyl, η-butyl, 2-methylpropyl, 1-methylpropyl, t-butyl, etc. A single unit of the repeating unit represented by the general formula (8) is provided. The body can be synthesized by a conventionally known method such as Tetrahedron Letters, Vol. 27, No. 32 p. 374 1 (1 986), Organic Letters, Vol. 4, Νο·15 ρ·2561 (2002), and the like. -26- 201126268 The general example of the repeating unit represented by the general formula (8), for example, the repeating unit represented by the general formula (8-1) ~ (8-22). The general formula (8-1) ~ (8 The R1 system in 22) has the same meaning as R1 in the general formula (8).

-27- 201126268 (8-7) (8-8) (8-9)-27- 201126268 (8-7) (8-8) (8-9)

(8-10) (8-11) (8-12) R1 R1 R1(8-10) (8-11) (8-12) R1 R1 R1

丫丫丫丫

(8-18) (8-19) (8-20)(8-18) (8-19) (8-20)

(8-17)(8-17)

HN.HN.

(8-22) 聚合物（A)可爲僅含有1種或2種以上之重複單位（4 )者。重複單位（4 )之含有比例係相對於聚合物（A )所含有之重複單位之合計lOOmol%，通常爲80mol%，較佳爲 20〜80mol%，更佳爲30~70mol%。重複單位（4)之含有比例爲此範圍內時，從同時兼具對於顯像液之溶解性之控制與形成第二光阻圖型時對曝光之耐性的觀點，特別有用。 (ii〇其他的重複單位：此外，聚合物（A)也可爲含有重複單位（3)及重複單位（4)以外之重複單位（以下也稱爲「其他的重複單位」）之1種以上者。其他的重複單位例如有一般式（9)表示之重複單位 -28 - 201126268 (以下也稱爲「重複單位（5)」）、一般式（1〇)表不之重複單位（以下也稱爲「重複單位（6)」）等。【化1 0】 R1(8-22) The polymer (A) may be one or more than two or more repeating units (4). The content ratio of the repeating unit (4) is 100 mol%, usually 80 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, based on the total of the repeating units contained in the polymer (A). When the content ratio of the repeating unit (4) is within this range, it is particularly useful from the viewpoint of controlling both the solubility of the developing solution and the resistance to exposure when forming the second resist pattern. (ii) Other repeating units: In addition, the polymer (A) may be one or more types of repeating units (hereinafter also referred to as "other repeating units") including a repeating unit (3) and a repeating unit (4). Other repeating units include, for example, a repeating unit of the general formula (9) -28 - 201126268 (hereinafter also referred to as "repetitive unit (5)"), and a general formula (1 〇) indicating a repeating unit (hereinafter also referred to as It is "repeating unit (6)"), etc. [Chemical 1 0] R1

十C-CH。十 (一般式（9)中，Ri係表示氫原子、甲基或三氟甲基。z 係表示單鍵或碳數^之〗價有機基。w係表示碳數7〜2〇之可被取代之多環型脂環式烴基。但是多環型脂環式烴基具有取代基時’取代基例如有甲基、乙基、碳數3~1〇之直鏈狀或支鍵狀院基、碳數4〜2〇之環烷基、羥基、氰基、碳數 10之羥基烷基、竣基、或氧代基。）【化1 1】十CrCH2十Ten C-CH. In the general formula (9), Ri represents a hydrogen atom, a methyl group or a trifluoromethyl group. z represents a single bond or a carbon number of the valence organic group. The w system represents a carbon number of 7 to 2 Å. a polycyclic alicyclic hydrocarbon group substituted, but when the polycyclic alicyclic hydrocarbon group has a substituent, the substituent includes, for example, a methyl group, an ethyl group, a linear or branched group having a carbon number of 3 to 1 Å, a cycloalkyl group having 4 to 2 carbon atoms, a hydroxyl group, a cyano group, a hydroxyalkyl group having a carbon number of 10, an anthracenyl group, or an oxo group.) [Chemical 1 1] Ten CrCH 2

(―般式（10)中，rm係表示氫原子 '甲基、三氟甲基(In the general formula (10), rm is a hydrogen atom 'methyl, trifluoromethyl

或羥基甲基。R 一般式（9 )中，係表示2價有機基。）中’以W所表示之碳數7~2〇之可被取代 •29- 201126268 之多環型脂環式烴基，例如有來自下式所示之雙環〔2.2.1 〕庚烷（9a )、雙環〔2_2.2〕辛烷（9b )、三環〔 5.2.1.02’6〕癸烷（9c)、四環〔6.2.1.13’6_02’7〕十二烷（ 9d)、三環〔3.3.1.I3,7〕癸烷（9e)等之環烷類之烴基等Or hydroxymethyl. R In the general formula (9), it represents a divalent organic group. The polycyclic alicyclic hydrocarbon group in which the carbon number represented by W is 7~2〇 can be substituted. 29-201126268, for example, there is a bicyclo [2.2.1] heptane (9a) represented by the following formula Bicyclo[2_2.2]octane (9b), tricyclo[5.2.1.02'6]decane (9c), tetracyclo[6.2.1.13'6_02'7]dodecane (9d), tricyclo[3.3 .1. I3, 7] a hydrocarbyl group such as a cycloalkane such as decane (9e)

來自環烷類之烴基具有取代基時，取代基例如有甲基、乙基、正丙基、異丙基、正丁基、2-甲基丙基、1-甲基丙基、第三丁基等之碳數3〜10之直鏈狀或支鏈狀烷基、環戊基、環己基、環辛基等之碳數4〜20之環狀烷基等。另外 ’取代基並不限於此等烷基，也可爲羥基、氰基、碳數 1〜10之羥基烷基、羧基、氧代基。 —般式（10)中，R15所表示之2價有機基，較佳爲2 價烴基，更佳爲鏈狀或環狀之2價烴基。也可爲伸烷二醇基、伸烷基酯基等。2價有機基，具體而言例如有伸甲基、伸乙基、二十伸甲基、1-甲基-1，3-伸丙基、2-甲基-1,3- 伸丙基、2 -亞丙基等之亞院基（alkanediyl groups); 1，3-伸環丁基、1，3-伸環戊基等之碳數3〜10之伸環烷基等之單環式烴環基；I，4-伸降莰基、1,5-伸金剛烷等之 2~4環式之碳數4~30之烴環基等之交聯環式烴環基等。此等中，較佳爲包含2,5-伸莰基之烴基、1,2-伸乙基、伸丙 -30- 201126268 基。又，R1 5含有2價脂肪族環式烴基時，在雙三氟甲；基-甲基（-C ( C F 3 ) 2 Ο Η )與2價脂肪族環式烴基之間作爲隔離基之碳數1~4之亞烷基較佳。 (2 )聚合物（Β ) 聚合物（Β)係包含具有交聯基之重複單位及具原子之重複單位者。第一敏輻射線性組成物係因含有性之聚合物（Β)，在形成光阻被膜時，其分布有在被膜表面變高的傾向。因此，在液浸曝光時，可抑制被膜中之酸產生劑（C )或酸擴散控制劑等溶出於水液浸液中。此外，因聚合物（Β )之撥水性的特長，阻被膜與液浸液之後退接觸角變高。因此，來自液浸水滴不易殘留於光阻被膜上，即使以高速進行掃描曝也可抑制水痕等因液浸液所產生的缺陷。此外，第一圖型藉由加熱或輻射線照射，可對於第二敏輻射線性物產生不溶化。其中，聚合物（Β)較佳爲再含有具有酸不安定重複單位者。此乃是聚合物（Β)藉由酸之作用，而對於鹼顯像液，具有溶解之性質的緣故。聚合物（Β)之含量係相對於聚合物（Α) 1〇〇質，通常爲1〜80質量份，較佳爲2〜50質量份，更佳爲量份。含量在此範圍內，可對於第二敏輻射線性組成有充分的耐性，同時可抑制第一光阻圖型形成時之解 S _羥配置有氟撥油光阻光阻等之使光液之光，光阻組成基之成爲量份 25質物具像不 -31 - 201126268 (i)具有交聯基之重複單位：具有交聯基之重複單位較佳爲前述重複單位（1)者。此外，交聯基較佳爲熱硬化性之反應性基。前述一般式（2)或（3)表示之基團中，以R6表示之碳數3〜10之直鏈狀或支鏈狀之烷基，例如有η-丙基、i-丙基、2-甲基丙基、1-甲基丙基、η-丁基、t-丁基等。前述一般式（1-1)表示之重複單位，具體而言，例如有下述一般式（1-1-a)〜（1-1-h)表示之重複單位。一般式（l-1-a)〜（l-1-h)中，R1係表示氫原子、甲基或三氟甲基。【化1 3】When the hydrocarbon group derived from the cycloalkane has a substituent, the substituent is, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, or a third group. A linear or branched alkyl group having a carbon number of 3 to 10 or the like, a cyclic alkyl group having 4 to 20 carbon atoms such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group. Further, the substituent is not limited to these alkyl groups, and may be a hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group or an oxo group. In the general formula (10), the divalent organic group represented by R15 is preferably a divalent hydrocarbon group, more preferably a chain or cyclic divalent hydrocarbon group. It may also be an alkylene glycol group, an alkyl ester group or the like. a divalent organic group, specifically, for example, a methyl group, an ethyl group, a tetramethyl group, a 1-methyl-1,3-propanyl group, a 2-methyl-1,3-propanyl group, 2 - alkaneiyl groups such as propylene, etc.; monocyclic hydrocarbons such as 1,3-cyclopentene butyl, 1,3-cyclopentyl group, etc., having a carbon number of 3 to 10, such as a cycloalkyl group a cyclic ring hydrocarbon group such as a ring group; an alkylene ring group such as a hydrocarbon ring group having a carbon number of 4 to 30 in a 2 to 4 ring type such as a 1,4-extended adamantane or the like. Among these, a hydrocarbon group containing a 2,5-anthracene group, a 1,2-extended ethyl group, and a propylene--30-201126268 group are preferable. Further, when R1 5 contains a divalent aliphatic cyclic hydrocarbon group, carbon as a spacer between bistrifluoromethyl; benzyl-((C(CF 3 ) 2 Ο Η ) and a divalent aliphatic cyclic hydrocarbon group The alkylene group having 1 to 4 is preferred. (2) Polymer (Β) The polymer (Β) contains a repeating unit having a crosslinking group and a repeating unit having an atom. The first sensitive radiation linear composition tends to have a high distribution on the surface of the film when the resist film is formed due to the polymer (含有). Therefore, in the immersion exposure, it is possible to suppress the acid generator (C) or the acid diffusion controlling agent in the film from being dissolved in the aqueous liquid immersion liquid. Further, due to the characteristic of the water repellency of the polymer (Β), the back contact angle of the resist film and the liquid immersion liquid becomes high. Therefore, water droplets from the liquid immersion do not easily remain on the resist film, and even if the scanning is performed at a high speed, defects such as water marks and the liquid immersion liquid can be suppressed. In addition, the first pattern can be insolubilized by the second sensitive radiation linear object by heating or radiation. Among them, the polymer (Β) preferably further contains those having an acid labile repeating unit. This is because the polymer (Β) acts as an acid and has a solubility property for the alkali developing solution. The content of the polymer (Β) is usually from 1 to 80 parts by mass, preferably from 2 to 50 parts by mass, more preferably parts by mass, based on the mass of the polymer. The content is within this range, and can have sufficient resistance to the linear composition of the second sensitivity radiation, and can suppress the solution of the first photoresist pattern when the first photoresist pattern is formed, and the light of the liquid is light. , the photoreceptor composition is a component of the mass of 25. The image is not -31 - 201126268 (i) Repeating unit having a crosslinking group: The repeating unit having a crosslinking group is preferably the aforementioned repeating unit (1). Further, the crosslinking group is preferably a thermosetting reactive group. In the group represented by the above general formula (2) or (3), a linear or branched alkyl group having a carbon number of 3 to 10 represented by R6, for example, η-propyl group, i-propyl group, 2 -methylpropyl, 1-methylpropyl, η-butyl, t-butyl, and the like. The repeating unit represented by the above general formula (1-1), specifically, for example, repeating units represented by the following general formulas (1-1-a) to (1-1-h). In the general formula (l-1-a) to (l-1-h), R1 represents a hydrogen atom, a methyl group or a trifluoromethyl group. 【化1 3】

32- 20112626832- 201126268

前述一般式（1-2)表示之重複單位，具體而言，例如有下述一般式（l-2-a)〜（l-2-d)表示之重複單位。一般式一'般式（l-2-a)〜（l-2-d)中’ Ri係表不氨原子、甲基或三氟甲基。【化1 4】The repeating unit represented by the above general formula (1-2), specifically, for example, repeating units represented by the following general formulas (1-2-a) to (l-2-d). In the general formula (1-2-a) to (l-2-d), the 'Ri' represents an ammonia atom, a methyl group or a trifluoromethyl group. [化1 4]

(1-2-a) (1-2-b) (1-2-c) 其中更佳爲（1-1-a) 、（1-1-e) 、（l-2-a)表示之重複單位。聚合物（B )所含有之重複單位（1 )的比例係相對於聚合物（B)所含有之重複單位之合計1 〇〇 mol%，較佳爲 1〜30mol°/。，更佳爲1〜25mol%，更佳爲5〜15mol%。重複單位（〗）之比例在此範圍內’鹼顯像部不易因鹼顯像液而膨潤，維持對鹼顯像液之溶解性，可抑制線寬變動或尺寸之精度降低。 -33- 201126268 (ii)具有氟原子之重複單位：具有氟原子之重複單位較佳爲前述重複單位（2)或 —般式（f-4 )表示之重複單位。前述一般式（4)中，以R7表示之基團中，碳數1〜2 0 之直鏈狀或支鏈狀之飽和或不飽和之2價烴基，例如有來自甲基、乙基、正丙基、異丙基、正丁基、2-甲基丙基、 1-甲基丙基、第三丁基、戊基、異戊基、新戊碁、己基、庚基、辛基、壬基、癸基等之碳數3〜2 0之直鏈狀或支鏈狀烷基之2價烴基等。另外，環狀之飽和或不飽和之2價烴基，例如有來自碳數3〜2 0之脂環式烴及芳香族烴之基團。脂環式烴例如有環丁烷、環戊烷、環己烷、雙環〔2.2.1〕庚烷、雙環〔 2.2.2〕辛烷、三環〔5.2.1.02’6〕癸烷、三環〔3.3.1.13,7〕癸烷、四環〔6.2.1.13’6.〇2’7〕十二烷等之環烷類等。另外，芳香族烴例如有苯、萘等。另外，上述R7之烴基可爲將上述非取代之烴基中之至少1個氫原子，以甲基、乙基、正丙基、異丙基、正丁基、2-甲基丙基、1-甲基丙基、第三丁基等之碳數3〜12之直鏈狀或支鏈狀之烷基、環烷基、羥基、氰基、碳數1〜10之羥基烷基、羧基、氧原子等之一種或兩種以上所取代的基團。一般式（4)中之R7之具體例有下列構造（al)〜（ a2 7)表示之基團等。此外，構造（al) ~(a2 7)中之「* •34- 201126268 」係表示鍵結部位。【化1 5】(1-2-a) (1-2-b) (1-2-c) Which is better (1-1-a), (1-1-e), (l-2-a) Repeat the unit. The ratio of the repeating unit (1) contained in the polymer (B) is 1 〇〇 mol%, preferably 1 to 30 mol%, based on the total of the repeating units contained in the polymer (B). More preferably, it is 1 to 25 mol%, more preferably 5 to 15 mol%. The ratio of the repeating unit (〗) is within this range. The alkali developing unit is not easily swollen by the alkali developing solution, and the solubility in the alkali developing solution is maintained, and the variation in line width or the dimensional accuracy can be suppressed. -33- 201126268 (ii) Repeating unit having a fluorine atom: The repeating unit having a fluorine atom is preferably a repeating unit represented by the above repeating unit (2) or the general formula (f-4). In the above general formula (4), in the group represented by R7, a linear or branched saturated or unsaturated divalent hydrocarbon group having 1 to 2 carbon atoms, for example, is derived from methyl group, ethyl group, or positive group. Propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, anthracene A divalent hydrocarbon group of a linear or branched alkyl group having 3 to 20 carbon atoms such as a fluorenyl group or a fluorenyl group. Further, the cyclic saturated or unsaturated divalent hydrocarbon group is, for example, a group derived from an alicyclic hydrocarbon having 3 to 20 carbon atoms and an aromatic hydrocarbon. The alicyclic hydrocarbons are, for example, cyclobutane, cyclopentane, cyclohexane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, tricyclo[5.2.1.0''6]nonane, tricyclic [3.3.1.13, 7] Cyclohexanes such as decane and tetracyclo [6.2.1.13'6.〇2'7] dodecane. Further, the aromatic hydrocarbon is, for example, benzene or naphthalene. Further, the hydrocarbon group of the above R7 may be at least one hydrogen atom of the above unsubstituted hydrocarbon group, and may be methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1- a linear or branched alkyl group having a carbon number of 3 to 12, a methyl propyl group, a third butyl group or the like, a cycloalkyl group, a hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxyl group, and an oxygen group. a group substituted with one or two or more of atoms. Specific examples of R7 in the general formula (4) include the groups represented by the following structures (al) to (a27). In addition, "* • 34- 201126268" in the structure (al) ~ (a2 7) indicates the bonding portion. [化1 5]

(al) (a2) (a3)(al) (a2) (a3)

(a 4) (a5) (a6) (a7)(a 4) (a5) (a6) (a7)

(a8) (a9) (a 10)(a8) (a9) (a 10)

(a25) (a26)(a25) (a26)

