TW200934755A - Novel sulfonate and radiation-sensitive resin composition - Google Patents

Novel sulfonate and radiation-sensitive resin composition Download PDF

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TW200934755A
TW200934755A TW097148531A TW97148531A TW200934755A TW 200934755 A TW200934755 A TW 200934755A TW 097148531 A TW097148531 A TW 097148531A TW 97148531 A TW97148531 A TW 97148531A TW 200934755 A TW200934755 A TW 200934755A
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group
acid
linear
formula
radiation
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Takuma Ebata
Tomoki Nagai
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Jsr Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/06—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/07—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
    • C07C205/11—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings
    • C07C205/12—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings the six-membered aromatic ring or a condensed ring system containing that ring being substituted by halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/19—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12—Sulfonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/96—Esters of carbonic or haloformic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Abstract

Disclosed is a sulfonate represented by the general formula (1) below. (In the formula, Rf's independently represent a fluorine atom or a perfluoroalkyl group having 1-3 carbon atoms; R1 represents a linear or branched alkyl group having 1-8 carbon atoms; R2's independently represent a hydrogen atom, a fluorine atom or a linear or branched alkyl group having 1-8 carbon atoms which may be substituted by a fluorine atom; m represents an integer of 0-3; n represents an integer of 1-3; Mk+ represents a k-valent cation; and k represents an integer of 1-4.) (1)

Description

200934755 九、發明說明 【發明所屬之技術領域】 本發明係關於一種新穎磺酸鹽及敏輻射線性樹脂組成 物’更詳言之，尤其是關於使用諸如KrF準分子雷射、 ArF準分子雷射、F2準分子雷射或EUV (極紫外線）等遠 紫外線，同步輻射線等X射線、電子束等帶電粒子束之各 種輻射線，在空氣下、氮氣下或真空下乾曝光，或者在鏡 φ 片與光阻膜間介以在曝光波長中折射率比空氣高之液浸曝 光用液體經輻射線照射之液浸曝光之細微加工有用之作爲 化學增幅型光阻劑使用之正型及負型敏輻射線性樹脂組成 物之敏輻射線性酸產生劑的新穎磺酸鹽以及含有該酸產生 劑之正型及負型敏輻射線性樹脂組成物。 【先前技術】 積體電路元件製造中所代表之細微加工領域，爲了獲 Q 得更高積體度’於最近，可在〇.20μηι以下等級之微細加 工之微影製程成爲必要。然而，以往之微影製程，一般係 使用i線等之近紫外線作爲輻射線，但以該近紫外線可謂 極難以進行次四分之一微米（Sub-Quarter-micron)等級 之微細加工。 因此’爲了可於0.20 μιη以下之等級微細加工，而檢 討利用更短波長之輻射線。作爲此種短波長輻射線，舉例 有例如以水銀燈之亮線光譜及準分子雷射爲代表之遠紫外 線、X線、電子束等’但該等中，以使用KrF準分子雷射 -4- 200934755 (波長248nm ) 、ArF準分子雷射（波長193nm ) 、F2準 分子雷射（波長157nm) 、EUV (波長13nm等）、電子 束等之技術尤其受到矚目。 作爲適用於以上述短波長之輻射線的敏輻射線性樹脂 組成物，多數提案有利用具有酸解離性官能基之成分及藉 由輻射線照射（以下稱爲「曝光」）而產生酸之敏輻射線 性酸產生劑之間之化學增幅效果之組成物（以下稱爲「化 φ 學增幅型敏輻射線性組成物」）。 作爲此化學增幅型敏輻射線性組成物，於例如專利文 獻1中提案有含有具有羧酸之第三丁基酯基或酚之第三丁 基碳酸酯基之聚合物及敏輻射線性酸產生劑之組成物。此 組成物係利用藉由因曝光產生酸之作用，使存在於聚合物 中之第三丁基酯基或第三丁基碳酸酯基解離，該聚合物形 成由羧基或酚性羥基所構成之酸性基，其結果，光阻劑被 膜之曝光區域於鹼顯像液中變成易溶性之現象。 Q 然而，化學增幅型敏輻射線性組成物中之敏輻射線性 酸產生劑要求之特性列舉爲對於幅射線之透明性優異，且 酸產生之量子產率高，產生之酸十分強，且產生之酸的沸 點夠高，且產生之酸在光阻被膜中之擴散距離（以下稱爲 「擴散長度」）適度。 又，在最近不僅微細加工，要求有可作更複雜圖型加 工之性能，需要孤立圖型與密集圖型的焦點深度之平衡或 良好的最小崩壞前尺寸、LWR等之性能。 此等中，關於透明性、酸產生之量子產率以外的項目 -5- 200934755 ’在離子性的敏輻射線性酸產生劑中陰離子部分構 要的’且一般的具磺醯基構造或磺酸酯構造之非離 輻射線性酸產生劑，磺醯基部分的構造爲重要。例 用之具全氟烷烴磺酸構造的敏輻射線性酸產生劑時 之酸成爲夠強之酸，作爲光阻之解像性雖變足夠高 含有率高，而與具酸解離性基的樹脂之相容性差， 劑膜中之具酸解離性基的樹脂與敏輻射線性酸產生 0 佈變不均一，有焦點深度之平衡或最小崩壞前尺寸 等惡化之缺點。另外，代表與具酸解離性基的樹脂 性高的樟腦磺酸等之烷烴磺酸，因酸強度不足，無 充分感度且解像性亦低。又，最近，雖亦開發僅於 Ct-位具含氟系電子吸引基的磺酸，但因要進行更複 加工用之性能不足，期望被改善。例如，孤立圖型 圖型之焦點深度的平衡或最小崩壞前尺寸、LWR的 此中，孤立圖型之焦點深度或最小崩壞前尺寸有酸 〇 長度愈長愈良好的傾向，但因酸之擴散爲長，則密 之焦點深度惡化，故考量此等的平衡，而期望有與 離性基的樹脂之相容性佳，具適當酸擴散長度的敏 性酸產生劑。 [專利文獻1]特公平2-27660號公報 【發明內容】 本發明之課題係提供一種新穎之磺酸鹽、以及 酸鹽之正型及負型的敏輻射線性樹脂組成物，該新 造爲重 子性敏 如爲常 ，產生 ，因氟 在光阻 劑之分 、LWR 之相容 法獲得 磺醯基 雜圖型 與密集 平衡。 之擴散 集圖型 具酸解 輻射線 含該磺 穎之磺 -6 - 200934755 酸鹽對於活性輻射線、例如，對於以KrF準分子雷射、 ArF準分子雷射、F2準分子雷射或EUV爲代表之遠紫外 線或電子線等之透明性優異，感應此等活性輻射線，或藉 由加熱，可產生酸性度及沸點夠高之酸，且極適用作爲孤 立圖型與密集圖型之焦點深度的平衡或最小崩壞前尺寸、 LWR爲良好的化學增幅型光阻劑之敏輻射線性樹脂組成物 的敏輻射線性酸產生劑。 〇 本發明者爲了達成上述課題，努力硏究之結果，發現 藉由以下所示化合物等’可達成上述課題，而完成本發明 。亦即，根據本發明，提供以下所示的磺酸鹽等。 [1]一種下述通式（1)所表示之磺酸鹽。200934755 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to a novel sulfonate and a radiation sensitive linear resin composition, 'in more detail, especially regarding the use of a laser such as KrF excimer laser, ArF excimer laser , F2 excimer laser or EUV (extreme ultraviolet), such as far ultraviolet rays, synchrotron radiation and other X-rays, electron beams and other charged particle beams of various radiation, dry exposure under air, under nitrogen or under vacuum, or in the mirror φ Fine processing of liquid immersion exposure between a sheet and a photoresist film through a liquid immersion exposure liquid having a refractive index higher than that of air at an exposure wavelength, which is useful as a chemical amplification type resist, positive and negative type A novel sulfonate of a sensitive radiation linear acid generator of a sensitive radiation linear resin composition and a positive and negative radiation sensitive linear resin composition containing the acid generator. [Prior Art] In the field of fine processing represented by the manufacture of integrated circuit components, in order to obtain a higher degree of integration of Q, it has recently become necessary to perform a microfabrication process of a fine processing level of 〇.20μηι or less. However, the conventional lithography process generally uses near-ultraviolet rays such as i-rays as radiation, but it is extremely difficult to perform sub-Quarter-micron microfabrication with the near-ultraviolet rays. Therefore, in order to be finely processed at a level of 0.20 μm or less, it is possible to examine radiation using a shorter wavelength. Examples of such short-wavelength radiation include, for example, a far-ultraviolet light, an X-ray, an electron beam, etc. represented by a bright line spectrum of a mercury lamp and an excimer laser, but in the case of using a KrF excimer laser -4- Technology such as 200934755 (wavelength 248nm), ArF excimer laser (wavelength 193nm), F2 excimer laser (wavelength 157nm), EUV (wavelength 13nm, etc.), electron beam, etc. are particularly attracting attention. As a linear radiation-sensitive resin composition suitable for the above-mentioned short-wavelength radiation, many proposals have been made to generate acid-sensitive radiation by using a component having an acid-dissociable functional group and irradiation by radiation (hereinafter referred to as "exposure"). A composition for chemically amplifying effects between linear acid generators (hereinafter referred to as "chemicalized linear radiation sensitive linear composition"). As the chemically amplified type radiation sensitive linear composition, for example, Patent Document 1 proposes a polymer containing a third butyl carbonate group having a carboxylic acid, or a third butyl carbonate group of a phenol, and a radiation sensitive linear acid generator. Composition. The composition is obtained by dissociating a third butyl ester group or a third butyl carbonate group present in the polymer by an acid generated by exposure, and the polymer is formed of a carboxyl group or a phenolic hydroxyl group. As a result, the exposed region of the photoresist film becomes easily soluble in the alkali developing solution. Q However, the characteristics of the sensitive radiation linear acid generator in the chemically amplified type sensitive radiation linear composition are listed as excellent transparency to the radiation, and the quantum yield of the acid generation is high, the acid produced is very strong, and is produced. The boiling point of the acid is sufficiently high, and the diffusion distance of the acid generated in the photoresist film (hereinafter referred to as "diffusion length") is moderate. Moreover, in recent years, not only microfabrication, but also performance for more complicated pattern processing is required, and the balance of the depth of focus of the isolated pattern and the dense pattern or the good size of the pre-collapse size, LWR, and the like are required. Among these, items other than the quantum yield of transparency and acid generation -5 to 200934755 'anionic moiety in an ionic radiation sensitive linear acid generator' and generally have a sulfonyl structure or a sulfonic acid The non-ionizing radiation linear acid generator of the ester structure, the structure of the sulfonyl moiety is important. When the perfluoroalkanesulfonic acid structure of the radiation sensitive linear acid generator is used as an acid, the acid becomes a strong enough acid, and although the resolution of the photoresist is sufficiently high, the content is high, and the resin having an acid dissociable group is used. The compatibility is poor, and the acid-dissociable group-containing resin in the film has a non-uniformity with the sensitive radiation linear acid, and has a disadvantage of a balance of the depth of focus or a size before the minimum collapse. Further, an alkanesulfonic acid such as camphorsulfonic acid having a high resinity with an acid dissociable group is insufficient in acid strength, and has insufficient sensitivity and low resolution. Further, recently, although a sulfonic acid having a fluorine-containing electron attracting group only at the Ct-position has been developed, it is expected to be improved because of insufficient performance for further processing. For example, the balance of the depth of the isolated pattern pattern or the size before the minimum collapse, the LWR, the depth of the isolated pattern or the size before the minimum collapse has a tendency that the acid length is longer and better, but due to acid When the diffusion is long, the depth of the dense focus is deteriorated. Therefore, such a balance is considered, and it is desirable to have a sensitive acid generator having a suitable acid diffusion length because of compatibility with an excipient-based resin. [Patent Document 1] Japanese Patent Publication No. Hei 2-27660. SUMMARY OF THE INVENTION The object of the present invention is to provide a novel sulfonate and a positive- and negative-type radiation sensitive linear resin composition of the acid salt, which is newly formed as a baryon. Sexual sensitivity is as usual, resulting in a sulfonium-based hybrid pattern and dense balance due to the compatibility of fluorine in the photoresist and LWR. Diffusion set pattern with acidolytic radiation containing the sulfonate sulfonate-6 - 200934755 acid salt for active radiation, for example, for KrF excimer laser, ArF excimer laser, F2 excimer laser or EUV It is excellent in transparency such as ultraviolet light or electron beam, and it can induce the acidity and high boiling point acid by heating, and it is very suitable as the focus of isolated and dense patterns. A deep-balanced or minimally pre-cracked size, LWR is a sensitive radiation linear acid generator of a sensitive radiation-linear resin composition of a good chemically amplified photoresist. In order to achieve the above-mentioned problems, the inventors of the present invention have found that the above problems can be attained by the following compounds, and the present invention has been completed. That is, according to the present invention, a sulfonate or the like shown below is provided. [1] A sulfonate represented by the following formula (1).

