TW202233518A - Photoacid generator and resin composition for photolithography - Google Patents

Abstract

Provided are: a novel photoacid generator which has high photosensitivity to EUV, EB, X-ray and the like; and a resin composition for photolithography, the resin composition containing this photoacid generator. The present invention provides a photoacid generator (P) which is characterized by containing a selenonium salt represented by general formula (1). (In formula (1), each of X1, X2 and X3 independently represents a halogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an arylthio group having 6 to 14 carbon atoms, or an arylseleno group having 6 to 14 carbon atoms (some or all of hydrogen atoms in the alkyl group, alkoxy group, aryl group, aryloxy group, arylthio group and arylseleno group may be substituted by fluorine atoms); each of y1, y2 and y3 independently represents a number from 0 to 5; and A represents a monovalent anion.).

Description

光酸產生劑及光微影用樹脂組成物Photoacid generator and resin composition for photolithography

本發明是有關於一種光酸產生劑及光微影用樹脂組成物。更詳細而言，是有關於一種適於使極紫外線（extreme ultraviolet，EUV）或電子束（electron beam，EB）起作用而產生強酸的含有硒鎓鹽的光酸產生劑、及含有其的光微影用樹脂組成物。The present invention relates to a photoacid generator and a resin composition for photolithography. More specifically, it relates to a photoacid generator containing a selenonium salt suitable for making extreme ultraviolet (EUV) or electron beam (EB) act to generate strong acid, and light containing the same Resin composition for lithography.

光酸產生劑是指藉由照射光、電子束或X射線等活性能量線發生分解而產生酸的化合物的總稱，將藉由活性能量線照射而產生的酸作為活性種，用於聚合、交聯、脫保護反應等各種反應。具體可列舉：陽離子聚合性化合物的聚合或酚醛樹脂與交聯劑存在下的交聯反應、以及於鹼可溶性樹脂中導入保護基而成的聚合物的酸觸媒脫保護反應等。Photoacid generators are a general term for compounds that are decomposed by active energy rays such as irradiated light, electron beams, or X-rays to generate acids, and the acids generated by irradiation with active energy rays are used as active species for polymerization, cross Various reactions such as coupling and deprotection reactions. Specifically, the polymerization of a cationically polymerizable compound, the crosslinking reaction of a phenol resin and a crosslinking agent in the presence of a crosslinking agent, and the acid-catalyzed deprotection reaction of a polymer obtained by introducing a protective group into an alkali-soluble resin can be mentioned.

運用光微影技術而盛行製造電子零件或形成半導體元件，廣泛使用利用自光酸產生劑產生的酸的化學增幅型抗蝕劑。正在進行使用KrF準分子雷射或ArF準分子雷射作為曝光光源的半導體元件的量產，但近年來隨著圖案的進一步微細化，亦對短波長（高能量）的極紫外線（EUV）、電子束（EB）或X射線等進行研究。The production of electronic parts and the formation of semiconductor elements by photolithography is prevalent, and chemically amplified resists using acids generated from photoacid generators are widely used. Mass production of semiconductor elements using KrF excimer lasers or ArF excimer lasers as exposure light sources is underway. Electron beam (EB) or X-ray etc. for research.

隨著光源的短波長化，每單位能量的光子數減少，因此仍然要求可有效利用有限的光子的高感度的光酸產生劑。 然而，於EUV、EB微影中使用KrF準分子雷射或ArF準分子雷射用的化學增幅抗蝕劑中一般所使用的三苯基鋶鹽等光酸產生劑的情況下，光感應性不充分，正在開發專用於EUV、EB、X射線等的高感度的光酸產生劑。 作為EUV抗蝕劑用光酸產生劑，提出了使陰離子具有特徵的光酸產生劑（專利文獻1）、及調整了陽離子結構的光酸產生劑（專利文獻2、專利文獻3、專利文獻4），但對於EUV的感度均不充分。 [現有技術文獻] [專利文獻] With the shortening of the wavelength of the light source, the number of photons per unit energy has decreased, and thus a photoacid generator with high sensitivity that can effectively utilize limited photons is still required. However, when photoacid generators such as triphenyl perionium salts, which are generally used in chemically amplified resists for KrF excimer lasers or ArF excimer lasers, are used in EUV and EB lithography, the photosensitivity of Insufficient, high-sensitivity photoacid generators dedicated to EUV, EB, X-ray, etc. are being developed. As photoacid generators for EUV resists, a photoacid generator characterized by an anion (Patent Document 1), and a photoacid generator with a cationic structure adjusted (Patent Document 2, Patent Document 3, Patent Document 4) have been proposed ), but neither has sufficient sensitivity for EUV. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本專利特開2009-237176號公報 [專利文獻2]日本專利5678747號 [專利文獻3]日本專利特開2014-234348號公報 [專利文獻4]日本專利特開2019-201404號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2009-237176 [Patent Document 2] Japanese Patent No. 5678747 [Patent Document 3] Japanese Patent Laid-Open No. 2014-234348 [Patent Document 4] Japanese Patent Laid-Open No. 2019-201404

[發明所欲解決之課題] 於所述背景下，本發明的第一目的在於提供一種對於EUV、EB、X射線等具有高的光感應性的新的光酸產生劑。 本發明的第二目的在於提供一種包含所述光酸產生劑而成的光微影用樹脂組成物。 [解決課題之手段] [The problem to be solved by the invention] Against such a background, the first object of the present invention is to provide a novel photoacid generator having high photosensitivity to EUV, EB, X-rays, and the like. A second object of the present invention is to provide a resin composition for photolithography containing the photoacid generator. [Means of Solving Problems]

本發明者等人為了達成所述目的而進行了研究，結果完成了本發明。 即，本發明是一種光酸產生劑（P）；及包含該光酸產生劑（P）的光微影用樹脂組成物（Q），所述光酸產生劑（P）的特徵在於：含有下述通式（1）所表示的硒鎓鹽。 The present inventors have completed the present invention as a result of studies in order to achieve the above-mentioned object. That is, the present invention is a photoacid generator (P); and a resin composition (Q) for photolithography comprising the photoacid generator (P) characterized by containing: A selenonium salt represented by the following general formula (1).

[化1]

[hua 1]

[式（1）中，X ¹、X ²及X ³分別獨立地為鹵素原子、羥基、碳數1～18的烷基、碳數1～18的烷氧基、碳數6～14的芳基、碳數6～14的芳氧基、碳數6～14的芳硫基、或碳數6～14的芳硒基（該些烷基、烷氧基、芳基、芳氧基、芳硫基及芳硒基的氫原子的一部分或全部可經氟原子取代），y ₁、y ₂及y ₃相互獨立地為0～5，A ^-為一價陰離子。] [發明的效果] [In formula (1), X ¹ , X ² and X ³ are each independently a halogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an aryl group having 6 to 14 carbon atoms. group, an aryloxy group having 6 to 14 carbon atoms, an arylthio group having 6 to 14 carbon atoms, or an arylselenyl group having 6 to 14 carbon atoms (these alkyl groups, alkoxy groups, aryl groups, aryloxy groups, aryl groups A part or all of the hydrogen atoms of the thio group and the arylselenyl group may be substituted by fluorine atoms), y ₁ , y ₂ and y ₃ are independently 0 to 5, and A ^- is a monovalent anion. ] [Effect of invention]

本發明的光酸產生劑（P）藉由使鎓骨架的中心元素為硒，具有高的EUV吸收與基於碳-硒鍵的解離容易度的易分解性。藉此，藉由照射EUV或EB，該光酸產生劑（P）容易分解，可產生包含磺酸等強酸的各種酸。另外，藉由向X ¹～X ³中導入取代基，可控制感度、溶解性、及儲存穩定性。 The photoacid generator (P) of the present invention has high EUV absorption and easy decomposability based on the ease of dissociation of carbon-selenium bonds by making the central element of the onium skeleton selenium. Thereby, by irradiating EUV or EB, the photoacid generator (P) is easily decomposed, and various acids including strong acids such as sulfonic acid can be generated. In addition, by introducing a substituent into X ¹ to X ³ , sensitivity, solubility, and storage stability can be controlled.

本發明的光酸產生劑（P）含有下述通式（1）所表示的硒鎓鹽。The photoacid generator (P) of the present invention contains a selenonium salt represented by the following general formula (1).

[化2]

[hua 2]

[式（1）中，X ¹、X ²及X ³分別獨立地為鹵素原子、羥基、碳數1～18的烷基、碳數1～18的烷氧基、碳數6～14的芳基、碳數6～14的芳氧基、碳數6～14的芳硫基、或碳數6～14的芳硒基（該些烷基、烷氧基、芳基、芳氧基、芳硫基及芳硒基的氫原子的一部分或全部可經氟原子取代），y ₁、y ₂及y ₃相互獨立地為0～5，A ^-為一價陰離子。] [In formula (1), X ¹ , X ² and X ³ are each independently a halogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an aryl group having 6 to 14 carbon atoms. group, an aryloxy group having 6 to 14 carbon atoms, an arylthio group having 6 to 14 carbon atoms, or an arylselenyl group having 6 to 14 carbon atoms (these alkyl groups, alkoxy groups, aryl groups, aryloxy groups, aryl groups A part or all of the hydrogen atoms of the thio group and the arylselenyl group may be substituted by fluorine atoms), y ₁ , y ₂ and y ₃ are independently 0 to 5, and A ^- is a monovalent anion. ]

式（1）中，X ¹、X ²及X ³分別獨立地為鹵素原子、羥基、碳數1～18的烷基、碳數1～18的烷氧基、碳數6～14的芳基、碳數6～14的芳氧基、碳數6～14的芳硫基、或碳數6～14的芳硒基（該些烷基、烷氧基、芳基、芳氧基、芳硫基及芳硒基的氫原子的一部分或全部可經氟原子取代）。 In formula (1), X ¹ , X ² and X ³ are each independently a halogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an aryl group having 6 to 14 carbon atoms. , aryloxy with 6-14 carbons, arylthio with 6-14 carbons, or arylselenyl with 6-14 carbons (these alkyl, alkoxy, aryl, aryloxy, arylthio A part or all of the hydrogen atoms of the arylselenyl group and the arylselenyl group may be substituted with a fluorine atom).

作為鹵素原子，可列舉：氟原子、氯原子、溴原子及碘原子等。As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

作為碳數1～18的烷基，可列舉直鏈、分支、或環狀的烷基（甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、新戊基、第三戊基、1-甲基丁基、環戊基、環己基、辛基、癸烷基、十氫萘基、降冰片烷基、金剛烷基等）等。另外，該些基的氫的一部分或全部可經氟取代。Examples of the alkyl group having 1 to 18 carbon atoms include linear, branched, or cyclic alkyl groups (methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, th Tributyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, cyclopentyl, cyclohexyl, octyl, decyl, decalinyl, norbornyl , adamantyl, etc.) and so on. In addition, some or all of the hydrogens of these groups may be substituted with fluorine.

作為碳數1～18的烷氧基，可列舉碳數1～18的直鏈或分支烷氧基（甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、第二丁氧基、第三丁氧基、己氧基、癸氧基、十二烷氧基及十八烷氧基等）等。另外，該些基的氫的一部分或全部可經氟取代。Examples of the alkoxy group having 1 to 18 carbon atoms include linear or branched alkoxy groups having 1 to 18 carbon atoms (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy) oxy, second butoxy, third butoxy, hexyloxy, decyloxy, dodecyloxy and octadecyloxy, etc.) and the like. In addition, some or all of the hydrogens of these groups may be substituted with fluorine.

作為碳數6～14的芳基，可列舉：苯基、1-萘基、2-萘基、1-薁基、蒽基、菲基等芳基。另外，該些基的氫的一部分或全部可經氟取代。Examples of the aryl group having 6 to 14 carbon atoms include aryl groups such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-azulene group, an anthracenyl group, and a phenanthryl group. In addition, some or all of the hydrogens of these groups may be substituted with fluorine.

作為碳數6～14的芳氧基，可列舉：苯氧基、萘氧基及蒽氧基等。 另外，該些基的氫的一部分或全部可經氟取代。 Examples of the aryloxy group having 6 to 14 carbon atoms include a phenoxy group, a naphthyloxy group, an anthracenyloxy group, and the like. In addition, some or all of the hydrogens of these groups may be substituted with fluorine.