* (a27) 特別是一般式（4)中之R7較佳爲伸甲基、1-甲基伸乙基、2-甲基伸乙基、碳數4〜20之2價脂環式烴基等。一般式（4 )中，以X表示之經氟原子取代之伸甲基或碳數2〜20之直鏈狀或支鏈狀之氟亞烷基，例如有下述式（ X-1)〜（X-8)等之構造表示之基團。 -35- 201126268 【化1 6】 F3C---CF3 F3C—C—CF3 F3C—C—CF3 f3c—c—cf3 f3c—c—cf3 F3C——C——CF3 f3c—c—cf3 F3C—C—CF3 F3C—C—CF3 F3C— —CF3 (X-1) (X-2) (X-3) (X-4) F—C—F F—( F—( ：—F ：—F F—C—F 1 F—C—F 1 F—C—F 1 (X-5) (X-6) (X-7)* (a27) In particular, R7 in the general formula (4) is preferably a methyl group, a 1-methyl-ethyl group, a 2-methyl-ethyl group, a divalent alicyclic hydrocarbon group having a carbon number of 4 to 20, and the like. . In the general formula (4), a methyl group substituted by a fluorine atom or a linear or branched fluoroalkylene group having a carbon number of 2 to 20 represented by X, for example, has the following formula (X-1)~ The group represented by the structure of (X-8) and the like. -35- 201126268 [Chemical 1 6] F3C---CF3 F3C-C-CF3 F3C-C-CF3 f3c-c-cf3 f3c-c-cf3 F3C-C-CF3 f3c-c-cf3 F3C-C- CF3 F3C—C—CF3 F3C—CF3 (X-1) (X-2) (X-3) (X-4) F—C—FF—( F—( :—F :—FF—C—F 1 F—C—F 1 F—C—F 1 (X-5) (X-6) (X-7)

F——C—F F—C—FF——C—F F—C—F

II

F—C—FF-C-F

II

F—C—F (X-8) 特別是一般式（4)表示之重複單位，較佳爲來自以式（4-；1 )〜（4-6)表示之化合物的重複單位。【化1 7】F-C-F (X-8) is specifically a repeating unit represented by the general formula (4), preferably a repeating unit derived from a compound represented by the formula (4-; 1) to (4-6). [化1 7]

(4-4) (4-3) 36- 201126268(4-4) (4-3) 36- 201126268

0H0H

OH (4-5) —般式（5)中，以R9表示之基團中，具有至少一個以上之氟原子之甲基、乙基、碳數3〜6之直鏈狀或支鏈狀之院基’例如有甲基、乙基、1-丙基、2 -丙基、1-丁基、 2-丁基、2-(2_甲基丙基）、丨_戊基、2_戊基、3_戊基、ι_ (2 -甲基丁基）、1-(3 -甲基丁基）、2-(2 -甲基丁基）、2- (3-甲基丁基）、新戊基、1-己基、2-己基、3-己基、1-(2-甲基戊基）、丨-^-甲基戊基）、^(心甲基戊基）、2-(2 -甲基戊基）、2-(3 -甲基戊基）、2-(4 -甲基戊基）、3-(2 —甲基戊基）、3-(3 -甲基戊基）等之直鏈狀或支鏈狀烷基之部分氟化或全氟烷基等。具體而言，例如有下述式（Y-1 ) ~ ( Y-8 )表示之基團。【化1 8】 :3 Ic F3 c Λ F3OH (4-5) In the formula (5), a group represented by R9 has a methyl group having at least one fluorine atom, an ethyl group, and a linear or branched chain having a carbon number of 3 to 6. The hospital base 'for example is methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-(2-methylpropyl), 丨-pentyl, 2-pentyl Base, 3-pentyl, i- (2-methylbutyl), 1-(3-methylbutyl), 2-(2-methylbutyl), 2-(3-methylbutyl), Neopentyl, 1-hexyl, 2-hexyl, 3-hexyl, 1-(2-methylpentyl), 丨-^-methylpentyl), ^(heart methylpentyl), 2-(2 -methylpentyl), 2-(3-methylpentyl), 2-(4-methylpentyl), 3-(2-methylpentyl), 3-(3-methylpentyl) A partially fluorinated or perfluoroalkyl group of a linear or branched alkyl group. Specifically, for example, there are groups represented by the following formulas (Y-1) to (Y-8). [化1 8] :3 Ic F3 c Λ F3

F2H (V- 3) (V- 2 3 )/ F F 4 —CICY-F2H (V- 3) (V- 2 3 ) / F F 4 —CICY-

2 2 3 F F F ICICIC 5)6 丨S—CF2_CF3| CF,—i—(v-a) 另外，具有至少一個以上之氟原子之碳數4〜20之一價脂環式烴基，例如有環戊基、環戊基甲基、^(1_環戊基乙基）、1-(2-環戊基乙基）、環己基 '環己基甲基、卜 (1-環己基乙基）、1-(2-環己基乙基） '環丁基、環丁基甲基、1-(1-環庚基乙基）、：1-(2-環庚基乙基）、2- -37- 201126268 降莰基等之脂環式烷基之部分氟化或全氟烷基等。提供重複單位（2 )之較佳的單體，例如有（甲基）丙烯酸三氟甲酯、（甲基）丙烯酸2, 2, 2-三氟乙酯、（甲基）丙烯酸全氟乙酯、（甲基）丙烯酸全氟正丙酯、（甲基）丙烯酸全氟異丙酯 '(甲基）丙烯酸全氟正丁酯、（甲基）丙烯酸全氟異丁酯、（甲基）丙烯酸全氟第三丁酯 ' (甲基）丙烯酸2-(1，1，1，3，3, 3-六氟丙基）酯、（甲基）丙烯酸1-(2，2，3，3，4，4，5，5-八氟戊基）酯、（甲基）丙烯酸全氟環己基甲酯、（甲基）丙烯酸-1-(2，2, 3，3，3-五氟丙基）酯、（甲基）丙烯酸1-(3，3，4，4, 5, 5, 6，6，7，7，8，8，9，9，10，10，10-十七氟癸基）酯、（甲基）丙烯酸1- ( 5 -三氟甲基_3，3，4，4，5, 6，6，6-八氟己基 )酯等。聚合物（B)可含有下述一般式（f_ 4)表示之重複單位（f)以下也稱爲（「重複單位（f)」）。【化1 9】2 2 3 FFF ICICIC 5)6 丨S—CF2_CF3| CF, —i—(va) Further, a carbon atom having 4 to 20 carbon atoms having at least one fluorine atom, for example, a cyclopentyl group, Cyclopentylmethyl, ^(1_cyclopentylethyl), 1-(2-cyclopentylethyl), cyclohexyl'cyclohexylmethyl, di(1-cyclohexylethyl), 1-( 2-cyclohexylethyl) 'cyclobutyl, cyclobutylmethyl, 1-(1-cycloheptylethyl), 1-(2-cycloheptylethyl), 2-37-2011-26268 A partial fluorinated or perfluoroalkyl group of an alicyclic alkyl group. Preferred monomers for repeating unit (2) are provided, for example, trifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate , (meth)acrylic acid perfluoro-n-propyl ester, (meth)acrylic acid perfluoroisopropyl ester (meth)acrylic acid perfluoro-n-butyl ester, (meth)acrylic acid perfluoroisobutyl ester, (meth)acrylic acid Perfluoro-t-butyl ester '2-(1,1,1,3,3,3-hexafluoropropyl) (meth)acrylate, 1-(2,2,3,3, (meth)acrylic acid 4,4,5,5-octafluoropentyl)ester, perfluorocyclohexylmethyl (meth)acrylate, 1-(2,2,3,3,3-pentafluoropropyl (meth)acrylate ) ester, 1-(3,3,4,4,5, 5, 6,6,7,7,8,8,9,9,10,10,10-heptadecafluoroindenyl (meth)acrylate An ester, 1-(5-trifluoromethyl_3,3,4,4,5,6,6-hexafluorohexyl) (meth)acrylate, and the like. The polymer (B) may contain a repeating unit (f) represented by the following general formula (f-4) and is also referred to as "(repeating unit (f)"). [化1 9]

(―般式（f-4)中，R1係表示氫原子、甲基或三氟甲基。 RM係表示（m+1 )價之連結基。Xf4係表示具有氟原子之2 價的連結基。R」4係表示氫原子或1價有機基。111係1〜3之整數。m爲2或3時，複數之R』4係分別獨立表示氫原子或1價 -38- 201126268 有機基。）一般式（f-O中，以Rk4表示之（m + 1 )價連結基’ 例如有可具有醚基或酯基之碳數1〜10之（m+l)價的烴基，更佳爲可具有醚基或酯基之碳數1〜8之（m+1)價的烴基，特佳爲可具有醚基或酯基之碳數1〜5之（m+l)價的烴基。此外，以Xf4表示之具有氟原子之2價連結基，較佳爲具有氟原子之碳數1~20之2價鏈狀烴基。具體而言，例如有前述式（X-1)〜（X-8)表示之基團。其中’ xf4較佳爲前述式（X-1)或（X-2)表示之基團。以Rj4表示之1價有機基例如有可具有酸不安定基或取代基之碳數卜30之烴基。Rj4較佳爲氫原子、t-丁氧羰基或烷氧基取代甲基。 —般式（f-4)中，m係1〜3之整數。因此’重複單位 (f-4)中，Rj4被導入1〜3個。m爲2或3時’複數之χΜ係構成1^4之碳原子中，可鍵結於相同的碳原子或可鍵結於不相同的碳原子。重複單位（f-4 )之具體例有下述一般式（f4-l )〜（ f4-4)表示之重複單位。一般式（f4-l)〜（f4-4)中，係表不氫原子、甲基或三氟（甲基。 -39 - 201126268 【化2 0】 R1 R1 R1 R1(In the general formula (f-4), R1 represents a hydrogen atom, a methyl group or a trifluoromethyl group. RM is a linking group having a (m+1) valence. Xf4 is a linking group having a valence of a fluorine atom. R"4 represents a hydrogen atom or a monovalent organic group. 111 is an integer of 1 to 3. When m is 2 or 3, the plural R"4 series independently represents a hydrogen atom or a monovalent-38-201126268 organic group. In the general formula (fO, the (m + 1 ) valent linking group represented by Rk4" is, for example, a hydrocarbon group having a valence of 1 to 10 (m + 1) having an ether group or an ester group, and more preferably having a hydrocarbon group having a (m+1)-valent carbon number of 1 to 8 carbon atoms of the ether group or the ester group, particularly preferably a hydrocarbon group having a valence of 1 to 5 (m+1) having an ether group or an ester group. The divalent linking group having a fluorine atom represented by Xf4 is preferably a divalent chain hydrocarbon group having 1 to 20 carbon atoms and having a fluorine atom. Specifically, for example, the above formula (X-1) to (X-8) a group represented by wherein 'xf4 is preferably a group represented by the above formula (X-1) or (X-2). The monovalent organic group represented by Rj4 is, for example, a carbon which may have an acid labyring group or a substituent a hydrocarbon group of 30. Rj4 is preferably a hydrogen atom, a t-butoxycarbonyl group or The alkoxy group is substituted with a methyl group. In the general formula (f-4), m is an integer of 1 to 3. Therefore, in the 'repetition unit (f-4), Rj4 is introduced 1 to 3. When m is 2 or 3 The plural χΜ is a carbon atom of 1^4, which may be bonded to the same carbon atom or may be bonded to a different carbon atom. Specific examples of the repeating unit (f-4) have the following general formula (f4) -l)~(f4-4) represents a repeating unit. In the general formula (f4-l)~(f4-4), the formula is not a hydrogen atom, a methyl group or a trifluoro group (methyl. -39 - 201126268) 2 0] R1 R1 R1 R1

(f4-1) (f4-2) (f4-3) (f4-4) 聚合物（B)可僅含有1種或含有2種以上之重複單位 (2 )。重複單位（2 )之含有比例係相對於聚合物（B ) 所含之重複單位之合計lOOmol%，較佳爲1〜60mol%，更佳爲5〜50mol%，更佳爲10〜45mol%。重複單位（2)之含有比例在此範圍內時，對於液浸液，可維持充分的後退接觸角，同時可以鹼顯像液進行充分顯像。 (iii)具有酸不安定基之重複單位：具有酸不安定基之重複單位無特別限定，例如有「（ 1)聚合物（A)」所記載之重複單位（3)等。聚合物（B )可僅含有1種或2種以上之重複單位（3 )者。重複單位 (3 )之含有比例係相對於聚合物（B )所含之重複單位的合計lOOmol%，較佳爲10〜90mol%，更佳爲10〜80mol%，更佳爲20〜70mol% »重複單位（3 )之含有比例在此範圍內時，對於液浸液，可維持充分的後退接觸角，同時可以鹼顯像液進行充分顯像。 -40- 201126268 (i v )其他的重複單位：聚合物（B)可爲含有上述重複單位（1)〜（3)以外的重複單位（以下也稱爲「其他的重複單位」）者。其他的重複單位例如有「（ 1 )聚合物（A )」所記載之重複單位（4)、重複單位（6)或下述一般式（11)表示之重複單位（7 )(以下也稱爲「重複單位（7 )」）。重複單位（4 )之含有比例係相對於聚合物（b )所含之重複單位的合g十lOOmol%，較佳爲5〜70mol%，更佳爲 5〜65mol%’更佳爲1〇〜60mol%，特佳爲1〇〜20mol%者。重複單位（4 )之含有比例在此範圍，可維持作爲光阻之顯像性及曝光量或焦距等之製程裕度（Margin )。重複單位（6 )之含有比例係相對於聚合物（b )所含之重複單位的合計lOOmol%。較佳爲30mol%以下，更佳爲 2 5 mol%以下者。重複單位（6)之含有比例在此範圍時，可抑制光阻圖型之頂部損失。重複單位（6 )係任意成分，因此可不含於聚合物（B)中。【化2 1】 R1(f4-1) (f4-2) (f4-3) (f4-4) The polymer (B) may contain only one type or two or more types of repeating units (2). The content ratio of the repeating unit (2) is 100 mol%, preferably 1 to 60 mol%, more preferably 5 to 50 mol%, still more preferably 10 to 45 mol%, based on the total of the repeating units contained in the polymer (B). When the ratio of the repeating unit (2) is within this range, a sufficient receding contact angle can be maintained for the liquid immersion liquid, and sufficient development can be performed by the alkali developing solution. (iii) Repeating unit having an acid-labile group: The repeating unit having an acid-labile group is not particularly limited, and examples thereof include "(1) a repeating unit (3) described in the polymer (A)". The polymer (B) may contain only one type or two or more types of repeat units (3). The content ratio of the repeating unit (3) is 100% by mole, preferably 10 to 90% by mole, more preferably 10 to 80% by mole, still more preferably 20 to 70% by mole based on the total of the repeating units contained in the polymer (B). When the content ratio of the repeating unit (3) is within this range, a sufficient receding contact angle can be maintained for the liquid immersion liquid, and sufficient development can be performed by the alkali developing solution. -40- 201126268 (i v ) Other repeating units: The polymer (B) may be a repeating unit other than the above repeating units (1) to (3) (hereinafter also referred to as "other repeating units"). Other repeating units include, for example, a repeating unit (4) described in "(1) Polymer (A)", a repeating unit (6), or a repeating unit (7) represented by the following general formula (11) (hereinafter also referred to as "Repeat unit (7)"). The ratio of the content of the repeating unit (4) is 10,000 mol%, preferably 5 to 70 mol%, more preferably 5 to 65 mol%, more preferably 1 Torr to the repeating unit contained in the polymer (b). 60 mol%, particularly preferably from 1 〇 to 20 mol%. The ratio of the repetition unit (4) is in this range, and the process margin (Margin) such as the visibility of the photoresist and the exposure amount or the focal length can be maintained. The content ratio of the repeating unit (6) is 100% by mole based on the total of the repeating units contained in the polymer (b). It is preferably 30 mol% or less, more preferably 25 mol% or less. When the content ratio of the repeating unit (6) is within this range, the top loss of the photoresist pattern can be suppressed. The repeating unit (6) is an optional component and thus may not be contained in the polymer (B). [Chem. 2 1] R1

(一般式（1 1 )中’ R1係表示氫原子、甲基或三氟甲基。 X係表示單鍵或2價連結基。Rc係表示可被取代之碳數3〜30 -41 - 201126268 之（n+l)價的脂環式烴基。Rf係表示具有1~1〇個氟原子之碳數卜30之1價鏈狀烴基、或具有1〜10個氟原子之碳數 3〜30之1價脂環式烴基。η係1〜3之整數。此外，η爲2或3時，複數之Rf係分別獨立表示具有1〜10個氟原子之碳數1〜30 之1價鏈狀烴基、或具有1〜10個氟原子之碳數3~30之1價脂環式烴基。）重複單位（7)較佳爲下述一般式（11-1)表示之重複單位者。【化2 2】 R1(In the general formula (1 1 ), R1 represents a hydrogen atom, a methyl group or a trifluoromethyl group. X represents a single bond or a divalent linking group. Rc represents a carbon number which can be substituted 3 to 30 -41 - 201126268 (n+1) alicyclic hydrocarbon group. Rf represents a monovalent chain hydrocarbon group having 1 to 1 ring of fluorine atoms, or a carbon number of 3 to 30 having 1 to 10 fluorine atoms. The monovalent alicyclic hydrocarbon group is an integer of 1 to 3. When η is 2 or 3, the plural Rf groups independently represent a monovalent chain having 1 to 10 carbon atoms of 1 to 10 fluorine atoms. A hydrocarbon group or a monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms and having 1 to 10 fluorine atoms.) The repeating unit (7) is preferably a repeating unit represented by the following general formula (11-1). [Chemical 2 2] R1

(11-1) (—般式（11-1)中，R1、X、Rf及η之定義係與一般式（ 11 )相同。Rs係表示-111>1、-111>2-0-111>1、-11132-(：0-111>1、-Rp2-CO-〇Rpl、-RP2-〇-CO-RP1、-RP2-OH、-RP2-CN、又-RP2-C0 0H ( RP1係表示碳數1〜10之1價鏈狀飽和烴基、碳數3〜2 0之1價脂肪族環狀飽和烴基或碳數6-30之1價芳香族烴基。此外，構成此等基之氫原子之一部份或全部可被氟原子取代。RP2係表示單鍵、碳數1~1〇之2價鏈狀飽和烴基 -42- 201126268 、碳數3〜20之2價脂肪族環狀飽和烴基、或碳數6〜3 0之2價芳香：族烴基。構成此等基之氫原子之一部份或全部可被氟原子取代。）。ns係0〜3之整數》) —般式（11-1)表示之重複單位，具體而言，例如有下述式（11-1-1)表示之重複單位。【化2 3】(11-1) (In the general formula (11-1), the definitions of R1, X, Rf, and η are the same as those of the general formula (11). Rs means -111>1, -111>2-0-111&gt ; 1,-11132-(:0-111>1, -Rp2-CO-〇Rpl, -RP2-〇-CO-RP1, -RP2-OH, -RP2-CN, and -RP2-C0 0H (RP1 series A monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a monovalent aliphatic cyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms. Further, hydrogen constituting the groups Part or all of the atom may be replaced by a fluorine atom. RP2 represents a single bond, a divalent chain saturated hydrocarbon group having a carbon number of 1 to 1 - -42 - 201126268, and a divalent aliphatic ring saturated with a carbon number of 3 to 20 a hydrocarbon group or a divalent aromatic having a carbon number of 6 to 30: a hydrocarbon group. Part or all of a hydrogen atom constituting such a group may be substituted by a fluorine atom.) ns is an integer of 0 to 3") (11-1) The repeating unit represented by the following formula (11-1-1) is specifically a repeating unit represented by the following formula (11-1-1).