【化1】【化1】

(1^各自獨立，表示氟原子或碳數1〜3之全氟烷基、R1 表示碳數1〜8之直鏈或分支之烷基、R2各自獨立，表示 氫原子、氟原子、或可以氟原子取代之碳數1〜8之直鏈 或分支之烷基。m爲0〜3之整數、n爲1〜3之整數。Mk + 表示k價的陽離子，k表示1〜4之整數）。 [2] —種上述[1]之磺酸鹽，其中，R2爲氫原子或碳數 200934755 1〜8之直鏈或分支之烷基。 [3] —種上述[1]之磺酸鹽，其中，R2係氫原 Μ原子。 [4] 一種上述[1]之磺酸鹽，其中，陽離子係 或碘鎗陽離子。 [5] —種敏輻射線性樹脂組成物，其係含有 [4]中任一項之磺酸鹽及含酸解離性基之樹脂。 [6] 如上述[5]之敏輻射線性樹脂組成物，其 含酸解離性基之樹脂係含下述通式（8)所表示 位。 子、Rf係 锍陽離子 上述[1]〜 中，上述 之重複單(1) each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms, R1 represents a linear or branched alkyl group having 1 to 8 carbon atoms, and R2 is independently represented by a hydrogen atom, a fluorine atom, or a linear or branched alkyl group having a carbon number of 1 to 8 substituted with a fluorine atom. m is an integer of 0 to 3, and n is an integer of 1 to 3. Mk + represents a k-valent cation, and k represents an integer of 1 to 4) . [2] The sulfonate of the above [1], wherein R2 is a hydrogen atom or a linear or branched alkyl group having a carbon number of 200934755 1 to 8. [3] The sulfonate of the above [1], wherein R2 is a hydrogen atom of ruthenium. [4] A sulfonate according to the above [1], which is a cation or an iodine cation. [5] A sensitive radiation linear resin composition comprising the sulfonate salt of any one of [4] and a resin containing an acid dissociable group. [6] The sensitive radiation linear resin composition according to [5] above, wherein the acid-dissociable group-containing resin contains a position represented by the following formula (8). Sub-Rf system 锍 cation The above [1]~, the above repeat

(通式（8)中，R15爲氫原子或1價之有機基， 之R15可互爲相同或相異，c及d分別爲1〜3之 複數存在 整數）。 中，上述 之重複單 種、與下 [7]如上述[5]之敏輻射線性樹脂組成物，其 含酸解離性基之樹脂係含下述通式（9)所表示 位及下述通式（1〇)所表示之重複單位之至少一 述通式（11)所表示之重複單位。 -8- 200934755(In the formula (8), R15 is a hydrogen atom or a monovalent organic group, and R15 may be the same or different from each other, and c and d are each an integer of 1 to 3, respectively. In the above-mentioned repeating single-type, and [7], the sensitive radiation linear resin composition of the above [5], the acid-dissociable group-containing resin contains the group represented by the following formula (9) and the following The repeating unit represented by the formula (1) represents at least one repeating unit represented by the formula (11). -8- 200934755

(通式（9)、通式（10)及通式（11)中，R16、R18及 R19相互獨立，表示氫原子或甲基，通式（9)中，各R17 相互獨立，表示氫原子、羥基、氰基或-COOR21 (惟，R21 爲氫原子、碳數1〜4之直鏈狀或分支狀之烷基或碳數3〜 20之環烷基）。通式（11)中，各R2<)相互獨立，表示碳 數4〜20之1價之脂環式烴基或其衍生物或碳數1〜4之 直鏈狀或分支狀之烷基，且R2G之至少一個係該脂環式烴 ^ 基或其衍生物，或任兩個之r2()相互鍵結，與各自鍵結的 碳原子共同形成碳數4〜20之2價之脂環式烴基或其衍生 物’其他的R2()表示碳數1〜4之直鏈狀或分支狀之烷基 或碳數4〜20之1價之脂環式烴基或其衍生物）。 本發明之化合物對於活性輻射線、例如，KrF準分子 雷射、ArF準分子雷射、F2準分子雷射或EUV爲代表的 遠紫外線或電子束等的透明性優異，藉由感應此等活性輻 射線乃至經加熱’可產生足夠酸性度及沸點之酸，且極適 宜用作爲孤立圖型與密集圖型之焦點深度的平衡或最小崩 -9- 200934755 壞前尺寸、lwr良好的化學增幅型光阻劑有用之敏輻射線 性樹脂組成物的敏輻射線性酸產生劑。 【實施發明之最佳形態】 以下說明本發明實施之最佳形態，但本發明並不受下 列實施形態之限制，應了解熟悉該技術者可在不脫離本發 明精神之範圍內，基於熟知該項技術者之知識可對以下之 0 實施形態進行適度之變更、改良，但均不離本發明之範圍 本發明之磺酸鹽爲下述通式（1)所表示。(In the general formula (9), the general formula (10) and the general formula (11), R16, R18 and R19 are each independently a hydrogen atom or a methyl group, and in the general formula (9), each R17 is independent of each other and represents a hydrogen atom. , hydroxy, cyano or -COOR21 (except that R21 is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms). In the formula (11), Each R 2 <) is independent of each other and represents a monovalent alicyclic hydrocarbon group having a carbon number of 4 to 20 or a derivative thereof or a linear or branched alkyl group having 1 to 4 carbon atoms, and at least one of R 2 G is a lipid. The cyclic hydrocarbon group or a derivative thereof, or any two of r2() are bonded to each other, and together with the carbon atom bonded thereto, form a divalent alicyclic hydrocarbon group having a carbon number of 4 to 20 or a derivative thereof. R2() represents a linear or branched alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof. The compound of the present invention is excellent in transparency for active radiation, for example, KrF excimer laser, ArF excimer laser, F2 excimer laser or EUV, or the like, by inducing such activity. Radiation or even heating's acid that produces sufficient acidity and boiling point, and is ideally used as a balance or minimum collapse of the depth of focus between the isolated and dense patterns. - 200934755 Pre-small size, lwr good chemical amplification A photoresist is a sensitive radiation linear acid generator useful for radiation-sensitive linear resin compositions. BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the invention is described below, but the present invention is not limited by the following embodiments, and it should be understood that those skilled in the art can understand the present invention without departing from the spirit of the invention. The knowledge of the skilled artisan can be appropriately modified or improved in the following 0 embodiments without departing from the scope of the invention. The sulfonate of the present invention is represented by the following formula (1).

【化4】【化4】

⑴ (1^各自獨立，表示氟原子或碳數1〜3之全氟烷基、R1 表示碳數1〜8之直鏈或分支之烷基、R2各自獨立，表示 氫原子、氟原子、或可以氟原子取代之碳數1〜8之直鏈 或分支之烷基。m爲0〜3之整數、η爲1〜3之整數。Mk + 表示k價的陽離子，k表示1〜4之整數）。 通式（1 )中，k=l時之M +之一價鑰陽離子可列舉爲 例如 0、S、Se、N、P、As、Sb、Cl、Br、I 等鑰陽離子 -10- 200934755 。該等鑰陽離子中，較好爲鏑陽離子、或碘鎗陽離子。 本發明之磺酸鹽（1)，因於其構造（1)中磺醯基的 CX-位具有強含氟系電子吸引基，故產生之酸的酸性度高， 且因沸點夠高，在光微影術步驟中不易揮發，且因具適當 長度的烷基鏈，所以具有在光阻劑被膜中的適當擴散長度 ，具孤立圖型與密集圖型之焦點深度的平衡或最小崩壞前 尺寸、LWR的平衡爲良好的性能。 φ 通式（1)中，M+之一價鎩陽離子中，S之鑰陽離子 可列舉爲例如以下述通式（i)表示者，又I之鎗陽離子可 列舉爲例如以下述通式（ii )表示者。 【化5】 R3 r4-s+-r5 (0 ❹ (通式（i)中’ R3、R4及R5相互獨立，表示取代或非取 代之碳數1〜之直鏈狀或分支狀之烷基或取代或非取代 之碳數6〜18的方基’或R3、R4及R5中任2個以上相互 鍵結與式中硫原子共同形成環）。 【化6】 R6—Γ-R7 ⑼ (通式（π)中，r6及R7相互獨立’表示取代或非取代 -11 - 200934755 之碳數1〜10之直鏈狀或分支狀之烷基或取代或非取代之 碳數6〜18的芳基，或R6與R7相互鍵結與式中碘原子共 同形成環）。 _ M+之一價鑰陽離子部位可以例如高等聚合物科學（ Advances in Polymer Science) ，V ο 1.6 2，p . 1 - 4 8 ( 1 9 8 4)中 所述之一般方法爲準加以製造。 較佳之一價鎗陽離子可列舉爲例如下述式（1 )〜（ 0 i-64)之鏑陽離子、下述式（Π-1)〜（m)之碘鎗陽離 子。 〇 -12- 200934755(1) (1) each independently represents a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms, R1 represents a linear or branched alkyl group having 1 to 8 carbon atoms, and R2 is independently represented by a hydrogen atom, a fluorine atom, or A linear or branched alkyl group having 1 to 8 carbon atoms which may be substituted by a fluorine atom. m is an integer of 0 to 3, and η is an integer of 1 to 3. Mk + represents a k-valent cation, and k represents an integer of 1 to 4. ). In the general formula (1), one of the M + valence cations at the time of k = 1 may be, for example, a key cation such as 0, S, Se, N, P, As, Sb, Cl, Br, I, etc.-10-200934755. Among these key cations, a phosphonium cation or an iodine cation is preferred. The sulfonate (1) of the present invention has a strong fluorine-containing electron attracting group at the CX-position of the sulfonyl group in the structure (1), so that the acidity of the acid generated is high, and the boiling point is high enough. It is not volatile in the photolithography step, and has an appropriate diffusion length in the photoresist film due to the alkyl chain of appropriate length, and has a balance of the depth of focus of the isolated pattern and the dense pattern or before the minimum collapse. The balance of size and LWR is good performance. φ In the general formula (1), among the M+ one-valent sulfonium cations, the key cation of S may be, for example, represented by the following formula (i), and the gun cation of I may be exemplified by, for example, the following formula (ii) Representation. R3 r4-s+-r5 (0 ❹ (in the formula (i), R3, R4 and R5 are independent of each other, and represent a substituted or unsubstituted alkyl group having a linear or branched alkyl group of 1 or The substituted or unsubstituted carbon group of 6 to 18 or the two or more of R3, R4 and R5 are bonded to each other to form a ring together with the sulfur atom in the formula. [Chemical 6] R6—Γ-R7 (9) (通In the formula (π), r6 and R7 are independent of each other', and a substituted or unsubstituted -11 - 200934755 is a linear or branched alkyl group having a carbon number of 1 to 10 or a substituted or unsubstituted carbon number of 6 to 18 a group, or R6 and R7 are bonded to each other to form a ring together with an iodine atom in the formula. _ M+ a valence cation moiety can be, for example, Advances in Polymer Science, V ο 1.6 2, p. 1 - 4 The general method described in 8 (1 9 8 4) is preferably produced. The preferred one-valent gun cation can be exemplified by a phosphonium cation such as the following formula (1) to (0 i-64), and the following formula (Π) -1) ~(m) iodine gun cation. 〇-12- 200934755

-13- 200934755 【化8】-13- 200934755 【化8】

-14- 200934755-14- 200934755

(i-17)(i-17)

(i-20)(i-20)

(H3C)3C-〇4-^-〇(H3C)3C-〇4-^-〇

(i-22) -15- 200934755(i-22) -15- 200934755

(i-24)(i-24)

(i-25)(i-25)

(i-26) 200934755 【化1 1】 OCH,(i-26) 200934755 [Chem. 1 1] OCH,

OCH,OCH,

(i-29)(i-29)

OHOH

0-32)0-32)

(i-34) -17- 200934755(i-34) -17- 200934755

(i-39) CH3I 3 h3c—s+-ch3 (i-40)(i-39) CH3I 3 h3c-s+-ch3 (i-40)

CH2CI h3c-s+-^) (i-41)CH2CI h3c-s+-^) (i-41)

CH3 ! 3 H3C—S+-CH2COCH3 ! 3 H3C-S+-CH2CO

(i-42)(i-42)

ch2ch2ch2ch3 h3ch2ch2ch2c—s+-ch2co (i-43)Ch2ch2ch2ch3 h3ch2ch2ch2c—s+-ch2co (i-43)

-18- 200934755 【化1 3】-18- 200934755 【化1 3】

(i-45)(i-45)

(i-46) (^Ό (i-47) Ο Η°-〇-〇 (i-48)(i-46) (^Ό (i-47) Ο Η°-〇-〇 (i-48)

(i-49)(i-49)

H3CH2CH2CH2C h3ch2ch2ch2cH3CH2CH2CH2C h3ch2ch2ch2c

(i-50)(i-50)

(i-54) -19- 200934755(i-54) -19- 200934755

o~ coch2-s (i-58)o~ coch2-s (i-58)

(i-60)(i-60)

❹ (i-61)❹ (i-61)

(i-62)(i-62)

H3C (i-63) -20- 200934755 【化1 5】H3C (i-63) -20- 200934755 [Chem. 1 5]

【化1 6】【化1 6】

(ii-l)(ii-l)

(ii-3)(ii-3)

(ii-4)(ii-4)

0^+_hC^c2H5 (ii-6)0^+_hC^c2H5 (ii-6)

(CH3)2CH -CH(CH3)2(CH3)2CH -CH(CH3)2

c(ch3)3 (ii-10) -21 - 200934755c(ch3)3 (ii-10) -21 - 200934755

(ii-12)(ii-12)

(ii-15)(ii-15)

OCH, H3CO ^^~丨+乂）~〇CH3OCH, H3CO ^^~丨+乂)~〇CH3

ClCl

(ii-18)(ii-18)

Cl (ii-20)Cl (ii-20)

-22 200934755-22 200934755

0^,+O~cf3 (ii-24)0^,+O~cf3 (ii-24)

FaC 1+' (ii-25)FaC 1+' (ii-25)

•CF 3 0^i+_hC)^cooch3 (ii-26)• CF 3 0^i+_hC)^cooch3 (ii-26)

OO

-0CH2C00C(CH3)3 (ii-28) o-c—o—C(CH3)3 C^,+O· oc(ch3)3 (ii-29) (ii-30) ❹ H3c〇〇c^D^i+_〇^ cooch3-0CH2C00C(CH3)3 (ii-28) oc-o-C(CH3)3 C^,+O· oc(ch3)3 (ii-29) (ii-30) ❹ H3c〇〇c^D^i +_〇^ cooch3

H3COOCH3COOC

P〇OCH3 (ϋ-32) 23 200934755P〇OCH3 (ϋ-32) 23 200934755

OCH2COOC(CH3)3 (H3C)3C—o—c—oOCH2COOC(CH3)3 (H3C)3C-o-c-o

0—C—0—C(CH3)3 (ii-34)0—C—0—C(CH3)3 (ii-34)

(ii-36)(ii-36)

該等一價之錙陽離子中較好爲例如式（i- 1 )、式（i- -24- 200934755 2)、式（i-6)、式（i-8)、式（i-13)、式（i-19)、 式（i-25 )、式（i_27 )、式（Ν29 )、式（卜33 )、式（ i-51)或式（i_54)之毓陽離子；式或式（ii-ll) 之碘鑰陽離子等。 製造方法： 碌酸鹽（1)可以高等聚合物科學（Advances inThe monovalent ruthenium cation is preferably, for example, the formula (i-1), the formula (i--24-200934755 2), the formula (i-6), the formula (i-8), and the formula (i-13). a cation of the formula (i-19), formula (i-25), formula (i_27), formula (Ν29), formula (Bu 33), formula (i-51) or formula (i-54); formula or formula ( Ii-ll) Iodine cations and the like. Manufacturing Method: Diacidate (1) can be advanced polymer science (Advances in

Polymer Science) , vol.62，p.1-48(1984)及無機化學（ Inorganic Chenistry)，vol.32, p.5007-501 0(1 993)中所述 之一般方法爲準加以合成。亦即，如下述反應式[1]中所示 般，可藉由使相對應之前驅化合物（la)在無機鹼共存在 下，與連二亞硫酸鈉反應’轉化成亞磺酸鹽（1¾) ’使亞 磺酸鹽（lb)藉由過氧化氫等氧化劑氧化’轉化成擴酸鹽 (lc)後，藉由與相對離子交換前驅物M + Z_進行離子交換 而製造。The general method described in Polymer Science), vol. 62, p. 1-48 (1984) and Inorganic Chenistry, vol. 32, p. 5007-501 0 (1 993) is synthesized. That is, as shown in the following reaction formula [1], it can be converted into a sulfinate (13⁄4) by reacting a corresponding precursor compound (la) with sodium dithionite in the presence of an inorganic base. The sulfinate (lb) is converted to a salt expansion salt (lc) by oxidation with an oxidizing agent such as hydrogen peroxide, and then produced by ion exchange with the relative ion exchange precursor M + Z_.