作為碳數6～14的芳硫基，可列舉：苯硫基、2-甲基苯硫基、3-甲基苯硫基、4-甲基苯硫基、2-乙基苯硫基、萘硫基及蒽硒基等。 另外，該些基的氫的一部分或全部可經氟取代。 Examples of the arylthio group having 6 to 14 carbon atoms include phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methylphenylthio, 2-ethylphenylthio, Naphthylthio and anthracene selenoyl, etc. In addition, some or all of the hydrogens of these groups may be substituted with fluorine.

作為碳數6～14的芳硒基，可列舉：苯硒基、萘硒基及蒽硒基等。 另外，該些基的氫的一部分或全部可經氟取代。 Examples of the arylselenyl group having 6 to 14 carbon atoms include a phenylselenyl group, a naphthylselenyl group, an anthraceneselenyl group, and the like. In addition, some or all of the hydrogens of these groups may be substituted with fluorine.

式（1）中，作為X ¹、X ²及X ³，就感度、穩定性、獲取的容易度的觀點而言，較佳為鹵素原子、碳數1～10的烷基、或碳數6～10的芳基（該些烷基及芳基的氫原子的一部分或全部可經氟原子取代），進而佳為F、CF ₃、C ₂F ₅、C ₃F ₇、C ₄F ₉、或C ₆F ₅。 In the formula (1), X ¹ , X ² and X ³ are preferably a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 6 carbon atoms from the viewpoint of sensitivity, stability, and ease of acquisition. Aryl groups of ~10 (a part or all of the hydrogen atoms of these alkyl groups and aryl groups may be substituted with fluorine atoms), more preferably F, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , or C ₆ F ₅ .

式（1）中，y ₁、y ₂、y ₃相互獨立地為0～5。較佳為0～2。 In the formula (1), y ₁ , y ₂ , and y ₃ are 0 to 5 independently of each other. Preferably it is 0-2.

式（1）中，A ^-表示一價陰離子。 作為一價陰離子，可列舉：Cl ^-、Br ^-、SbF ₆ ^-、PF ₆ ^-、BF ₄ ^-、(CF ₃CF ₂) ₃PF ₃ ^-、(CF ₃CF ₂) ₂PF ₄ ^-、(CF ₃CF ₂)PF ₅ ^-、(C ₆F ₅) ₄B ^-、{(CF ₃) ₂C ₆H ₃} ₄B ^-、(C ₆F ₅) ₄Ga ^-、{(CF ₃) ₂C ₆H ₃} ₄Ga ^-、(CF ₃SO ₂) ₃C ^-、(CF ₃SO ₂) ₂N ^-、(C ₄F ₉SO ₂) ₂N ^-及R ¹SO ₃ ^-等。 In formula (1), A ^- represents a monovalent anion. Examples of the monovalent anions include Cl ^- , Br ^- , SbF ₆ ^- , PF ₆ ^- , BF ₄ ^- , (CF ₃ CF ₂ ) ₃ PF ₃ ^- , (CF ₃ CF ₂ ) ₂ PF ₄ ^{- , (CF 3 CF 2 ) 2 PF 4 -} , (CF 4 - ) ₃ CF ₂ )PF ₅ ^- , (C ₆ F ₅ ) ₄ B ^- , {(CF ₃ ) ₂ C ₆ H ₃ } ₄ B ^- , (C ₆ F ₅ ) ₄ Ga ^- , {(CF ₃ ) ₂ C ₆ H ₃ } ₄ Ga ^- , (CF ₃ SO ₂ ) ₃ C ^- , (CF ₃ SO ₂ ) ₂ N ^- , (C ₄ F ₉ SO ₂ ) ₂ N ^- and R ¹ SO ₃ ^- and the like.

作為R ¹SO ₃ ^-所表示的磺酸根陰離子，可列舉：三氟甲磺酸根陰離子（三氟甲磺酸鹽（triflate））、五氟乙磺酸根陰離子、七氟丙磺酸根陰離子、九氟丁磺酸根陰離子（全氟丁磺酸鹽（nonaflate））、五氟苯基磺酸根陰離子、對甲苯磺酸根陰離子、苯磺酸根陰離子、樟腦磺酸根陰離子、甲磺酸根陰離子、乙磺酸根陰離子、丙磺酸根陰離子、丁磺酸根陰離子及下述通式（2）所表示的磺酸根陰離子等。 Examples of the sulfonate anion represented by R ¹ SO ₃ ^- include trifluoromethanesulfonate anion (triflate), pentafluoroethanesulfonate anion, heptafluoropropanesulfonate anion, and nonafluoro Butanesulfonate anion (perfluorobutanesulfonate (nonaflate)), pentafluorophenylsulfonate anion, p-toluenesulfonate anion, benzenesulfonate anion, camphorsulfonate anion, mesylate anion, ethanesulfonate anion, A propanesulfonate anion, a butanesulfonate anion, a sulfonate anion represented by the following general formula (2), and the like.

[化3]

[hua 3]

[式（2）中，R ²為碳數1～18的直鏈、分支鏈或環狀的烷基（其氫的一部分或全部可經氟取代，其亞甲基鏈的一部分可經-O-、-CO-、-COO-、-OCO-、-OCOO-、-S-、-SO-、-SO ₂-基取代，可形成雙環結構或螺環結構），R ³及R ⁴分別獨立地為氫原子、氟原子或碳數1～4的氟烷基，Z為單鍵、或碳數1～8的直鏈或分支鏈的烷基（其氫的一部分或全部可經氟取代，其亞甲基鏈的一部分可經-O-、-CO-、-COO-、-OCO-、-OCOO-、-S-、-SO-、-SO ₂-基取代）。] [In formula (2), R ² is a linear, branched or cyclic alkyl group with 1 to 18 carbon atoms (a part or all of its hydrogen may be substituted with fluorine, and a part of its methylene chain may be substituted with -O -, -CO-, -COO-, -OCO-, -OCOO-, -S-, -SO-, -SO ₂ - group substitution, can form bicyclic structure or spiro ring structure), R ³ and R ⁴ are independent Z is a hydrogen atom, a fluorine atom or a fluoroalkyl group with 1 to 4 carbon atoms, Z is a single bond, or a straight or branched chain alkyl group with 1 to 8 carbon atoms (a part or all of its hydrogen may be substituted by fluorine, A part of its methylene chain may be substituted with -O-, -CO-, -COO-, -OCO-, -OCOO-, -S-, -SO-, _-SO2- groups). ]

作為A ^-，就感度、粗糙度降低、及獲取的容易度的觀點而言，較佳為R ¹SO ₃ ^-所表示的磺酸根陰離子，進而佳為三氟甲磺酸根陰離子（三氟甲磺酸鹽）、九氟丁磺酸根陰離子（全氟丁磺酸鹽）、或式（2）所表示者中R ³及R ⁴為氟原子或碳數1～4的氟烷基者。 A ^- is preferably a sulfonate anion represented by R ¹ SO ₃ ^- , and more preferably a trifluoromethanesulfonate anion (trifluoromethanesulfonate) from the viewpoints of sensitivity, reduction in roughness, and ease of acquisition. acid salt), nonafluorobutanesulfonate anion (perfluorobutanesulfonate), or those represented by formula (2) wherein R ³ and R ⁴ are fluorine atoms or fluoroalkyl groups having 1 to 4 carbon atoms.

本發明的硒鎓鹽的合成方法只要可合成目標物，則並無特別限定，例如可藉由以下敘述的製造方法來製造。The method for synthesizing the selenonium salt of the present invention is not particularly limited as long as the target product can be synthesized. For example, it can be produced by the production method described below.

[化4]

[hua 4]

所述反應式中的X ¹～X ³、y ₁～y ₃表示與通式（1）所表示的光酸產生劑（P）中的X ¹～X ³、y ₁～y ₃相同者。 第一階段的反應是使芳基硒醇與芳基溴及鹼於有機溶劑（DMAc等）中、反應溫度60℃～140℃下反應6小時～48小時。 X ¹ to X ³ and y ₁ to y ₃ in the reaction formula are the same as X ¹ to X ³ and y ₁ to y ₃ in the photoacid generator (P) represented by the general formula (1). The first stage of the reaction is to react arylselenol, aryl bromide and base in an organic solvent (DMAc, etc.) at a reaction temperature of 60°C to 140°C for 6 hours to 48 hours.

作為鹼，只要為可自芳基硒醇中的SeH去除質子者，則並無特別限定，可列舉：鹼金屬的氫氧化物（KOH、NaOH等）、碳酸根陰離子的鹼金屬鹽（K ₂CO ₃、Na ₂CO ₃等）、或有機鹼（二氮雜雙環十一烯、三乙胺、吡啶等）、鹼金屬的氫化物（LiH、NaH等）等。 The base is not particularly limited as long as it can remove protons from SeH in arylselenol, and examples thereof include hydroxides of alkali metals (KOH, NaOH, etc.), alkali metal salts of carbonate anions (K ₂ ). CO ₃ , Na ₂ CO ₃ , etc.), or organic bases (diazabicycloundecene, triethylamine, pyridine, etc.), alkali metal hydrides (LiH, NaH, etc.), and the like.

第二階段的反應可繼第一階段的反應而進行，亦可於分離（視需要精製）前驅物硒化物之後進行。將前驅物硒化物與有機溶劑（乙腈、二噁烷、四氫呋喃、DMF等）混合並攪拌，使該混合物與二芳基錪三氟甲磺酸鹽反應。反應時間為1小時～50小時，反應溫度為80℃～120℃。反應完成後，將反應液冷卻，並加入水與二氯甲烷等有機溶劑，藉此進行分液、精製。The reaction of the second stage can be carried out following the reaction of the first stage, or it can be carried out after isolating (if necessary refining) the precursor selenide. The precursor selenide is mixed with an organic solvent (acetonitrile, dioxane, tetrahydrofuran, DMF, etc.) and stirred to react the mixture with the diaryl iodonium triflate. The reaction time is 1 hour to 50 hours, and the reaction temperature is 80°C to 120°C. After the completion of the reaction, the reaction liquid was cooled, and organic solvents such as water and dichloromethane were added to perform liquid separation and purification.

第三階段的反應是將生成物（P1）、強酸的金屬鹽（NaSbF ₆、KPF ₆、NaB(C ₆F ₅) ₄、R ¹SO ₃NBu ₄等）於有機溶劑（乙腈、氯仿、二氯甲烷、DMF等）與水的混合體系中進行鹽交換。反應溫度為0℃～30℃，反應時間為10分鐘～2小時。反應完成後，藉由進行水洗來獲得（P2）。 The third stage of the reaction is to mix the product (P1), metal salts of strong acids (NaSbF ₆ , KPF ₆ , NaB(C ₆ F ₅ ) ₄ , R ¹ SO ₃ NBu ₄ , etc.) in organic solvents (acetonitrile, chloroform, dimethicone, etc.) Salt exchange is carried out in a mixed system of methyl chloride, DMF, etc.) and water. The reaction temperature is 0°C to 30°C, and the reaction time is 10 minutes to 2 hours. After completion of the reaction, (P2) was obtained by performing water washing.

為了容易溶解於抗蝕劑材料中，本發明的光酸產生劑（P）可預先溶解於不阻礙反應的溶劑中。The photoacid generator (P) of the present invention may be dissolved in a solvent that does not inhibit the reaction in advance in order to be easily dissolved in the resist material.

作為溶劑，可列舉：碳酸酯類（碳酸伸丙酯、碳酸伸乙酯、碳酸1,2-伸丁酯、碳酸二甲酯及碳酸二乙酯等）、酯類（乙酸乙酯、乳酸乙酯、β-丙內酯、β-丁內酯、γ-丁內酯、δ-戊內酯及ε-己內酯等）、醚類（乙二醇單甲醚、丙二醇單***、二乙二醇單丁醚、二丙二醇二甲醚、三乙二醇二***、三丙二醇二丁醚等）、及醚酯類（乙二醇單甲醚乙酸酯、丙二醇單***乙酸酯及二乙二醇單丁醚乙酸酯等）等。Examples of the solvent include carbonates (propylene carbonate, ethylidene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.), esters (ethyl acetate, ethyl lactate, etc.) Esters, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone and ε-caprolactone, etc.), ethers (ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethyl ether Glycol monobutyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol dibutyl ether, etc.), and ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and ethylene glycol monobutyl ether acetate, etc.), etc.

於使用溶劑的情況下，相對於本發明的光酸產生劑（P）100重量份，溶劑的使用比例較佳為15重量份～1000重量份，進而佳為30重量份～500重量份。When a solvent is used, the use ratio of the solvent is preferably 15 to 1000 parts by weight, more preferably 30 to 500 parts by weight, relative to 100 parts by weight of the photoacid generator (P) of the present invention.