(11-1-1) 重複單位（7 )之含有比例係相對於聚合物（B )所含之重複單位的合計1 OOmol%，較佳爲90mol%以下，更佳爲 7 5 m ο 1 %以下。重複單位（7 )之含有比例在此範圍內時，光阻圖型之形狀良好，故較佳。重複單位（7 )係任意成分，因此，可不含於聚合物（B)中。 (各聚合物之調製方法）各聚合物係例如將提供前述各種重複單位之聚合性不飽和單體，使用過氧化氫類、二烷基過氧化物類、二醯基 -43- 201126268 過氧化物類、偶氮化合物等自由基聚合起始劑，且必要時在鏈轉移劑之存在下，於適當溶劑中聚合而調製。聚合所使用之溶劑例如有正戊烷、正己烷等烷類；環己烷、環庚烷、環辛烷等環烷類；苯、甲苯等芳香族烴類 ;氯丁烷、溴己烷等鹵化烴類；乙酸乙酯、乙酸正丁酯等飽和羧酸酯類；丙酮、2-丁酮等酮類；四氫呋喃、二甲氧基乙烷等醚類等。另外，此等溶劑可單獨使用一種，或可混合兩種以上使用。 (聚合物之物性値）各聚合物之以凝膠滲透層析（GPC )換算成聚苯乙烯之重量平均分子量（以下也稱爲「Mw」）並無特別限制。但較佳爲1，000〜100,000，更佳爲1，000〜30,000，更佳爲 1，000~20,000。Mw在此範圍時，可同時兼具第一光阻層之耐熱性與鹼顯像部之顯像性。另外，各聚合物之Mw與各聚合物之以凝膠滲透層析 (GPC )換算成聚苯乙烯之數平均分子量（以下也稱爲「 Μη」）之比（Mw/Mn )分別通常爲1〜5，較佳爲1〜3。另外，各聚合物中有時含有來自調製時使用之單體的低分子量成分的情形。此低分子量成分之含有比例係相對於各聚合物1 00質量％ (換算成固形成分），較佳爲0.1質量％以下，更佳爲0.07質量％以下，又更佳爲〇.〇5質量％以下。低分子量成分之含有比例在0.1質量％以下時，可減少在液浸曝光時所接觸之水等液浸液之溶出物的量。又，光 -44 - 201126268 阻保管時，在光阻中產生異物較少，即使在塗佈光阻劑時 ’塗佈不均之發生較少’可充分地抑制光阻圖型形成時之缺陷發生。各聚合物不含有低分子量成分特佳。又’本說明書中所g胃「低分子量成分」意指Mw爲500 以下之成分，具體而言，例如有單體、二聚物、三聚物、寡聚物。低分子量成分可藉由例如水洗、液液萃取等化學純化法’或此等化學純化法與超過濾、離心分離等物理純化法之組合等去除。另外，可藉由高速液體層析（HP LC )進行分析。再者，各聚合物較佳爲鹵素、金屬等雜質較少者。此乃是因爲藉由減少雜質，可進一步提高形成之第一光阻層之耐蝕刻性及防止來自光阻圖型之雜質所造成之裝置之電特性劣化等的緣故。各聚合物之純化方法例如有水洗、液液萃取等之化學純化法，或此等化學純化法與超過濾、離心分離等之物理純化法之組合等。 (3 )酸產生劑（C ) 所謂的酸產生劑（C)意指藉由曝光產生酸者。藉由使第一敏輻射線性組成物含有酸產生劑（C )，可因曝光產生之酸的作用，使聚合物中存在之酸不安定基，具體而言爲重複單位（3)所具有之酸不安定基解離（使保護基脫離）。其結果，鹼顯像部對鹼顯像液成爲易溶性，可形成光阻圖型。又，酸產生劑（C )較佳爲含有以一般式（ -45- 201126268 12)表示之化合物（以下也稱爲「酸產生劑（i)」）者〇酸產生劑（C)之含量係從確保作爲光阻之感度及顯像性的觀點，相對於聚合物（A) 100質量份，通常爲〇.1~20質量份’較佳爲〇·5~10質量份，更佳爲5〜10質量份。含量在此範圍時，在感度及顯像性不會降低的狀態，可得到對輻射線之充分的透明性，可得到矩形的光阻圖型。 (i )酸產生劑（1 ): 酸產生劑（1)係一般式（12)表示之化合物。【化2 4】 R16(11-1-1) The content ratio of the repeating unit (7) is 10,000 mol%, preferably 90 mol% or less, more preferably 7 5 m ο 1 %, based on the total of the repeating units contained in the polymer (B). the following. When the content ratio of the repeating unit (7) is within this range, the shape of the resist pattern is good, which is preferable. The repeating unit (7) is an optional component and, therefore, may not be contained in the polymer (B). (Preparation method of each polymer) For each polymer type, for example, a polymerizable unsaturated monomer which provides the above various repeating units, and hydrogen peroxide, a dialkyl peroxide, and a dimercapto-43-201126268 peroxidation are used. A radical polymerization initiator such as a substance or an azo compound, and if necessary, is polymerized in a suitable solvent in the presence of a chain transfer agent to prepare a radical polymerization initiator. The solvent used for the polymerization is, for example, an alkane such as n-pentane or n-hexane; a cycloalkane such as cyclohexane, cycloheptane or cyclooctane; an aromatic hydrocarbon such as benzene or toluene; chlorobutane or bromohexane; Halogenated hydrocarbons; saturated carboxylic acid esters such as ethyl acetate and n-butyl acetate; ketones such as acetone and 2-butanone; and ethers such as tetrahydrofuran and dimethoxyethane. Further, these solvents may be used alone or in combination of two or more. (The physical properties of the polymer) The weight average molecular weight (hereinafter also referred to as "Mw") of the polystyrene in terms of gel permeation chromatography (GPC) of each polymer is not particularly limited. However, it is preferably from 1,000 to 100,000, more preferably from 1,000 to 30,000, still more preferably from 1,000 to 20,000. When Mw is in this range, the heat resistance of the first photoresist layer and the developability of the alkali developing portion can be simultaneously achieved. Further, the ratio (Mw/Mn) of the Mw of each polymer to the number average molecular weight (hereinafter also referred to as "Μη") of each polymer by gel permeation chromatography (GPC) is usually 1 〜5, preferably 1 to 3. Further, each of the polymers may contain a low molecular weight component derived from a monomer used in preparation. The content ratio of the low molecular weight component is 100% by mass (in terms of solid content) per component of the polymer, preferably 0.1% by mass or less, more preferably 0.07% by mass or less, and still more preferably 〇.5% by mass%. the following. When the content ratio of the low molecular weight component is 0.1% by mass or less, the amount of the eluted material of the liquid immersion liquid such as water which is contacted during immersion exposure can be reduced. In addition, when light-44 - 201126268 is stored, there is less foreign matter generated in the photoresist, and even when coating the photoresist, 'the occurrence of uneven coating is small' can sufficiently suppress the defects in the formation of the photoresist pattern. occur. It is particularly preferred that each polymer does not contain a low molecular weight component. Further, the "low molecular weight component" in the present invention 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 by, for example, chemical purification such as water washing or liquid-liquid extraction, or a combination of such chemical purification methods with physical purification methods such as ultrafiltration or centrifugation. Alternatively, the analysis can be carried out by high speed liquid chromatography (HP LC). Further, each of the polymers is preferably one having less impurities such as halogen or metal. This is because the etching resistance of the first photoresist layer formed and the deterioration of the electrical characteristics of the device due to impurities from the photoresist pattern can be further improved by reducing impurities. The purification method of each polymer may, for example, be a chemical purification method such as water washing or liquid-liquid extraction, or a combination of such a chemical purification method and a physical purification method such as ultrafiltration or centrifugation. (3) Acid generator (C) The so-called acid generator (C) means an acid which is produced by exposure. By causing the first sensitive radiation linear composition to contain the acid generator (C), the acid which is present in the polymer may be unstable due to the action of the acid generated by the exposure, specifically, the repeating unit (3) The acid is unstable and dissociates (the protective group is detached). As a result, the alkali developing portion is easily soluble in the alkali developing solution, and a resist pattern can be formed. Further, the acid generator (C) is preferably a content of a citric acid generator (C) containing a compound represented by the general formula (-45-201126268 12) (hereinafter also referred to as "acid generator (i)"). From the viewpoint of ensuring the sensitivity and developing property of the photoresist, it is usually from 1 to 20 parts by mass, preferably from 5 to 10 parts by mass, more preferably from 5 to 10 parts by mass, based on 100 parts by mass of the polymer (A). ~10 parts by mass. When the content is in this range, sufficient transparency to the radiation can be obtained in a state where the sensitivity and the developability are not lowered, and a rectangular resist pattern can be obtained. (i) Acid generator (1): The acid generator (1) is a compound represented by the general formula (12). [Chem. 2 4] R16

(―般式（12)中，R16表示氫原子、氟原子、羥基、甲基、乙基、碳數3〜10之直鏈狀或支鏈狀烷基、甲氧基、乙氧基、碳數3~10之直鏈狀或支鏈狀烷氧基、甲氧基羰基、乙氧基羰基、或碳數4〜11之直鏈狀或支鏈狀烷氧基羰基。又，R17表示甲基、乙基、碳數3〜10之直鏈狀或支鏈狀烷基、甲氧基、乙氧基、碳數3〜10之直鏈狀或支鏈狀烷氧基、或甲基磺醯基、乙基磺醯基、碳數3~10之直鏈狀、支鏈狀或環狀烷基磺醯基。另外，R18係彼此獨立表示甲基、 -46- 201126268 乙基、碳數3~1〇之直鏈狀或支鏈狀烷基、苯基或萘基。但是兩個R18彼此鍵結可形成含有硫陽離子之碳數2〜10之二價基。苯基、萘基及碳數2〜10之二價基也可具有取代基。 k表示0~2之整數，r表不〇〜8之整數（較佳爲〇〜2之整數）。X·表示以一般式（12-1)〜（12-4)表示之陰離子。）【化2 5】 R19CpF2qS03· R19S03-(In the general formula (12), R16 represents a hydrogen atom, a fluorine atom, a hydroxyl group, a methyl group, an ethyl group, a linear or branched alkyl group having a carbon number of 3 to 10, a methoxy group, an ethoxy group, or a carbon group. a linear or branched alkoxy group having 3 to 10, a methoxycarbonyl group, an ethoxycarbonyl group, or a linear or branched alkoxycarbonyl group having a carbon number of 4 to 11. Further, R17 represents a a straight or branched alkyl group having a carbon number of 3 to 10, a methoxy group, an ethoxy group, a linear or branched alkoxy group having a carbon number of 3 to 10, or a methyl group. a mercapto group, an ethylsulfonyl group, a linear, branched or cyclic alkylsulfonyl group having a carbon number of 3 to 10. In addition, R18 independently of each other represents a methyl group, -46-201126268 ethyl group, carbon number a linear or branched alkyl group of 3 to 1 Å, a phenyl group or a naphthyl group, but two R18 groups are bonded to each other to form a divalent group having a carbon number of 2 to 10 containing a sulfur cation. Phenyl, naphthyl and The divalent group having 2 to 10 carbon atoms may have a substituent. k represents an integer of 0 to 2, and r represents an integer of ～8 (preferably an integer of 〇~2). X· represents a general formula (12) -1) Anion represented by ~(12-4).) [Chemical 2 5] R19CpF2qS03 R19S03-

(12-1) (12-2) (12-3) (12-4) 一般式（12-1)及（12-2)中，R19表示氟原子或也可經取代之碳數1〜12之烴基。一般式（12-1)中，q表示 1~1〇之整數。一般式（12-3)及（12-4)中，R2。彼此獨立表不經氣原子取代之甲基、乙基、碳數3~10之直鍵狀或支鏈狀烷基。但是兩個R2G彼此鍵結可形成經氟原子取代之碳數2~ 10之二價有機基。但是以氟原子取代之碳數2〜1〇之二價有機基也可具有氟原子以外之取代基。）另外，酸產生劑（C)可含有單獨丨種或2種以上之酸產生劑（1 )。酸產生劑（C)可含有酸產生劑（1 )以外的敏輻射線性酸產生劑（以下也稱爲「酸產生劑（2 )」）者。 (ii)酸產生劑（2): -47- 201126268 酸產生劑（2 )例如有鑰鹽化合物、含有鹵素之化合物、重氮酮化合物、颯化合物、磺酸化合物等。另外，酸產生劑（C)可含有單獨1種或2種以上之酸產生劑（2)。使用酸產生劑（C )時，其使用比例係相對於酸產生劑（C ) 100質量％，通常爲80質量％以下，較佳爲60質量 %以下。 (4 )溶劑（D )：溶劑（D )例如有2-丁酮、2-戊酮等之直鏈狀或支鏈狀酮類；環戊酮、3 -甲基環戊酮、環己酮等之環狀酮類；丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯等之丙二醇單烷醚乙酸酯類；2-羥基丙酸甲酯、2-羥基丙酸乙酯等之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-乙氧基丙酸甲酯等之3-烷氧基丙酸烷酯類；及正丙醇、異丙醇等之醇類；乙二醇單甲醚、乙二醇單 ***等之乙二醇單烷醚類；二乙二醇二甲醚、二乙二醇二 ***等之二乙二醇二烷醚類；乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、乙二醇單正丙醚乙酸酯、丙二醇單甲醚、丙二醇單***、丙二醇單正丙醚、甲苯、二甲苯、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯 '乙酸乙酯、乙酸正丙酯、乙酸正丁酯、乙醯基乙酸甲酯、乙醯基乙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、N-甲基吡咯啶酮、N，N-二甲基甲醯胺、N，N-二甲基乙醯胺、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、碳酸乙烯酯 -48- 201126268 、碳酸丙烯酯等。此等溶劑中，較佳爲直鏈狀或支鏈狀酮類、環、丙二醇單烷醚乙酸酯類、2_羥基丙酸烷酯類、3_ 丙酸烷酯類、γ-丁內酯等。第一敏輻射線性組成物可含有單獨1種或2種以劑（D )。溶劑（D )之使用量係第一敏輻射線性組成物形成分濃度通常成爲1〜50質量％的量，較佳爲成爲量％的量。 (5 )添加劑：第一敏輻射線性組成物必要時可含有酸擴散控脂環族添加劑、界面活性劑、增感劑等各種添加劑 (i )酸擴散控制劑：酸擴散控制劑爲具有抑制藉由曝光由酸產生齊產生之酸擴散至第一光阻層中之擴散現象，且抑制區域中不期待之化學反應之作用的成分。藉由含有擴散控制劑，可提高第一敏輻射線性組成物之圖型又，進一步提升作爲光阻劑之解像度，且可抑制因至曝光後之加熱處理爲止之放置時間（PED)變動之光阻圖型之線寬變化，而獲得製程安定性極優異物。酸擴散控制劑例如有單（環）烷基胺類；二（狀酮類烷氧基上之溶之總固 1〜25質制劑、 1(c) 非曝光這種酸形狀》由曝光所引起之組成環）烷 -49- 201126268 基胺類；三（環）烷基胺類；取代烷基苯胺或其衍生物；乙二胺、N，N，N’，N’-四甲基乙二胺、四亞甲基二胺等之胺化合物；N -第三丁氧羰基二正辛基胺、N —第三丁氧羰基二正壬基胺、N -第三丁氧羰基吡咯烷、甲醯胺、N—甲基甲醯胺、Ν,Ν-二甲基甲醯胺、乙醯胺、N_甲基乙醯胺、N，N_: 甲基乙醯胺、丙醯胺、苯甲醯胺、吡咯烷酮、N -甲基吡咯烷酮等之含醯胺基之化合物、1，1-二甲基脲等之脲化合物、咪唑類：吡啶類；哌嗪類；及吡嗪、吡唑、噠嗪、喹噁啉、嘌啉、吡咯烷、哌啶等之含氮雜環化合物或光崩壞性驗等。光崩壞性鹼之一例爲藉由曝光分解使酸擴散控制性喪失活性之鑰鹽化合物。此種鐵鹽化合物之具體例有以一般式（1 3 )表示之锍鹽化合物及以一般式（1 4 )表示之碘鑰鹽化合物。【化2 6】(12-1) (12-2) (12-3) (12-4) In the general formulae (12-1) and (12-2), R19 represents a fluorine atom or a carbon number which may also be substituted 1 to 12 Hydrocarbyl group. In the general formula (12-1), q represents an integer of 1 to 1 。. In the general formulae (12-3) and (12-4), R2. Independent of each other, a methyl group, an ethyl group, a linear bond or a branched alkyl group having a carbon number of 3 to 10, which is not substituted by a gas atom. However, the two R2Gs are bonded to each other to form a divalent organic group having 2 to 10 carbon atoms which is substituted by a fluorine atom. However, the divalent organic group having 2 to 1 carbon atoms substituted by a fluorine atom may have a substituent other than a fluorine atom. Further, the acid generator (C) may contain a single species or two or more acid generators (1). The acid generator (C) may contain a radiation sensitive acid generator other than the acid generator (1) (hereinafter also referred to as "acid generator (2)"). (ii) Acid generator (2): -47- 201126268 The acid generator (2) is, for example, a key salt compound, a halogen-containing compound, a diazoketone compound, a hydrazine compound, a sulfonic acid compound or the like. Further, the acid generator (C) may contain one or two or more acid generators (2) alone. When the acid generator (C) is used, the use ratio is 100% by mass based on the acid generator (C), usually 80% by mass or less, preferably 60% by mass or less. (4) Solvent (D): The solvent (D) is, for example, a linear or branched ketone of 2-butanone or 2-pentanone; cyclopentanone, 3-methylcyclopentanone, cyclohexanone a cyclic ketone; a propylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate or propylene glycol monoethyl ether acetate; 2-hydroxy-2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. An alkyl alkoxypropionate; a 3-alkoxypropionic acid alkyl ester such as methyl methoxypropionate, ethyl 3-methoxypropionate or methyl 3-ethoxypropionate; Alcohols such as n-propanol and isopropanol; ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, etc. Diethylene glycol dialkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol single N-propyl ether, toluene, xylene, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate 'ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoxyacetate, Acetyl ethyl acetate, methyl pyruvate, pyruvic acid Ethyl ester, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, Diethyl maleate, γ-butyrolactone, ethylene carbonate-48- 201126268, propylene carbonate and the like. Among these solvents, preferred are linear or branched ketones, rings, propylene glycol monoalkyl ether acetates, 2-hydroxypropionic acid alkyl esters, 3-propionic acid alkyl esters, γ-butyrolactone, and the like. . The first sensitive radiation linear composition may contain one or two of the agents (D) alone. The solvent (D) is used in an amount of from 1 to 50% by mass, preferably from 1 to 50% by mass, based on the first sensitive radiation linear composition. (5) Additives: The linear composition of the first sensitive radiation may contain various additives such as an acid diffusion-controlled cycloaliphatic additive, a surfactant, a sensitizer, etc. if necessary (i) an acid diffusion controlling agent: the acid diffusion controlling agent has a suppression A component which is caused by diffusion of an acid generated by acid diffusion into a diffusion phenomenon in the first photoresist layer and which suppresses an effect of a chemical reaction which is not expected in the region. By including the diffusion controlling agent, the pattern of the first sensitive radiation linear composition can be improved, the resolution of the photoresist can be further improved, and the light of the standing time (PED) due to the heat treatment after the exposure can be suppressed. The line width of the resistance pattern is changed, and the excellent stability of the process is obtained. The acid diffusion controlling agent is, for example, a mono(cyclo)alkylamine; a total solid 1 to 25 preparation dissolved on a di- ketone alkoxy group, and 1 (c) a non-exposure acid shape is caused by exposure Composition ring) alkane-49- 201126268 amides; tri(cyclo)alkylamines; substituted alkylanilines or derivatives thereof; ethylenediamine, N, N, N', N'-tetramethylethylene An amine compound such as an amine or a tetramethylene diamine; N-tert-butoxycarbonyldi-n-octylamine, N-t-butoxycarbonyldi-n-decylamine, N-tert-butoxycarbonylpyrrolidine, A Indoleamine, N-methylformamide, hydrazine, hydrazine-dimethylformamide, acetamide, N-methylacetamide, N,N_: methyl acetamide, acetamide, benzo a guanamine-containing compound such as guanamine, pyrrolidone or N-methylpyrrolidone; a urea compound such as 1,1-dimethylurea; an imidazole: a pyridine; a piperazine; and pyrazine, pyrazole, and anthracene. A nitrogen-containing heterocyclic compound such as a azine, a quinoxaline, a porphyrin, a pyrrolidine or a piperidine, or a photo-disintegration test. An example of a photodisintegrating base is a key salt compound which is controlled to be deactivated by acid diffusion by exposure decomposition. Specific examples of such an iron salt compound include an onium salt compound represented by the general formula (13) and an iodonium salt compound represented by the general formula (14). [Chem. 2 6]