-25- 200934755 [反應式[1]中’ Z表示脫離性之—價基，z-表示一價陰離 子] 則驅化合物（1 a )中之Z之脫離性一價基可列舉例如 氯原子、溴原子、碘原子等鹵素原子，以及甲烷磺酸根基 、對-甲苯磺酸根基等’較好爲氯原子、溴原子、碘原子 等。 〇 前驅化合物（la)與連二亞硫酸鈉之反應中，連二亞 硫酸鈉相對於前驅物（la)之莫耳比通常爲〇.01~1〇〇，較 好爲1.0〜1 0。 反應時使用之無機鹼可列舉爲例如碳酸鋰、碳酸鈉、 碳酸鉀、碳酸氫鋰、碳酸氫鈉 '碳酸氫鉀等，較好爲碳酸 氫鈉、碳酸氫鉀等。該等無機鹼可單獨使用或混合兩種以 上使用，無機鹼相對於連二亞硫酸鈉之莫耳比通常爲 1.0-10.0 > 較好爲 2.0〜4.0。 ❹ 該反應較好在有機溶劑與水之混合溶劑中進行，上述 有機溶劑較好爲例如低級醇類、四氫呋喃、N，N-二甲基甲 醯胺、Ν,Ν-二甲基乙醯胺、乙腈、二甲亞颯等與水相溶性 良好之溶劑，更好爲Ν，Ν-二甲基乙醯胺、乙腈、二甲亞碾 等，最好爲乙腈及二甲亞砸。該等有機溶劑可單獨使用或 混合兩種以上使用。 有機溶劑之使用比例相對於有機溶劑與水之合計1 0 0 質量份，通常爲5質量份以上’較好爲1〇質量份以上’ 更好爲2 0〜9 0質量份。上述混合溶劑相對於前驅化合物（ -26- 200934755 la) 100質量份之使用量通常爲5〜 10〜100質量份，更好爲20~90質量份 反應溫度通常爲40〜200°C，較好 間通常爲0.5〜72小時，較好爲2〜24 機溶劑或水之沸點高時，使用高壓釜 又，亞磺酸鹽（lb)之氧化反應 氫外，可列舉爲間氯過苯甲酸、第三 0 氧基硫酸鉀、過錳酸鉀、過硼酸鈉、 鉻酸、重鉻酸鈉、鹵素、碘苯二氯化 氧化餓（VII)、氧化釕（VII)、次 、氧氣、臭氧氣體等，較好爲過氧化 第三丁基氫過氧化物等。該等氧化劑 種以上使用。氧化劑相對於亞磺酸鹽 爲 1_0〜10.0，較好爲 1.5~4.0。 另外，可將過渡金屬觸媒與上述 〇 述過渡金屬觸媒可列舉爲例如鎢酸二 氯化釕（III )、氧化硒（IV )等，較 過渡金屬觸媒可單獨使用或混合兩種 觸媒相對於亞磺酸鹽（lb)之莫耳比 較好爲0.01〜1.0,更好爲0.03〜0.5。 而且，除上述氧化劑及過渡金屬 應溶液之pH，亦可倂用緩衝劑。上 如磷酸氫二鈉、磷酸二氫鈉、磷酸氫 。該等緩衝劑可單獨使用或混合兩種 100質量份，較好爲 〇 爲60〜120°C，反應時 小時。反應溫度比有 等耐壓容器。 中，氧化劑除過氧化 丁基氫過氧化物、過 Sodium metaiodate、 物、碘苯二乙酸鹽、 亞氯酸鈉、亞氯酸鈉 氫、間氯過苯甲酸、 可單獨使用或混合兩 (1 b )之莫耳比通常 氧化劑一起倂用。上 鈉、氯化鐵（III)、 好爲鎢酸二鈉。該等 以上使用。過渡金屬 ]通常爲 0.001〜2.0， 觸媒以外，爲調整反 述緩衝劑可列舉爲例 二鉀、磷酸二氫鉀等 以上使用。緩衝劑相 -27- 200934755 對於亞磺酸鹽（lb)之莫耳比通常爲〇.〇1〜2.〇，較好爲 0.03〜1.0，更好爲 0.05〜0.5。 該反應通常在反應溶劑中進行。上述反應溶劑較好爲 水’或例如低級院醇類、四氫咲喃、Ν,Ν -二甲基甲醯胺、 Ν，Ν-二甲基乙醯胺、乙腈、二甲亞楓、乙酸、三氟乙酸等 有機溶劑’更好爲水、甲醇、Ν,Ν-二甲基乙醯胺、乙腈、 二甲亞颯等，最好爲水及甲醇。該等有機溶劑可單獨使用 〇 或混合兩種以上使用。又亦可依據需要倂用有機溶劑及水 。此時有機溶劑之使用比例相對於有機溶劑與水之合計 1〇〇質量份’通常爲5質量份以上，較好爲1〇質量份以上 ，更好爲20〜90質量份。反應溶劑相對於亞磺酸鹽（lb) 100質量份之使用量通常爲5〜100質量份，較好爲ioq 00 質量份，更好爲20〜50質量份。 反應溫度通常爲0〜100 °C ’較好爲5〜60 〇C，更好爲 5〜40°C，反應時間通常爲〇.5〜72小時，較好爲2~24小時 ❹ 擴酸鹽（lc)之離子交換反應可依據例如j. Photopolym. Sci_ Tech.，p.57 1 -576 (1 998)所述之一般方法 ’離子交換層析等方法，或以下所述之各合成例中所記載 之方法進行。 反應式[1]中之Z·之一價陰離子可列舉爲例如F-、c「 、Br_、Γ、過氯酸離子、硫酸氫離子、磷酸二氫離子、四 氟化硼酸離子、脂肪族磺酸離子、芳香族磺酸離子、三氟 甲院碌酸離子、氟磺酸離子、六氟化磷酸離子、六氯化銻 -28- 200934755 酸離子等，較好爲cr、Br·、硫酸氫離子、四氟化硼酸離 子、卩曰肪族擴酸離子等’更好爲Cl·、Br·、硫酸氣離子等 。相對離子（Counter ion)交換前驅物相對於磺酸鹽（lc )之莫耳比通常爲0·1〜1〇·〇，較好爲〇.3〜4.0，更好爲 0.7~2.0 。 該反應通常在反應溶劑中進行。上述反應溶劑較好爲 水’或例如低級院醇類、四氫咲喃、N，N -二甲基甲酿胺、 Ο N，N-二甲基乙醯胺、乙腈、二甲亞楓等有機溶劑，更好爲 水、甲醇、N，N-二甲基乙醯胺、乙腈、二甲亞楓等，最好 爲水。該等有機溶劑可單獨使用或混合兩種以上使用。又 亦可依據需要倂用水及有機溶劑。此時有機溶劑之使用比 例相對於水及有機溶劑之合計1 〇 〇質量份，通常爲5質量 份以上’較好爲10質量份以上，更好爲20〜9〇質量份。 反應溶劑對於相對離子交換前驅物100質量份之使用量通 常爲5~100質量份’較好爲10〜10〇質量份，更好爲 〇 20〜50質量份。 反應溫度通常爲0〜80°c，較好爲5〜30°c，反應時間通 常爲1 〇分鐘〜6小時，較好爲3 0分鐘〜2小時。 如此般獲得之磺酸鹽（1 )可以有機溶劑萃取純化。 純化時使用之有機溶劑較好爲例如乙酸乙酯、乙酸正丁酯 等酯類；二乙醚等醚類；二氯甲烷、氯仿等鹵化烷類等之 不與水混合之有機溶劑。該等有機溶劑可單獨使用或混合 兩種以上使用。 又，前驅化合物（la)，可例如下述反應式[2]所示般 -29- 200934755 藉由將對應之含氟化合物加成至對應之烯烴化合物（2a) ，可變換爲前驅物化合物（2b)，藉由進行鹵化移動反應 後，使用有機銅試藥，可製造前驅物化合物（la)。 ❹-25- 200934755 [In the reaction formula [1], "Z represents a detachment-valent group, and z- represents a monovalent anion]] The detached monovalent group of Z in the compound (1a) may, for example, be a chlorine atom, A halogen atom such as a bromine atom or an iodine atom, and a methanesulfonate group or a p-toluenesulfonate group are preferably a chlorine atom, a bromine atom or an iodine atom. 〇 In the reaction of the precursor compound (la) with sodium dithionite, the molar ratio of sodium dithionite to the precursor (la) is usually 〇.01~1〇〇, preferably 1.0~1 0. The inorganic base to be used in the reaction may, for example, be lithium carbonate, sodium carbonate, potassium carbonate, lithium hydrogencarbonate or sodium hydrogencarbonate, potassium hydrogencarbonate or the like, preferably sodium hydrogencarbonate or potassium hydrogencarbonate. These inorganic bases may be used singly or in combination of two or more. The molar ratio of the inorganic base to sodium dithionite is usually from 1.0 to 10.0 > preferably from 2.0 to 4.0. ❹ The reaction is preferably carried out in a mixed solvent of an organic solvent and water, and the above organic solvent is preferably, for example, a lower alcohol, tetrahydrofuran, N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide. The solvent which is compatible with water, such as acetonitrile or dimethyl hydrazine, is preferably hydrazine, hydrazine-dimethylacetamide, acetonitrile, dimethyl arsenate, etc., preferably acetonitrile and dimethyl hydrazine. These organic solvents may be used singly or in combination of two or more. The ratio of use of the organic solvent to the total of 100 parts by mass of the organic solvent and water is usually 5 parts by mass or more, preferably 1 part by mass or more, more preferably 2 to 90 parts by mass. The amount of the above mixed solvent relative to 100 parts by mass of the precursor compound (-26-200934755 la) is usually 5 to 10 to 100 parts by mass, more preferably 20 to 90 parts by mass, and usually 40 to 200 ° C, preferably 40 to 200 ° C. The interval is usually 0.5 to 72 hours, preferably 2 to 24, when the solvent or water has a high boiling point, and the autoclave is used, and the sulfinate (lb) is oxidized to react with hydrogen, which is exemplified by m-chloroperbenzoic acid. Third potassium oxysulfate, potassium permanganate, sodium perborate, chromic acid, sodium dichromate, halogen, iodobenzene dichloride, bismuth (VII), cerium oxide (VII), secondary, oxygen, ozone gas Etc., preferably, a third butyl hydroperoxide or the like is peroxidized. These oxidizing agents are used above. The oxidizing agent is from 1_0 to 10.0, preferably from 1.5 to 4.0, based on the sulfinate. In addition, the transition metal catalyst and the transition metal catalyst described above may be exemplified by, for example, lanthanum dichloride (III), selenium oxide (IV), etc., and the transition metal catalyst may be used alone or in combination. The medium is preferably 0.01 to 1.0, more preferably 0.03 to 0.5, relative to the sulfinate (lb). Further, a buffer may be used in addition to the pH of the above oxidizing agent and the transition metal solution. Such as disodium hydrogen phosphate, sodium dihydrogen phosphate, hydrogen phosphate. These buffering agents may be used alone or in combination of two kinds of 100 parts by mass, preferably 〇 60 to 120 ° C, and the reaction time is small. The reaction temperature ratio has a pressure vessel. In addition to oxidative butyl hydroperoxide, sodium metaiodate, iodobenzene diacetate, sodium chlorite, sodium chlorite, m-chloroperbenzoic acid, either alone or in combination (1) b) Mohr is used together with the usual oxidizing agent. Sodium, iron (III) chloride, preferably disodium tungstate. These are used above. The transition metal is usually 0.001 to 2.0, and other than the catalyst, the above-mentioned buffer can be used as an example of potassium dihydrogen phosphate or potassium dihydrogen phosphate. Buffer phase -27- 200934755 The molar ratio for the sulfinate (lb) is usually 〇.〇1~2.〇, preferably 0.03 to 1.0, more preferably 0.05 to 0.5. This reaction is usually carried out in a reaction solvent. The above reaction solvent is preferably water' or, for example, a lower alcohol, tetrahydrofuran, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, acetonitrile, dimethyl sulfoxide, acetic acid. The organic solvent such as trifluoroacetic acid is preferably water, methanol, hydrazine, hydrazine-dimethylacetamide, acetonitrile, dimethyl hydrazine, etc., preferably water and methanol. These organic solvents may be used singly or in combination of two or more. Organic solvents and water can also be used as needed. In this case, the use ratio of the organic solvent to the total amount of the organic solvent and water is usually 5 parts by mass or more, preferably 1 part by mass or more, more preferably 20 to 90 parts by mass. The amount of the reaction solvent to be used is usually 5 to 100 parts by mass, preferably ioq 00 parts by mass, more preferably 20 to 50 parts by mass, per 100 parts by mass of the sulfinate (lb). The reaction temperature is usually 0 to 100 ° C. Preferably, it is 5 to 60 〇C, more preferably 5 to 40 ° C, and the reaction time is usually 〇5 to 72 hours, preferably 2 to 24 hours. The ion exchange reaction of (lc) can be carried out according to, for example, the general method 'ion exchange chromatography' described in j. Photopolym. Sci_Tech., p. 57 1 -576 (1 998), or each of the synthesis examples described below. The method described is carried out. The Z-valent valent anion in the reaction formula [1] can be exemplified by, for example, F-, c", Br_, hydrazine, perchlorate ion, hydrogen sulfate ion, dihydrogen phosphate ion, boron tetrafluoride ion, aliphatic sulfonate. Acid ion, aromatic sulfonate ion, trifluoromethane acid ion, fluorosulfonic acid ion, hexafluorophosphate ion, ruthenium hexachloride-28-200934755 acid ion, etc., preferably cr, Br, hydrogen sulfate Ions, boron tetrafluoride acid ions, cesium aliphatic acid ions, etc. are better for Cl·, Br·, sulfuric acid gas ions, etc. Counter ion exchange precursors relative to sulfonate (lc) The ear ratio is usually from 0.1 to 1 〇·〇, preferably from 〇.3 to 4.0, more preferably from 0.7 to 2.0. The reaction is usually carried out in a reaction solvent. The above reaction solvent is preferably water' or, for example, a lower grade hospital. Alcohol, tetrahydrofuran, N,N-dimethylamine, ΟN,N-dimethylacetamide, acetonitrile, dimethyl sulfoxide and other organic solvents, preferably water, methanol, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, etc., preferably water. These organic solvents may be used singly or in combination of two or more. The water and the organic solvent are used as needed. The ratio of the organic solvent to the total amount of water and the organic solvent is usually 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 20 to 9 parts by mass. The amount of the reaction solvent used is usually from 5 to 100 parts by mass, preferably from 10 to 10 parts by mass, more preferably from 20 to 50 parts by mass, based on 100 parts by mass of the relative ion exchange precursor. The reaction temperature is usually 0 to 80 ° C, preferably 5 to 30 ° C, the reaction time is usually from 1 Torr to 6 hours, preferably from 30 minutes to 2 hours. The sulfonate (1) thus obtained can be extracted by an organic solvent. The organic solvent used for the purification is preferably an ester such as ethyl acetate or n-butyl acetate; an ether such as diethyl ether; or an organic solvent which is not mixed with water, such as a halogenated alkane such as dichloromethane or chloroform. The organic solvent may be used alone or in combination of two or more. Further, the precursor compound (la) may be, for example, represented by the following reaction formula [2] -29-200934755 by adding the corresponding fluorine-containing compound to the corresponding Olefin compound (2a), which can be converted into Flooding compound (2B), by moving the halogenation reaction, using an organic copper reagent, can be manufactured precursor compounds (la). ❹