本發明的光微影用樹脂組成物（Q）包含式（1）所示的硒鎓鹽作為必需成分，因此藉由進行紫外線等光化射線照射及曝光後加熱（PEB），曝光部與未曝光部對顯影液的溶解性產生差異。該硒鎓鹽可單獨使用一種，或者將兩種以上組合而使用。 作為光微影用樹脂組成物（Q），可列舉：負型化學增幅樹脂（QN）與光酸產生劑（P）的混合物；及正型化學增幅樹脂（QP）與光酸產生劑（P）的混合物。 The resin composition (Q) for photolithography of the present invention contains the selenonium salt represented by the formula (1) as an essential component, and therefore, by performing actinic radiation such as ultraviolet rays and post-exposure heating (PEB), the exposed portion and the untreated area are separated from each other. A difference occurs in the solubility of the exposure portion to the developer. The selenonium salt may be used alone or in combination of two or more. Examples of the resin composition (Q) for photolithography include: a mixture of a negative-type chemically amplified resin (QN) and a photoacid generator (P); and a positive-type chemically amplified resin (QP) and a photoacid generator (P) )mixture.

作為負型化學增幅樹脂（QN），包含含酚性羥基的樹脂（QN1）與交聯劑（QN2）。The negative-type chemically amplified resin (QN) includes a phenolic hydroxyl group-containing resin (QN1) and a crosslinking agent (QN2).

作為含酚性羥基的樹脂（QN1），若為含有酚性羥基的樹脂，則並無特別限制，例如可使用：酚醛清漆樹脂、聚羥基苯乙烯、羥基苯乙烯的共聚物、羥基苯乙烯與苯乙烯的共聚物、羥基苯乙烯、苯乙烯及(甲基)丙烯酸衍生物的共聚物、苯酚-苯二甲醇縮合樹脂、甲酚-苯二甲醇縮合樹脂、含有酚性羥基的聚醯亞胺、含有酚性羥基的聚醯胺酸、苯酚-二環戊二烯縮合樹脂。該些中，較佳為酚醛清漆樹脂、聚羥基苯乙烯、羥基苯乙烯的共聚物、羥基苯乙烯與苯乙烯的共聚物、羥基苯乙烯、苯乙烯及(甲基)丙烯酸衍生物的共聚物、苯酚-苯二甲醇縮合樹脂。再者，該些含酚性羥基的樹脂（QN1）可單獨使用一種，亦可將兩種以上混合而使用。The phenolic hydroxyl group-containing resin (QN1) is not particularly limited as long as it is a phenolic hydroxyl group-containing resin, and for example, novolak resin, polyhydroxystyrene, copolymer of hydroxystyrene, hydroxystyrene and Copolymers of styrene, hydroxystyrene, copolymers of styrene and (meth)acrylic acid derivatives, phenol-benzenedimethanol condensation resins, cresol-xylenedimethanol condensation resins, polyimide containing phenolic hydroxyl groups , Polyamide acid containing phenolic hydroxyl group, phenol-dicyclopentadiene condensation resin. Among these, preferred are novolak resins, polyhydroxystyrene, copolymers of hydroxystyrene, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and (meth)acrylic derivatives , Phenol-benzenedimethanol condensation resin. In addition, these phenolic hydroxyl group containing resin (QN1) may be used individually by 1 type, and may be used in mixture of 2 or more types.

所述酚醛清漆樹脂例如可藉由在觸媒的存在下使酚類與醛類進行縮合而獲得。 作為所述酚類，例如可列舉：苯酚、鄰甲酚、間甲酚、對甲酚、鄰乙基苯酚、間乙基苯酚、對乙基苯酚、鄰丁基苯酚、間丁基苯酚、對丁基苯酚、2,3-二甲酚、2,4-二甲酚、2,5-二甲酚、2,6-二甲酚、3,4-二甲酚、3,5-二甲酚、2,3,5-三甲基苯酚、3,4,5-三甲基苯酚、鄰苯二酚、間苯二酚、五倍子酚、1-萘酚、2-萘酚。 另外，作為所述醛類，可列舉：甲醛、對甲醛、乙醛、苯甲醛等。 The novolak resin can be obtained, for example, by condensing phenols and aldehydes in the presence of a catalyst. Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p- Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol Phenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, gallic phenol, 1-naphthol, 2-naphthol. Moreover, as said aldehyde, formaldehyde, p-formaldehyde, acetaldehyde, benzaldehyde, etc. are mentioned.

作為具體的酚醛清漆樹脂，例如可列舉：苯酚/甲醛縮合酚醛清漆樹脂、甲酚/甲醛縮合酚醛清漆樹脂、苯酚-萘酚/甲醛縮合酚醛清漆樹脂。As a specific novolak resin, a phenol/formaldehyde condensed novolak resin, a cresol/formaldehyde condensed novolak resin, and a phenol-naphthol/formaldehyde condensed novolak resin are mentioned, for example.

另外，於所述含酚性羥基的樹脂（QN1）中亦可含有酚性低分子化合物作為成分的一部分。 作為所述酚性低分子化合物，例如可列舉：4,4'-二羥基二苯基甲烷、4,4'-二羥基二苯基醚、三(4-羥基苯基)甲烷、1,1-雙(4-羥基苯基)-1-苯基乙烷、三(4-羥基苯基)乙烷、1,3-雙[1-(4-羥基苯基)-1-甲基乙基]苯、1,4-雙[1-(4-羥基苯基)-1-甲基乙基]苯、4,6-雙[1-(4-羥基苯基)-1-甲基乙基]-1,3-二羥基苯、1,1-雙(4-羥基苯基)-1-[4-〔1-(4-羥基苯基)-1-甲基乙基〕苯基]乙烷、1,1,2,2-四(4-羥基苯基)乙烷、4,4'-{1-[4-〔1-(4-羥基苯基)-1-甲基乙基〕苯基]亞乙基}雙酚。該些酚性低分子化合物可單獨使用一種，亦可將兩種以上混合而使用。 Moreover, you may contain a phenolic low molecular weight compound as a part of components in the said phenolic hydroxyl group containing resin (QN1). As the phenolic low molecular compound, for example, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, tris(4-hydroxyphenyl)methane, 1,1 -Bis(4-hydroxyphenyl)-1-phenylethane, tris(4-hydroxyphenyl)ethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl ]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl] ]-1,3-dihydroxybenzene, 1,1-bis(4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethyl Alkane, 1,1,2,2-Tetrakis(4-hydroxyphenyl)ethane, 4,4'-{1-[4-[1-(4-hydroxyphenyl)-1-methylethyl] Phenyl]ethylene}bisphenol. These phenolic low molecular weight compounds may be used alone or in combination of two or more.

於將含酚性羥基的樹脂（QN1）設為100重量%的情況下，該酚性低分子化合物於含酚性羥基的樹脂（QN1）中的含有比例較佳為40重量%以下，進而佳為1重量%～30重量%。When the phenolic hydroxyl group-containing resin (QN1) is 100% by weight, the content of the phenolic low molecular weight compound in the phenolic hydroxyl group-containing resin (QN1) is preferably 40% by weight or less, and more preferably It is 1% by weight to 30% by weight.

就所獲得的絕緣膜的解析性、熱衝擊性、耐熱性、殘膜率等觀點而言，含酚性羥基的樹脂（QN1）的重量平均分子量較佳為2000以上，進而佳為2000～20000。 另外，於將除溶劑以外的組成物的整體設為100重量%的情況下，負型化學增幅樹脂（QN）中的含酚性羥基的樹脂（QN1）的含有比例較佳為30重量%～90重量%，進而佳為40重量%～80重量%。於該含酚性羥基的樹脂（QN1）的含有比例為30重量%～90重量%的情況下，使用感光性絕緣樹脂組成物所形成的膜具有由鹼性水溶液帶來的充分的顯影性，故較佳。 The weight-average molecular weight of the phenolic hydroxyl group-containing resin (QN1) is preferably 2,000 or more, and more preferably 2,000 to 20,000, from the viewpoints of the analytical properties, thermal shock resistance, heat resistance, and residual film ratio of the obtained insulating film. . Moreover, when making the whole composition except a solvent into 100 weight%, it is preferable that the content rate of the phenolic hydroxyl group-containing resin (QN1) in the negative type chemically amplified resin (QN) is 30 weight% - 90% by weight, more preferably 40% by weight to 80% by weight. When the content ratio of the phenolic hydroxyl group-containing resin (QN1) is 30% by weight to 90% by weight, the film formed using the photosensitive insulating resin composition has sufficient developability by an alkaline aqueous solution, So better.

作為交聯劑（QN2），若為可利用自該光酸產生劑（P）產生的強酸使含酚性羥基的樹脂（QN1）交聯的化合物，則並無特別限定。The crosslinking agent (QN2) is not particularly limited as long as it is a compound capable of crosslinking the phenolic hydroxyl group-containing resin (QN1) with a strong acid generated from the photoacid generator (P).

作為交聯劑（QN2），例如可列舉：雙酚A系環氧化合物、雙酚F系環氧化合物、雙酚S系環氧化合物、酚醛清漆樹脂系環氧化合物、可溶酚醛樹脂系環氧化合物、聚(羥基苯乙烯)系環氧化合物、氧雜環丁烷化合物、含羥甲基的三聚氰胺化合物、含羥甲基的苯並胍胺化合物、含羥甲基的脲化合物、含羥甲基的酚化合物、含烷氧基烷基的三聚氰胺化合物、含烷氧基烷基的苯並胍胺化合物、含烷氧基烷基的脲化合物、含烷氧基烷基的酚化合物、含羧基甲基的三聚氰胺樹脂、含羧基甲基的苯並胍胺樹脂、含羧基甲基的脲樹脂、含羧基甲基的酚樹脂、含羧基甲基的三聚氰胺化合物、含羧基甲基的苯並胍胺化合物、含羧基甲基的脲化合物及含羧基甲基的酚化合物。As a crosslinking agent (QN2), for example, a bisphenol A-based epoxy compound, a bisphenol F-based epoxy compound, a bisphenol S-based epoxy compound, a novolak resin-based epoxy compound, and a resol-based epoxy compound can be mentioned. Oxygen compound, poly(hydroxystyrene)-based epoxy compound, oxetane compound, methylol-containing melamine compound, methylol-containing benzoguanamine compound, methylol-containing urea compound, hydroxyl group-containing Methyl phenolic compounds, alkoxyalkyl-containing melamine compounds, alkoxyalkyl-containing benzoguanamine compounds, alkoxyalkyl-containing urea compounds, alkoxyalkyl-containing phenolic compounds, Carboxymethyl-containing melamine resin, carboxymethyl-containing benzoguanamine resin, carboxymethyl-containing urea resin, carboxymethyl-containing phenol resin, carboxymethyl-containing melamine compound, carboxymethyl-containing benzoguanamine Amine compounds, carboxymethyl-containing urea compounds, and carboxymethyl-containing phenolic compounds.

於該些交聯劑（QN2）中，較佳為含羥甲基的酚化合物、含甲氧基甲基的三聚氰胺化合物、含甲氧基甲基的酚化合物、含甲氧基甲基的甘脲化合物、含甲氧基甲基的脲化合物及含乙醯氧基甲基的酚化合物，進而佳為含甲氧基甲基的三聚氰胺化合物（例如六甲氧基甲基三聚氰胺）、含甲氧基甲基的甘脲化合物及含甲氧基甲基的脲化合物等。含甲氧基甲基的三聚氰胺化合物以賽麥盧（CYMEL）300、賽麥盧（CYMEL）301、賽麥盧（CYMEL）303、賽麥盧（CYMEL）305（三井氰胺（Mitsui Cyanamid）（股）製造）等商品名市售，含甲氧基甲基的甘脲化合物以賽麥盧（CYMEL）1174（三井氰胺（Mitsui Cyanamid）（股）製造）等商品名市售，且含甲氧基甲基的脲化合物以MX290（三和化學（股）製造）等商品名市售。Among these crosslinking agents (QN2), preferred are methylol-containing phenolic compounds, methoxymethyl-containing melamine compounds, methoxymethyl-containing phenolic compounds, and methoxymethyl-containing glycerol compounds. Urea compounds, methoxymethyl-containing urea compounds, and acetoxymethyl-containing phenolic compounds, more preferably methoxymethyl-containing melamine compounds (for example, hexamethoxymethyl melamine), methoxymethyl-containing Methyl glycoluril compounds and methoxymethyl-containing urea compounds, etc. Methoxymethyl-containing melamine compounds are CYMEL 300, CYMEL 301, CYMEL 303, CYMEL 305 (Mitsui Cyanamid) ( Co., Ltd.) and other trade names are commercially available, and methoxymethyl-containing glycoluril compounds are commercially available under such trade names as CYMEL 1174 (Mitsui Cyanamid Co., Ltd.), and methyl-containing Oxymethyl urea compounds are commercially available under trade names such as MX290 (manufactured by Sanwa Chemical Co., Ltd.).