(―般式（13)中之R21〜R23及一般式（14)中之R24〜R2 5 相互獨立表示氫原子、烷基、烷氧基、羥基或鹵素原子。 50- 201126268 又，一般式（13)及（14)中 ’ Ζ·表示 OH·、R26-C〇CT、 R26-S〇r (但是R26表示烷基、芳基或烷芳基），或以一般式（15 )表示之陰離子【化2 7】 (R27),(R21 to R23 in the general formula (13) and R24 to R2 5 in the general formula (14) independently represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group or a halogen atom. 50- 201126268 Further, the general formula ( 13) and (14) ''· denotes OH·, R26-C〇CT, R26-S〇r (but R26 represents an alkyl group, an aryl group or an alkylaryl group), or an anion represented by the general formula (15) [化2 7] (R27),

0C (15) (―般式（15)中，R27係表示甲基、乙基、碳數3~12之直鏈狀或支鏈狀之烷基、甲氧基、乙氧基、或碳數之直鏈狀或支鏈狀之烷氧基。但是甲基、乙基、碳數3~12之直鏈狀或支鏈狀之烷基可被氟原子取代。η係表示0〜2之整數。）此等之酸擴散控制劑可單獨1種使用或混合2種以上使用。酸擴散控制劑之含有量係相對於聚合物（A ) 1 00質量份，較佳爲0.001〜15質量份，更佳爲0.01〜10質量份，更佳爲（K05〜5質量份，特佳爲0.5〜1.5質量份。含量在此範圍時，光阻之感度不會降低，可維持光阻之圖型形狀及尺寸忠實度。 (ii)脂環族添加劑：脂環族添加劑係顯示更改善乾蝕刻耐性、圖型形狀、與基板之接著性等之作用的成分。脂環族添加劑例如有極性基取代金剛烷類；脫氧膽酸 -51 · 201126268 酯類；石膽酸酯類；烷基羧酸酯類；3-(2-羥基-2,2-雙（三氟甲基）乙基）四環〔6.2.1.13’6.〇2’7〕十二烷等。此等之脂環族添加劑可一種單獨使用或混合二種以上使用。 (iii)界面活性劑：界面活性劑係顯示改良塗佈性、條紋、顯像性等之作用的成分。界面活性劑例如有聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、聚氧乙烯正辛基苯基醚、聚氧乙烯正壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯等非離子性界面活性劑，及下列商品名KP34 1 (信越化學工業公司製）、POLYFLOW No.75 ' POLYFLOW No.95 (共榮社化學公司製）、EFTOP EF301、EFTOP EF3 03、EFTOP EF3 5 2 ( TOHKEM PRODUCTS公司製）、 Megafac F171、同F173(大日本油墨化學工業公司製）、 Fluorad FC430、同 FC431 (住友 3M 公司製）、AsahiGuard AG710、Surflon S-382、同 SC-101、同 SC-102、同 SC-103 、同SC-104、同SC-105、同SC-106 (旭硝子公司製）等。此等界面活性劑可單獨使用1種、或可混合2種以上使用。 (i v )增感劑：增感劑係顯示吸收輻射線的能量，將該能量傳達至酸產生劑（C)，藉此增加酸之生成量之作用者，具有提高第一敏輻射線性組成物之表觀感度的效果。 -52- 201126268 增感劑例如有咔唑類'苯乙酮類、二苯甲酮類、萘類、酚類、雙乙醯、曙紅、玫瑰紅（rose bengal )、芘類、蒽類、吩噻嗪類等。此等之增感劑可一種單獨使用或混合二種以上使用。 (v )其他添加劑：第一敏輻射線性組成物也可含有前述添加劑以外的添加劑（以下也稱爲「其他添加劑」）。其他添加劑例如有具有酸解離性之保護基之低分子的鹼溶解性控制劑、光暈防止劑、保存安定化劑、消泡劑等。又，藉由含有染料或顏料，使曝光部分之潛像可見化，可緩和曝光時之光暈的影響。另外，藉由含有接著助劑，可改善與基板的接著性〇第一敏輻射線性組成物係將各構成成分溶解於溶劑（ D )後，以例如孔徑0.2 μηι左右之過濾器過濾調製塗佈液，可塗佈於基板上。 2 .第二敏輻射線性組成物：形成第二光阻層時所使用之第二敏輻射線性組成物係含有藉由酸之作用成爲鹼可溶性之聚合物（a)(以下也稱爲「聚合物（a )」）及溶劑（b )的組成物。 (1 )聚合物（a): 聚合物（a)只要是藉由酸之作用成爲鹼可溶性之鹼 -53- 201126268 不溶性或鹼難溶性之聚合物時，即無特別限定。具體而言，含有前述重複單位（3)者。聚合物（a)可含有一般式（16)表示之重複單位（以下也稱爲「重複單位（8)」）。【化2 8】0C (15) (In the general formula (15), R27 represents a methyl group, an ethyl group, a linear or branched alkyl group having a carbon number of 3 to 12, a methoxy group, an ethoxy group, or a carbon number. a linear or branched alkoxy group, but a methyl group, an ethyl group, a linear or branched alkyl group having a carbon number of 3 to 12 may be substituted by a fluorine atom, and a η system represents an integer of 0 to 2. These acid diffusion control agents may be used alone 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, even more preferably (K05 to 5 parts by mass, based on 100 parts by mass of the polymer (A). It is 0.5 to 1.5 parts by mass. When the content is within this range, the sensitivity of the photoresist is not lowered, and the pattern shape and dimensional fidelity of the photoresist can be maintained. (ii) Alicyclic additive: The alicyclic additive system shows improvement. a component having a function of dry etching resistance, pattern shape, adhesion to a substrate, etc. alicyclic additives such as a polar group-substituted adamantane; deoxycholic acid-51 · 201126268 an ester; a stone cholate; an alkyl group Carboxylic acid esters; 3-(2-hydroxy-2,2-bis(trifluoromethyl)ethyl)tetracyclo[6.2.1.13'6.〇2'7]dodecane, etc. These alicyclic rings The group additive may be used singly or in combination of two or more kinds. (iii) Surfactant: The surfactant is a component which exhibits an effect of improving coatability, streaking, developing property, etc. The surfactant is, for example, a polyoxyethylene laurel. Ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl , non-ionic surfactants such as polyoxyethylene n-decyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and the following trade name KP34 1 (manufactured by Shin-Etsu Chemical Co., Ltd.) POLYFLOW No.75 ' POLYFLOW No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP EF301, EFTOP EF3 03, EFTOP EF3 5 2 (manufactured by TOHKEM PRODUCTS), Megafac F171, and F173 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) ), Fluorad FC430, with FC431 (manufactured by Sumitomo 3M), AsahiGuard AG710, Surflon S-382, same SC-101, same SC-102, same SC-103, same SC-104, same SC-105, same SC- 106 (made by Asahi Glass Co., Ltd.), etc. These surfactants may be used alone or in combination of two or more. (iv) Sensitizer: The sensitizer shows the energy of absorbing radiation and transmits the energy to The acid generator (C), which acts to increase the amount of acid generated, has the effect of increasing the apparent sensitivity of the linear composition of the first sensitive radiation. -52- 201126268 The sensitizer is, for example, an oxazole-acetophenone Classes, benzophenones, naphthalenes, phenols, diacetyl, blush, roses Red (rose bengal), anthraquinones, anthraquinones, phenothiazines, etc. These sensitizers may be used alone or in combination of two or more. (v) Other additives: The first sensitive radiation linear composition may also be used. An additive other than the above additives (hereinafter also referred to as "other additive") is contained. Other additives include, for example, a low molecular alkali solubility control agent having an acid dissociable protecting group, a halo preventing agent, a storage stabilizer, and defoaming. Agents, etc. Further, by containing a dye or a pigment, the latent image of the exposed portion can be visualized, and the influence of the halation at the time of exposure can be alleviated. Further, the adhesion to the substrate can be improved by the inclusion of the auxiliary agent. The first sensitive radiation linear composition is prepared by dissolving the respective constituent components in the solvent (D), and then filtering and coating the filter with a filter having a pore diameter of, for example, about 0.2 μm. The liquid can be applied to the substrate. 2. Second sensitive radiation linear composition: The second sensitive radiation linear composition used in forming the second photoresist layer contains a polymer (a) which is alkali-soluble by the action of an acid (hereinafter also referred to as "polymerization" The composition of the substance (a)") and the solvent (b). (1) Polymer (a): The polymer (a) is not particularly limited as long as it is an alkali-soluble base by the action of an acid -53-201126268. Specifically, the above repeating unit (3) is contained. The polymer (a) may contain a repeating unit represented by the general formula (16) (hereinafter also referred to as "repeating unit (8)"). [化2 8]