正型敏輻射線性樹脂組成物及負型敏輻射線性樹脂組成物 ❹ [敏輻射線性酸產生劑] 在本發明之正型敏輻射線性樹脂組成物及負型敏輻射 線性樹脂組成物，搭配有具通式（1 )的構造之磺酸鹽所 成之敏輻射線性酸產生劑。本發明之正型敏輻射線性樹脂 組成物及負型敏輻射線性樹脂組成物中，敏輻射線性酸產 生劑可單獨或2種以上混合使用。 本發明之正型敏輻射線性樹脂組成物及負型敏輻射線 性樹脂組成物中，具有通式（1)構造之磺酸鹽所成之敏 -30- 200934755 輻射線性酸產生劑之使用量隨著敏輻射線性酸產生劑或視 情況所使用之下述其他酸產生劑之種類而異，但相對於含 有酸解離性基之樹脂或鹼可溶性樹脂100質量份，通常爲 0.1〜2 0質量份，較好爲〇.1~15質量份，更好爲0.2〜12質 量份。此時，當敏輻射線性酸產生劑之使用量未達〇. 1質 量份時，會有難以充分發揮本發明期望效果之情況，另一 方面若超過20質量份，則有相對於輻射線之透明性、圖 φ 型形狀、耐熱性等下降之情況。 本發明之正型敏輻射線性樹脂組成物及負型敏輻射線 性樹脂組成物，可倂用一種以上通式（1 )的磺酸鹽所成 之敏輻射線性酸產生劑以外的敏輻射線性酸產生劑（以下 、稱「其他酸產生劑」）。 其他酸產生劑可列舉爲例如鑰鹽化合物、楓化合物、 磺酸酯化合物、磺醯亞胺化合物、重氮甲烷化合物、二磺 醯基甲烷化合物、肟磺酸酯化合物、聯胺磺酸酯化合物等 ❹ 上述鎗鹽化合物可列舉爲例如碘鎗鹽、毓鹽（其中， 包含四氫噻吩鑰鹽）、錢鹽、重氮鎗鹽、銨鹽、吡啶鎗鹽 等。又，上述碾化合物可列舉爲例如β-酮颯、β-磺醯基颯 或該等之α-重氮化合物等。又，上述磺酸酯化合物可列舉 爲例如烷基磺酸酯、鹵烷基磺酸酯、芳基磺酸酯 '亞胺基 磺酸酯等。另外，上述磺醯亞胺化合物可列舉爲以下述通 式（2 )表示之化合物。 -31 - (2) II II200934755 【化2 2】 N一Ο—S—Rw ο C 丨1Positive Sensitive Radiation Linear Resin Composition and Negative Sensitive Radiation Linear Resin Composition ❹ [Sensor Radiation Linear Acid Generator] The positive sensitive radiation linear resin composition and the negative sensitive radiation linear resin composition of the present invention are matched with A sensitive radiation linear acid generator formed from a sulfonate having the structure of the formula (1). In the positive-type radiation-sensitive linear resin composition of the present invention and the negative-type radiation-sensitive linear resin composition, the radiation-sensitive linear acid generator may be used alone or in combination of two or more. In the positive-type sensitive radiation linear resin composition and the negative-type sensitive radiation linear resin composition of the present invention, the sulfonate having the structure of the general formula (1) is used as a sensible -30-200934755 radiation linear acid generator. The sensitive radiation linear acid generator or the other acid generator described below may be used, but it is usually 0.1 to 20 parts by mass based on 100 parts by mass of the resin containing the acid dissociable group or the alkali-soluble resin. It is preferably from 1 to 15 parts by mass, more preferably from 0.2 to 12 parts by mass. In this case, when the amount of the sensitive radiation linear acid generator is less than 0.1 part by mass, it may be difficult to sufficiently exert the desired effect of the present invention. On the other hand, if it exceeds 20 parts by mass, it is relative to the radiation. The transparency, the shape of the figure φ, and the heat resistance are lowered. The positive type sensitive radiation linear resin composition and the negative type sensitive radiation linear resin composition of the present invention can be used with a sensitive radiation linear acid other than the sensitive radiation linear acid generator formed by the above sulfonate of the general formula (1) A generator (hereinafter referred to as "another acid generator"). Other acid generators may, for example, be a key salt compound, a maple compound, a sulfonate compound, a sulfonimide compound, a diazomethane compound, a disulfonylmethane compound, an oxime sulfonate compound, a hydrazine sulfonate compound. The above-mentioned gun salt compound may, for example, be an iodine salt, a phosphonium salt (including a tetrahydrothiophene key salt), a money salt, a diazo gun salt, an ammonium salt, a pyridine gun salt or the like. Further, the above-mentioned milled compound may, for example, be β-ketooxime, β-sulfonylhydrazine or the α-diazo compound or the like. Further, examples of the sulfonic acid ester compound include an alkyl sulfonate, a haloalkyl sulfonate, and an aryl sulfonate 'imine sulfonate. Further, the above sulfonimide compound is exemplified by the compound represented by the following formula (2). -31 - (2) II II200934755 [Chem. 2 2] N-Ο-S-Rw ο C 丨1

II ο (通式（2)中，R8爲2價之有機基，R9爲1價之有機基 )° ^ 通式（2)中，R8可列舉爲例如亞甲基、碳數2-20之 直鏈狀或分支狀伸烷基、碳數7〜20之伸芳烷基、二氟亞 甲基、碳數2〜20之直鏈狀或分支狀全氟伸烷基、伸環己 基、伸苯基、具有原冰片烷骨架之二價基，或該等基經碳 數6以上之芳基或碳數1以上之烷氧基取代之基等。 又，R9可列舉爲例如碳數1〜10之直鏈狀或分支狀烷 基、碳數1〜10之直鏈狀或分支狀全氟院基、碳數3〜10之 全氟環烷基、具有雙環之碳數7〜15之一價烴基、碳數 Q 6~12之芳基等。 另外，上述重氮甲烷化合物可列舉爲例如以下述通式 (3)表示之化合物。 【化2 3】 〇 Ν2 Ο R10-S—C—S—R10 (3)II ο (In the formula (2), R8 is a divalent organic group, and R9 is a monovalent organic group). In the formula (2), R8 may be, for example, a methylene group or a carbon number of 2-20. a linear or branched alkyl group, a 7- to 20-membered aralkyl group, a difluoromethylene group, a linear or branched perfluoroalkyl group having a carbon number of 2 to 20, a cyclohexylene group, and a stretch A phenyl group, a divalent group having an orphanane skeleton, or a group in which the group is substituted with an aryl group having 6 or more carbon atoms or an alkoxy group having 1 or more carbon atoms. Further, R9 may, for example, be a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched perfluorocarbon group having 1 to 10 carbon atoms, or a perfluorocycloalkyl group having 3 to 10 carbon atoms. And having a double ring carbon number of 7 to 15 one-valent hydrocarbon group, carbon number Q 6 to 12 aryl group, and the like. In addition, the diazomethane compound may, for example, be a compound represented by the following formula (3). [化2 3] 〇 Ν2 Ο R10-S-C-S-R10 (3)

II II ο ο (通式（3)中，各R1G相互獨立，表示直鏈狀或分支狀 之烷基、環烷基、芳基、鹵取代烷基、鹵取代環烷基、鹵 -32- 200934755 取代芳基等1價之基）。 又，上述二磺醯基甲烷化合物可列舉爲例如以下述通 式（4)表示之化合物。 R1 J o=s=o 4]| 2 I--c·Iu w OHSnno 1 R1 (通式（4)中，各R11相互獨立，表示直鏈狀或分支狀 之1價之脂肪族烴基、環烷基、芳基、芳烷基或具雜原子 的1價其他有機基，T及U相互獨立，表示芳基、氫原子 、直鏈狀或分支狀之1價之脂肪族烴基、環烷基、芳烷基 或具雜原子的1價其他有機基，且T及U之至少一者爲芳 基，或T與ϋ相互鍵結形成具有至少1個不飽和鍵結的單 環或多環，或Τ與ϋ相互鍵結形成下述式（5)所表示之 基）。 【化2 5】II II ο ο (In the general formula (3), each R1G is independent of each other, and represents a linear or branched alkyl group, a cycloalkyl group, an aryl group, a halogen-substituted alkyl group, a halogen-substituted cycloalkyl group, a halogen-32- 200934755 Substituted aryl group and other monovalent base). Further, the disulfonylmethane compound may, for example, be a compound represented by the following formula (4). R1 J o=s=o 4]| 2 I--c·Iu w OHSnno 1 R1 (In the general formula (4), each R11 is independent of each other, and represents a linear or branched monovalent aliphatic hydrocarbon group or ring. An alkyl group, an aryl group, an aralkyl group or a monovalent other organic group having a hetero atom, T and U are independent of each other, and represent an aryl group, a hydrogen atom, a linear or branched monovalent aliphatic hydrocarbon group, or a cycloalkyl group. An aralkyl group or a monovalent other organic group having a hetero atom, and at least one of T and U is an aryl group, or T and fluorene are bonded to each other to form a monocyclic or polycyclic ring having at least one unsaturated bond, Or Τ and ϋ are bonded to each other to form a group represented by the following formula (5). [化2 5]

(5) (惟，Τ’及U’相互獨立，表示氫原子、鹵原子、直鏈狀或 分支狀之院基、環院基、芳基或芳院基，或鍵結於相同或 不同之碳原子的Τ’與U’相互鍵結形成碳單環構造，且複 數存在之τ’及複數存在之υ’可互爲相同或相異，b爲2〜 -33- 200934755 1 〇之整數）。 另外，肟磺酸酯化合物可列舉爲例如以下述通式（6 1 )或通式（6-2 )表示之化合物等。 【化2 6】(5) (However, Τ' and U' are independent of each other, and represent a hydrogen atom, a halogen atom, a linear or branched garden base, a ring-based base, an aryl group or an aromatic base, or are bonded to the same or different The Τ' and U' of the carbon atom are bonded to each other to form a carbon monocyclic structure, and the τ' of the plural and the υ' of the plural are mutually identical or different, and b is 2~-33- 200934755 1 〇 an integer) . In addition, the oxime sulfonate compound is, for example, a compound represented by the following formula (6 1 ) or formula (6-2). [Chem. 2 6]

Fi12 Ο (6-1) (6-2) NC—C=N—0—S—R13Fi12 Ο (6-1) (6-2) NC—C=N—0—S—R13

II οII ο

o R12 ο R13-S—Ο—N=C—C=N—Ο—S—R13o R12 ο R13-S—Ο—N=C—C=N—Ο—S—R13

A b A (通式（6-1)及通式（6-2)中，R12及R13相互獨立’表 示一價有機基，通式（6-2)中複數存在之R1 2及複數存在 之R13可分別相同亦可不同）。 通式（6-1 )及通式（6-2 )中，R12之具體例可列舉 爲甲基、乙基、正丙基、苯基、對一甲苯基等。 又，R13之具體例可列舉爲苯基、對-甲苯基、卜蔡 基等。 又，聯胺磺酸酯化合物可列舉爲例如以下述通式1 ( 7 1)或通式（7-2)表示之化合物等。 -34- 200934755 【化2 7】 Ο II Η R14-S—Ν—ΝΗ2 (7-1) II ’ ο ο οA b A (in the general formula (6-1) and the general formula (6-2), R12 and R13 are independent of each other' represent a monovalent organic group, and the plural number of R1 2 and the plural present in the general formula (6-2) exist R13 can be the same or different). In the general formula (6-1) and the general formula (6-2), specific examples of R12 include a methyl group, an ethyl group, a n-propyl group, a phenyl group, and a p-tolyl group. Further, specific examples of R13 include a phenyl group, a p-tolyl group, and a butyl group. In addition, the hydrazine sulfonate compound is, for example, a compound represented by the following formula 1 (71) or formula (7-2). -34- 200934755 [Chem. 2 7] Ο II Η R14-S-Ν-ΝΗ2 (7-1) II ’ ο ο ο