就殘膜率的下降、圖案的彎曲或膨潤及顯影性的觀點而言，相對於含酚性羥基的樹脂（QN1）中的所有酸性官能基，交聯劑（QN2）的含量通常為5莫耳%～60莫耳%，較佳為10莫耳%～50莫耳%，進而佳為15莫耳%～40莫耳%。The content of the crosslinking agent (QN2) is usually 5 mol with respect to all the acidic functional groups in the phenolic hydroxyl group-containing resin (QN1) from the viewpoint of the reduction of the residual film ratio, the warpage or swelling of the pattern, and the developability. % to 60 mol %, preferably 10 mol % to 50 mol %, more preferably 15 mol % to 40 mol %.

作為正型化學增幅樹脂（QP），可列舉含有酚性羥基、羧基、或磺醯基等中的一種以上的酸性官能基的鹼可溶性樹脂（QP1）中酸性官能基的氫原子的一部分或全部被酸解離性基取代而成的保護基導入樹脂（QP2）。 再者，酸解離性基為可於自該光酸產生劑（P）產生的強酸的存在下進行解離的基。 保護基導入樹脂（QP2）其自身為鹼不溶性或鹼難溶性。 The positive chemically amplified resin (QP) includes a part or all of the hydrogen atoms of the acidic functional group in the alkali-soluble resin (QP1) containing one or more acidic functional groups such as a phenolic hydroxyl group, a carboxyl group, or a sulfonyl group. A protective group substituted with an acid dissociable group is introduced into the resin (QP2). In addition, an acid dissociable group is a group which can be dissociated in the presence of the strong acid generated from the photoacid generator (P). The protective group-introducing resin (QP2) itself is alkali-insoluble or alkali-hardly soluble.

作為鹼可溶性樹脂（QP1），例如可列舉：含酚性羥基的樹脂（QP11）、含羧基的樹脂（QP12）、及含磺酸基的樹脂（QP13）等。 作為含酚性羥基的樹脂（QP11），可使用與所述含羥基的樹脂（QN1）相同者。 As alkali-soluble resin (QP1), a phenolic hydroxyl group-containing resin (QP11), a carboxyl group-containing resin (QP12), a sulfonic acid group-containing resin (QP13), etc. are mentioned, for example. As the phenolic hydroxyl group-containing resin (QP11), the same thing as the above-mentioned hydroxyl group-containing resin (QN1) can be used.

作為含羧基的樹脂（QP12），若為具有羧基的聚合物，則並無特別限制，例如可藉由使含羧基的乙烯基單體（Ba）與視需要的含疏水基的乙烯基單體（Bb）進行乙烯基聚合來獲得。The carboxyl group-containing resin (QP12) is not particularly limited as long as it is a polymer having a carboxyl group. For example, a carboxyl group-containing vinyl monomer (Ba) can be mixed with an optional hydrophobic group-containing vinyl monomer. (Bb) is obtained by vinyl polymerization.

作為含羧基的乙烯基單體（Ba），例如可列舉：不飽和單羧酸[(甲基)丙烯酸、丁烯酸及肉桂酸等]、不飽和多元（二價～四價）羧酸[(無水)馬來酸、衣康酸、富馬酸及檸康酸等]、不飽和多元羧酸烷基（碳數1～10的烷基）酯[馬來酸單烷基酯、富馬酸單烷基酯及檸康酸單烷基酯等]、以及該些的鹽[鹼金屬鹽（鈉鹽及鉀鹽等）、鹼土金屬鹽（鈣鹽及鎂鹽等）、胺鹽及銨鹽等]。 該些中，就聚合性、及獲取的容易度的觀點而言，較佳為不飽和單羧酸，進而佳為(甲基)丙烯酸。 Examples of the carboxyl group-containing vinyl monomer (Ba) include unsaturated monocarboxylic acids [(meth)acrylic acid, crotonic acid, cinnamic acid, etc.], unsaturated polyvalent (divalent to tetravalent) carboxylic acids [ (anhydrous) maleic acid, itaconic acid, fumaric acid, citraconic acid, etc.], unsaturated polycarboxylic acid alkyl (alkyl with 1 to 10 carbon) esters [monoalkyl maleate, fumaric acid, etc.] Acid monoalkyl esters and citraconic acid monoalkyl esters, etc.], and their salts [alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), amine salts, and ammonium salts salt, etc.]. Among these, from the viewpoint of polymerizability and easiness of acquisition, unsaturated monocarboxylic acid is preferable, and (meth)acrylic acid is more preferable.

作為含疏水基的乙烯基單體（Bb），可列舉(甲基)丙烯酸酯（Bb1）、及芳香族烴單體（Bb2）等。As the hydrophobic group-containing vinyl monomer (Bb), a (meth)acrylate (Bb1), an aromatic hydrocarbon monomer (Bb2), and the like are exemplified.

作為(甲基)丙烯酸酯（Bb1），可列舉：烷基的碳數1～20的(甲基)丙烯酸烷基酯[(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸正己酯及(甲基)丙烯酸2-乙基己酯等]及含脂環基的(甲基)丙烯酸酯[(甲基)丙烯酸二環戊烷酯、(甲基)丙烯酸二環戊烯酯及(甲基)丙烯酸異冰片酯等]等。Examples of the (meth)acrylate (Bb1) include alkyl (meth)acrylate having 1 to 20 carbon atoms in the alkyl group [methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylate] base) n-propyl acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, etc.] and alicyclic (meth)acrylate [(meth)acrylate dicyclopentyl, (meth)acrylate dicyclopentenyl and (meth)acrylate isobornyl, etc.] and the like.

作為芳香族烴單體（Bb2），例如可列舉：具有苯乙烯骨架的烴單體[苯乙烯、α-甲基苯乙烯、乙烯基甲苯、2,4-二甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、苯基苯乙烯、環己基苯乙烯及苄基苯乙烯等]及乙烯基萘。Examples of the aromatic hydrocarbon monomer (Bb2) include hydrocarbon monomers having a styrene skeleton [styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylbenzene Ethylene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene and benzyl styrene, etc.] and vinyl naphthalene.

含羧基的樹脂（QP12）中的（Ba）/（Bb）的投入單體莫耳比通常為10～100/0～90，就顯影性的觀點而言，較佳為10～80/20～90，進而佳為25～85/15～75。The molar ratio of the input monomers (Ba)/(Bb) in the carboxyl group-containing resin (QP12) is usually 10 to 100/0 to 90, and preferably 10 to 80/20 to 10 from the viewpoint of developability 90, more preferably 25 to 85/15 to 75.

作為含磺酸基的樹脂（QP13），若為具有磺酸基的聚合物，則並無特別限制，例如可藉由使含磺酸基的乙烯基單體（Bc）與視需要的含疏水基的乙烯基單體（Bb）進行乙烯基聚合來獲得。 作為含疏水基的乙烯基單體（Bb），可使用與所述相同者。 The sulfonic acid group-containing resin (QP13) is not particularly limited as long as it is a polymer having a sulfonic acid group. It can be obtained by vinyl polymerization of the vinyl monomer (Bb) based on the base. As the hydrophobic group-containing vinyl monomer (Bb), the same ones as described above can be used.

作為含磺酸基的乙烯基單體（Bc），例如可列舉：乙烯基磺酸、(甲基)烯丙基磺酸、苯乙烯磺酸、α-甲基苯乙烯磺酸、2-(甲基)丙烯醯基醯胺-2-甲基丙磺酸及該些的鹽。作為鹽，可列舉：鹼金屬（鈉及鉀等）鹽、鹼土金屬（鈣及鎂等）鹽、一級胺鹽～三級胺鹽、銨鹽及四級銨鹽等。Examples of the sulfonic acid group-containing vinyl monomer (Bc) include vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, α-methylstyrenesulfonic acid, 2-( Meth)acryloamide-2-methylpropanesulfonic acid and salts of these. Examples of the salt include alkali metal (sodium, potassium, etc.) salts, alkaline earth metal (calcium, magnesium, etc.) salts, primary to tertiary amine salts, ammonium salts, and quaternary ammonium salts.

含磺酸基的樹脂（QP13）中的（Bc）/（Bb）的投入單體莫耳比通常為10～100/0～90，就顯影性的觀點而言，較佳為10～80/20～90，進而佳為25～85/15～75。The molar ratio of the charged monomers (Bc)/(Bb) in the sulfonic acid group-containing resin (QP13) is usually 10 to 100/0 to 90, preferably 10 to 80/ from the viewpoint of developability 20 to 90, more preferably 25 to 85/15 to 75.

鹼可溶性樹脂（QP1）的HLB值根據鹼可溶性樹脂（QP1）的樹脂骨架而較佳的範圍不同，但較佳為4～19，進而佳為5～18，特佳為6～17。 若HLB值為4以上，則於進行顯影時顯影性更良好，若為19以下，則硬化物的耐水性更良好。 The preferred range of the HLB value of the alkali-soluble resin (QP1) varies depending on the resin skeleton of the alkali-soluble resin (QP1). When the HLB value is 4 or more, the developability at the time of image development is more favorable, and when it is 19 or less, the water resistance of the cured product is more favorable.

再者，本發明中的HLB值是利用小田法而得的HLB值，且為親水性-疏水性平衡值，可根據有機化合物的有機性的值與無機性的值的比率來計算。 ＜HLB的評價方法＞ HLB≒10×無機性/有機性 另外，無機性的值及有機性的值於文獻「界面活性劑的合成及其應用」（槙書店發行、小田、寺村著）的501頁；或者「新-界面活性劑入門」（藤本武彥著、三洋化成工業股份有限公司發行）的198頁中有詳細記載。 The HLB value in the present invention is an HLB value obtained by the Oda method, is a hydrophilic-hydrophobic balance value, and can be calculated from the ratio of the organic value and the inorganic value of the organic compound. ＜Evaluation method of HLB＞ HLB≒10×inorganic/organic In addition, the values of inorganic and organic properties are listed on page 501 of the document "Synthesis and Application of Surfactants" (published by Maki Shoten, written by Oda and Teramura); or "New-Introduction to Surfactants" (Takehiko Fujimoto). Published by Sanyo Chemical Industry Co., Ltd.) on page 198.

作為保護基導入樹脂（QP2）中的酸解離性基，可列舉：取代甲基、1-取代乙基、1-分支烷基、矽烷基、甲鍺烷基（germyl）、烷氧基羰基、醯基及環式酸解離性基等。該些可單獨使用一種，亦可將兩種以上組合而使用。Examples of acid dissociable groups to be introduced into the resin (QP2) as protecting groups include substituted methyl groups, 1-substituted ethyl groups, 1-branched alkyl groups, silyl groups, germyl groups, alkoxycarbonyl groups, Acyl group and cyclic acid dissociable group, etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

作為取代甲基，例如可列舉：甲氧基甲基、甲硫基甲基、乙氧基甲基、乙硫基甲基、甲氧基乙氧基甲基、苄氧基甲基、苄硫基甲基、苯甲醯甲基、溴代苯甲醯甲基、甲氧基苯甲醯甲基、甲硫基苯甲醯甲基、α-甲基苯甲醯甲基、環丙基甲基、苄基、二苯基甲基、三苯基甲基、溴代苄基、硝基苄基、甲氧基苄基、甲硫基苄基、乙氧基苄基、乙硫基苄基、胡椒基、甲氧基羰基甲基、乙氧基羰基甲基、正丙氧基羰基甲基、異丙氧基羰基甲基、正丁氧基羰基甲基、第三丁氧基羰基甲基。Examples of the substituted methyl group include methoxymethyl, methylthiomethyl, ethoxymethyl, ethylthiomethyl, methoxyethoxymethyl, benzyloxymethyl, benzylthio Benzylmethyl, benzylmethyl, bromobenzylmethyl, methoxybenzylmethyl, methylthiobenzylmethyl, α-methylbenzylmethyl, cyclopropylmethyl , benzyl, diphenylmethyl, triphenylmethyl, bromobenzyl, nitrobenzyl, methoxybenzyl, methylthiobenzyl, ethoxybenzyl, ethylthiobenzyl , piperonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, tert-butoxycarbonylmethyl .