HO CF3 (16) (一般式（16)中，R1係表示氫原子、甲基或三氟甲基， R2 8表示單鍵、亞甲基、碳數2~6之直鏈狀或支鏈狀之亞烷基、或碳數4〜12之單環或多環之脂環式之亞烷基。）重複單位（8 ) 提供重複單位（8)之單體之較佳例爲（甲基）丙烯酸（1,1,1-三氟-2-三氟甲基-2-羥基-3-丙基）酯、（甲基 )丙烯酸三氟-2-三氟甲基-2-羥基-4-丁基）酯、 (甲基）丙烯酸（1，1，1-三氟-2-三氟甲基-2-羥基-5-戊基 )酯、（甲基）丙烯酸（1,1,1-三氟-2-三氟甲基-2-羥基-4-戊基）酯、（甲基）丙烯酸2-((5-(1-三氟ΙΕ 氟甲基 -2’-羥基）丙基）雙環〔2.2.1〕庚基）酯、 (甲基）丙烯酸3-( (8-(1’，1’，1’-三氟-2’-三氟甲基-2’-羥基 -54- 201126268 )丙基）四環〔6.2.1.13，6.02，7〕十二烷基）酯等。此外’聚合物（a )係可僅含有1種或兩種以上之重複單位（8 )者。聚合物（a)除了重複單位（3)及重複單位（8)外，也可含有其他的重複單位者。 (聚合物（a)中所含之各重複單位的比例）聚合物（a )中所含重複單位（3 )之比例係相對於聚合物（a)中所含之重複單位的合計lOOmol%，較佳爲 10〜70mol%，更佳爲1〇〜60mol%，更佳爲20〜60mol%。重複單位（3 )之比例在此範圍內，可兼具鹼顯像部之解像性與顯像性。聚合物（a )所含有之重複單位（8 )之比例係相對於聚合物（a)所含之重複單位的合計l〇〇m〇l%，較佳爲 0〜90mol°/。，更佳爲30〜80mol°/。，更佳爲40〜80mol%。重複單位（3 )之比例在此範圍內，可維持鹼顯像部之解像性〇聚合物（a )所含有之其他重複單位之比例係相對於聚合物（a )所含之重複單位的合計1 0 0 m ο 1 %，較佳爲 5 0 m ο 1 %以下，更佳爲4 0 m ο 1 %以下。其他的重複單位爲任意成分，因此可包含於聚合物（B)中。第二敏輻射線性組成物可含有單獨1種或2種以上之聚合物（a )。 -55- 201126268 (聚合物（a)之調製方法）聚合物（a )係使用例如提供各重複單位之聚合性不飽和單體’與前述聚合物（A)或聚合物（b)同樣來調製 (聚合物（a)之物性値）聚合物（a )之Mw無特別限制。但是較佳爲 1，000 〜100, 〇〇〇 ’ 更佳爲1，000〜30,000，更佳爲 1，00 0~2 0,000。聚合物（a)之Mw在此範圍，可兼具第二光阻層之耐熱性與驗顯像部之顯像性。又，聚合物（a ) 之Mw與Μη之比（Mw/Mn)通常爲1〜5，較佳爲1〜3。又’聚合物（a)有時也可含有來自調製時所使用之單體的低分子量成分。低分子量之含有比例係相對於聚合物（a) 100質量％ (換算成固成分），較佳爲0.1質量％以下，更佳爲0.07質量％以下，更佳爲〇.〇5質量％以下。低分子量成分之含有比例爲0· 1質量％以下時，可減少溶出於液浸曝光時所接觸之水等之液浸液中之溶出物的量。此外，光阻保管時，在光阻中不會產生異物，塗佈光阻時也不會發生塗佈不均，可充分抑制光阻圖型形成時之缺陷產生。聚合物（a)特佳爲不含有低分子量成分。又’聚合物（a)係鹵素、金屬等雜質較少者較佳。如此減少雜質，可進一步改善第二光阻層之感度、解像度、製程穩定性、圖型形狀等。此外’聚合物（a )之純化方法例如有與前述相同的 -56- 201126268 方法。 (2 )溶劑：溶劑（b )並無特別限制。但是以溶解聚合物（a )而不溶解第一光阻圖型者較佳。例如有直鏈狀或分支狀之酮類、環狀的酮類、烷二醇單烷醚乙酸酯類、2-羥基丙酸烷酯類、3-烷氧基丙酸烷酯類及γ-丁內酯等。其中較佳爲丙二醇單甲醚乙酸酯或環己酮等。溶劑（b )之使用量係第二敏輻射線性組成物之全固形分濃度通常成爲1〜50質量％的量，較佳爲成爲1〜25質量 %的量。 (3 )敏輻射線性酸產生劑第二敏輻射線性組成物通常爲含有敏輻射線性酸產生劑者。敏輻射線性酸產生劑可使用與前述第一敏輻射線性組成物中之酸產生劑（C )相同者。第一敏輻射線性組成物所含有的酸產生劑（C )與第二敏輻射線性組成物所含有的敏輻射線性酸產生劑可相同或不相同。敏輻射線性酸產生劑之含量，從確保作爲光阻之感度及顯像性的觀點，相對於聚合物（a ) 1 0 0質量份，通常爲 0.1〜20質量份’較佳爲0.5〜10質量份，更佳爲5〜1〇質量份。含量在此範圍時，感度及顯像性不會降低，可維持對轄射線之透明性，可獲得矩形之第二光阻圖型。 -57- 201126268 (4 )添加劑：第二敏輻射線性組成物也可含有添加劑。又，此添加劑係與第一敏輻射線性組成物中，前述酸擴散控制劑等各種添加劑相同者。第二敏輻射線性組成物含有酸擴散控制劑作爲添加劑時，其含量係相對於聚合物（a) 100質量份，較佳爲 0.001~15質量份，更佳爲0.01-10質量份，更佳爲〇.〇5~5質量份’特佳爲〇_5〜1.5質量份。含量在此範圍內，光阻劑之感度不會降低，可維持光阻之圖型形狀及尺寸忠實度。第二敏輻射線性組成物可在使各構成成分溶解於溶劑 (b )後，以例如孔徑0.2 μπι左右之過濾器過濾調製成塗佈液，塗佈於基板上。【實施方式】〔實施例〕以下依據實施例具體說明本發明，但本發明並非限定於這些實施例者。且’實施例、比較例中之「份」及r % 」右無特別說明時皆爲質量基準。又，各種物性値的測定方法、及各特性之評估方法如下所示。〔重量平均分子量（Mw)及數平均分子量（Μη)〕 :使用東曹公司製GPC管柱（「G2000HXL」2支、「 G3000HXL」1支、「G4000HXL」1支）在流量：l.〇mL/分鐘、溶離溶劑··四氫呋喃、管柱溫度：4〇t：之分析條件下 ’藉由凝膠滲透層析（GPC ) ’以單分散聚苯乙烯作爲標 -58- 201126268 準進行測定。〔l3C-NMR分析〕：各聚合物之13C-NMR分析係使用日本電子公司製「JNM-EX270」進行測定。〔後退接觸繳（° )之測定〕：使用SOD塗佈成膜装置 ((商品名「CLEAN TRACK ACT8」、東京電子公司製）將敏輻射線性組成物旋轉塗佈於Si基板上，以1 00°C進行預烘烤（PB) 60秒，形成膜厚lOOnm的被膜。然後，迅速的使用接觸角計（商品名「DSA-10」' KRUS公司製）在室溫23 °C、濕度45%、常壓之環境下，依以下順序測定後退接觸角。首先，調整前述接觸角計之晶圓檯位置，將基板設置於此經調整的檯上。接著，將水注入針中，將針的位置微調至在設置之基板上可形成水滴的初期位置。然後，自該針中排出水，且於基板上形成2 5 μί的水滴，接著，將針自此水滴中抽離，再使針降至初期位置，配置於水滴內。接著，以1 0 μ L / m i η之速度、9 0秒，以針吸取水滴，同時，每秒測定一次液面與基板之接觸角（合計90次）。其中，計算自接觸角之測定値穩定的時點開始20秒之接觸角的平均値，作爲後退接觸角。〔DP圖型評價〕：使用掃描型電子顯微鏡（日立計測器公司製、CG-4000 )觀察形成第二光阻圖型後之後述的評價用基板C。當第一光阻圖型有損失或開口部底部有不溶物時’評價爲「不良」，當無頂部損失、殘渣進行解像，形成第一光阻圖型與第二光阻圖型兩者的圖型時，評價爲「 -59- 201126268 良好」。實施例34〜36係與第一光阻圖型正交’形成48nm 線/ 96nm間距（48nmlL/lS)的線圖型’然後形成接觸孔圖型。此接觸孔圖型未埋至底部’進行解像形成時’評價爲「良好」。〔線寬變動〕：使用掃描型電子顯微鏡（日立計測器公司製、CG-4〇00 )觀察基板C之光阻圖型的線寬變動。評價用基板C之光阻圖型的線部分中，對於任意5條的線部部分以各任意2〇個點測定其線寬。任意5條線部之線寬（計1〇〇點 )的平均値作爲平均線寬。形成第一光阻圖型後之平均線寬與 '雙重曝光（形成第二光阻圖型）後之平均線寬之差作爲線寬變動的變動値。測定後的線寬變動之變動値未達 4nm未者’評價爲「◎(優）」，4〜7nm者評價爲「〇（良 )」，超過7nm者評價爲「X (不良）」。以下記載聚合物（A)及（B)之調製方法。以下表示聚合物（A)及（B)之調製用的單體〔化合物（M-1) ~ (M-22 )〕。 -60- 201126268 【化2 9】HO CF3 (16) (In the general formula (16), R1 represents a hydrogen atom, a methyl group or a trifluoromethyl group, and R2 8 represents a single bond, a methylene group, a linear or branched chain having a carbon number of 2 to 6. An alkylene group or a monocyclic or polycyclic alicyclic alkylene group having 4 to 12 carbon atoms.) Repeating unit (8) A preferred example of a monomer which provides a repeating unit (8) is (methyl) (1,1,1-Trifluoro-2-trifluoromethyl-2-hydroxy-3-propyl)acrylate, trifluoro-2-trifluoromethyl-2-hydroxy-4-(meth)acrylate Butyl) ester, (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-5-pentyl) (meth)acrylate, (meth)acrylic acid (1,1,1- Trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl)ester, 2-((5-(1-trifluorofluorenefluoromethyl-2'-hydroxy)propyl)(meth)acrylate Bicyclo[2.2.1]heptyl)ester, 3-((8-(1',1',1'-trifluoro-2'-trifluoromethyl-2'-hydroxy-54-) 201126268 ) propyl) tetracyclo [6.2.1.13, 6.02, 7] dodecyl) ester and the like. Further, the polymer (a) may contain only one type or two or more types of repeat units (8). The polymer (a) may contain other repeating units in addition to the repeating unit (3) and the repeating unit (8). (Proportion of each repeating unit contained in the polymer (a)) The ratio of the repeating unit (3) contained in the polymer (a) is 100% by mole based on the total of the repeating units contained in the polymer (a). It is preferably from 10 to 70 mol%, more preferably from 1 to 60 mol%, still more preferably from 20 to 60 mol%. The ratio of the repeating unit (3) is within this range, and both the resolution and the developing property of the alkali developing portion can be achieved. The ratio of the repeating unit (8) contained in the polymer (a) is from 10 to 90 mol%, preferably from 0 to 90 mol%, based on the total of the repeating units contained in the polymer (a). More preferably 30 to 80 mol ° /. More preferably, it is 40 to 80 mol%. The ratio of the repeating unit (3) is within this range, and the resolution of the alkali developing portion can be maintained. The ratio of other repeating units contained in the polymer (a) is relative to the repeating unit contained in the polymer (a). The total is 100 m ο 1 %, preferably 5 0 m ο 1 % or less, more preferably 4 0 m ο 1 % or less. The other repeating unit is an arbitrary component and thus may be contained in the polymer (B). The second sensitive radiation linear composition may contain one or more of the polymers (a) alone. -55-201126268 (Preparation method of polymer (a)) Polymer (a) is prepared by using, for example, a polymerizable unsaturated monomer which provides each repeating unit, in the same manner as the above polymer (A) or polymer (b). (Physical Properties of Polymer (a)) The Mw of the polymer (a) is not particularly limited. However, it is preferably 1,000 to 100, and 〇〇〇 ' is preferably 1,000 to 30,000, more preferably 1,00 to 2,0,000. The Mw of the polymer (a) is in this range, and both the heat resistance of the second photoresist layer and the developability of the image forming portion can be achieved. Further, the ratio (Mw/Mn) of Mw to Μη of the polymer (a) is usually from 1 to 5, preferably from 1 to 3. Further, the polymer (a) may sometimes contain a low molecular weight component derived from a monomer used in the preparation. The content ratio of the low molecular weight is preferably 0.1% by mass or less, more preferably 0.07% by mass or less, even more preferably 5% by mass or less based on 100% by mass of the polymer (a) (in terms of solid content). When the content ratio of the low molecular weight component is 0.1% by mass or less, the amount of the eluted matter in the liquid immersion liquid which is dissolved in the water or the like which is exposed during the immersion exposure can be reduced. Further, in the storage of the photoresist, foreign matter does not occur in the photoresist, and uneven coating does not occur even when the photoresist is applied, and the occurrence of defects in the formation of the photoresist pattern can be sufficiently suppressed. The polymer (a) is particularly preferably free of low molecular weight components. Further, the polymer (a) is preferably a halogen or a metal having less impurities. By reducing impurities in this way, the sensitivity, resolution, process stability, pattern shape, and the like of the second photoresist layer can be further improved. Further, the purification method of the polymer (a) is, for example, the same as the above-mentioned -56-201126268 method. (2) Solvent: The solvent (b) is not particularly limited. However, it is preferred to dissolve the polymer (a) without dissolving the first photoresist pattern. For example, a linear or branched ketone, a cyclic ketone, an alkylene glycol monoalkyl ether acetate, a 2-hydroxypropionic acid alkyl ester, a 3-alkoxypropionic acid alkyl ester, and γ- Butyrolactone and the like. Among them, preferred are propylene glycol monomethyl ether acetate or cyclohexanone. The solvent (b) is used in an amount such that the total solid concentration of the linear composition of the second-sensitive radiation is usually from 1 to 50% by mass, preferably from 1 to 25% by mass. (3) Sensitive radiation linear acid generator The second sensitive radiation linear composition is usually a linear acid generator containing a radiation. The sensitive radiation linear acid generator may be the same as the acid generator (C) in the aforementioned first radiation-sensitive linear composition. The acid generator (C) contained in the first sensitive radiation linear composition may be the same as or different from the sensitive radiation linear acid generator contained in the second sensitive radiation linear composition. The content of the sensitive radiation linear acid generator is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass from the viewpoint of ensuring the sensitivity and developing property of the photoresist as compared with 100 parts by mass of the polymer (a). The mass part is more preferably 5 to 1 part by mass. When the content is in this range, the sensitivity and the developing property are not lowered, and the transparency to the ray is maintained, and a rectangular second resist pattern can be obtained. -57- 201126268 (4) Additives: The second sensitive radiation linear composition may also contain additives. Further, the additive is the same as the first sensitive radiation linear composition, and the respective additives such as the acid diffusion controlling agent are the same. When the second sensitive radiation linear composition contains an acid diffusion controlling agent as an additive, the content thereof is preferably 0.001 to 15 parts by mass, more preferably 0.01 to 10 parts by mass, more preferably 100 to 10 parts by mass, more preferably 100 parts by mass of the polymer (a). 〇.〇5~5 parts by mass 'extra good is 〇5~1.5 parts by mass. When the content is within this range, the sensitivity of the photoresist is not lowered, and the shape and dimensional loyalty of the photoresist can be maintained. The second sensitizing radiation linear composition can be prepared by dissolving each component in the solvent (b), and then filtering it into a coating liquid by, for example, a filter having a pore size of about 0.2 μm, and applying it onto the substrate. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. Moreover, the "parts" and "r%" in the examples and comparative examples are all based on the quality unless otherwise specified. Further, the measurement methods of various physical properties and the evaluation methods of the respective characteristics are as follows. [Weight average molecular weight (Mw) and number average molecular weight (Μη)]: GPC pipe column ("G2000HXL" 2 pieces, "G3000HXL" 1 piece, "G4000HXL" 1 piece) made by Tosoh Corporation at flow rate: l.〇mL /min, Dissolved Solvent··Tetrahydrofuran, Column Temperature: 4〇t: The analytical conditions were determined by gel permeation chromatography (GPC) using monodisperse polystyrene as the standard -58-201126268. [13C-NMR analysis]: 13C-NMR analysis of each polymer was carried out using "JNM-EX270" manufactured by JEOL Ltd. [Measurement of the back contact payment (°)]: The SOD coating film forming apparatus (trade name "CLEAN TRACK ACT8", manufactured by Tokyo Electronics Co., Ltd.) was used to spin-coat the sensitive radiation linear composition on the Si substrate to 100 Å. The film was pre-baked (PB) for 60 seconds to form a film having a film thickness of 100 nm. Then, a contact angle meter (trade name "DSA-10" 'KRUS) was used at room temperature of 23 ° C and a humidity of 45%. In the normal pressure environment, the receding contact angle is measured in the following order. First, the wafer table position of the contact angle meter is adjusted, and the substrate is placed on the adjusted table. Then, water is injected into the needle to position the needle. Fine-tuning to the initial position where water droplets can be formed on the set substrate. Then, water is drained from the needle, and 2 5 μί of water droplets are formed on the substrate, and then the needle is pulled away from the water droplet, and then the needle is lowered. The initial position is placed in the water droplets. Then, at a speed of 10 μL / mi η, 90 seconds, the water droplets are sucked by the needle, and the contact angle between the liquid surface and the substrate is measured every second (total 90 times). , calculate the self-contact angle measurement 値 stable time The average 値 of the contact angle of 20 seconds was started as the receding contact angle. [DP pattern evaluation]: The second resist pattern was observed by a scanning electron microscope (manufactured by Hitachi Metro Co., Ltd., CG-4000). Evaluation substrate C. When the first photoresist pattern is lost or there is insoluble matter at the bottom of the opening, it is evaluated as "poor", and when there is no top loss and the residue is resolved, the first photoresist pattern and the second light are formed. In the pattern of both of the resistance patterns, the evaluation was "-59-201126268 is good." Examples 34 to 36 are orthogonal to the first photoresist pattern to form a line diagram of 48 nm line/96 nm pitch (48 nmL/L). The shape of the contact hole pattern is formed. The contact hole pattern is not buried in the bottom. When the image is formed, it is evaluated as "good". [Line width variation]: Scanning electron microscope (manufactured by Hitachi Metro Co., Ltd., CG) -4〇00) Observing the line width variation of the photoresist pattern of the substrate C. In the line portion of the resist pattern of the evaluation substrate C, the line is measured for any five line portions at any two points. Width. The average line width of any 5 line parts (1 point) The average line width is the difference between the average line width after forming the first photoresist pattern and the average line width after the double exposure (forming the second photoresist pattern) as the variation of the line width variation. The change of the change was less than 4 nm, and it was evaluated as "(Excellent)", 4 to 7 nm was evaluated as "〇 (good)", and when it was more than 7 nm, it was evaluated as "X (bad)". And the preparation method of (B). The monomers (compounds (M-1) to (M-22)) for the preparation of the polymers (A) and (B) are shown below. -60- 201126268 [Chem. 2 9]

(M-11) (M-12)(M-11) (M-12)

61 201126268 【化3 0】61 201126268 【化3 0】

ο (Μ-15) οο (Μ-15) ο

ο (Μ-16)ο (Μ-16)