II Ν Μ II R14-S—Ν—Ν—S—R14 (7-2) II ιι ο ο (通式（7-1)及通式（7-2)中，R14表示一價 ® 通式（7-2)中複數存在之R14可彼此相同亦可不 通式（7-1)及通式（7-2)中，R14之具體 爲甲基、乙基、正丙基、苯基、對一甲苯基、三 九氟正丁基等。 該等其他酸產生劑中，較好爲鎗鹽化合物、 合物及重氮甲烷化合物之群組之一種或兩種以上 最佳之其他酸產生劑可列舉爲例如二苯基碘 烷磺酸鹽、二苯基碘鑰九氟正丁烷磺酸鹽、二苯 ◎ W -甲苯磺酸鹽、二苯基碘鑰10-樟腦磺酸鹽、二 2 -三氟甲基苯磺酸鹽、二苯基碘鎗4 -三氟甲基苯 二苯基碘鎗2,4_二氟苯磺酸鹽、二苯基碘鎗1，1， 2-(原冰片烷-2-基）乙烷磺酸鹽、二苯基碘鎗2. 丁氧基羰基氧基雙環[2.21]庚-2_基）-1，1，2,2-四 酸鹽、二苯基碘鑰2_(6_第三丁氧基羰基氧基雙 庚-2-基）-1，1,2,2-四氟乙烷磺酸鹽、二苯基碘彳 氟-2-(雙環[2.2.1]庚-2_基）乙烷磺酸鹽、雙（ 基苯基）碘鑰三氟甲烷磺酸鹽、雙（4-第三丁基 有機基， 同）。 例可列舉 氟甲基、 磺醯胺化 〇 鎗三氟甲 基碘鎗對 苯基碘鑷 磺酸鹽、 2,2-四氟--(5-第三 氟乙烷磺 環[2.2.1] 潑 1, ；!-二 4-第三丁 苯基）碗 -35- 200934755 鑰九氟正丁烷磺酸鹽、雙（4-第三丁基苯基）碘鑰對-甲 苯磺酸鹽、雙（4-第三丁基苯基）碘鎗10-樟腦磺酸鹽、 雙（4-第三丁基苯基）碘鑰2-三氟甲基苯磺酸鹽、雙（4-第三丁基苯基）碘鎗4-三氟甲基苯磺酸鹽、雙（4-第三丁 基苯基）碘鑰2,4-二氟苯磺酸鹽、雙（4-第三丁基苯基） 碘鑰1，1，2,2-四氟- 2-(原冰片烷-2-基）乙烷磺酸鹽、雙（ 4- 第三丁基苯基）碘錙1，1-二氟-2-(雙環[2.2.1]庚-2-基 φ )乙烷磺酸鹽、 三苯基鏑三氟甲烷磺酸鹽、三苯基毓九氟正丁烷磺酸 鹽、三苯基锍對-甲苯磺酸鹽、三苯基锍10-樟腦磺酸鹽 、三苯基锍2-三氟甲基苯磺酸鹽、三苯基锍4-三氟甲基苯 磺酸鹽、三苯基锍2,4-二氟苯磺酸鹽、三苯基锍1，1，2,2-四氟-2-(原冰片烷-2-基）乙烷磺酸鹽、三苯基锍2- ( 5-第三丁氧基羰基氧基雙環[2.2.1]庚-2-基）-1,1，2,2-四氟乙 烷磺酸鹽、三苯基毓2- (6-第三丁氧基羰基氧基雙環 φ [2.2.1]庚-2-基）-1,1，2,2-四氟乙烷磺酸鹽、三苯基锍2-( 5- 特戊醯基氧基雙環[2.2.1]庚-2-基）-1,1,2,2-四氟乙烷磺 酸鹽、三苯基鏑2- (6-特戊醯基氧基雙環[2.2.1]庚-2-基 )-1，1,2,2-四氟乙烷磺酸鹽、三苯基锍2- (5-羥基雙環 [2.2.1]庚-2-基）-1，1,2,2-四氟乙烷磺酸鹽、三苯基鏑2-( 6- 羥基雙環[2.2.1]庚-2-基）-1,1,2,2-四氟乙烷磺酸鹽、 三苯基毓2- (5-甲烷磺醯基氧基雙環[2.2.1]庚-2-基 )-1,1,2,2-四氟乙烷磺酸鹽、三苯基毓2- (6-甲烷磺醯基 氧基雙環[2.2.1]庚-2-基）-1，1，2,2-四氟乙烷磺酸鹽、三苯 -36- 200934755 基鏑2- ( 5-異丙烷磺醯 職基氧基雙環[2.2.1]庚-2-基）- 1，1，2,2 -四氟乙院磺酸鹽、— & 二本基銃2- ( 6_異丙基磺醯基 氧基雙環[2.2.1]庚-2-某、，， 垂）-1，1，2,2-四氟乙烷磺酸鹽、三苯 基鏑2- (5-正己烷磺驢 、0®基氧基雙環[2.2.1]庚-2-基）- 1，1，2,2-四氟乙烷磺酸鹽、 —本基鏑2- ( 6-正己基磺醯基 氧基雙環[2.2.1]庚-2-基〉。 ^ )-1，1，2,2-四氟乙烷磺酸鹽、三苯 基銃2-(5-氧代雙環[2.2 e •Π庚·2-基）-mi四氟乙烷磺 酸鹽、二本基鏑2-(6-氧什雜措|~。<_)11!±： 與代雙環[2.2.1]庚-2-基）-i，i，2,2- 雙環[2.2.1]庚- 四氟乙烷磺酸鹽、三苯基銃Ul_二氟_2_ 2-基）乙烷磺酸鹽、 1-(4-正丁氧基萘基）四氫唾吩鑰三氟甲烷磺酸鹽 、1-(4 -正丁氧基萘-1-基）四氫噻吩鑰九氟正丁烷磺酸鹽 、1-(4-正丁氧基萘-1·基）四氫噻吩鑰四氟·2_ ( 原冰片烷-2-基）乙烷磺酸鹽、1-(4_正丁氧基萘_丨_基） 四氫噻吩鎗2-(5-第三丁氧基羰基氧基雙環[221]庚_2_基 ® ) -1，1,2，2·四氟乙院擴酸鹽、1-(4-正丁氧基萘-1-基）四 氫噻吩鑰2-(6-第三丁氧基羰基氧基雙環[221]庚-2_基 )-1，1，2,2-四氟乙烷磺酸鹽、丨_(4_正丁氧基萘-丨_基）四 氫噻吩鎗1，1-二氟-2·(雙環[221]庚_2_基）乙烷磺酸鹽 N-(一氟甲院振醯基氧基）號拍醯亞胺、& ( 1〇_樟 腦擴酿基氧基）號拍醯亞胺、N-[(5 -甲基-5-殘基甲基雙 環[2.2.1]庚-2-基）磺醯基氧基]琥珀醯亞胺、n-(三氟甲 烷磺醯基氧基）雙環[2.2.1]庚-5 -烯-2,3 -二羧醯亞胺、 -37- 200934755II Ν Μ II R14-S—Ν—Ν—S—R14 (7-2) II ιι ο ο (In general formula (7-1) and formula (7-2), R14 represents a monovalent® formula ( 7-2) R14 in the plural plural may be the same as each other or in the formula (7-1) and formula (7-2), and R14 is specifically methyl, ethyl, n-propyl, phenyl, p- Toluene group, trinonafluoro-n-butyl group, etc. Among the other acid generators, one or two or more of the other acid generators preferably selected from the group consisting of a gun salt compound, a compound and a diazomethane compound may be used. Listed as, for example, diphenyl iodonane sulfonate, diphenyl iodine hexafluoro n-butane sulfonate, diphenyl ◎ W - tosylate, diphenyl iodine 10 - camphor sulfonate, 2 -trifluoromethylbenzenesulfonate, diphenyl iodide 4-trifluoromethylbenzenediphenyl iodine 2,4-difluorobenzenesulfonate, diphenyl iodine 1,1, 2-( Orbornane-2-yl)ethanesulfonate, diphenyl iodine 2. Butoxycarbonyloxybicyclo[2.21]heptan-2-yl)-1,1,2,2-tetraate, Diphenyl iodide 2_(6_t-butoxycarbonyloxybisheptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium fluoride-2- (double [2.2.1] hept--2_ yl) ethanesulfonate, bis (phenyl) iodonium trifluoromethanesulfonate key, bis (4-tert-butyl organic group, the same). Examples include fluoromethyl, sulfoximine oxime gun trifluoromethyl iodine gun phenyl iodonium sulfonate, 2,2-tetrafluoro-(5-trifluoroethane sulfonate ring [2.2.1] ]Pour 1 , ;!-di 4-tert-butylphenyl) bowl-35- 200934755 key nonafluoro-n-butane sulfonate, bis(4-t-butylphenyl) iodine p-toluene sulfonate , bis(4-tert-butylphenyl) iodine gun 10-camphorsulfonate, bis(4-t-butylphenyl) iodine 2-trifluoromethylbenzenesulfonate, double (4- Tributylphenyl) iodine gun 4-trifluoromethylbenzenesulfonate, bis(4-tert-butylphenyl) iodine 2,4-difluorobenzenesulfonate, double (4-third Iridyl phenyl iodide 1,1,2,2-tetrafluoro-2-(n-bornee-2-yl)ethanesulfonate, bis(4-t-butylphenyl)iodonium 1,1 -difluoro-2-(bicyclo[2.2.1]hept-2-ylφ)ethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluorobutane sulfonate, Triphenylphosphonium p-toluenesulfonate, triphenylsulfonium 10-camphorsulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 4-trifluoromethylbenzenesulfonic acid Salt, triphenylsulfonium 2,4-difluorobenzenesulfonate, triphenyl锍1,1,2,2-tetrafluoro-2-(albornane-2-yl)ethanesulfonate, triphenylsulfonium 2-(5-tert-butoxycarbonyloxybicyclo[2.2. 1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2-(6-t-butoxycarbonyloxybicyclo[2.2.1]g -2-yl)-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2-(5-pententyloxybicyclo[2.2.1]hept-2-yl)- 1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2-(6-pententyloxybicyclo[2.2.1]hept-2-yl)-1,1,2, 2-tetrafluoroethane sulfonate, triphenylsulfonium 2-(5-hydroxybicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, three Phenylhydrazine 2-(6-hydroxybicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2-(5-methanesulfonate) Baseoxybicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2-(6-methanesulfonyloxybicyclo[2.2 .1]hept-2-yl)-1,1,2,2-tetrafluoroethane sulfonate, triphenyl-36- 200934755 base 镝2-( 5-isopropane sulfonyloxycarbonyl double ring [2.2 .1]hept-2-yl)- 1,1,2,2-tetrafluoroethane sulfonate, — & di-based 铳2- (6- Alkylsulfonyloxybicyclo[2.2.1]hept-2-yl,, drool-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2-(5-n-hexane Sulfonium, 0. yloxybicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethane sulfonate, —benyl 2-(6-n-hexylsulfonate Alkoxybicyclo[2.2.1]hept-2-yl>. ^)-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2-(5-oxobicyclo[2.2 e •Πg·2-yl)-mi tetrafluoroethanesulfonic acid Salt, dibasic hydrazine 2-(6-oxo oxazepine|~.<_)11!±: and substituted bicyclo[2.2.1]hept-2-yl)-i,i,2,2-bicyclic [2.2.1] G-tetrafluoroethane sulfonate, triphenylsulfonium Ul-difluoro-2-phenyl]ethanesulfonate, 1-(4-n-butoxynaphthyl)tetrahydropyrene Palladium trifluoromethanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene-non-nonafluoro-n-butane sulfonate, 1-(4-n-butoxynaphthalene-1· Tetrahydrothiophene quaternary hexafluoro-2-(pronorborol-2-yl)ethanesulfonate, 1-(4-?-butoxynaphthalene-indoleyl) tetrahydrothiophene gun 2-(5- Tributoxycarbonyloxybicyclo[221]hept-2-yl®)-1,1,2,2·tetrafluoroethane compound, 1-(4-n-butoxynaphthalen-1-yl) Tetrahydrothiophene 2-(6-t-butoxycarbonyloxybicyclo[221]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 丨_(4_正Butoxynaphthalene-indole-yl) tetrahydrothiophene gun 1,1-difluoro-2·(bicyclo[221]hept-2-yl)ethanesulfonate N-(fluorinated fluorenyloxy) )) 醯 醯 imine, & ( 1〇 _ 樟Expanded oxyalkyl), N-[(5-methyl-5-resylmethylbicyclo[2.2.1]hept-2-yl)sulfonyloxy]succinimide, N-(Trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-carbosalimine, -37- 200934755