作為1-取代乙基，例如可列舉：1-甲氧基乙基、1-甲硫基乙基、1,1-二甲氧基乙基、1-乙氧基乙基、1-乙硫基乙基、1,1-二乙氧基乙基、1-乙氧基丙基、1-丙氧基乙基、1-環己氧基乙基、1-苯氧基乙基、1-苯硫基乙基、1,1-二苯氧基乙基、1-苄氧基乙基、1-苄硫基乙基、1-環丙基乙基、1-苯基乙基、1,1-二苯基乙基、1-甲氧基羰基乙基、1-乙氧基羰基乙基、1-正丙氧基羰基乙基、1-異丙氧基羰基乙基、1-正丁氧基羰基乙基、1-第三丁氧基羰基乙基。Examples of 1-substituted ethyl groups include 1-methoxyethyl, 1-methylthioethyl, 1,1-dimethoxyethyl, 1-ethoxyethyl, and 1-ethylthio ethyl, 1,1-diethoxyethyl, 1-ethoxypropyl, 1-propoxyethyl, 1-cyclohexyloxyethyl, 1-phenoxyethyl, 1- Phenylthioethyl, 1,1-diphenoxyethyl, 1-benzyloxyethyl, 1-benzylthioethyl, 1-cyclopropylethyl, 1-phenylethyl, 1, 1-diphenylethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-n-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-n-butyl Oxycarbonylethyl, 1-tert-butoxycarbonylethyl.

作為1-分支烷基，例如可列舉：異丙基、第二丁基、第三丁基、1,1-二甲基丙基、1-甲基丁基、1,1-二甲基丁基。Examples of the 1-branched alkyl group include isopropyl, 2-butyl, 3-butyl, 1,1-dimethylpropyl, 1-methylbutyl, and 1,1-dimethylbutyl base.

作為矽烷基，例如可列舉：三甲基矽烷基、乙基二甲基矽烷基、二乙基甲基矽烷基、三乙基矽烷基、異丙基二甲基矽烷基、二異丙基甲基矽烷基、三異丙基矽烷基、第三丁基二甲基矽烷基、二-第三丁基甲基矽烷基、三-第三丁基矽烷基、二甲基苯基矽烷基、甲基二苯基矽烷基、三苯基矽烷基等三碳基（carbyl）矽烷基。As a silyl group, a trimethylsilyl group, an ethyldimethylsilyl group, a diethylmethylsilyl group, a triethylsilyl group, an isopropyldimethylsilyl group, a diisopropylmethylsilyl group are mentioned, for example. Silyl, triisopropylsilyl, tert-butyldimethylsilyl, di-tert-butylmethylsilyl, tri-tert-butylsilyl, dimethylphenylsilyl, methylbis Tri-carbyl silyl groups such as phenylsilyl, triphenylsilyl, etc.

作為甲鍺烷基，例如可列舉：三甲基甲鍺烷基、乙基二甲基甲鍺烷基、甲基二乙基甲鍺烷基、三乙基甲鍺烷基、異丙基二甲基甲鍺烷基、甲基二異丙基甲鍺烷基、三異丙基甲鍺烷基、第三丁基二甲基甲鍺烷基、二-第三丁基甲基甲鍺烷基、三-第三丁基甲鍺烷基、二甲基苯基甲鍺烷基、甲基二苯基甲鍺烷基、三苯基甲鍺烷基等三碳基甲鍺烷基。As the germanyl group, for example, trimethylgermanyl, ethyldimethylgermanyl, methyldiethylgermanyl, triethylgermanyl, isopropyldimethylgermanyl, etc. may be mentioned. Methylgermanyl, methyldiisopropylgermanyl, triisopropylgermanyl, tert-butyldimethylgermyl, di-tert-butylmethylgermanyl, Tri-carbonylgermanyl such as tri-tert-butylgermanyl, dimethylphenylgermanyl, methyldiphenylgermanyl, triphenylgermanyl and the like.

作為烷氧基羰基，例如可列舉：甲氧基羰基、乙氧基羰基、異丙氧基羰基、第三丁氧基羰基。As an alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a tertiary butoxycarbonyl group are mentioned, for example.

作為醯基，例如可列舉：乙醯基、丙醯基、丁醯基、庚醯基、己醯基、戊醯基、三甲基乙醯基、異戊醯基、月桂醯基、肉豆蔻醯基、棕櫚醯基、硬脂醯基、乙二醯基、丙二醯基、琥珀醯基、戊二醯基、己二醯基、庚二醯基、辛二醯基、壬二醯基、癸二醯基、丙烯醯基、丙炔醯基、甲基丙烯醯基、丁烯醯基、油醯基、馬來醯基、富馬醯基、中康醯基、樟腦二醯基、苯甲醯基、鄰苯二甲醯基、間苯二甲醯基、對苯二甲醯基、萘甲醯基、甲苯甲醯基、氫阿托醯基、阿托醯基、肉桂醯基、呋喃甲醯基、噻吩甲醯基、菸醯基、異菸醯基、對甲苯磺醯基、甲磺醯基。Examples of the acyl group include an acetyl group, a propionyl group, a butyl group, a heptyl group, a hexyl group, a pentamyl group, a trimethyl acetyl group, an isopentyl group, a lauryl group, and a myristyl group. , palmityl, stearyl, ethylene glycol, malonyl, succinyl, glutaryl, adipyl, heptadiyl, caprylyl, azela, decyl Dialyl, acrylyl, propynyl, methacryloyl, butenyl, oleoyl, maleic, fumaric, mesacanoyl, camphordiyl, benzyl, ortho Phthaloyl, isophthaloyl, terephthaloyl, naphthyl, tolyl, hydroatoryl, atoryl, cinnamyl, furocarbyl, Thienocarbyl, nicotinyl, isonicotinyl, p-toluenesulfonyl, methanesulfonyl.

作為環式酸解離性基，例如可列舉：環丙基、環戊基、環己基、環己烯基、4-甲氧基環己基、四氫吡喃基、四氫呋喃基、四氫噻喃基（thiopyranyl）、四氫硫代呋喃基（thiofuranyl）、3-溴代四氫吡喃基、4-甲氧基四氫吡喃基、4-甲氧基四氫噻喃基、3-四氫噻吩-1,1-二氧化物基。Examples of cyclic acid dissociable groups include cyclopropyl, cyclopentyl, cyclohexyl, cyclohexenyl, 4-methoxycyclohexyl, tetrahydropyranyl, tetrahydrofuranyl, and tetrahydrothiopyranyl (thiopyranyl), tetrahydrothiofuranyl (thiofuranyl), 3-bromotetrahydropyranyl, 4-methoxytetrahydropyranyl, 4-methoxytetrahydrothiopyranyl, 3-tetrahydro Thiophene-1,1-dioxide group.

於該些酸解離性基中，較佳為第三丁基、苄基、1-甲氧基乙基、1-乙氧基乙基、三甲基矽烷基、第三丁氧基羰基、第三丁氧基羰基甲基、四氫吡喃基、四氫呋喃基、四氫噻喃基及四氫硫代呋喃基。Among these acid dissociable groups, tert-butyl, benzyl, 1-methoxyethyl, 1-ethoxyethyl, trimethylsilyl, tert-butoxycarbonyl, Tributoxycarbonylmethyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl and tetrahydrothiofuranyl.

保護基導入樹脂（QP2）中的酸解離性基的導入率{相對於保護基導入樹脂（QP2）中的未經保護的酸性官能基與酸解離性基的合計數而言的酸解離性基的數量的比例}無法根據酸解離性基或導入有該基的鹼可溶性樹脂的種類統一規定，但較佳為10%～100%，進而佳為15%～100%。Rate of introduction of acid dissociable groups in protective group-introduced resin (QP2) {acid dissociable groups relative to the total number of unprotected acidic functional groups and acid dissociable groups in protective group-introduced resin (QP2) The ratio of the number of α} cannot be uniformly defined depending on the acid dissociable group or the type of the alkali-soluble resin into which the group is introduced, but is preferably 10% to 100%, more preferably 15% to 100%.

保護基導入樹脂（QP2）的利用凝膠滲透層析法（GPC）而測定的聚苯乙烯換算重量平均分子量（以下，稱為「Mw」）較佳為1,000～150,000，進而佳為3,000～100,000。The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the protecting group-introducing resin (QP2) measured by gel permeation chromatography (GPC) is preferably 1,000 to 150,000, more preferably 3,000 to 100,000 .

另外，保護基導入樹脂（QP2）的Mw與利用凝膠滲透層析法（GPC）而測定的聚苯乙烯換算數量平均分子量（以下，稱為「Mn」）之比（Mw/Mn）通常為1～10，較佳為1～5。In addition, the ratio (Mw/Mn) of the Mw of the protecting group-introducing resin (QP2) to the number average molecular weight in terms of polystyrene (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC) is usually 1-10, preferably 1-5.

基於光微影用樹脂組成物（Q）的固體成分的重量的光酸產生劑（P）的含量較佳為0.001重量%～20重量%，進而佳為0.01重量%～15重量%，特佳為0.05重量%～7重量%。 若為0.001重量%以上，則可更良好地發揮相對於紫外線的感度，若為20重量%以下，則可更良好地發揮不溶於鹼性顯影液的部分的物性。 The content of the photoacid generator (P) based on the weight of the solid content of the resin composition for photolithography (Q) is preferably from 0.001% by weight to 20% by weight, more preferably from 0.01% by weight to 15% by weight, particularly preferably It is 0.05 weight% - 7 weight%. When it is 0.001% by weight or more, the sensitivity to ultraviolet rays can be more favorably exhibited, and when it is 20% by weight or less, the physical properties of the portion insoluble in the alkaline developer can be more favorably exhibited.

使用本發明的光微影用樹脂組成物（Q）的抗蝕劑例如可藉由如下方式來形成：使用旋塗、簾幕式塗佈、輥塗、噴霧塗佈、網版印刷等公知的方法，將溶解（於包含無機微粒子的情況下為溶解與分散）於規定的有機溶劑中的樹脂溶液塗佈於基板上後，利用加熱或熱風吹附來使溶劑乾燥。The resist using the resin composition (Q) for photolithography of the present invention can be formed, for example, by using known methods such as spin coating, curtain coating, roll coating, spray coating, and screen printing. In the method, after applying a resin solution dissolved (dissolving and dispersing in the case of including inorganic fine particles) in a predetermined organic solvent on a substrate, the solvent is dried by heating or blowing with hot air.

作為使光微影用樹脂組成物（Q）溶解的有機溶劑，若為可溶解樹脂組成物，並可將樹脂溶液調整為可適用於旋塗等的物性（黏度等）的有機溶劑，則並無特別限定。例如可使用N-甲基吡咯啶酮、N,N-二甲基甲醯胺、二甲基亞碸、甲苯、乙醇、環己酮、甲醇、甲基乙基酮、乙酸乙酯、乙酸丁酯、乳酸乙酯、丙二醇單甲醚乙酸酯、丙酮及二甲苯等公知的溶媒。 該些溶劑中，就乾燥溫度等觀點而言，較佳為沸點為200℃以下者（甲苯、乙醇、環己酮、甲醇、甲基乙基酮、乙酸乙酯、乙酸丁酯、乳酸乙酯、丙二醇單甲醚乙酸酯、丙酮及二甲苯），亦可單獨或將兩種以上組合而使用。 於使用有機溶劑的情況下，溶劑的調配量並無特別限定，但基於光微影用樹脂組成物（Q）的固體成分的重量，通常較佳為30重量%～1,000重量%，進而佳為40重量%～900重量%，特佳為50重量%～800重量%。 As the organic solvent for dissolving the resin composition (Q) for photolithography, if the resin composition can be dissolved and the resin solution can be adjusted to have physical properties (viscosity, etc.) suitable for spin coating etc. There is no particular limitation. For example, N-methylpyrrolidone, N,N-dimethylformamide, dimethylsulfoxide, toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate can be used known solvents such as ester, ethyl lactate, propylene glycol monomethyl ether acetate, acetone, and xylene. Among these solvents, from the viewpoint of drying temperature and the like, those having a boiling point of 200° C. or lower (toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate) are preferred. , propylene glycol monomethyl ether acetate, acetone and xylene), can also be used alone or in combination of two or more. When an organic solvent is used, the compounding amount of the solvent is not particularly limited, but based on the weight of the solid content of the resin composition for photolithography (Q), it is usually preferably 30% by weight to 1,000% by weight, and more preferably 40% by weight to 900% by weight, particularly preferably 50% by weight to 800% by weight.