c2h5C2h5

(調製例1:聚合物（Ad)之調製）首先，將作爲單體之化合物（M-14 ) 15mol%、化合物（M-13) 35mol%、化合物（M-8) 50mol%、及重合起始劑（二甲基-2,2’-偶氮雙異丁酸酯（MAIB ))溶解於 l〇〇g之甲基乙基酮中，製備單體溶液。將投入時之單體的合計量調製成50g。另外，各單體之mol%係表示相對於單體總量的mol%，聚合起始劑之使用比例係相對於單體與聚合起始劑之合計量設定爲2mol%。另外’將乙基甲基酮50g添加於具備溫度計及滴加漏斗之5 00mL之三口燒瓶中，然後進行氮氣沖洗30分鐘。然後’燒瓶內部以磁攪拌子攪拌，同時加熱至80〇c。接著，使用滴加漏斗以3小時準備的單體溶液滴加於燒瓶中。滴加結束後’經熟成3小時後，冷卻至3 〇°c以下得到聚合物溶液。其後，將聚合物溶液投入i 000g之甲醇中進行混合 -62- 201126268 。接著，進行吸引過濾。然後回收粉體，再度投入2OOg之甲醇中，進行洗淨、過濾。再度進行本洗淨，回收之粉體在60°C下減壓乾燥。所得之聚合物作爲聚合物（A-1 )。此聚合物（A·l)之Mw爲 10000，Mw/Mn爲1.5，13C^NMR 分析結果，源自各單體之各重複單位之含有比率（mol%) 爲（M-14)/(M-13)/(M- 8 )= 1 4.6/3 5.9/49·5的共聚合物。 (調製例9 :聚合物（B -1 )之調製）首先，將作爲單體之化合物（M-2 ) 55mol% '化合物 (M-19) 5mol%、化合物（M-8) 20mol%、化合物（M-20 )20mol%及聚合起始劑（二甲基-2,2’-偶氮雙異丁酸酯（ MAIB))溶解於100g之甲基乙基酮中，製備單體溶液。投入時之單體之合計量調製成5 0g。另外，各單體之mol% 係表示相對於單體總量之mol%，聚合起始劑之使用比例係相對於單體與聚合起始劑之合計量設爲8mol %。另外，將乙基甲基酮5 0g添加於具備溫度計及滴加漏斗之50〇mL之三口燒瓶中，進行氮氣沖洗3 0分鐘。其後，燒瓶內部以磁攪拌子攪拌，同時加熱至80°C。接著，使用滴加漏斗以3小時準備的單體溶液滴加於燒瓶中。滴加結束後’經熟成3小時後，冷卻至3 0°C以下得到聚合物溶液。其後，將聚合物溶液投入1 〇〇〇g之甲醇中進行混合。接著’進行吸引過濾。然後回收粉體’再度投入200g之甲醇中’進行洗淨、過濾。再度進行本洗淨，回收之粉體在 -63- 201126268 60t下減壓乾燥。所得之聚合物作爲聚合物（Β-l)。此聚合物（B-1)之 Mw 爲 5500，Mw/Mn 爲 1.5，13C-NMR 分析結果，源自各單體之各重複單位的含有比率（mol% )爲（ M-2) /( M-19) /( M-8) /( M-20 ) =54.5/5.5/ 1 9.5/2 0.5 的共聚合物。 (調製例2〜27:聚合物（A-2)〜（A-10)、聚合物（B-2 )〜（B-13)、及聚合物（F-1)〜（F-4)之調製）除了使用表1所示之種類及投入量的化合物（單體）外，聚合物（A-2 )〜（A-10 )係與調製例1同樣手法調製，而聚合物（B-2) ~(B-13)及聚合物（F-1)〜（F-4) 係與調製例9同樣的手法調製。表2中記載聚合物（a-2) ~ (A-10)、聚合物（B-2)〜（B-13)、及聚合物 (F-4)之藉由13C-NMR分析源自各單體之各重複單位的含有比率、Mw、及Mw/Mn。 -64- 201126268 【表1】聚合物單體1 投入量 (mol%) 單體2 投入量 (mol%) 單體3 投入量 (mol%) 單體4 投入量 (mol%) 調製例1 A-1 M-14 15 M-13 35 M-8 50 一調製例2 A-2 M-13 50 M-8 50 - - 調製例3 A-3 M-17 35 M-22 15 M-8 50 一調製例4 A-4 M-14 5 M-13 45 M-8 50 — 調製例5 A—5 M-14 15 M-13 35 M-8 40 M-11 10 調製例6 A-6 M-17 35 M-22 15 M-8 40 Μ-11 10 調製例7 A-7 Μ —14 15 M-13 35 M-8 40 M —4 10 調製例8 A-8 Μ-17 15 M-13 35 M-8 50 - 調製例9 B-1 Μ-2 55 M-19 5 M-8 20 M-20 20 調製例10 B-2 Μ —14 45 M-19 5 M-8 20 M-21 30 調製例11 B-3 Μ-1 55 M-19 5 M-8 10 M-21 30 調製例12 B-4 Μ— 1 55 M-18 5 M-8 10 M-21 30 調製例13 B-5 Μ一 1 45 M-19 5 M-8 20 M-7 30 調製例14 B-6 Μ-1 55 M-18 5 M-11 10 M-21 30 調製例15 B-7 Μ-13 45 M-19 5 Μ-11 20 M-7 30 調製例16 B-8 Μ-14 40 M-15 10 Μ — 8 20 M-21 30 調製例17 F-1 Μ-13 50 M-8 50 — 一調製例18 F-2 Μ—1 50 M-19 5 Μ-8 45 一調製例19 A-9 Μ—17 15 M-13 35 Μ-9 50 - 調製例20 A-10 Μ-17 15 M-13 35 Μ —10 50 - 調製例21 B-9 Μ-1 55 M-19 5 Μ-8 10 M-3 30 調製例22 B-10 Μ — 1 55 M-19 5 Μ-8 15 M-5 25 調製例23 B-11 Μ — 1 50 M-19 5 Μ-8 5 Μ — 6 35 調製例24 B-12 Μ —1 55 M-19 5 Μ-8 20 Μ-12 20 調製例25 B —13 Μ-1 55 M-16 5 Μ-8 10 Μ-21 30 調製例26 F-3 Μ-21 70 — Μ-8 30 — 調製例27 F-4 Μ-1 50 M-19 | 30 Μ-8 20 - -65 - 201126268 【表2】聚合物單體1 (mol%) 單體2 (mol%) 單體3 (mol%) 單體4 (mol%) Mw Mw/Mn 調製例1 A—1 14.6 35.9 49.5 — 10000 1.5 調製例2 A—2 50.2 48.8 — — 10000 1.6 調製例3 A_3 35.5 14.5 50.5 — 10000 1.6 調製例4 Aw4 15.2 35.2 49.6 — 10000 1.6 調製例5 A—5 14.5 35.5 39.6 9.4 11000 1.5 調製例6 A—6 35.2 14.8 39.0 11.0 12000 1.5 調製例7 A-7 15.1 35.8 39.5 9.6 11000 1.5 調製例8 A-8 15.1 35.3 49.6 — 10000 1.6 調製例9 B-1 54·5 5.5 19.5 20.5 5500 1.5 調製例10 B-2 44.0 5.5 20.5 30.0 5000 1.6 調製例11 B-3 55.2 5.2 10.5 29.1 4500 1.5 調製例12 B-4 54.7 5.1 10.3 29.9 5100 1.4 調製例13 B»5 45.2 5.3 20.2 30.0 4700 1.5 調製例14 B-6 55.0 5.0 10.0 29.3 4800 1.5 調製例15 B-7 45.4 4.9 19.8 29.9 5200 1.6 調製例16 B-8 41.2 9.8 21.2 27.8 6100 1.7 調製例17 F_1 50.2 48.8 一一 5500 1.5 調製例18 F—2 50.5 5.1 44.4 — 5500 1.5 調製例19 A—9 14.7 35.1 50,2 — 10000 1.5 調製例20 A-10 15.1 35.3 49.6 一 10000 1.4 調製例21 B-9 55.0 4.9 10.5 30.1 4800 1.5 調製例22 B-10 55.2 5.2 14.8 24.8 5000 1.6 調製例23 B-11 55.2 5.2 5.0 34.6 4750 1.6 調製例24 B-12 55.1 5.3 19.8 19.8 4950 1.5 調製例25 B-13 54.9 5.3 10.4 29.4 5100 1.6 調製例26 F-3 70.2 — 29.8 — 4800 1.7 調製例27 F-4 49.9 30.1 20.0 — 5300 1.6 (實施例1 :第一敏輻射線性組成物之調製）(Preparation Example 1: Preparation of Polymer (Ad)) First, 15 mol% of a compound (M-14) as a monomer, 35 mol% of a compound (M-13), 50 mol% of a compound (M-8), and a combination The starting agent (dimethyl-2,2'-azobisisobutyrate (MAIB)) was dissolved in 1 g of methyl ethyl ketone to prepare a monomer solution. The total amount of the monomers at the time of the input was adjusted to 50 g. Further, the mol% of each monomer is expressed by mol% based on the total amount of the monomers, and the use ratio of the polymerization initiator is set to 2 mol% based on the total amount of the monomer and the polymerization initiator. Further, 50 g of ethyl methyl ketone was placed in a 500-neck three-necked flask equipped with a thermometer and a dropping funnel, and then nitrogen purged for 30 minutes. Then, the inside of the flask was stirred with a magnetic stirrer while heating to 80 〇c. Next, a monomer solution prepared by using a dropping funnel for 3 hours was dropped into the flask. After the completion of the dropwise addition, the mixture was aged for 3 hours, and then cooled to 3 ° C or lower to obtain a polymer solution. Thereafter, the polymer solution was poured into i 000 g of methanol for mixing -62-201126268. Next, suction filtration is performed. Then, the powder was collected, and again, it was poured into 2,000 g of methanol, and washed and filtered. This washing was again carried out, and the recovered powder was dried under reduced pressure at 60 °C. The obtained polymer was used as the polymer (A-1). The polymer (A·l) had Mw of 10,000 and Mw/Mn of 1.5, and the content of each repeating unit derived from each monomer (mol%) was (M-14)/(M). -13) / (M-8) = 1 4.6/3 5.9/49·5 of the copolymer. (Preparation Example 9: Preparation of Polymer (B-1)) First, compound (M-2) as a monomer 55 mol% 'Compound (M-19) 5 mol%, Compound (M-8) 20 mol%, Compound (M-20) 20 mol% and a polymerization initiator (dimethyl-2,2'-azobisisobutyrate (MAIB)) were dissolved in 100 g of methyl ethyl ketone to prepare a monomer solution. The total amount of the monomers at the time of input was adjusted to 50 g. Further, the mol% of each monomer is expressed by mol% based on the total amount of the monomers, and the use ratio of the polymerization initiator is set to 8 mol% based on the total amount of the monomer and the polymerization initiator. Further, 50 g of ethyl methyl ketone was placed in a 50 〇mL three-necked flask equipped with a thermometer and a dropping nozzle, and nitrogen purge was performed for 30 minutes. Thereafter, the inside of the flask was stirred with a magnetic stirrer while heating to 80 °C. Next, a monomer solution prepared by using a dropping funnel for 3 hours was dropwise added to the flask. After the completion of the dropwise addition, the mixture was aged for 3 hours, and then cooled to 30 ° C or lower to obtain a polymer solution. Thereafter, the polymer solution was poured into 1 〇〇〇g of methanol and mixed. Followed by 'attraction filtering. Then, the recovered powder was returned to 200 g of methanol again, and washed and filtered. The washing was again carried out, and the recovered powder was dried under reduced pressure at -63 - 201126268 60t. The obtained polymer was used as a polymer (Β-1). The polymer (B-1) had a Mw of 5,500 and a Mw/Mn of 1.5. As a result of 13C-NMR analysis, the content ratio (mol%) of each repeating unit derived from each monomer was (M-2) / (M -19) /( M-8) /( M-20 ) = 54.5/5.5/ 1 9.5/2 0.5 copolymer. (Preparation Examples 2 to 27: Polymers (A-2) to (A-10), Polymers (B-2) to (B-13), and Polymers (F-1) to (F-4) Modulation) The polymers (A-2) to (A-10) were prepared in the same manner as in Preparation Example 1 except that the compound (monomer) of the type and the amount shown in Table 1 was used, and the polymer (B-2) ~(B-13) and polymers (F-1) to (F-4) were prepared in the same manner as in Preparation Example 9. Table 2 shows that the polymers (a-2) to (A-10), the polymers (B-2) to (B-13), and the polymer (F-4) are derived from each by 13C-NMR analysis. The content ratio of each repeating unit of the monomer, Mw, and Mw/Mn. -64- 201126268 [Table 1] Polymer monomer 1 input amount (mol%) Monomer 2 Input amount (mol%) Monomer 3 Input amount (mol%) Monomer 4 Input amount (mol%) Preparation example 1 A -1 M-14 15 M-13 35 M-8 50 One Modulation Example 2 A-2 M-13 50 M-8 50 - - Modulation Example 3 A-3 M-17 35 M-22 15 M-8 50 Modulation Example 4 A-4 M-14 5 M-13 45 M-8 50 - Modulation Example 5 A-5 M-14 15 M-13 35 M-8 40 M-11 10 Modulation Example 6 A-6 M-17 35 M-22 15 M-8 40 Μ-11 10 Modulation example 7 A-7 Μ —14 15 M-13 35 M-8 40 M —4 10 Modulation example 8 A-8 Μ-17 15 M-13 35 M -8 50 - Modulation example 9 B-1 Μ-2 55 M-19 5 M-8 20 M-20 20 Modulation example 10 B-2 Μ —14 45 M-19 5 M-8 20 M-21 30 Modulation example 11 B-3 Μ-1 55 M-19 5 M-8 10 M-21 30 Modulation example 12 B-4 Μ— 1 55 M-18 5 M-8 10 M-21 30 Modulation example 13 B-5 Μ 1 45 M-19 5 M-8 20 M-7 30 Modulation Example 14 B-6 Μ-1 55 M-18 5 M-11 10 M-21 30 Modulation Example 15 B-7 Μ-13 45 M-19 5 Μ-11 20 M-7 30 Modulation Example 16 B-8 Μ-14 40 M-15 10 Μ — 8 20 M-21 30 Modulation Example 17 F-1 Μ-13 50 M-8 50 — One Modulation Example 18 F -2 Μ—1 50 M-19 5 Μ-8 45 A Modification Example 19 A-9 Μ—17 15 M-13 35 Μ-9 50 - Modulation example 20 A-10 Μ-17 15 M-13 35 Μ —10 50 - Modulation example 21 B-9 Μ-1 55 M-19 5 Μ-8 10 M-3 30 Modification Example 22 B-10 Μ — 1 55 M-19 5 Μ-8 15 M-5 25 Modification Example 23 B-11 Μ — 1 50 M-19 5 Μ-8 5 Μ — 6 35 Modulation Example 24 B-12 Μ —1 55 M-19 5 Μ-8 20 Μ-12 20 Modification Example 25 B —13 Μ-1 55 M-16 5 Μ-8 10 Μ-21 30 Modulation Example 26 F-3 Μ-21 70 — Μ -8 30 — Preparation Example 27 F-4 Μ-1 50 M-19 | 30 Μ-8 20 - -65 - 201126268 [Table 2] Polymer monomer 1 (mol%) Monomer 2 (mol%) Monomer 3 (mol%) Monomer 4 (mol%) Mw Mw/Mn Modification Example 1 A-1 14.6 35.9 49.5 - 10000 1.5 Modification Example 2 A-2 50.2 48.8 — — 10000 1.6 Modulation Example 3 A_3 35.5 14.5 50.5 — 10000 1.6 Modification Example 4 Aw4 15.2 35.2 49.6 - 10000 1.6 Modulation Example 5 A-5 14.5 35.5 39.6 9.4 11000 1.5 Modulation Example 6 A-6 35.2 14.8 39.0 11.0 12000 1.5 Modulation Example 7 A-7 15.1 35.8 39.5 9.6 11000 1.5 Modulation Example 8 A -8 15.1 35.3 49.6 — 10000 1.6 Modulation Example 9 B-1 54·5 5.5 19.5 20.5 5500 1.5 Modulation Example 10 B-2 44.0 5.5 20.5 30.0 5000 1.6 Modulation Example 11 B-3 55.2 5.2 10.5 29.1 4500 1.5 Modulation Example 12 B-4 54.7 5.1 10.3 29.9 5100 1.4 Modulation Example 13 B»5 45.2 5.3 20.2 30.0 4700 1.5 Modulation Example 14 B-6 55.0 5.0 10.0 29.3 4800 1.5 Modulation Example 15 B-7 45.4 4.9 19.8 29.9 5200 1.6 Modulation Example 16 B-8 41.2 9.8 21.2 27.8 6100 1.7 Modulation Example 17 F_1 50.2 48.8 One 5500 1.5 Modulation Example 18 F-2 50.5 5.1 44.4 — 5500 1.5 Modulation Example 19 A—9 14.7 35.1 50, 2 — 10000 1.5 Modification Example 20 A-10 15.1 35.3 49.6 A 10000 1.4 Modulation Example 21 B-9 55.0 4.9 10.5 30.1 4800 1.5 Modulation Example 22 B-10 55.2 5.2 14.8 24.8 5000 1.6 Modulation Example 23 B-11 55.2 5.2 5.0 34.6 4750 1.6 Modulation Example 24 B-12 55.1 5.3 19.8 19.8 4950 1.5 Modification Example 25 B-13 54.9 5.3 10.4 29.4 5100 1.6 Preparation Example 26 F-3 70.2 — 29.8 — 4800 1.7 Preparation Example 27 F-4 49.9 30.1 20.0 — 5300 1.6 (Example 1: Modulation of the first sensitive radiation linear composition)

添加作爲聚合物（A )之聚合物（A-1 ) 90份、作爲聚合物（B)之聚合物（B-1) 10份、作爲酸產生劑（C)之酸產生劑（C-1)(三苯基锍九氟正丁烷磺酸鹽）7.5份、作爲含氮化合物（E )之酸擴散控制劑（E-1 ) ( N-第三T -66 - 201126268 氧羰基吡咯烷）0.94份、及作爲溶劑（D )之名 (丙二醇單甲醚乙酸酯）1287份及溶劑（D-2 )5 5 1份，將各成分混合成均勻溶液。然後 2 OOntn之薄膜過濾器過濾，調製由第一敏輻射所構成之塗佈液（1 )。 (實施例2〜22及比較例1〜5 :第一敏輻射線性製）除了設定爲表3所記載之調配處方外，與I 調製各塗佈液。各成分之使用量係聚合物（A (B)及聚合物（F)之合計量爲1〇〇份者。容劑（D - 1 ) )(環己酮，使用孔徑線性組成物組成物之調【施例1同樣 )、聚合物 -67- 20112626890 parts of the polymer (A-1) as the polymer (A), 10 parts of the polymer (B-1) as the polymer (B), and an acid generator (C-1) as the acid generator (C) ((triphenylphosphonium nonafluorobutane sulfonate) 7.5 parts, as a nitrogen diffusion compound (E) acid diffusion control agent (E-1) (N-third T-66 - 201126268 oxycarbonylpyrrolidine) 0.94 parts, and 1287 parts of the solvent (D) (propylene glycol monomethyl ether acetate) and 515 parts of the solvent (D-2) were mixed, and the components were mixed into a homogeneous solution. Then, a membrane filter of 2 OO ntn was filtered to prepare a coating liquid (1) composed of the first sensitive radiation. (Examples 2 to 22 and Comparative Examples 1 to 5: First Sensitivity Linearity) In addition to the formulation described in Table 3, each coating liquid was prepared with I. The amount of each component used is a polymer (a total of A (B) and polymer (F) is 1 part. A monomer (D - 1 )) (cyclohexanone, using a linear composition of pore size) Adjust [same example 1), polymer -67- 201126268