(九氟正丁院龍基氧基）冑環[2 2 im_5U，3二竣 醯亞fe： N-tmr四氣_2•(原冰片院_2·基）乙院擴釀 基氧基]雙環[2.2.1]庚-5_嫌_2,3_二竣釀亞胺、心（1〇_棒 腦磺醯基氧基）雙環[2·2.·_5_烯_2,3_二羧醯亞胺、Ν· [2- (5-氧代雙環[2.21]庚-2_基）m2·四氟乙院磺酿基 氧基]雙環[2·2·1]庚-5-嫌-2，3_二殘醯亞胺、N-[2- (6-氧 代雙環[2.2.1]庚_2_基）四氟乙烷磺醯基氧基]雙 環[2.2.1]庚_5_烯_2,3_二羥醯亞胺、-二氟_2_ (雙環 [2.2.1]庚-2-基）乙烷磺醯基氧基]雙環[221]庚_5_烯·2,3_ 一殘酿亞胺、雙（環己院磺醯基）重氮甲院、雙（第三丁 基磺醯基）重氮甲烷、雙二氧雜螺[45]癸-7_磺醯基 )重氮甲烷等。 其他酸產生劑之使用比例可依據其他酸產生劑之種類 適當選擇’但相對於本發明之磺酸鹽所成的敏輻射線性酸 產生劑（I )與其他酸產生劑之合計1 〇 〇質量份，通常爲 〇 95質量份以下，較好爲90質量份以下，更好爲80質量份 以下。此時’若其他酸產生劑之使用比例超過95質量份 ，則有損及本發明期望效果之情況。 [含有酸解離性基之樹脂] 本發明之正型敏輻射線性樹脂組成物中，調配有具有 酸解離性基之鹼不溶性或鹼難溶性之樹脂且該酸解離性基 解離時變成鹼易溶性之樹脂（以下稱爲「含有酸解離性基 之樹脂」）。此處所謂「鹼不溶性或鹼難溶性」意指自使 -38- 200934755 用含有含酸解離性基之樹脂之敏輻射線性樹脂 之光阻被膜形成光阻圖型時採用之鹼顯像條件 含酸解離性基之樹脂取代該光阻被膜的被膜顯 膜之初期厚度之50%以上在顯像後殘存之性質 含有酸解離性基之樹脂中之酸解離性基意 經基、竣基、磺酸基等酸性官能基中取代氫原 酸存在下解離之基。該等酸解離性基可列舉爲 Ο 基、1_取代乙基、1-取代正丙基、1-分支烷基 組成物形成 下，僅使用 像時，該被 〇 指例如酚性 子之基，在 例如取代甲 、烷氧基羰 甲硫基甲基 基）甲基、 4-溴苯甲醯 甲基、α-甲 基、三苯基 、4-甲硫基 、甲氧基羰 、異丙氧基 S甲基等。 氧基乙基、 乙基、1 -乙 、卜苯硫基 1 -苄基硫基 、1-苯基乙 基'釀基、環式酸解離性基等。 上 述 取 代 甲 基 可 列 舉 爲 例 如 甲 氧 基 甲 基 、 乙 氧 棊 甲 基 乙 硫 基 甲 基 、 ( 2- 甲 氧 基 乙 氧 苄 基 氧 基 甲 基 苄 基 硫 基 甲 基 、 苯 甲 醯 甲 基 、 甲 基 、 4- 甲 氧 基 苯 甲 醯 甲 基 4- 甲 硫 基 苯 甲 醯 基 苯 甲 醯 甲 基 壞 丙 基 甲 基 苄 基 二 苯 基 甲 甲 基 、 4- 溴 苄 基 、 4- 硝 基 苄 基 4- 甲 氧 基 苄 基 苄 基 、 4- 乙 氧 基 苄 基 4- 乙 硫 基 苄 基 胡 椒 基 基 甲 基 乙 氧 基 W. 基 甲 基 ' 正 丙 氧 基 Υμΐ im 基 甲 基 νμι 拔 基 甲 基 正 丁 氧 基 基 甲 基 、 第 二 丁 氧 基i 取 另 外 上 述 1-取 代 乙 基 可 列 舉 爲 例 如 1 - 甲 1 - 甲 硫 基 乙 基 、 1， 1 - 二 甲 氧 基 乙 基 > 1 - 乙 氧 基 硫 基 乙 基 、 1， 1 - 二 乙 氧 基 乙 基 1-苯 氧 基 乙 基 乙 基 、 1， Κ — 苯 氧 基 乙 基 、 1-苄 基 氧 基 乙 基 、 乙 基 、 1 - 環 丙 基 氧 基 乙 基 、 1 - 環 己 基 氧 基 乙 基 200934755 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等。 另外，上述1 -取代正丙基可列舉爲例如1 -甲氧基-正 丙基、1-乙氧基-正丙基等，又，上述1-分支烷基可列舉 爲例如異丙基、1-甲基丙基、第三丁基、1,1-二甲基丙基 、1-甲基丁基、1，1-二甲基丁基等。另外，上述烷氧基羰 基可列舉爲例如甲氧基羰基、乙氧基羰基、異丙氧基羰基 Φ 、第三丁氧基羰基等。 又，上述醯基可列舉爲例如乙醯基、丙醯基、丁醯基 、庚醯基、己醯基、戊醯基、特戊醯基、異戊醯基、月桂 醯基、肉宣蔻醯基、棕櫚醯基、硬脂醯基、草醯基、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、巴豆醯基、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 〇 甲醯基、對苯二甲醯基、萘甲醯基、甲苯醯基、氫阿托醯 基、阿托醯基、桂皮醯基、呋喃甲醯基、噻吩甲醯基、菸 鹼醯基、異菸鹼醯基、對一甲苯磺醯基、甲磺醯基等。 又，上述環式酸解離性基可列舉爲例如環丙基、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、四氫硫吡喃基、四氫硫呋喃基、3 -溴四氫吡 喃基、4-甲氧基四氫吡喃基、4-甲氧基四氫硫耻喃基、3-四氫噻吩-1,1-二氧化物基等。 該等酸解離性基中，較佳者爲苄基、第三丁氧基羰基 -40- 200934755 甲基、1-甲氧基乙基、1-乙氧基乙基、1-環己 、1-乙氧基正丙基、第三丁基、1，1-二甲基丙 氧基羰基、四氫吡喃基、四氫呋喃基、四氫硫 氫硫呋喃基。含有酸解離性基之樹脂中可存在 酸解離性基。 含有酸解離性基之樹脂中之酸解離性基之 酸解離性基之樹脂中，相對於酸性官能基及酸 Φ 合計數，酸解離性基之數之比例）可依酸解離 有該基之樹脂之種類作適當選擇，但較好爲 好爲10〜100%。 又，含酸解離性基之樹脂之構造只要具有 無特別限制，可爲各種構造，但尤其以聚（4-基）中之酚性羥基之氫原子之一部分或全部經 取代之樹脂，4-羥基苯乙烯及/或4-羥基-α-甲 (甲基）丙烯酸之共聚物中之酚性羥基之氫ί 〇 基之氫原子之一部分或全部經酸解離性基取代 佳。 又，含酸解離性基之樹脂之構造可依據所 線種類而作各種選擇。例如，使用KrF準分子 敏輻射線性樹脂組成物中特別適用之含酸解離 較好爲例如具有以下列通式（8 )表示之重複 稱爲「重複單位（8 )」）及以酸解離性基保 (8)中之酚性羥基之重複單位之鹼不溶性或 脂。而且，該樹脂亦可適當使用於ArF準分 基氧基乙基 基、第三丁 吡喃基、四 一種以上之 導入率（含 解離性基之 性基或導入 5-100% -更 上述特性則 •羥基苯乙烯 酸解離性基 基苯乙烯與 鼠子及/或羧 之樹脂等較 使用之輻射 雷射之正形 性基之樹脂 單位（以下 護重複單位 鹼難溶性樹 子雷射、F2 -41 - 200934755 準分子雷射、電子束等其他輻射線之正型敏輻射線性樹脂 組成物中。 【化2 8】(nonafluoro-n-butyl diphenyloxy) anthracene ring [2 2 im_5U, 3 bismuth fe: N-tmr four gas _2 • (formerly the ice film institute _2 · base) Bicyclo[2.2.1]gly-5_discriminate _2,3_di-branched imine, heart (1〇_ cerebral sulfonyloxy) bicyclo[2·2··_5_ene_2,3_ Dicarboxylated imine, Ν·[2-(5-oxobicyclo[2.21]hept-2-yl)m2·tetrafluoroethane sulfonyloxy]bicyclo[2·2·1]hept-5- -2-2,3_二残醯imino, N-[2-(6-oxobicyclo[2.2.1]heptan-2-yl)tetrafluoroethanesulfonyloxy]bicyclo[2.2.1] Hg-5-ene-2,3-dihydroxyindoleimine, -difluoro-2-((bicyclo[2.2.1]hept-2-yl)ethanesulfonyloxy]bicyclo[221]hept_5_ Alkene 2,3_ a residual imine, bis(cyclohexylsulfonyl)diazide, bis(t-butylsulfonyl)diazomethane, bisdioxospiro[45]癸-7 _sulfonyl) diazomethane and the like. The ratio of use of other acid generators may be appropriately selected depending on the kind of other acid generators, but the total amount of the sensitive radiation linear acid generator (I) and other acid generators formed with respect to the sulfonate of the present invention is 1 〇〇 The portion is usually 95 parts by mass or less, preferably 90 parts by mass or less, more preferably 80 parts by mass or less. At this time, if the ratio of use of the other acid generator exceeds 95 parts by mass, the desired effect of the present invention may be impaired. [Resin-containing resin-containing resin] The positive-type radiation-sensitive linear resin composition of the present invention is formulated with an alkali-insoluble or alkali-insoluble resin having an acid-dissociable group and becomes an alkali-soluble property upon dissociation of the acid-dissociable group. Resin (hereinafter referred to as "resin containing acid dissociable group"). Here, the term "alkali-insoluble or alkali-insoluble" means an alkali-developing condition for use in forming a photoresist pattern from a photoresist film containing a photosensitive radiation-containing linear resin containing an acid-dissociable group-containing resin from -38 to 200934755. The resin of the acid dissociable group replaces 50% or more of the initial thickness of the film of the photoresist film, and the acid dissociable base group, sulfhydryl group, and sulfonate in the resin having an acid dissociable group remaining after development An acidic functional group such as an acid group is substituted in the presence of a hydrogenoic acid. The acid-dissociable group may be exemplified by a thiol group, a 1-substituted ethyl group, a 1-substituted n-propyl group or a 1-branched alkyl group. When only an image is used, the element is referred to as a phenolic group. For example, a substituted methyl, alkoxycarbonylmethylmethyl)methyl, 4-bromobenzylidenemethyl, a-methyl, triphenyl, 4-methylthio, methoxycarbonyl, isopropyl Oxy S methyl group and the like. An oxyethyl group, an ethyl group, a 1-ethyl group, a phenylthio group, a 1-benzylthio group, a 1-phenylethyl group, a cyclic acid dissociable group, and the like. The above substituted methyl group may, for example, be methoxymethyl, ethoxymethyl methylthiomethyl, (2-methoxyethoxybenzyloxymethylbenzylthiomethyl, benzoguanidine) Base, methyl, 4-methoxybenzimidylmethyl 4-methylthiobenzimidylbenzhydrylmethyl-d-propylmethylbenzyldiphenylmethyl, 4-bromobenzyl, 4 - Nitrobenzyl 4-methoxybenzyl benzyl, 4-ethoxybenzyl 4-ethylthiobenzyl piperonylmethyl ethoxy W. Methyl-n-propoxy Υμΐ im Methyl νμι benzylmethyl n-butoxymethyl, second butoxy i, and the above 1-substituted ethyl may be exemplified by, for example, 1-methyl-1-methylthioethyl, 1,1-dimethyl Oxyethylethyl> 1 -ethoxythioethyl, 1,1-diethoxyethyl 1-phenoxyethylethyl, 1, fluorenyl-phenoxyethyl, 1-benzyl Oxyethyl, ethyl , 1 -cyclopropyloxyethyl, 1 -cyclohexyloxyethyl 200934755 ethyl, 1-n-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-n-butoxycarbonyl Ethyl, 1-tert-butoxycarbonylethyl, etc. Further, the above 1-substituted n-propyl group may, for example, be a 1-methoxy-n-propyl group, a 1-ethoxy-n-propyl group or the like, The above 1-branched alkyl group may, for example, be isopropyl, 1-methylpropyl, tert-butyl, 1,1-dimethylpropyl, 1-methylbutyl, 1,1-dimethyl Further, the alkoxycarbonyl group may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group Φ or a third butoxycarbonyl group. Ethyl, propyl, butyl, gamma, hexyl, pentyl, pentylene, isoamyl, laurel, fenganyl, palmitoyl, stearyl , glyphosyl, propylenediyl, amber, pentane, hexamethylene, hexamethylene, octyl, fluorenyl, fluorenyl, propylene, propyne Mercapto group, methacryloyl fluorenyl Croton, sulfonyl, maleic, fumarine, zhongkang, camphor, benzylidene, phthalic acid, m-benzoic fluorenyl, p-xylylene , naphthylmethyl, tolylhydrazyl, hydrogen atropine, atovarenyl, cinnamyl, furanyl, thiophenemethyl, nicotine sulfhydryl, isonicotinic fluorenyl, p-toluene Sulfhydryl, methanesulfonyl and the like. Further, the above cyclic acid dissociable group may, for example, be a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 4-methoxycyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group or a tetrahydropyridinium group. Cyclol, tetrahydrothiofuranyl, 3-bromotetrahydropyranyl, 4-methoxytetrahydropyranyl, 4-methoxytetrahydrothiopyranyl, 3-tetrahydrothiophene-1,1 - a dioxide group or the like. Among the acid dissociable groups, preferred are benzyl, tert-butoxycarbonyl-40-200934755 methyl, 1-methoxyethyl, 1-ethoxyethyl, 1-cyclohexyl, 1 - ethoxy-n-propyl, tert-butyl, 1,1-dimethylpropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiohydrofuranyl. An acid dissociable group may be present in the resin containing an acid dissociable group. In the resin of the acid dissociable group of the acid dissociable group in the acid dissociable group-containing resin, the ratio of the number of the acid dissociable groups relative to the acid functional group and the acid Φ can be dissociated by the acid. The kind of the resin is appropriately selected, but it is preferably from 10 to 100%. Further, the structure of the acid-dissociable group-containing resin may be various structures as long as it is not particularly limited, but in particular, a resin partially or wholly substituted with one of the hydrogen atoms of the phenolic hydroxyl group in the poly(4-group), 4- The hydrogen of the phenolic hydroxyl group in the copolymer of hydroxystyrene and/or 4-hydroxy-α-methyl (meth)acrylic acid is partially or completely substituted by the acid dissociable group. Further, the structure of the acid-dissociable group-containing resin can be variously selected depending on the type of the line. For example, an acid-containing dissociation particularly suitable for use in a KrF excimer-sensitive radiation linear resin composition is preferably, for example, a repeat represented by the following formula (8) as a "repeating unit (8)") and an acid-dissociable group. An alkali-insoluble or fat of a repeating unit of a phenolic hydroxyl group in (8). Further, the resin may be suitably used in the ArF quasi-based oxyethyl group, the third butylpyranyl group, or the introduction ratio of four or more kinds (the dissociative group-containing group or the introduction of 5-100% - more) The characteristics are: hydroxy styrene acid dissociable styrene and the resin unit of the radiation laser which is used in comparison with the mouse and/or carboxy resin (the following repeating unit alkali poorly soluble tree laser, F2) -41 - 200934755 Positive sensitized radiation linear resin composition of excimer laser, electron beam and other radiation. [Chem. 2 8]

(通式（8)中’ R15爲氫原子或1價之有機基，複數存在 之R15可互爲相同或相異，c及d分別爲1〜3之整數）。 重複單位（8 )，尤其以4-羥基苯乙烯之非芳香族雙 鍵開裂之單位較佳。又，該樹脂亦可含有其他重複單位。 上述其他重複單位可列舉爲例如苯乙烯、α-甲基苯乙 _等乙烯基芳香族化合物；（甲基）丙烯酸第三丁酯、（ Q 甲基）丙烯酸金剛烷酯、（甲基）丙烯酸2-甲基金剛烷酯 等（甲基）丙烯酸酯類之聚合性不飽和鍵開裂之單位等。 又，使用ArF準分子雷射之正型敏輻射線性樹脂組成 物中最適用之含酸解離性基之樹脂較好爲例如具有以下列 通式（9)表示之重複單位（以下稱爲「重複單位（9)」 )及/或以下列通式（1〇)表示之重複單位（以下稱爲「 重複單位（10)」）及以下列通式（11)表示之重複單位 (以下稱爲「重複單位（11)」）之鹼不溶性或鹼難溶性 之樹脂。再者，該樹脂亦可適當的用於使用KrF準分子雷 射、F2準分子雷射、電子束等其他輻射線之正型敏輻射 -42- 200934755 線性樹脂組成物中。(In the formula (8), R15 is a hydrogen atom or a monovalent organic group, and R15 of the plural number may be the same or different from each other, and c and d are each an integer of 1 to 3). The repeating unit (8) is particularly preferably a unit of non-aromatic double bond cracking of 4-hydroxystyrene. Further, the resin may contain other repeating units. The above other repeating unit may, for example, be a vinyl aromatic compound such as styrene or α-methylphenylethyl group; a third butyl (meth)acrylate, an adamantyl (Q-methyl)acrylate, or a (meth)acrylic acid; A unit of polymerizable unsaturated bond cracking of a (meth) acrylate such as 2-methyladamantyl ester. Further, the most suitable acid-dissociable group-containing resin in the positive-type radiation-sensitive linear resin composition using the ArF excimer laser is preferably, for example, a repeating unit represented by the following formula (9) (hereinafter referred to as "repeating" Unit (9)") and/or a repeating unit represented by the following general formula (1) (hereinafter referred to as "repetition unit (10)") and a repeating unit represented by the following general formula (11) (hereinafter referred to as " Repeat the unit (11)") of alkali-insoluble or alkali-insoluble resin. Further, the resin can also be suitably used in a linear resin composition using positive radiation of a radiation such as KrF excimer laser, F2 excimer laser, electron beam or the like.