塗佈後的樹脂溶液的乾燥條件根據所使用的溶劑而不同，但較佳為於50℃～200℃且2分鐘～30分鐘的範圍內實施，藉由乾燥後的光微影用樹脂組成物（Q）的殘留溶劑量（重量%）等適宜決定。The drying conditions of the resin solution after coating vary depending on the solvent used, but it is preferably carried out in the range of 50° C. to 200° C. for 2 minutes to 30 minutes. The residual solvent amount (% by weight) of (Q) is appropriately determined.

於基板上形成抗蝕劑後，進行配線圖案形狀的光照射。之後，進行曝光後加熱（PEB）後進行鹼顯影，從而形成配線圖案。After the resist is formed on the substrate, light irradiation in the shape of the wiring pattern is performed. Then, after performing post-exposure heating (PEB), alkali development is performed to form a wiring pattern.

作為進行光照射的方法，可列舉介隔具有配線圖案的光罩，利用光化射線進行抗蝕劑的曝光的方法。作為用於光照射的光化射線，若可使本發明的光微影用樹脂組成物（Q）中的該光酸產生劑（P）分解，則並無特別限制。 作為光化射線，存在極紫外線（EUV）、電子束（EB）、低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、氙氣燈、金屬鹵素燈、電子束照射裝置、X射線照射裝置、雷射（氬雷射、色素雷射、氮雷射、LED、氦鎘雷射等）等。該些中，就發揮本發明的效果的方面而言，較佳為極紫外線（EUV）及電子束（EB）。 As a method of performing light irradiation, a method of exposing a resist with actinic rays through a photomask having a wiring pattern is exemplified. The actinic ray used for light irradiation is not particularly limited as long as the photoacid generator (P) in the resin composition (Q) for photolithography of the present invention can be decomposed. Examples of actinic rays include extreme ultraviolet (EUV), electron beam (EB), low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, metal halide lamps, electron beam irradiation devices, X-ray irradiation devices, lightning Laser (argon laser, pigment laser, nitrogen laser, LED, helium cadmium laser, etc.), etc. Among these, extreme ultraviolet rays (EUV) and electron beams (EB) are preferable in terms of exhibiting the effects of the present invention.

作為曝光後加熱（PEB）的溫度，通常為40℃～200℃，較佳為50℃～190℃，進而佳為60℃～180℃。未滿40℃時，無法充分地進行脫保護反應、或交聯反應，因此紫外線照射部與紫外線未照射部的溶解性的差不足而無法形成圖案，若高於200℃，則存在生產性下降的問題。 作為加熱時間，通常為0.5分鐘～120分鐘，未滿0.5分鐘時，難以控制時間與溫度，若大於120分鐘，則存在生產性下降的問題。 The temperature of post-exposure heating (PEB) is usually 40°C to 200°C, preferably 50°C to 190°C, and more preferably 60°C to 180°C. When the temperature is lower than 40°C, the deprotection reaction or the crosslinking reaction cannot sufficiently proceed, and the difference in solubility between the ultraviolet-irradiated portion and the ultraviolet-unirradiated portion is insufficient to form a pattern. When the temperature is higher than 200°C, the productivity decreases. The problem. The heating time is usually 0.5 minutes to 120 minutes, and when it is less than 0.5 minutes, it is difficult to control the time and temperature, and when it exceeds 120 minutes, there is a problem that the productivity decreases.

作為進行鹼顯影的方法，可列舉使用鹼性顯影液以配線圖案形狀進行溶解去除的方法。作為鹼性顯影液，若為光微影用樹脂組成物（Q）的紫外線照射部與紫外線未照射部的溶解性形成差的條件，則並無特別限制。 作為鹼性顯影液，存在氫氧化鈉水溶液、氫氧化鉀水溶液、碳酸氫鈉及四甲基銨鹽水溶液等。 該些鹼性顯影液亦可加入水溶性的有機溶劑。作為水溶性的有機溶劑，存在甲醇、乙醇、異丙醇、四氫呋喃、N-甲基吡咯啶酮等。 As a method of performing alkali development, the method of dissolving and removing in the shape of a wiring pattern using an alkali developing solution is mentioned. The alkaline developer is not particularly limited as long as it is a condition that the solubility of the ultraviolet-irradiated part and the ultraviolet-unirradiated part of the resin composition for photolithography (Q) is poor. As an alkaline developing solution, there exist a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, sodium hydrogencarbonate, a tetramethylammonium salt aqueous solution, etc.. Water-soluble organic solvents can also be added to these alkaline developing solutions. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, tetrahydrofuran, N-methylpyrrolidone, and the like.

作為顯影方法，存在使用鹼性顯影液的浸漬方式、噴淋方式、及噴霧方式，但較佳為噴霧方式。 關於顯影液的溫度，較佳為於25℃～40℃下使用。顯影時間是根據抗蝕劑的厚度來適宜決定。 [實施例] As a developing method, there exist a dipping method using an alkaline developer, a shower method, and a spray method, but the spray method is preferable. The temperature of the developer is preferably used at 25°C to 40°C. The development time is appropriately determined according to the thickness of the resist. [Example]

以下，藉由實施例及比較例來對本發明進一步進行說明，但本發明並不限定於該些。以下，只要未特別規定，則%表示重量%，份表示重量份。Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited to these. Hereinafter, unless otherwise specified, % refers to % by weight, and parts refers to parts by weight.

＜製造例1＞ ＜(2-甲基苯基)苯基硒化物的合成＞ 使2-甲基苯基溴化物1.0份、苯基硒醇1.1份、氫氧化鉀0.5份分散於二甲基乙醯胺10份中，於120℃下攪拌5小時。繼而冷卻至室溫後，加入水30份與二氯甲烷30份，並回收有機層後，減壓去除溶劑，藉此獲得粗生成物。利用環己烷20份對該粗精製物進行再結晶，藉此獲得(2-甲基苯基)苯基硒化物0.6份。 <Production Example 1> <Synthesis of (2-methylphenyl)phenylselenide> 1.0 part of 2-methylphenyl bromide, 1.1 part of phenylselenol, and 0.5 part of potassium hydroxide were dispersed in 10 parts of dimethylacetamide, and the mixture was stirred at 120° C. for 5 hours. Then, after cooling to room temperature, 30 parts of water and 30 parts of dichloromethane were added, and after collecting the organic layer, the solvent was removed under reduced pressure to obtain a crude product. This crude product was recrystallized from 20 parts of cyclohexane to obtain 0.6 part of (2-methylphenyl)phenylselenide.

＜製造例2＞ ＜(3,5-二甲基苯基)苯基硒化物的合成＞ 將2-甲基苯基溴化物1.0份變更為3,5-二甲基苯基溴化物1.0份，除此以外利用與製造例1相同的方法獲得(3,5-二甲基苯基)苯基硒化物0.5份。 <Production Example 2> <Synthesis of (3,5-dimethylphenyl)phenylselenide> (3,5-dimethylphenyl) 0.5 part of phenylselenide.

＜製造例3＞ ＜(4-甲基苯基)苯基硒化物的合成＞ 將2-甲基苯基溴化物1.0份變更為4-甲基苯基溴化物1.0份，除此以外利用與製造例1相同的方法獲得(4-甲基苯基)苯基硒化物0.6份。 <Production Example 3> <Synthesis of (4-methylphenyl)phenylselenide> Except having changed 1.0 part of 2-methylphenyl bromide to 1.0 part of 4-methylphenyl bromide, 0.6 part of (4-methylphenyl)phenylselenide was obtained by the same method as Production Example 1 .

＜製造例4＞ ＜(3-三氟甲基苯基)苯基硒化物的合成＞ 將2-甲基苯基溴化物1.0份變更為3-三氟甲基苯基溴化物1.2份，除此以外利用與製造例1相同的方法獲得(4-甲基苯基)苯基硒化物0.5份。 <Production Example 4> <Synthesis of (3-trifluoromethylphenyl)phenylselenide> (4-methylphenyl)phenylselenide was obtained in the same manner as in Production Example 1, except that 1.0 parts of 2-methylphenyl bromide was changed to 1.2 parts of 3-trifluoromethylphenyl bromide 0.5 servings.

＜製造例5＞ ＜(3-三氟甲基苯基)苯基硒亞碸的合成＞ 使製造例4中獲得的(3-三氟甲基苯基)苯基硒化物1.0份溶解於乙腈18.0份中，加入次氯酸鈉五水合物0.8份、四丁基銨硫酸氫鹽0.1份，於室溫下攪拌2小時。將反應液投入至水中，過濾分離析出物，從而獲得白色固體。將該白色固體水洗並乾燥，藉此獲得(3-三氟甲基苯基)苯基硒亞碸0.8份。 <Production Example 5> <Synthesis of (3-trifluoromethylphenyl)phenylselenosene> 1.0 part of (3-trifluoromethylphenyl)phenylselenide obtained in Production Example 4 was dissolved in 18.0 parts of acetonitrile, 0.8 part of sodium hypochlorite pentahydrate and 0.1 part of tetrabutylammonium hydrogensulfate were added to the room Stir at warm temperature for 2 hours. The reaction solution was poured into water, and the precipitate was separated by filtration to obtain a white solid. This white solid was washed with water and dried to obtain 0.8 part of (3-trifluoromethylphenyl)phenylselenide.

＜實施例1＞ ＜三苯基硒鎓三氟甲磺酸鹽（P-1-1）的合成＞ 使二苯基硒化物1.0份分散於氯苯20份中，加入二苯基錪三氟甲磺酸鹽1.3份，於120℃下攪拌17小時。將反應液投入至水20份中，冷卻後加入甲醇20份，並萃取回收水層。繼而於水層中加入二氯甲烷10份並萃取回收有機層後，將溶劑減壓乾燥，藉此獲得三苯基硒鎓三氟甲磺酸鹽（P-1-1）0.5份。 <Example 1> <Synthesis of triphenylselenonium triflate (P-1-1)> 1.0 parts of diphenylselenide was dispersed in 20 parts of chlorobenzene, 1.3 parts of diphenyl iodonium triflate was added, and the mixture was stirred at 120° C. for 17 hours. The reaction liquid was put into 20 parts of water, and after cooling, 20 parts of methanol was added, and the aqueous layer was extracted and recovered. Then, after adding 10 parts of dichloromethane to the aqueous layer, extracting and recovering the organic layer, the solvent was dried under reduced pressure to obtain 0.5 part of triphenylselenonium trifluoromethanesulfonate (P-1-1).

＜實施例2＞ ＜(4-溴苯基)二苯基硒鎓三氟甲磺酸鹽（P-1-2）的合成＞ 將二苯基錪三氟甲磺酸鹽1.3份變更為雙(4-溴苯基)錪三氟甲磺酸鹽1.7份，將反應時間設為48小時，除此以外利用與實施例1相同的方法獲得(4-溴苯基)二苯基硒鎓三氟甲磺酸鹽（P-1-2）0.4份。 <Example 2> <Synthesis of (4-bromophenyl)diphenylselenonium triflate (P-1-2)> The same procedure as in Example 1 was used except that 1.3 parts of diphenyl iodonium triflate was changed to 1.7 parts of bis(4-bromophenyl) iodonium triflate, and the reaction time was set to 48 hours. 0.4 part of (4-bromophenyl)diphenylselenonium triflate (P-1-2) was obtained by the method of .

＜實施例3＞ ＜(4-第三丁基苯基)二苯基硒鎓三氟甲磺酸鹽（P-1-3）的合成＞ 將二苯基錪三氟甲磺酸鹽1.3份變更為雙(4-第三丁基苯基)錪三氟甲磺酸鹽1.5份，除此以外利用與實施例1相同的方法獲得(4-第三丁基苯基)二苯基硒鎓三氟甲磺酸鹽（P-1-3）0.5份。 <Example 3> <Synthesis of (4-tert-butylphenyl)diphenylselenonium triflate (P-1-3)> Except having changed 1.3 parts of diphenyl iodonium triflate to 1.5 parts of bis(4-tert-butylphenyl) iodonium triflate - 0.5 part of tert-butylphenyl)diphenylselenonium triflate (P-1-3).