劑生 clic 產劑劑酸溶溶Agent, clic, agent, acid solution

D D 2D D 2

C 正醋 m酸九乙硫醚基甲苯單三醇酮 :二己 }丙環 -68 - 201126268 含氮化合物（E-l) : N-第三丁氧羰基吡咯烷 (第二敏輻射線性組成物之調製）添加作爲聚合物（a)之式（B-9)表示之聚合物（B-9 ) 1 00份、作爲敏輻射性酸產生劑之三苯基锍九氟正丁烷磺酸鹽7 · 0份之、作爲酸擴散控制劑（E )之化合物（E - 2 )2.64份、及作爲溶劑（b)之丙二醇單甲醚乙酸酯2014 份’將各成分混合成均勻溶液。然後，使用孔徑200nm之薄膜過濾器過濾，調製由第二敏輻射線性組成物所構成之塗佈液（2 8 )。【化3 1】C vinegar m acid hexaethyl thioether toluene monotriol ketone: dihexyl} propyl ring -68 - 201126268 nitrogen-containing compound (El): N-tert-butoxycarbonylpyrrolidine (second-sensitive radiation linear composition) Modification) Adding 100 parts of the polymer (B-9) represented by the formula (B-9) of the polymer (a), triphenylsulfonium nonafluorobutane sulfonate 7 as a radiation-sensitive acid generator - 0 parts of the compound (E - 2 ) as the acid diffusion controlling agent (E), 2.64 parts, and the propylene glycol monomethyl ether acetate as the solvent (b), 2014 parts, and the components were mixed into a homogeneous solution. Then, it was filtered using a membrane filter having a pore size of 200 nm to prepare a coating liquid (28) composed of a linear composition of the second radiation. [化3 1]

(B-9)(B-9)

(E-2) (實施例23 :光阻圖型之形成）使用塗佈機/顯像器（商品名「Lithius Pro-i」（東京電子公司製）將下層抗反射膜（商品名「ARC29A」， BURUWA SCIENCES公司製）旋轉塗佈於1 2英吋矽晶圓上後，藉由PB ( 2 05 °C，60秒）形成膜厚77nm的塗膜。使用 SOD塗佈成膜裝置（商品名「CLEAN TRACK ACT12」東 -69- 201126268 京電子公司製）旋轉塗佈實施例1調製的塗佈液（1 )(第 —敏輻射線性組成物），進行PB ( 130°C，60秒）後，冷卻（23°C，3 0秒）形成膜厚90nm之第一光阻層。接著，使用ArF液浸曝光裝置（商品名「S610C」， NIKON公司製），以NA: 1.30、Dipole之光學條件，將純水配置於第一光阻層之表面上的狀態下，使用線圖型之光罩進行曝光。在前述塗佈機/顯像器之加熱板上進行PEB ( 125°C、60秒），然後冷却（23°C、30秒）後，以顯像杯之 GP噴嘴，以2.38%四甲基氫氧化銨水溶液作爲顯像液進行攪拌（Paddle )顯像（10秒），以超純水清洗。以 2〇OOrpm甩動15秒進行旋轉乾燥，獲得形成有26nm線 /104nm間距之第一光阻圖型的評價用基板a。對於所得之評價用基板A之第一光阻圖型，在前述 SOD塗佈成膜裝置之加熱板上進行PDB ( 2 00°C，60秒），獲得評價用基板B。使用前述SOD塗佈成膜裝置將塗佈液（28 )(第二敏輻射線性組成物）旋轉塗佈於評價用基板B上，進行PB ( 100°C，60秒）後，冷卻（23°C，30秒）形成膜厚70nm之第二光阻層。使用前述ArF液浸曝光裝置以NA : 1.30、 Dipole之光學條件，將純水配置於第二光阻層之表面上的狀態下，使用線圖型之光罩進行曝光。在前述塗佈機/顯像器（coater/developer)之加熱板上進行 PEB ( 105°C、60 秒），然後冷却（23°C、30秒）後，以顯像杯之GP噴嘴，以2.3 8%四甲基氫氧化銨水溶液作爲顯像液進行攪拌（ -70- 201126268(E-2) (Example 23: Formation of a resist pattern) The lower anti-reflection film (trade name "ARC29A" was used for the product under the trade name "Lithius Pro-i" (manufactured by Tokyo Electronics Co., Ltd.). After being applied by spin coating on a 12-inch wafer, a coating film having a film thickness of 77 nm was formed by PB (25 ° C, 60 seconds). The film forming apparatus was coated with SOD (product). "CLEAN TRACK ACT12" East-69-201126268 (manufactured by Kyo Electronics Co., Ltd.) spin coating the coating liquid (1) prepared by the first embodiment (linear composition of the first sensitive radiation), and PB (130 ° C, 60 seconds) Thereafter, the first photoresist layer having a film thickness of 90 nm was formed by cooling (23 ° C, 30 seconds). Next, an ArF liquid immersion exposure apparatus (trade name "S610C", manufactured by NIKON Co., Ltd.) was used, and NA: 1.30, Dipole Under optical conditions, in the state where pure water is disposed on the surface of the first photoresist layer, exposure is performed using a line pattern type photomask. PEB (125 ° C, on the hot plate of the coater/imager) 60 seconds), then cooled (23 ° C, 30 seconds), with the GP nozzle of the imaging cup, with 2.38% tetramethylammonium hydroxide aqueous solution as the display The liquid was stirred (Paddle) for 10 seconds, and washed with ultrapure water. The mixture was spin-dried at 2 OO rpm for 15 seconds to obtain a first photoresist pattern having a 26 nm line/104 nm pitch. Substrate a. The first photoresist pattern of the obtained evaluation substrate A was subjected to PDB (200 ° C, 60 seconds) on a hot plate of the SOD coating film forming apparatus to obtain an evaluation substrate B. The SOD coating film forming apparatus spin-coated the coating liquid (28) (second sensitivity radiation linear composition) on the evaluation substrate B, and after performing PB (100 ° C, 60 seconds), cooling (23 ° C, 30 seconds) forming a second photoresist layer having a film thickness of 70 nm. Using the ArF immersion exposure apparatus, the pure water was placed on the surface of the second photoresist layer under the optical conditions of NA: 1.30 and Dipole, and the line was used. The mask of the pattern is exposed. After PEB (105 ° C, 60 seconds) on the hot plate of the coater/developer, and then cooling (23 ° C, 30 seconds), The GP nozzle of the image cup is stirred with 2.3 8% aqueous solution of tetramethylammonium hydroxide as a developing solution ( -70- 201126268

Paddle )顯像（1 〇秒），以超純水清洗。以2000rpm甩動 15秒進行旋轉乾燥，獲得形成有26nm線/l〇4nm間距之第二光阻圖型的評價用基板C。評價用基板C之D P圖型評價爲「良好」’線寬變動之評價爲「◎(優）」。 (實施例22~44 ) 除設定爲表4所記載的條件外，與實施例23相同得到評價用基板C。所得之各評價用基板C之評價結果一倂記載於表4中。又，實施例34〜36係使用48nm線/96nm間距形成用（48nmlL/lS )的光罩，將純水配置於第一光阻層之表面上，對於曝光後之光阻圖型形成正交，使用48nm線 /96ηηι間距形成用（48nmlL/lS)的光罩，進行液浸曝光形成接觸孔圖型。但是實施例25係取代PDB，對於所得之評價用基板A 的第一光阻圖型使用封入有乂6氣體的燈（牛尾電機公司製 )進行UV照射（172nm、10秒），得到評價用基板C。 -71 - 201126268 【寸彬】骧现 /"S 怒 ◎ /-N 雎 Sm/ ◎ /-N m ◎ 豳 s_/ ◎ /-N m ◎ m ◎ /—S 嗶 N-/ 皤 ◎ m s_y ◎ m V»/ ◎ /—s 围 ◎ 雎 ◎ 'μ/ ◎ m ◎ /-N 睡 N·*/ m ◎ ^-s m ◎ m ◎ ® ◎ r-s 曄 N_/ ◎ 到 tk % 襄 % Ϊ& tk & ft & 1 5 jn i -Η Τη a tn 3 v> 3 Τη a jn Η g 3 jo 3 In H jn Η .¾ jn -Μ Ξί to -H Ξ$ tn -M .¾ jn •H g 3 vn •H ρ tn VQ -Η p In In -H p in i m s 1§ s 8 s s S s 8 δ s 8 s 3 s s s S s S s s s s le s § § § S § S g 没没 S 5Ϊ 没 8 » m £ fi s s s s s δ s 8 S s S s s s s 8 S s S s s 8 δ «Μ 8 8 8 8 s 8 S 8 8 8 s 8 δ 8 8 8 mm 8 8 8 8 Ϊ® 00 CM s_</ 00 w /-N 00 CVJ 00 CVJ CO CO s_/ /—s 00 CM 00 CV] /•N 00 CJ >»·/ <^N 00 CM N-/ 00 CvJ 00 <N ««-N 00 CM >—✓ /*-v CO Cvj «>_/ <«"N CO CJ ^-N 00 CM s—/ /-S 00 CNJ /-S 00 CM >_/ /-N 00 00 S—/ /•N CO CO V-/ 00 〇〇 v^/ /"S 00 CJ /-N 00 CsJ s_^ m 埋陛 ii 1 1 S 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 :銎 X w 1 1 ε c «Ν 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 #： m § Ou 蜃菡 S 8 1 S S S S s S S S s s S s S S S S S s S 鐘s § § 1 § g § § § § g § § § g S § § S § § § § i m s (X li S S S S s S 8 S S S S s s S 8 S S S S S s S ss S 3 3 Ώ 3 3 3 3 3 » 3 S s S 3 9 3 s 3 社: m s li S S S 3 S S 8 S s s s s s S S s s S s 8 S s Se § g § >»· g § § g § § § g § § § § § M im V»/ CM CO /-> •^* in /-> CO 卜 /—s 00 σ> /-"V o »-H /•s s_/ eg »—H /"s CO w np t-H <*«✓ /—v in rH W /—N 05 rH /—s o CO /—N C4 /•s eg CO s_/ CO CM s_</ CM in CO ><_·/ S m 揭 K 闺賊 w-> cs 匡揖 m 截铒 s i 闺 Μ a g K 穸闺 w m 辑 w m m K 闺 κ 辑麵闺 v£> CO s 握 Ik 匡 m n 00 cn 匡闺 κ 闺恤〇 i 握佩 r—H i 揭 K CS i 捶 K CJ i 闺 n 闺 κ (比較例6 ~ 1 0 ) 除設定爲表5所記載的條件外，與實施例23同樣得至IJ 各評價用基板C。所得之各評價用基板C的評價結果一併記載於表5中。 -72- 201126268 線寬變動 x(不良） x(不良） ◎(優） x(不良） X(不良） DP圖型之評價不良不良良好不良不良後退接觸角 ΐο in ίο m 0 75°以上 0 ΙΟ 步驟⑶ PEB條件時間 (秒） § g g S § 溫度 (°C) S s s s 105 m 時間 (秒） g g s s s ώ Oh 溫度 ΓΟ ο o o o ο 塗佈液種類 (28) (28) (28) (28) (28) 步驟⑵ 時間 (秒） 1 I I I 1 父02燈 (波長） 1 I I I 1 PDB條件時間 (秒） g § s s s 溫度 (°〇 200 o CM 200 200 200 步驟(1) PEB條件時間 (秒） s s s § s 溫度 (°C) s s T— 125 in Oi in Cvi PB條件時間 (秒） s g s s g 溫度 (°C) 130 130 130 130 130 塗佈液麵 (16) (17) (18) (26) (27) 比較例6 比較例7 比較例8 比較例9 |比較例io -73- 201126268 由表4及表5得知，依據使用本發明之感放射線組成物知光阻圖型的形成方法時，DP圖型良好，且無較大的線寬變動，可形成超過波長臨界的圖型。此外，僅單獨使用聚合物（A)時，或使用不含有具有交聯基知重複單位及具有氟原子知重複單位的聚合物（F-1)時，DP圖型之評價爲「不良」，線寬變動爲「X (不良）」，後退接觸角爲 5 5 ° (比較例6、7 )。此外，使用不含有具有氟原子知重複單位的聚合物（F-2)時，DP圖型之評價爲「良好」，線寬變動爲「◎(優）」，但是後退接觸角爲57°，曝光後，水滴殘留於線圖型上（比較例8 )。如此，在線圖型上殘留水滴時，圖型化會產生不理想的情況。而使用含有過多具有交聯基知重複單位或具有氟原子知重複單位的聚合物（F-3 )或（F-4 )時，DP圖型之評價爲「不良」，線寬變動爲「x(不良）」（比較例9、10)。〔產業上之可利用性〕依據使用本發明之感放射線組成物之光阻圖型之形成方法時，可以良好且符合經濟形成超過波長臨界的圖型。因此，極適合使用於今後越來越微細化之積體電路元件製造所代表之微細加工的領域。【圖式簡單說明】〔圖1A〕表示本發明之光阻圖型之形成方法之步驟（ 1)中之形成於基板上之第一光阻層之一例的模式圖。 -74- 201126268 之型圖阻光之明發本示表 I—\ B IX 圖的例1 之態狀光曝之層阻光1 第之中 \ly 驟步之法。方圖成式形模驟步之法方成形之型圖阻光之明發本示表 /—'V C 11 圖圖式模的例一之部像顯鹼之層阻光1 第於成形之中明發本示表 /~~~v D 11 圖第之上板基於成形之中驟。步圖之式法模方的成例形一之之型型圖圖阻阻光光之一圖型圖 ί 圖 t 阻光阻光之明發本示表 -—S 2 圖式模的態狀化溶不之Paddle) (1 sec.), washed with ultrapure water. The substrate for evaluation C on which the second photoresist pattern having a pitch of 26 nm line/l 4 nm was formed was spin-dried at 2000 rpm for 15 seconds. The D P pattern of the evaluation substrate C was evaluated as "good". The evaluation of the line width variation was "◎ (excellent)". (Examples 22 to 44) A substrate C for evaluation was obtained in the same manner as in Example 23 except that the conditions described in Table 4 were set. The evaluation results of the obtained evaluation substrates C are shown in Table 4. Further, in Examples 34 to 36, a mask of 48 nm line/96 nm pitch formation (48 nml L/lS) was used, and pure water was disposed on the surface of the first photoresist layer to form an orthogonal pattern for the exposed photoresist pattern. A contact mask pattern was formed by using a 48 nm line/96 nηι spacer to form a (48 nml L/lS) mask and performing immersion exposure. However, Example 25 was substituted for PDB, and the first resist pattern of the obtained evaluation substrate A was subjected to UV irradiation (172 nm, 10 seconds) using a lamp (manufactured by Oxtail Electric Co., Ltd.) in which 乂6 gas was sealed, to obtain a substrate for evaluation. C. -71 - 201126268 [寸彬] 骧现/"S 怒◎ /-N 雎Sm/ ◎ /-N m ◎ 豳s_/ ◎ /-N m ◎ m ◎ /—S 哔N-/ 皤◎ m s_y ◎ m V»/ ◎ /—s circumference ◎ 雎 ◎ 'μ/ ◎ m ◎ /-N sleep N·*/ m ◎ ^-sm ◎ m ◎ ® ◎ rs 晔N_/ ◎ to tk % 襄% Ϊ& tk & ft & 1 5 jn i -Η Τη a tn 3 v> 3 Τη a jn Η g 3 jo 3 In H jn Η .3⁄4 jn -Μ Ξί to -H Ξ$ tn -M .3⁄4 jn •H g 3 vn •H ρ tn VQ -Η p In In -H p in ims 1§ s 8 ss S s 8 δ s 8 s 3 sss S s S ssss le s § § § S § S g No S 5Ϊ No 8 » m £ fi sssss δ s 8 S s S ssss 8 S s S ss 8 δ «Μ 8 8 8 8 s 8 S 8 8 8 s 8 δ 8 8 8 mm 8 8 8 8 Ϊ® 00 CM s_</ 00 w /-N 00 CVJ 00 CVJ CO CO s_/ /—s 00 CM 00 CV] /•N 00 CJ >»·/ <^N 00 CM N-/ 00 CvJ 00 <N ««-N 00 CM >—✓ /*-v CO Cvj «>_/ <«"N CO CJ ^-N 00 CM s—/ /-S 00 CNJ /-S 00 CM >_/ /-N 00 00 S—/ /•N CO CO V-/ 00 〇〇v^/ /"S 00 CJ /-N 00 CsJ s_^ m Buried ii 1 1 S 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 :銎X w 1 1 ε c «Ν 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 #: m § Ou 蜃菡S 8 1 SSSS s SSS ss S s SSSSS s S s § § 1 § g § § § § g § § § g S § § S § § § § ims (X li SSSS s S 8 SSSS ss S 8 SSSSS s S ss S 3 3 Ώ 3 3 3 3 3 » 3 S s S 3 9 3 s 3 Society: ms li SSS 3 SS 8 S sssss SS ss S s 8 S s Se § g § &gt ;»·g § § g § § § g § § § § § M im V»/ CM CO /-> •^* in /-> CO 卜/-s 00 σ>/-"V o » -H /•s s_/ eg »—H /"s CO w np tH <*«✓ /—v in rH W /—N 05 rH /—so CO /—N C4 /•s eg CO s_/ CO CM s_</ CM in CO ><_·/ S m 揭 K 闺 w w-> cs 匡揖m 铒铒 si 闺Μ ag K 穸闺wm series wmm K 闺 κ 闺闺 v £ gt ; CO s grip Ik 匡 mn 00 cn 匡闺 κ 闺〇 i gripper r-H i 揭 K CS i 捶 K CJ i 闺n 闺 κ (Comparative Example 6 ~ 1 0 ) except as set in Table 5 In addition to the conditions, as in the case of Example 23, IJ was obtained. Evaluation substrate C. The evaluation results of the obtained evaluation substrates C are collectively shown in Table 5. -72- 201126268 Line width variation x (bad) x (bad) ◎ (excellent) x (bad) X (bad) DP pattern evaluation bad defect Good bad defect Back contact angle ΐο in ίο m 0 75° or more 0 ΙΟ Step (3) PEB condition time (seconds) § gg S § temperature (°C) S sss 105 m time (seconds) ggsss ώ Oh temperature ΓΟ ο ooo ο coating liquid type (28) (28) (28) (28) ( 28) Step (2) Time (seconds) 1 III 1 Parent 02 lamp (wavelength) 1 III 1 PDB condition time (seconds) g § sss Temperature (°〇200 o CM 200 200 200 Step (1) PEB condition time (seconds) sss § s Temperature (°C) ss T—125 in Oi in Cvi PB Condition Time (seconds) sgssg Temperature (°C) 130 130 130 130 130 Coating Level (16) (17) (18) (26) (27 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 | Comparative Example io - 73 - 201126268 It is known from Tables 4 and 5 that DP is formed in accordance with the method for forming a photoresist pattern using the radiation sensitive composition of the present invention. The pattern is good, and there is no large line width variation, which can form a pattern that exceeds the wavelength criticality. In addition, it is used alone. In the case of the compound (A), or when a polymer (F-1) having no crosslinking unit and a repeating unit having a fluorine atom is used, the DP pattern is evaluated as "poor" and the line width variation is " X (poor), the receding contact angle was 5 5 ° (Comparative Examples 6 and 7). When the polymer (F-2) containing no known repeating unit of fluorine atom was used, the DP pattern was evaluated as "good". The line width variation is "◎ (excellent)", but the receding contact angle is 57°. After exposure, water droplets remain on the line pattern (Comparative Example 8). Thus, when water droplets remain on the line pattern, patterning An undesired situation occurs. When a polymer (F-3) or (F-4) containing too many crosslinking units or a repeating unit having a fluorine atom is used, the DP pattern is evaluated as "poor". The line width variation is "x (poor)" (Comparative Examples 9 and 10). [Industrial Applicability] According to the method for forming a photoresist pattern using the radiation sensitive composition of the present invention, it is good and consistent. The economy forms patterns that exceed the wavelength threshold. Therefore, it is extremely suitable for use in the future. The field of microfabrication represented by the manufacture of the integrated integrated circuit component. [Schematic description of the drawing] [Fig. 1A] shows the first step formed on the substrate in the step (1) of the method for forming a photoresist pattern of the present invention. A pattern diagram of an example of a photoresist layer. -74- 201126268 The type of light block is shown in Table I - \ B IX Figure 1 of the state of the light exposed layer block light 1 in the middle \ly step method. The pattern of the square pattern is formed by the method of forming the pattern. The pattern of the block is blocked. The table is shown in the table. Mingfa this table /~~~v D 11 The upper plate is based on the forming process. The pattern of the method of the step diagram is a type of graph. The pattern of the block diagram is one of the graphs of the block light. Figure t The block diagram of the block light and the light block - the state of the S 2 pattern Dissolve