[化2 9】[化2 9]

R17R17

0=C I 0 r20-c-r20 R20 (9) (10) (ii) (通式（9)、通式（10)及通式（11)中，R16、R18及 R19相互獨立，表示氫原子或甲基，通式（9)中，各R17 相互獨立，表示氫原子、羥基、氰基或-COOR21 (惟，R21 爲氫原子、碳數1〜4之直鏈狀或分支狀之烷基或碳數3〜 20之環烷基。），通式（11)中，各R2G相互獨立，表示 ® 碳數4〜20之1價之脂環式烴基或其衍生物或碳數1〜4 之直鏈狀或分支狀之烷基，且r2°之至少一個係該脂環式 烴基或其衍生物’或任兩個之r2()相互鍵結’與各自鍵結 的碳原子共同形成碳數4〜20之2價之脂環式烴基或其衍 生物，其他的R2()表示碳數1〜4之直鏈狀或分支狀之烷 基或碳數4〜20之1價之脂環式烴基或其衍生物）。 較佳之重複單位（9 )可列舉爲例如（甲基）丙嫌酸 3 -羥基金剛院-卜基酯、（甲基）丙烯酸3，5_二羥基金剛 烷-1-基酯、（甲基）丙烯酸3_氰基金剛院基醋、（甲 -43- 200934755 基）丙烯酸3-羧基金剛烷-1-基酯、（甲基）丙烯酸3,5-二羧基金剛烷-1-基酯、（甲基）丙烯酸3-羧基-5-羥基金 剛烷-1-基酯、（甲基）丙烯酸3-甲氧基羰基-5-羥基金剛 烷-1·基酯等。 又，較佳之重複單位（1 1 )可列舉爲例如（甲基）丙 烯酸1-甲基環戊酯、（甲基）丙烯酸1-乙基環戊酯、（甲 基）丙烯酸1-甲基環己酯、（甲基）丙烯酸1-乙基環己酯 〇 、（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-正丙基金剛 烷-2-基酯、（甲基）丙烯酸2-異丙基金剛烷-2-基酯、（ 甲基）丙烯酸1-(金剛烷-1-基）-1-甲基乙酯等。 上述樹脂亦可進而具有其他重複單位。賦予上述其他 重複單位之單體可列舉爲例如（甲基）丙烯酸7-氧代_6_ 氧雜雙環[3.2.1]辛-4-基酯、（甲基）丙烯酸2-氧代四氫 吡喃-4-基酯、（甲基）丙烯酸4-甲基-2-氧代四氫吡喃-4_ 〇 基酯、（甲基）丙烯酸5-氧代四氫呋喃-3-基酯、（甲基 )丙烯酸2-氧代四氫呋喃-3-基酯、（甲基）丙烯酸（5_ 氧代四氫呋喃-2-基）甲酯、（甲基）丙烯酸（3,3-二甲 基-5-氧代四氫呋喃-2-基）甲酯等（甲基）丙烯酸酯類； (甲基）丙烯醯胺、N，N-二甲基（甲基）丙烯醯胺、巴g 醯胺、馬來醯胺、富馬醯胺、中康醯胺、甲順丁烯二酿胺 (Citraconamide )、依康醯胺等不飽和醯胺化合物；馬來 酸酐、依康酸酐等不飽和聚羧酸酐；雙環[2.2.1]庚-其衍生物；四環[6.2.1.13’6.02’7]癸-3-烯或其衍生物等單官 -44- 200934755 能基單體，或亞甲二醇一（甲基）两燃酸酯、乙二醇二（ 甲基）丙烯酸酯、2,5 -二甲基-2，5 -己烷二醇二（甲基）丙 稀酸酯、1,2 -金剛院二醇二（甲基）丙嫌酸酯、L3 -金剛 院二醇二（甲基）丙嫌酸醋、1,4-金剛院二醇二（甲基） 丙烯酸酯、三環癸烷二羥甲基二（甲基）丙烯酸酯等多官 能性單體。 再者’使用F2準分子雷射之正型敏輻射線性樹脂組 ❹ 成物中特別適用之含酸解離性基之樹脂，較好爲具有以下 述通式（12)表示之構造單位（以下稱爲「構造單位（12 )」）及/或以下述通式（13)表示之構造單位（以下稱 爲「構造單位（13)」）之鹼不溶性或鹼難溶性聚矽氧烷 。再者，該樹脂亦適用於使用KrF準分子雷射、ArF準分 子雷射、電子束等其他輻射線之正型敏輻射線性樹脂組成 物中。0=CI 0 r20-c-r20 R20 (9) (10) (ii) (In the formula (9), the formula (10) and the formula (11), R16, R18 and R19 are independent of each other and represent a hydrogen atom. Or a methyl group, in the formula (9), each R17 is independent of each other and represents a hydrogen atom, a hydroxyl group, a cyano group or -COOR21 (except that R21 is a hydrogen atom, a linear or branched alkyl group having a carbon number of 1 to 4) Or a cycloalkyl group having a carbon number of 3 to 20.), in the formula (11), each R2G is independent of each other, and represents an alicyclic hydrocarbon group or a derivative thereof having a carbon number of 4 to 20 or a carbon number of 1 to 4. a linear or branched alkyl group, and at least one of r2° is the alicyclic hydrocarbon group or a derivative thereof' or any two of r2() are bonded to each other to form a carbon with each bonded carbon atom a 4 to 20 alicyclic alicyclic hydrocarbon group or a derivative thereof, and the other R 2 () represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic ring having a carbon number of 4 to 20 a hydrocarbon group or a derivative thereof). Preferred repeating units (9) are exemplified by (meth)acrylic acid 3-hydroxy-dragon-d-butyl ester, (meth)acrylic acid 3,5-dihydroxyadamantan-1-yl ester, (methyl) Acrylic acid 3_Cyanide fund, ketone, (carboxy-43-200934755), 3-carboxyadamantan-1-yl (meth)acrylate, 3,5-dicarboxyadamantan-1-yl (meth)acrylate, 3-carboxy-5-hydroxyadamantan-1-yl (meth)acrylate, 3-methoxycarbonyl-5-hydroxyadamantan-1-yl (meth)acrylate, and the like. Further, preferred repeating units (1 1 ) are, for example, 1-methylcyclopentanyl (meth)acrylate, 1-ethylcyclopentanyl (meth)acrylate, and 1-methylcyclo(meth)acrylate. Hexyl ester, 1-ethylcyclohexyl (meth)acrylate, 2-methyladamantan-2-yl (meth)acrylate, 2-ethyladamantan-2-yl (meth)acrylate , 2-n-propyladamantan-2-yl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, 1-(adamantane-1-(meth)acrylate Base)-1-methylethyl ester and the like. The above resin may further have other repeating units. The monomer to which the above other repeating unit is given may, for example, be 7-oxo-6-oxabicyclo[3.2.1]oct-4-yl (meth)acrylate or 2-oxotetrahydropyridyl (meth)acrylate.喃-4-yl ester, 4-methyl-2-oxotetrahydropyran-4- decyl (meth) acrylate, 5-oxotetrahydrofuran-3-yl (meth) acrylate, (methyl) ) 2-oxotetrahydrofuran-3-yl acrylate, (5-oxotetrahydrofuran-2-yl)methyl (meth)acrylate, (meth)acrylic acid (3,3-dimethyl-5-oxotetrahydrofuran (2-)methyl esters such as methyl esters; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, benzylamine, maleamide, rich Unsaturated guanamine compounds such as melamine, mesaconamine, Citraconamide, and econazole; unsaturated polycarboxylic anhydrides such as maleic anhydride and isaconic anhydride; bicyclo[2.2.1 Geng-derivative; tetracyclo[6.2.1.13'6.02'7] indole-3-ene or its derivatives, such as mono-44-200934755, or methylene glycol mono(methyl) Acid ester, ethylene glycol di(meth)acrylate, 2,5 - Methyl-2,5-hexanediol di(meth)propionic acid ester, 1,2-diamond diol di(methyl)propionic acid acrylate, L3-diamond diol di(methyl) A polyfunctional monomer such as acrylic acid vinegar, 1,4-golden diol di(meth) acrylate, or tricyclodecane dimethylol di(meth) acrylate. Further, the resin containing an acid-dissociable group, which is particularly suitable for use in a positive-type radiation-sensitive linear resin group of an F2 excimer laser, preferably has a structural unit represented by the following formula (12) (hereinafter referred to as It is an alkali-insoluble or alkali-insoluble polyoxyalkylene which is a "structural unit (12)") and/or a structural unit (hereinafter referred to as "structural unit (13)") represented by the following general formula (13). Further, the resin is also suitable for use in a positive-sensitive radiation linear resin composition using a KrF excimer laser, an ArF quasi-laser laser, an electron beam or the like.

【化3 0】 E E | Si- 1 0 1 R22 (12) (13)[Chemical 3 0] E E | Si- 1 0 1 R22 (12) (13)

(通式（12)及通式（13)中’各E相互獨立，表示具酸 解離性基的1價之有機基，R22爲取代或非取代之碳數1 〜20之直鏈狀、分支狀或環狀的1價之烴基）。 通式（12)及通式（13)中之E較好爲環烷基、原冰 -45- 200934755 片烷基、三環癸基、四環十二烷基、金剛烷基等脂環式烴 基中具有酸解離性基之基、或鹵化芳香族烴基中具有酸解 離性基之基等。 上述樹脂中特佳之構造單位（1 2 )，可例舉以下述式 (12-1)〜（12-4)所表示之構造單位等。 [化3 1】 ο(In the general formula (12) and the general formula (13), each E is independent of each other, and represents a monovalent organic group having an acid-dissociable group, and R22 is a substituted or unsubstituted linear group having a carbon number of 1 to 20 and a branch. a cyclic or cyclic monovalent hydrocarbon group). The E in the general formula (12) and the general formula (13) is preferably an alicyclic group such as a cycloalkyl group, an original ice-45-200934755 alkyl group, a tricyclodecyl group, a tetracyclododecyl group or an adamantyl group. The group having an acid dissociable group in the hydrocarbon group or a group having an acid dissociable group in the halogenated aromatic hydrocarbon group. The structural unit (1 2 ) which is particularly preferable in the above-mentioned resin may be a structural unit represented by the following formulas (12-1) to (12-4). [化3 1] ο

H2C—C—0—C—0—C(CH3)3 cf3 C-〇-C(CH3)3ο (12-1) (12-2)H2C—C—0—C—0—C(CH3)3 cf3 C-〇-C(CH3)3ο (12-1) (12-2)

(12-3) (12-4) -46 - 200934755 上述樹脂可含有一種以上之上述以外之構造單位（以 下稱爲「其他構造單位」）。較佳之其他構造單位可列舉 爲例如甲基三甲氧基砂院、甲基二乙氧基砂院、乙基三甲 氧基砂院、乙基三乙氧基矽烷等烷基烷氧基矽烷類經水解 •縮合之構造單位；以下述式（14_n〜（14_4)表示 造單位等。(12-3) (12-4) -46 - 200934755 The above resin may contain one or more structural units other than the above (hereinafter referred to as "other structural units"). Preferred other structural units are, for example, alkyl alkoxy decanes such as methyltrimethoxy sand, methyl diethoxy sand, ethyl trimethoxy sand, and ethyl triethoxy decane. A structural unit of hydrolysis and condensation; and a unit or the like is represented by the following formula (14_n to (14_4)).

OH -2) 14-OH -2) 14-

(14-3)(14-3)