＜實施例4＞ ＜(4-氟苯基)二苯基硒鎓三氟甲磺酸鹽（P-1-4）的合成＞ 將二苯基錪三氟甲磺酸鹽1.3份變更為雙(4-氟苯基)錪三氟甲磺酸鹽1.4份，將反應時間設為48小時，將反應溶媒設為N,N-二甲基乙醯胺，除此以外利用與實施例1相同的方法獲得(4-氟苯基)二苯基硒鎓三氟甲磺酸鹽（P-1-4）0.3份。 <Example 4> <Synthesis of (4-fluorophenyl)diphenylselenonium triflate (P-1-4)> 1.3 parts of diphenyl iodonium triflate was changed to 1.4 parts of bis(4-fluorophenyl) iodonium triflate, the reaction time was 48 hours, and the reaction solvent was N,N- Except for dimethylacetamide, 0.3 part of (4-fluorophenyl)diphenylselenonium triflate (P-1-4) was obtained in the same manner as in Example 1.

＜實施例5＞ ＜(4-甲氧基苯基)二苯基硒鎓三氟甲磺酸鹽（P-1-5）的合成＞ 將二苯基錪三氟甲磺酸鹽1.3份變更為雙(4-甲氧基苯基)錪三氟甲磺酸鹽1.5份，除此以外利用與實施例1相同的方法獲得(4-甲氧基苯基)二苯基硒鎓三氟甲磺酸鹽（P-1-5）0.5份。 <Example 5> <Synthesis of (4-methoxyphenyl)diphenylselenonium triflate (P-1-5)> Except having changed 1.3 parts of diphenyl iodonium triflate to 1.5 parts of bis(4-methoxyphenyl) iodonium triflate 0.5 part of methoxyphenyl) diphenylselenonium triflate (P-1-5).

＜實施例6＞ ＜(3-三氟甲基苯基)二苯基硒鎓三氟甲磺酸鹽（P-1-6）的合成＞ 將製造例5中獲得的(3-三氟甲基苯基)苯基硒亞碸1.0份溶解於二氯甲烷20份與苯20份的混合溶媒中，於0℃以下滴加三氟甲磺酸酐1.2份。 將反應液投入至水50份中並淬滅，加入甲醇30份進行萃取。 進而利用水30份與甲醇20份萃取三次。利用甲苯20份將萃取的水、甲醇層清洗兩次，利用二氯甲烷20份萃取三次。 將二氯甲烷層投入至TBME（第三丁基甲醚）200份中，對析出的黏稠物進行減壓乾燥，藉此獲得(3-三氟甲基苯基)二苯基硒鎓三氟甲磺酸鹽（P-1-6）0.2份。 <Example 6> <Synthesis of (3-trifluoromethylphenyl)diphenylselenonium triflate (P-1-6)> 1.0 part of (3-trifluoromethylphenyl)phenylselenide obtained in Production Example 5 was dissolved in a mixed solvent of 20 parts of dichloromethane and 20 parts of benzene, and trifluoromethanesulfonic acid was added dropwise at 0°C or lower. 1.2 parts of acid anhydride. The reaction liquid was poured into 50 parts of water and quenched, and 30 parts of methanol was added for extraction. Furthermore, it extracted three times with 30 parts of water and 20 parts of methanol. The extracted water and methanol layers were washed twice with 20 parts of toluene, and extracted three times with 20 parts of dichloromethane. The dichloromethane layer was put into 200 parts of TBME (tertiary butyl methyl ether), and the precipitated viscous material was dried under reduced pressure to obtain (3-trifluoromethylphenyl)diphenylselenonium trifluoromethanesulfonate. Acid (P-1-6) 0.2 part.

＜實施例7＞ ＜(2-甲基苯基)二苯基硒鎓全氟丁磺酸鹽（P-2-1）的合成＞ 將二苯基硒化物1.0份變更為製造例1中獲得的(2-甲基苯基)苯基硒化物1.0份，除此以外利用與實施例1相同的方法獲得生成物0.5份。 將所獲得的(2-甲基苯基)二苯基硒鎓三氟甲磺酸鹽0.5份溶解於二氯甲烷10份中，加入水10份與九氟丁磺酸鉀0.4份並攪拌30分鐘。去除水層，加入水10份進行三次水洗。對二氯甲烷層進行減壓乾燥，藉此獲得(2-甲基苯基)二苯基硒鎓全氟丁磺酸鹽（P-2-1）0.6份。 <Example 7> <Synthesis of (2-methylphenyl)diphenylselenonium perfluorobutanesulfonate (P-2-1)> Except having changed 1.0 part of diphenyl selenide to 1.0 part of (2-methylphenyl) phenyl selenide obtained in Production Example 1, it carried out similarly to Example 1, and obtained 0.5 part of products. 0.5 part of the obtained (2-methylphenyl)diphenylselenonium triflate was dissolved in 10 parts of methylene chloride, 10 parts of water and 0.4 part of potassium nonafluorobutanesulfonate were added and stirred for 30 parts minute. The water layer was removed, and 10 parts of water was added to perform three washings. The dichloromethane layer was dried under reduced pressure to obtain 0.6 part of (2-methylphenyl)diphenylselenonium perfluorobutanesulfonate (P-2-1).

＜實施例8＞ ＜(3,5-甲基苯基)二苯基硒鎓全氟丁磺酸鹽（P-2-2）的合成＞ 將二苯基硒化物1.0份變更為製造例2中獲得的(3,5-甲基苯基)苯基硒化物1.0份，除此以外利用與實施例1相同的方法獲得(3,5-甲基苯基)二苯基硒鎓三氟甲磺酸鹽0.6份。 將所獲得的(3,5-甲基苯基)二苯基硒鎓三氟甲磺酸鹽0.6份溶解於二氯甲烷12份中，加入水10份與九氟丁磺酸鉀0.5份並攪拌30分鐘。去除水層，加入水10份進行三次水洗。對二氯甲烷層進行減壓乾燥，藉此獲得(3,5-甲基苯基)二苯基硒鎓全氟丁磺酸鹽（P-2-2）0.7份。 <Example 8> <Synthesis of (3,5-methylphenyl)diphenylselenonium perfluorobutanesulfonate (P-2-2)> Except having changed 1.0 parts of diphenylselenide to 1.0 part of (3,5-methylphenyl)phenylselenide obtained in Production Example 2, (3,5-phenylselenide) was obtained by the same method as in Example 1. 0.6 part of methylphenyl) diphenylselenonium triflate. 0.6 part of the obtained (3,5-methylphenyl)diphenylselenonium trifluoromethanesulfonate was dissolved in 12 parts of methylene chloride, 10 parts of water and 0.5 part of potassium nonafluorobutanesulfonate were added to make the solution. Stir for 30 minutes. The water layer was removed, and 10 parts of water was added to perform three washings. The dichloromethane layer was dried under reduced pressure to obtain 0.7 part of (3,5-methylphenyl)diphenylselenonium perfluorobutanesulfonate (P-2-2).

＜實施例9＞ ＜(4-第三丁基苯基)(4-甲基苯基)苯基硒鎓全氟丁磺酸鹽（P-2-3）的合成＞ 將二苯基硒化物1.0份變更為製造例3中獲得的(4-甲基苯基)苯基硒化物1.0份，並將二苯基錪三氟甲磺酸鹽1.3份變更為雙(4-第三丁基苯基)錪三氟甲磺酸鹽1.5份，除此以外利用與實施例1相同的方法獲得(4-第三丁基苯基)(4-甲基苯基)苯基硒鎓三氟甲磺酸鹽0.5份。 將所獲得的(4-第三丁基苯基)(4-甲基苯基)苯基硒鎓三氟甲磺酸鹽0.5份溶解於二氯甲烷12份中，加入水10份與九氟丁磺酸鉀0.4份並攪拌30分鐘。去除水層，加入水10份進行三次水洗。對二氯甲烷層進行減壓乾燥，藉此獲得(4-第三丁基苯基)(4-甲基苯基)苯基硒鎓全氟丁磺酸鹽（P-2-3）0.6份。 <Example 9> <Synthesis of (4-tert-butylphenyl)(4-methylphenyl)phenylselenonium perfluorobutanesulfonate (P-2-3)> 1.0 part of diphenyl selenide was changed to 1.0 part of (4-methylphenyl)phenyl selenide obtained in Production Example 3, and 1.3 parts of diphenyl iodonium triflate was changed to bis(4 (4-tert-butylphenyl)(4-methylphenyl)phenyl was obtained in the same manner as in Example 1 except for 1.5 parts of -tert-butylphenyl) iodotrifluoromethanesulfonate 0.5 part of selenonium triflate. 0.5 part of the obtained (4-tert-butylphenyl)(4-methylphenyl)phenylselenonium triflate was dissolved in 12 parts of methylene chloride, and 10 parts of water and nonafluoro were added. 0.4 part of potassium butanesulfonate and stirred for 30 minutes. The water layer was removed, and 10 parts of water was added to perform three washings. The dichloromethane layer was dried under reduced pressure to obtain 0.6 part of (4-tert-butylphenyl)(4-methylphenyl)phenylselenonium perfluorobutanesulfonate (P-2-3) .

＜實施例10＞ ＜三苯基硒鎓四-五氟苯基硼酸鹽（P-2-4）的合成＞ 將實施例1中獲得的三苯基硒鎓三氟甲磺酸鹽（P-1-1）1.0份溶解於二氯甲烷20份中，加入四-五氟苯基硼酸鋰-***複合物（TCI（股）製造）2.2份與水10份並攪拌1小時。去除水層後，加入水10份與甲醇5份並進行三次水洗。對二氯甲烷層進行減壓濃縮，加入甲醇20份並再次濃縮。藉由將濃縮後的甲醇層投入至水50份中而獲得沈澱物，對其進行過濾、減壓乾燥，藉此獲得三苯基硒鎓四-五氟苯基硼酸鹽（P-2-4）1.8份。 <Example 10> <Synthesis of triphenylselenonium tetra-pentafluorophenyl borate (P-2-4)> 1.0 part of triphenylselenonium trifluoromethanesulfonate (P-1-1) obtained in Example 1 was dissolved in 20 parts of dichloromethane, and tetrakis-pentafluorophenyl borate lithium-diethyl ether complex ( 2.2 parts of TCI (stock) and 10 parts of water were stirred for 1 hour. After removing the water layer, 10 parts of water and 5 parts of methanol were added and washed with water three times. The dichloromethane layer was concentrated under reduced pressure, 20 parts of methanol were added, and the mixture was concentrated again. The concentrated methanol layer was poured into 50 parts of water to obtain a precipitate, which was filtered and dried under reduced pressure to obtain triphenylselenonium tetra-pentafluorophenyl borate (P-2-4 ) 1.8 servings.

＜實施例11＞ ＜三苯基硒鎓三(三氟甲磺醯基)甲烷化物（P-2-5）的合成＞ 將實施例1中獲得的三苯基硒鎓三氟甲磺酸鹽（P-1-1）1.0份溶解於二氯甲烷20份中，加入三(三氟甲磺醯基)甲烷化物鉀（TCI（股）製造）1.1份與水20份並攪拌1小時。去除水層，加入水20份並進行水洗。對二氯甲烷層進行減壓濃縮，投入至TBME 150份中，藉此獲得沈澱物，對其進行過濾、減壓乾燥，藉此獲得三苯基硒鎓三(三氟甲磺醯基)甲烷化物（P-2-5）1.3份。 <Example 11> <Synthesis of triphenylselenonium tris(trifluoromethanesulfonyl)methanide (P-2-5)> 1.0 part of triphenylselenonium trifluoromethanesulfonate (P-1-1) obtained in Example 1 was dissolved in 20 parts of methylene chloride, and potassium tris(trifluoromethanesulfonyl)methanide (P-1-1) was added. TCI (stock) 1.1 parts and 20 parts of water were stirred for 1 hour. The water layer was removed, and 20 parts of water was added and washed with water. The dichloromethane layer was concentrated under reduced pressure and put into 150 parts of TBME to obtain a precipitate, which was filtered and dried under reduced pressure to obtain triphenylselenonium tris(trifluoromethanesulfonyl)methane Compound (P-2-5) 1.3 parts.

以下記載實施例1～實施例11中獲得的光酸產生劑（P-1-1）～光酸產生劑（P-2-5）的結構。The structures of the photoacid generator (P-1-1) to the photoacid generator (P-2-5) obtained in Examples 1 to 11 are described below.