阻光之明發本示表 /—\ A 第之上板基於成形之中 Nly 3 圖The light block is shown in the table /-\ A The upper plate is based on the Nly 3 figure in the shape

B 第之中法方成形之驟步之法方成形之型。圖第之中 \1/ 3 驟。步圖之式法。模方圖的成式例形模一之的之型例層圖一阻PI之光Μ態二之明發本示表狀光曝之層阻光圖驟步之法方成形之型圖阻光之明發本示二表第 3於 C 成 fy 形之中 \1/ 3 圖式模的例1 之部像顯鹼之層阻光驟步之法方成形之型圖阻光之明發本示表 /—v D 3 圖圖式模的例一之型圖阻光二第之上板基於成形之中 ΧΪ/ 3 成形之中法方成形之型圖阻光之明發本示表 •—v 4 圖上板基於圖成形之中法。方圖成面形平之的型式圖模阻的光例之 1 明之發型本圖示阻表光3 之 5 板基於板基於成形之中法。。方圖圖成面面形平側之的的型式式圖模模阻之之光例例之他 1 明其之發之型本型圖一下圖阻表阻光彳光之 6 之上圖上【主要元件符號說明】 -75- 201126268 1 :基板 2 :第一光阻層 3 :液浸液 4 :光罩 5、3 5 :驗顯像部 6 :透鏡 12、22:第一光阻圖型 12a、22a:第一線部分 12b、22b :第一間距部分 1 5 :接觸孔圖型 3 2 :第二光阻層 42 :第二光阻圖型 4 2 a :第二線部分 42b :第二間距部分 -76In the second part, the method of the formation of the French side is formed into a form. In the figure, \1/ 3 steps. Step method. The pattern of the square-shaped pattern is a type of pattern. The pattern of the pattern is one. The light of the light is in the state of the light. The light is in the form of a light-exposed layer. The pattern of the light-blocking pattern is blocked. The Ming Dynasty issued the second table in the third form of C into the fy shape of the \1/3 pattern of the example of the part of the image of the base of the base of the light block step by step method of forming the pattern of the light block示表/—v D 3 Illustrator of the pattern of the first example of the pattern of the light-blocking second upper plate based on the forming of the ΧΪ / 3 forming during the formation of the form of the pattern of light blocking the light of the table •—v 4 The upper panel is based on the method of forming the graph. The square pattern is flat. The pattern is exemplified. The light is shown in the figure. The figure shows that the 5th plate of the resistance light 3 is based on the plate-based forming method. . The square diagram is in the form of a flat surface. The pattern of the pattern is blocked by the light. The example of the light is shown in the figure. Explanation of main component symbols] -75- 201126268 1 : Substrate 2 : First photoresist layer 3 : Liquid immersion liquid 4 : Photomask 5 , 3 5 : Inspection image portion 6 : Lens 12 , 22 : First photoresist pattern 12a, 22a: first line portion 12b, 22b: first pitch portion 15: contact hole pattern 3 2: second photoresist layer 42: second photoresist pattern 4 2 a: second line portion 42b: Two-pitch part -76

Claims

201126268 七、申請專利範圍： 1 . 一種敏輻射線性組成物，其特徵係含有：於包含使用第一敏輻射線性組成物，在基板上形成第一光阻圖型的步驟（1 );使前述第一光阻圖型對於第二敏輻射線性組成物不溶化的步驟（2 );及使用前述第二敏輻射線性組成物，在形成有前述第一光阻圖型的基板上形成第二光阻圖型的步驟（3)之光阻圖型之形成方法之前述步驟（1 )所使用的下述（A )〜（D)成分， (A) 含有具有酸不安定基之重複單位的聚合物、 (B) 含有具有交聯基之重複單位及具有氟原子之重複單位的聚合物、 (C )敏輻射線性酸產生劑、 (D )溶劑。 2. 如申請專利範圍第1項之敏輻射線性組成物，其中前述聚合物（B)相對於前述聚合物（A) 100質量份，含有1〜8 0質量份。 3. 如申請專利範圍第1或2項之敏輻射線性組成物，其中前述交聯基爲熱硬化性之反應性基。 4. 如申請專利範圍第1〜3項中任一項之敏輻射線性組成物，其中前述聚合物（B)爲含有以下述一般式（1-1) 表示之重複單位及下述一般式（1_2)表不之重複單位之至少任一表示的重複單位（1 )， -77- 201126268 【化1】 R1 R1201126268 VII. Patent application scope: 1. A sensitive radiation linear composition, characterized in that: comprising the step (1) of forming a first photoresist pattern on a substrate by using a first sensitive radiation linear composition; a first photoresist pattern for insolubilizing the second sensitivity radiation linear composition (2); and using the foregoing second radiation radiation linear composition to form a second photoresist on the substrate on which the first photoresist pattern is formed The following (A) to (D) components used in the aforementioned step (1) of the method for forming a photoresist pattern of the step (3), (A) a polymer having a repeating unit having an acid labile group (B) a polymer containing a repeating unit having a crosslinking group and a repeating unit having a fluorine atom, (C) a linear radiation generator for a radiation radiation, and (D) a solvent. 2. The linear composition for sensitive radiation according to the first aspect of the invention, wherein the polymer (B) contains 1 to 80 parts by mass based on 100 parts by mass of the polymer (A). 3. The sensitive radiation linear composition according to claim 1 or 2, wherein the crosslinking group is a thermosetting reactive group. 4. The radiation sensitive linear composition according to any one of claims 1 to 3, wherein the polymer (B) is a repeating unit represented by the following general formula (1-1) and the following general formula ( 1_2) Repeating units expressed by at least one of the repeating units (1), -77- 201126268 [Chemical 1] R1 R1

(前述一般式（1-1)及（1-2)中，R1係表示氫原子、甲基或三氟甲基，前述一般式（1-1)中，R2係表示亞甲基、伸乙基或伸丙基，R3係表示下述一般式（2)或（3)表示之基團，前述一般式（1-2)中，R4係表示亞甲基或碳數2〜6之亞烷基（alkanediyl) ，R5係表示氫原子、甲基或乙基，η係表示0或1 )(In the above general formulae (1-1) and (1-2), R1 represents a hydrogen atom, a methyl group or a trifluoromethyl group, and in the above general formula (1-1), R2 represents a methylene group and a stretching group B. Or a propyl group, and R3 represents a group represented by the following general formula (2) or (3), and in the above general formula (1-2), R4 represents a methylene group or an alkylene group having 2 to 6 carbon atoms. Alkanediyl, R5 represents a hydrogen atom, methyl or ethyl, and η represents 0 or 1)

(前述一般式（2)及（3)中，複數之R6係相互獨立表示氫原子、甲基、乙基、或碳數3〜10之直鏈狀或支鏈狀的烷基）。 5.如申請專利範圍第1〜4項中任一項之敏輻射線性組成物，其中前述聚合物（Β)爲含有以下述一般式（4)表 -78- 201126268 示之重複單位及下述—般式（5)表示之重複單位之至少任一表示的重複單位（2)，【化3】 R1(In the above general formulas (2) and (3), the plural R6 groups independently represent a hydrogen atom, a methyl group, an ethyl group, or a linear or branched alkyl group having a carbon number of 3 to 10). 5. The radiation sensitive linear composition according to any one of claims 1 to 4, wherein the polymer (Β) is a repeating unit represented by the following general formula (4) -78-201126268 and a repeating unit (2) representing at least one of the repeating units represented by the general formula (5), [Chemical 3] R1

(前述一般式（4)中，R1係表示氫原子、甲基或三氟甲基，R7係表示單鍵或碳數1〜2 0之直鏈狀、支鏈狀或環狀之飽和或不飽和之2價烴基，X係表示被氟原子取代之亞甲基或碳數2〜2〇之直鏈狀或支鏈狀之氟亞烷基，R8係表示氫原子或1價有機基）【化4】 R1(In the above general formula (4), R1 represents a hydrogen atom, a methyl group or a trifluoromethyl group, and R7 represents a single bond or a linear, branched or cyclic saturated or unsubstituted carbon number of 1 to 20; a saturated divalent hydrocarbon group, X represents a methylene group substituted by a fluorine atom or a linear or branched fluoroalkylene group having 2 to 2 carbon atoms, and R 8 represents a hydrogen atom or a monovalent organic group) 4] R1

c-ch2^- 人 I R9 (前述一般式（5)中’ R1係表示氫原子、甲基或三氟甲基’ A係表示具有單鍵、醚鍵、硫醚鍵、羰基、酯基、醯胺基、磺醯胺基、胺基甲酸酯基之2價有機基，R9係表示具有至少1個以上之氟原子之甲基、乙基、碳數3〜6之直鏈狀或支鏈狀之烷基、或碳數4〜20之1價脂環式烴基）。 6.如申請專利範圍第1〜5項中任一項之敏輻射線性組成物’其中前述聚合物（B)進一步含有具有酸不安定基的重複單位。 -79- 201126268 7 .如申請專利範圍第6項之敏輻射線性組成物，其中前述具有酸不安定基之重複單位爲以下述一般式（6)表示的重複單位（3 )，【化5】 R1 -i-C-CH9-4-C-ch2^-Human I R9 (In the above general formula (5), 'R1 means a hydrogen atom, a methyl group or a trifluoromethyl group' A system has a single bond, an ether bond, a thioether bond, a carbonyl group, an ester group, a divalent organic group of a decylamino group, a sulfonylamino group or a urethane group, and R9 means a methyl group having at least one or more fluorine atoms, an ethyl group, and a linear or branched carbon number of 3 to 6. A chain alkyl group or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms). 6. The radiation sensitive linear composition of any one of claims 1 to 5 wherein the aforementioned polymer (B) further contains a repeating unit having an acid labiness. -79-201126268 7. The sensitive radiation linear composition of claim 6, wherein the aforementioned repeating unit having an acid restless group is a repeating unit (3) represented by the following general formula (6), [Chemical 5] R1 -iC-CH9-4-

(前述一般式（6)中，R1係表示氫原子、甲基或三氟甲基，R1()係相互獨立表示甲基、乙基、碳數3~4之直鏈狀或支鏈狀之烷基、或碳數4~20之1價脂環式烴基，但是任2個 R 爲相互結合與各自結合之碳原子一·同形成碳數4~20之2 價脂環式烴基，剩餘之R1G可表示甲基、乙基、碳數3~4之直鏈狀或支鏈狀之烷基、或碳數4〜20之1價脂環式烴基）〇 8 .如申請專利範圍第2〜7項中任一項之敏輻射線性組成物，其中前述聚合物（A)爲不含具有交聯基的重複單位。 9 ·如申請專利範圍第4〜8項中任一項之敏輻射線性組成物，其中前述重複單位（1)之含有比例爲相對於前述聚合物（B )所含之重複單位之合計1()〇m〇i%，含有 1 ~30mol% 〇 1 〇 ·如申請專利範圍第5〜9項中任一項之敏輻射線性 -80- 201126268 組成物，其中前述重複單位（2 )之含有比例爲相對述聚合物（B)所含之重複單位之合計loomol%’ 1 〜7 0 m ο 1 % ° 11.—種光阻圖型之形成方法，其特徵係包含：使用如申請專利範圍第1 ~ 1 0項中任一項之敏輻射組成物，在基板上形成第一光阻圖型的步驟（1 ); 使前述第一光阻圖型對於第二敏輻射線性組成物化的步驟（2 );及使用前述第二敏輻射線性組成物形成有前述第一光阻圖型的基板上形成第二光阻圖型驟（3 )。 1 2 .如申請專利範圍第1 1項之光阻圖型之形成方其中前述第一光阻圖型具有線部分及間距部分，前述光阻圖型具有線部分及間距部分，使前述第一光阻圖前述線部分與前述第二光阻圖型之前述線部分相互交方式，形成前述第二光阻圖型。 1 3 .如申請專利範圍第1 1項之光阻圖型之形成方其中前述第一光阻圖型具有線部分及間距部分，前述光阻圖型具有線部分及間距部分，使前述第—光阻圖前述線部分與前述第二光阻圖型之前述線部分平行的，形成前述第二光阻圖型。 1 4 ·如申請專利範圍第1 1〜i 3項中任一項之光阻之形成方法’其中前述步驟（1 )爲將前述敏輻射線成物塗佈於前述基板上’形成第一光阻層，經加熱後前述第一光阻層在最表面，進行曝光處理形成前述第於前含有線性不溶，在的步法’ 第二型之錯的法，第二型之方式圖型性組，使一光 -81 - 201126268 阻圖型的步驟。 1 5 .如申請專利範圍第1 1〜1 4項中任之形成方法，其中前述步驟（3)爲將前性組成物塗佈於形成有前述第一光阻圖型第二光阻層，經加熱後，使前述第二光阻行曝光處理形成前述第二光阻圖型的步驟一項之光阻圖型述第二敏輻射線之基板上，形成層在最表面，進 -82-(In the above general formula (6), R1 represents a hydrogen atom, a methyl group or a trifluoromethyl group, and R1() independently represents a methyl group, an ethyl group, and a linear or branched chain having 3 to 4 carbon atoms. An alkyl group or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, but any two R groups are bonded to each other and a carbon atom of 4 to 20 carbon atoms is formed. R1G may represent a methyl group, an ethyl group, a linear or branched alkyl group having a carbon number of 3 to 4, or a monovalent alicyclic hydrocarbon group having a carbon number of 4 to 20) 〇8. The sensitive radiation linear composition according to any one of the items 7, wherein the polymer (A) is a repeating unit having no crosslinking group. The sensitive radiation linear composition according to any one of claims 4 to 8, wherein the content of the aforementioned repeating unit (1) is 1 in total with respect to the repeating unit contained in the polymer (B). 〇m〇i%, containing 1 to 30 mol% 〇1 〇 · The sensitive radiation linear-80-201126268 composition according to any one of claims 5 to 9, wherein the ratio of the aforementioned repeating unit (2) The method for forming a photoresist pattern is characterized by the total of the repeating units contained in the polymer (B), loomol% ' 1 〜 7 0 m ο 1 % ° 11. a step (1) of forming a first photoresist pattern on a substrate by the sensitive radiation composition of any one of the items 1 to 10; and the step of structuring the linear composition of the first photoresist pattern by the first photoresist pattern ( 2); and forming a second photoresist pattern pattern (3) on the substrate on which the first photosensitive radiation linear composition is formed by the first photoresist pattern. 1 2 . The formation of the photoresist pattern according to claim 11 wherein the first photoresist pattern has a line portion and a pitch portion, and the photoresist pattern has a line portion and a pitch portion, so that the first The line portion of the photoresist pattern intersects with the line portion of the second photoresist pattern to form the second photoresist pattern. 1 3 . The formation of the photoresist pattern according to claim 1 wherein the first photoresist pattern has a line portion and a pitch portion, and the photoresist pattern has a line portion and a pitch portion, so that the first portion is The line portion of the photoresist pattern is parallel to the line portion of the second photoresist pattern to form the second photoresist pattern. The method for forming a photoresist according to any one of the claims 1 to 3, wherein the step (1) is to apply the radiation sensitive product onto the substrate to form a first light. After the heating layer is heated, the first photoresist layer is exposed on the outermost surface to form a linear insoluble first, and the second type is wrong. To make a light-81 - 201126268 resistance pattern type of steps. The method of forming a method according to any one of claims 1 to 4, wherein the step (3) is to apply the precursor composition to the second photoresist layer on which the first photoresist pattern is formed. After heating, the second photoresist exposure treatment is performed on the substrate of the second resistive radiation pattern of the step of forming the second photoresist pattern, and the layer is formed on the outermost surface.