[化5]

[hua 5]

＜比較例1＞ ＜離子系光酸產生劑（P'-1）的合成＞ 直接使用三苯基鋶三氟甲磺酸鹽（富士膠片和光化學（股）製造）。 <Comparative Example 1> <Synthesis of ionic photoacid generator (P'-1)> Triphenyl perionium triflate (manufactured by Fujifilm and Photochemical Co., Ltd.) was used directly.

＜比較例2＞ ＜離子系光酸產生劑（P'-2）的合成＞ 依照專利編號4934306的實施例1，獲得(4-苯硫基苯基)二苯基鋶三氟甲磺酸鹽（P'-2）。 <Comparative Example 2> <Synthesis of ionic photoacid generator (P'-2)> According to Example 1 of Patent No. 4934306, (4-phenylthiophenyl)diphenylperylium triflate (P'-2) was obtained.

[化6]

[hua 6]

＜比較例3＞ ＜離子系光酸產生劑（P'-3）的合成＞ 依照日本專利特開2014-234348的實施例6，獲得(3-三氟甲基苯基)二苯基鋶三氟甲磺酸鹽（P'-3）。 <Comparative Example 3> <Synthesis of ionic photoacid generator (P'-3)> According to Example 6 of Japanese Patent Laid-Open No. 2014-234348, (3-trifluoromethylphenyl)diphenylperylium trifluoromethanesulfonate (P'-3) was obtained.

[化7]

[hua 7]

＜比較例4＞ 利用與日本專利特開2014-234348的實施例1相同的方法，使4-氯溴苯與二苯基亞碸反應並精製，從而獲得4-氯苯基二苯基鋶三氟甲磺酸鹽。 將所獲得的4-氯苯基二苯基鋶三氟甲磺酸鹽5份溶解於乙腈40份中，加入苯基硒醇2份、50%氫氧化鉀水溶液2.6份，於50℃下加熱10小時。 向反應液中加入二氯甲烷50份及水50份，藉由過濾去除析出物。 向濾液中加入氯仿120份、甲苯50份並進行分液清洗，對氯仿層進行減壓濃縮，藉此獲得(4-苯硒基苯基)二苯基鋶三氟甲磺酸鹽（P'-4）。 <Comparative Example 4> Using the same method as Example 1 of Japanese Patent Laid-Open No. 2014-234348, 4-chlorophenyl diphenyl perylene triflate is obtained by reacting and refining 4-chlorobromobenzene with diphenylene . 5 parts of the obtained 4-chlorophenyldiphenyl perylene triflate was dissolved in 40 parts of acetonitrile, 2 parts of phenylselenol and 2.6 parts of a 50% potassium hydroxide aqueous solution were added, and heated at 50°C 10 hours. To the reaction liquid were added 50 parts of dichloromethane and 50 parts of water, and the precipitate was removed by filtration. To the filtrate, 120 parts of chloroform and 50 parts of toluene were added and washed by liquid separation, and the chloroform layer was concentrated under reduced pressure to obtain (4-phenylselenophenyl) diphenyl perylene triflate (P' -4).

[化8]

[hua 8]

＜比較例5＞ 將比較例1中使用的三苯基鋶三氟甲磺酸鹽5份溶解於二氯甲烷50份中，加入三(三氟甲磺醯基)甲烷化物鉀（TCI（股）製造）6份與水50份並攪拌1小時。去除水層，加入水30份並進行水洗。對二氯甲烷層進行減壓濃縮，投入至TBME 150份中，藉此獲得沈澱物，對其進行過濾、減壓乾燥，藉此獲得三苯基鋶三(三氟甲磺醯基)甲烷化物（P'-5）。 <Comparative Example 5> 5 parts of triphenyl perylene trifluoromethanesulfonate used in Comparative Example 1 was dissolved in 50 parts of methylene chloride, and 6 parts of potassium tris(trifluoromethanesulfonyl)methanide (manufactured by TCI Corporation) was added. It was mixed with 50 parts of water and stirred for 1 hour. The water layer was removed, and 30 parts of water was added and washed with water. The dichloromethane layer was concentrated under reduced pressure, poured into 150 parts of TBME to obtain a precipitate, which was filtered and dried under reduced pressure to obtain triphenyl perylene tris(trifluoromethanesulfonyl)methanate (P'-5).

[化9]

[Chemical 9]

＜感度評價＞ 利用以下所示的方法測定並評價感度。 （試樣溶液的調整） 將本發明的光酸產生劑（P）與以重量比計為20倍的感光性樹脂（聚羥基苯乙烯與丙烯酸第三丁氧基酯的共聚物）混合，以光酸產生劑的莫耳濃度為2.0 mM的方式溶解於丙二醇單甲醚乙酸酯（PGMEA）中。 <Sensitivity evaluation> The sensitivity was measured and evaluated by the method shown below. (Adjustment of sample solution) The photoacid generator (P) of the present invention is mixed with a photosensitive resin (copolymer of polyhydroxystyrene and tertiary butoxy acrylate) in a weight ratio of 20 times, and the molar ratio of the photoacid generator is used. It was dissolved in propylene glycol monomethyl ether acetate (PGMEA) at a concentration of 2.0 mM.

（製膜） 於進行了六甲基二矽氮烷（hexamethyl disilazane，HMDS）處理的基盤上，使用旋塗機展開試樣溶液，藉由130℃、60秒鐘的加熱去除溶劑，藉此製成約50 nm的膜厚。 (film making) On the substrate treated with hexamethyldisilazane (HMDS), the sample solution was developed using a spin coater, and the solvent was removed by heating at 130°C for 60 seconds to prepare a sample solution of about 50 nm. film thickness.

（曝光） 將製膜後的樣品投入至兵庫縣立大學紐斯巴魯（Newsubaru）放射光設施的BL-3，照射13.5 nm的放射光。 (exposure) The film-formed sample was put into BL-3 of the Newsubaru Radiation Light Facility of Hyogo Prefectural University, and irradiated with 13.5 nm radiation.

（顯影） 將曝光後的樣品於110℃下加熱90秒鐘，使用氫氧化四甲基銨2.38%水溶液顯影60秒鐘，並利用流水進行30秒鐘淋洗。 (development) The exposed sample was heated at 110° C. for 90 seconds, developed using a 2.38% aqueous solution of tetramethylammonium hydroxide for 60 seconds, and rinsed with running water for 30 seconds.

（感度） 利用顯微鏡測定曝光後的樣品，確認用以完全去除抗蝕劑膜的最低曝光量（膜去除感度）。 為了排除放射光的日照的影響，以下按照以下的基準評價將當天測定的比較例P'-1的感度設為1時的相對感度。 將比較例P'-1的感度設為1時感度1以上：× 將比較例P'-1的感度設為1時感度未滿1且為0.75以上：Δ 將比較例P'-1的感度設為1時感度未滿0.75且為0.5以上：○ 將比較例P'-1的感度設為1時感度未滿0.5：◎ (Sensitivity) The sample after exposure was measured with a microscope, and the minimum exposure amount (film removal sensitivity) for completely removing a resist film was confirmed. In order to exclude the influence of the sunlight of the radiated light, the relative sensitivity when the sensitivity of the comparative example P'-1 measured on that day was set to 1 was evaluated according to the following criteria. When the sensitivity of the comparative example P'-1 is set to 1, the sensitivity is 1 or more: × When the sensitivity of Comparative Example P'-1 is set to 1, the sensitivity is less than 1 and 0.75 or more: Δ When the sensitivity of Comparative Example P'-1 is set to 1, the sensitivity is less than 0.75 and 0.5 or more: ○ When the sensitivity of Comparative Example P'-1 is set to 1, the sensitivity is less than 0.5: ◎

利用所述方法測定實施例1～實施例11中製成的光酸產生劑（P-1-1）～光酸產生劑（P-2-5）、及比較例1～比較例5中製成的光酸產生劑（P'-1）～光酸產生劑（P'-5）的感度。將其結果示於表1。Photoacid generators (P-1-1) to photoacid generators (P-2-5) prepared in Examples 1 to 11, and those prepared in Comparative Examples 1 to 5 were measured by the method described above. The sensitivity of the photoacid generator (P'-1) to the photoacid generator (P'-5) formed. The results are shown in Table 1.

[表1]    感度 評價 實施例1 0.29 ◎ 實施例2 0.32 ◎ 實施例3 0.60 ○ 實施例4 0.26 ◎ 實施例5 0.60 ○ 實施例6 0.24 ◎ 實施例7 0.52 ○ 實施例8 0.55 ○ 實施例9 0.65 ○ 實施例10 0.24 ◎ 實施例11 0.48 ◎ 比較例1 1.00 × 比較例2 0.88 Δ 比較例3 0.75 Δ 比較例4 1.75 × 比較例5 1.67 × [Table 1] Sensitivity Evaluation Example 1 0.29 ◎ Example 2 0.32 ◎ Example 3 0.60 ○ Example 4 0.26 ◎ Example 5 0.60 ○ Example 6 0.24 ◎ Example 7 0.52 ○ Example 8 0.55 ○ Example 9 0.65 ○ Example 10 0.24 ◎ Example 11 0.48 ◎ Comparative Example 1 1.00 × Comparative Example 2 0.88 Δ Comparative Example 3 0.75 Δ Comparative Example 4 1.75 × Comparative Example 5 1.67 ×

如表1所示，可知本發明的硒鎓鹽的光酸產生劑（P）與先前的鋶鹽的光酸產生劑相比，對於EUV顯示出高感度。 [產業上之可利用性] As shown in Table 1, it was found that the photoacid generator (P) of the selenonium salt of the present invention shows a higher sensitivity to EUV than the photoacid generator of the conventional pernium salt. [Industrial Availability]

本發明的光酸產生劑（P）對於EUV或EB具有高的感度，因此有效用作以半導體的製造為代表的微細加工用的光微影材料。The photoacid generator (P) of the present invention has high sensitivity to EUV or EB, and thus is effectively used as a photolithography material for microfabrication including semiconductor production.

Claims (5)

一種光酸產生劑（P），其特徵在於：含有下述通式（1）所表示的硒鎓鹽，

式（1）中，X ¹、X ²及X ³分別獨立地為鹵素原子、羥基、碳數1～18的烷基、碳數1～18的烷氧基、碳數6～14的芳基、碳數6～14的芳氧基、碳數6～14的芳硫基、或碳數6～14的芳硒基，該些烷基、烷氧基、芳基、芳氧基、芳硫基及芳硒基的氫原子的一部分或全部可經氟原子取代，y ₁、y ₂及y ₃相互獨立地為0～5，A ^-為一價陰離子。 A photoacid generator (P), characterized in that it contains a selenonium salt represented by the following general formula (1),

In formula (1), X ¹ , X ² and X ³ are each independently a halogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and an aryl group having 6 to 14 carbon atoms. , an aryloxy group with a carbon number of 6-14, an arylthio group with a carbon number of 6-14, or an arylselenyl group with a carbon number of 6-14, these alkyl groups, alkoxy groups, aryl groups, aryloxy groups, aryl sulfur groups A part or all of the hydrogen atoms of the group and the arylselenyl group may be substituted by fluorine atoms, y ₁ , y ₂ and y ₃ are independently 0 to 5, and A ^- is a monovalent anion. 如請求項1所述的光酸產生劑（P），其中通式（1）中，X ¹、X ²及X ³為鹵素原子、碳數1～10的烷基、或碳數6～10的芳基，該些烷基及芳基的氫原子的一部分或全部可經氟原子取代。 The photoacid generator (P) according to claim 1, wherein in the general formula (1), X ¹ , X ² and X ³ are a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 6 to 10 carbon atoms. In the aryl group, a part or all of the hydrogen atoms of these alkyl groups and aryl groups may be substituted with fluorine atoms. 如請求項1所述的光酸產生劑（P），其中通式（1）中，X ¹、X ²及X ³為F、CF ₃、C ₂F ₅、C ₃F ₇、C ₄F ₉、或C ₆F ₅。 The photoacid generator (P) according to claim 1, wherein in the general formula (1), X ¹ , X ² and X ³ are F, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , and C ₄ F ₉ , or C ₆ F ₅ . 如請求項1至請求項3中任一項所述的光酸產生劑（P），用於極紫外線（EUV）或電子束（EB）。The photoacid generator (P) according to any one of claims 1 to 3, for extreme ultraviolet (EUV) or electron beam (EB). 一種光微影用樹脂組成物（Q），包含如請求項1至請求項4中任一項所述的光酸產生劑（P）。A resin composition (Q) for photolithography, comprising the photoacid generator (P) according to any one of claim 1 to claim 4.