(14-4) 47- 200934755 上述樹脂可藉由使具有酸解離性基之一種以上之矽烷 化合物（共）聚合、或在預先合成之有機聚矽氧烷上導入 一種以上之酸解離性基而製造。 使具有酸解離性基之矽烷化合物（共）聚合時，較好 使用酸性觸媒作爲觸媒，尤其，在酸性觸媒存在下使矽烷 化合物聚縮合後，添加鹼性觸媒再進行反應較佳。 上述酸性觸媒可列舉爲例如鹽酸、硫酸、硝酸、硼酸 Q 、磷酸、四氯化鈦、氯化鋅、氯化鋁等無機酸類；甲酸、 乙酸、正丙酸、丁酸、戊酸、草酸、丙二酸、琥珀酸、馬 來酸、富馬酸、己二酸、苯二甲酸、對苯二甲酸、乙酸酐 、馬來酸酐、檸檬酸' 苯磺酸、對甲苯磺酸、甲烷磺酸等 有機酸類。該等酸性觸媒中’以鹽酸、硫酸、乙酸、草酸 、丙二酸、馬來酸、富馬酸、乙酸酐、馬來酸酐等較佳。 又，上述鹼性觸媒可列舉爲例如氫氧化鋰、氫氧化鈉 、氫氧化鉀、氫氧化鈣、氫氧化鋇、碳酸氫鈉、碳酸氫鉀 〇 、碳酸鈉、碳酸鉀等無機鹼類；三乙胺、三正丙基胺、三 正丁基胺、吡啶等有機鹼類。 含有酸解離性基之樹脂係藉聚合性不飽和單體之聚合 或經由該聚合製造時，該樹脂可導入源自具有2個以上聚 合性不飽和鍵之多官能性單體之單位及/或乙縮醛性交聯 基之分支構造。藉由如此般導入分支構造’可提高含酸解 離性基之樹脂之耐熱性。 此時，含酸解離性基之樹脂中之分支構造之導入率可 藉由該分支構造或導入有該構造之樹脂之種類而適當選擇 -48- 200934755 ，但相對於全部重複單位較好爲1 0莫耳％以下。 含酸解離性基之樹脂之分子量並無特別限制，且可適 當選擇，但以凝膠滲透層析（GPC )換算成聚苯乙烯之重 量分子量（以下稱爲「Mw」），通常爲1,000〜500,000， 較好爲 2,000〜400,000，更好爲 3,000〜300,000。 又，不具分支構造之含酸解離性基之樹脂之Mw較好 爲1,000〜150,000，更好爲3,000〜100, 〇〇〇，具有分支構造 0 之含酸解離性基之樹脂（B)之Mw較好爲5,000〜500,000 ，更好爲8,000〜300,000。藉由使用具有該等範圍之Mw 的含酸解離性基之樹脂，使所得光阻劑成爲鹼顯像性優異 者。 另外，含酸解離性基之樹脂之Mw與藉GPC測定且換 算成聚苯乙烯之數平均分子量（以下稱爲「Μη」）之比（ Mw/Mn )並無特別限制，可適當選擇，但通常爲1〜10, 較好爲1~8，更好爲1~5。藉由使用具有該等範圍之 φ Mw/Mn之含酸解離性基之樹脂，所得光阻劑成爲解像性能 優異者。本發明之正型敏輻射線性樹脂組成物中，上述含 酸解離性基之樹脂可單獨使用或混合兩種以上使用。 含酸解離性基之樹脂之製造方法並無特別限制，可藉 由例如在預先製造之鹼可溶性樹脂中之酸性官能基中導入 一種以上之酸解離性基之方法；使具有酸解離性基之一種 以上聚合性不飽和單體視情況與一種以上之其他聚合性不 飽和單體一起聚合之方法；使具有酸解離性基之一種以上 聚縮合性成分視情況與其他聚縮合性成分聚縮合之方法等 -49- 200934755 而製造。 製造上述鹼可溶性樹脂時之聚合性不飽和單體之聚合 及具有上述酸解離性基之聚合性不飽和單體之聚合，係依 據所使用之聚合性不飽和單體或反應介質種類等，適當的 選擇自由基聚合起始劑、陰離子聚合觸媒、配位陰離子聚 合觸媒、陽離子聚合觸媒等聚合起始劑或聚合觸媒，可以 塊狀聚合、溶液聚合、沉澱聚合、乳化聚合、懸浮聚合、 Ο 塊狀-懸浮聚合等適宜之聚合形態實施。 又，具有上述酸解離性基之聚縮合性成分之聚縮合較 好在酸性觸媒存在下，於水介質中或水與親水性溶劑之混 合介質中進行。 本發明之正型敏輻射線性樹脂組成物中，敏輻射線性 酸產生劑之使用量，可依據光阻劑所需特性做各種選擇， 但相對於含酸解離性基之樹脂1 〇〇質量份，較好爲 0.00 1 ~70質量份，更好爲0.01〜50質量份，最好爲0.1 ~20 Q 質量份。此時，藉由使敏輻射線性酸產生劑之使用量成爲 0.001質量份以上，可抑制感度及解像度之降低，又藉由 使成爲70質量份以下，可抑制光阻劑塗佈性及圖型形狀 之降低。 [鹼可溶性樹脂] 本發明之負型敏輻射線性樹脂組成物中，具有一種以 上之與鹼性顯像液顯示親和性之官能基，例如酚性羥基、 醇性羥基、羧基等含氧之官能基，亦可在鹼顯像液中搭配 -50- 200934755 可溶之鹼可溶性樹脂。 該鹼可溶性樹脂可列舉爲例如具有選自由 (15)表示之重複單位（以下稱爲「重複單位 、以下述通式（16)表示之重複單位（以下稱 位（16)」）及以下述通式（17)表示之重複 稱爲「重複單位（17)」）組成之群之至少一 合系樹脂等。 (通式（15)及通式（16)中，R23及R25相 〇 示氫原子或甲基，R24爲羥基、羧基、-R OR26COOH、-OCOR26COOH 或-COOR26COOH ( 相互獨立’表不·（CH〗）。-’ e爲1〜4之整數）。 鹼可溶性樹脂亦可僅由重複單位（1 5 )、 16)或重複單位（17)構成，但只要生成之樹 顯像液中，則亦可更具有一種以上之其他重複 其他重複單位可列舉爲例如與上述含酸解離性 之其他重複單位相同之單位等。 鹼可溶性樹脂中之重複單位（15)、重複 以下述通式 (15 )」） 爲「重複單 單位（以下 種之加成聚 【化3 3】 R23u R25u ρ十 十P十 / Η Η、 4c—c+ 〇=? 1 i o=c c=o OH | | OH OH ^24 ：15) (16) (17) 互獨立，表 26COOH、· 惟，各R26 重複單位（ 脂可溶於鹼 單位。上述 基之樹脂中 單位（1 6 ) -51 - 200934755 及重複單位（1 7 )之合計含有率，視情況下隨所含其他重 複單位之種類而定而無法一槪規定，但較好爲10〜100莫 耳％，更好爲20〜1 00莫耳％。 鹼可溶性樹脂在具有如重複單位（15)般之具有碳-碳不飽和鍵之重複單位時，亦可以氫化物加以使用。該情 況之氫化率爲該重複單位中所含碳一碳不飽和鍵之通常爲 7 0 %以下，較好爲5 0 %以下，更好爲4 0 %以下。此時，當 〇 氫化率超過70%時，會有鹼可溶性樹脂之鹼顯像性降低之 情況。 本發明中之鹼可溶性樹脂尤其以聚（4 -羥基苯乙烯） 、4-羥基苯乙烯/4-羥基-α-甲基苯乙烯共聚物、4-羥基苯 乙烯/苯乙烯共聚物等作爲主要成分之樹脂較佳。 鹼可溶性樹脂之Mw係依據負型敏輻射線性樹脂組成 物之所需特性而變，但通常爲1,000〜1 50,000，較好爲 3,000〜1 〇〇,〇〇〇 〇 G 本發明之負型敏輻射線性樹脂組成物中之鹼可溶性樹 脂可單獨使用或混合兩種以上使用。 [交聯劑] 本發明之負型敏輻射線性樹脂組成物中，亦可搭配在 酸存在下可使鹼可溶性樹脂交聯之化合物（以下稱爲「交 聯劑」）。至於交聯劑可列舉爲例如含有一種以上之與鹼 可溶性樹脂具有交聯反應性之官能基（以下稱爲「交聯性 官能基」）之化合物。 -52- 200934755 上述交聯性官能基可列舉爲例如縮水 甘油酯基、縮水甘油胺基、甲氧基甲基、 氧基甲基、乙醯氧基甲基、苯甲醯基氧基 乙醯基、乙烯基、異丙烯基、（二甲胺基 胺基）甲基、（二羥甲基胺基）甲基、（ 甲基、嗎啉基甲基等。 交聯劑可列舉爲例如雙酚A系環氧化 Φ 環氧化合物、雙酚S系環氧化合物、酚醛 化合物、可溶酚醛（resole )樹脂系環氧 基苯乙烯）系環氧化合物、含羥甲基之三 含羥甲基之苯并胍胺化合物、含羥甲基之 羥甲基之酚化合物、含烷氧基烷基之三聚 烷氧基烷基之苯并胍胺化合物、含烷氧基 物、含烷氧基烷基之酚化合物、含羧基甲 脂、含羧基甲基之苯并胍胺樹脂、含羧基 〇 、含羧基甲基之酚樹脂、含羧基甲基之三 含羧基甲基之苯并胍胺化合物、含羧基甲 、含羧基甲基之酚化合物等。 該等交聯劑中，較好爲含羥甲基之酚 基甲基之三聚氰胺化合物、含甲氧基甲基 甲氧基甲基之甘脲化合物、含甲氧基甲基 含乙醯氧基甲基之酚化合物，更好爲含甲 氰胺化合物（例如六甲氧基甲基三聚氰胺 甲基之甘脲化合物、含甲氧基甲基之尿素 甘油醚基、縮水 乙氧基甲基、苄 甲基、甲醯基、 )甲基、（二乙 二羥乙基胺基） 合物、雙酚F系 清漆樹脂系環氧 化合物、聚（羥 聚氰胺化合物、 尿素化合物、含 氰胺化合物、含 烷基之尿素化合 基之三聚氰胺樹 甲基之尿素樹脂 聚氰胺化合物、 基之尿素化合物 化合物、含甲氧 之酚化合物、含 之尿素化合物及 氧基甲基之三聚 等）、含甲氧基 化合物等。含甲 -53- 200934755 氧基甲基之三聚氰胺化合物分別以CYMEL 300、CYMEL 301、CYMEL 303、CYMEL 305 (以上爲三井氰胺公司製 造）等商品名銷售’含有甲氧基甲基之甘脲化合物係以 CYMEL 1174(三井氰胺公司製造）等商品名銷售，又含 有甲氧基甲基之尿素化合物係以MX 290 (三和化學公司 製造）等商品名銷售。 又，以上述交聯性官能基取代上述鹼可溶性樹脂中之 φ 含氧官能基之氫原子而賦予作爲交聯劑性質之樹脂亦可適 當的作爲交聯劑。該情況下交聯性官能基之導入率係隨交 聯性官能基及導入有該基之鹼可溶性樹脂之種類而定而無 法一槪規定，但相對於鹼可溶性樹脂中之全部含氧官能基 ，通常爲 5〜60莫耳％，較好爲1 0~50莫耳％，更好爲 1 5〜40莫耳％。該情況下，若交聯性官能基之導入率未達5 莫耳％，則殘膜率下降，會有出現圖型蛇行或膨潤等之傾 向’另一方面’若超過6 0莫耳％，則會有鹼顯像性下降之 ❿ 傾向。 本發明中之交聯劑尤其以含甲氧基甲基之化合物，更 具體而言爲二甲氧基甲基尿素、四甲氧基甲基甘脲等較佳 。本發明之負型敏輻射線性樹脂組成物中，交聯劑可單獨 使用或混合兩種以上使用。 本發明之負型敏輻射線性樹脂組成物中，敏輻射線性 酸產生劑之使用量相對於鹼可溶性樹之100質量份，較好 爲 0.01~70質量份’更好爲 0.1〜50質量份，最好爲 〇·5〜20質量份。該情況下，敏輻射線性酸產生劑之使用量 -54- 200934755 若未達0.01質量份，則有感度及解像度下 一方面若超過70質量份，則有光阻劑之塗 狀變得容易劣化之傾向。_ 另外，交聯劑之使用量相對於鹼可溶性 ，較好爲5~95質量份，更好爲15〜85質 20〜75質量份。該情況下，若交聯劑之使用 份，則有容易使殘膜率下降、圖型蛇行及膨 © 另一方面，若超過95質量份，則有鹼顯像 [其他添加劑] 本發明之正型敏輻射線性樹脂組成物及 性樹脂組成物，較好搭配具有控制由於曝光 性酸產生劑產生之酸在光阻被膜中之擴散現 曝光區域中不期望之化學反應作用之酸擴散 © 搭配該等酸擴散控制劑，可提升敏輻射線性 儲存安定性’且進一步提升解像度，另外可 像處理之前之放置時間（PED )之變動所引 線寬變化’結果，可獲得製程安定性極優異 樹脂組成物。 至於該等酸擴散控制劑，較好爲在光阻 驟中不會因曝光或加熱處理而改變鹼性之含 。至於上述含氮有機化合物可列舉爲例如以 )表示之化合物（以下稱爲「含氮化合物 降之傾向，另 佈性或圖型形 樹1 0 0質量份 量份，最好爲 量未達5質量 潤等之傾向， 性下降之傾向 負型敏輻射線 而自敏輻射線 象，且抑制非 控制劑。藉由 樹脂組成物之 抑制曝光至顯 起之光阻圖型 之敏輻射線性 圖型之形成步 氮有機化合物 下述通式（18 (a)」）、同 -55- 200934755 一分子內具有兩個氮原子之二胺基化合物（以下稱爲「含 氮化合物（β)」）、具有3個以上氮原子之多胺基化合 物或聚合物（以下稱爲「含氮化合物（γ)」）、含醯胺 基之化合物、尿素化合物、含氮雜環式化合物等。 [化3 4】 R27 R27_N_R27 〇 (18) (通式（18)中，各R2 7相互獨立，表示氫原子、烷基、 芳基或芳烷基，此等之各基可被取代）。 通式（1 8 )中，R27之可經取代之烷基可列舉爲例如 碳數1〜15’較好1〜10者，具體而言爲甲基、乙基、正丙 基、異丙基、正丁基、2 -甲基丙基、丨_甲基丙基、第三丁 基、正戊基、新戊基、正己基、正庚基、正辛基、正乙基 © 己基、正壬基、正癸基、羥基甲基、2-羥基乙基、3-羥基 丙基等。 又，R27之可經取代之芳基可列舉爲例如碳數6~1 2者 ，具體而言爲苯基、鄰一甲苯基、間一甲苯基、對一甲苯 基、2,3-二甲苯基、2,4-二甲苯基、2,5_二甲苯基、2,6_二 甲苯基、3，4-二甲苯基、3，5-二甲苯基、異丙苯基、i_萘 基等。而且，R2 7之可經取代之上述芳烷基可列舉爲例如 碳數7〜19’較好7〜13者’具體而言爲苄基、心甲基苄基 、苯乙基、1-萘基甲基等。 -56- 200934755 含氮化合物（α )可列舉爲例如正己基胺、正庚基胺 、正辛基胺、正壬基胺、正癸基胺等單烷基胺類；二正丁 基胺、二正戊基胺、二正己基J安、二正庚基胺、二正辛基 胺、二正壬基胺、二正癸基胺等二烷基胺類；三乙胺、三 正丙基胺、三正丁基胺、三正戊基胺、三正己基胺、三正 庚基胺、三正辛基胺、三正壬基胺、三正癸基胺等三烷基 胺類；乙醇胺、二乙醇胺、三乙醇胺等烷醇胺類；苯胺、 φ N-甲基苯胺、N，N-二甲基苯胺、2-甲基苯胺、3-甲基苯胺 、4 -甲基苯胺、4 -硝基苯胺、二苯基胺、三苯基胺、1-萘 基胺等芳香族胺類等。 含氮化合物（P )可列舉爲例如乙二胺、N，N，N’，N’-四 甲基乙二胺、四亞甲基二胺、六亞甲基二胺、n,n,n’，n’-肆（2-羥基乙基）乙二胺、Ν，Ν,Ν’，Ν’-肆（2-羥基丙基） 乙二胺、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、 4,4’-二胺基二苯甲酮、4,4’-二胺基二苯基胺、2,2’-雙（4_ Q 胺基苯基）丙烷、2-(3-胺基苯基）-2- (4-胺基苯基）丙 院、2- (4 -胺基苯基）-2- (3 -羥基苯基）丙垸、2- (4 -胺 基苯基）-2- (4-羥基苯基）丙烷、1，4 -雙[1-(4-胺基苯基 )-1-甲基乙基]苯、丨，3·雙π-(4-胺基苯基）-1·甲基乙基] 苯等。至於含氮化合物（γ)可列舉爲例如聚伸乙亞胺、 聚烯丙基胺、Ν- ( 2-二甲胺基乙基）丙烯醯胺之聚合物等 〇 上述含醯胺基之化合物可列舉爲例如甲酿胺、Ν-甲基 甲醯胺、Ν,Ν -二甲基甲酸胺、乙酿胺、Ν_甲基乙醯胺、 -57- 200934755 N，N -二甲基乙醯胺、丙醯胺、苯甲醯胺、吡咯烷酮、N_甲 基吡咯烷酮等° 上述尿素化合物可列舉爲例^如尿素、甲基尿素、丨，1· 二甲基尿素、ι，3 -二甲基尿素、1，丨，3,3-四甲基尿素、1，3-二苯基尿素、三正丁基硫尿素等。 上述含氮雜環化合物可列舉爲例如咪哩、苯并咪唑、 2-甲基咪唑、4-甲基咪唑、1,2-二甲基咪唑、2-苯基咪唑 φ 、4-苯基咪唑、4-甲基-2-苯基咪唑、2-苯基苯并咪唑等咪 哗類；吡啶、2 -甲基吡啶、4 -甲基卩比U定、2 -乙基卩比D定、4 _ 乙基吡啶、2 -苯基吡啶、4 -苯基吡啶、2 -甲基-4 -苯基吡啶 、菸鹼、菸鹼酸、菸鹼酸醯胺、唾啉、8_氧基喹啉、氮丙 啶等吡啶類，又列舉爲吡嗪、吡唑、噠嗪、喹噁啉、嘌呤 、吡咯啶、哌啶、1 -哌啶乙醇、2 -哌啶乙醇、嗎啉、4 -甲 基嗎啉、哌嗪、1，4-二甲基哌嗪、1,4-二氮雜雙環[2.2.2] 辛烷等。 〇 又，可使用具有酸解離性基之化合物作爲上述含氮有 機化合物。至於上述具有酸解離性基之含氮有機化合物可 列舉爲例如N-(第三丁氧基羰基）哌啶、N-(第三丁氧 基羰基）咪唑、N-(第三丁氧基羰基）苯并咪唑、N-(第 三丁氧基羰基）-2-苯基苯并咪唑、N-(第三丁氧基羰基 )二正辛基胺、N-(第三丁氧基羰基）二乙醇胺、N-(第 三丁氧基羰基）二環己胺、N-(第三丁氧基羰基）二苯基 胺、第三丁基-4-羥基-1-哌啶羧酸酯等。 該等含氮有機物中較好爲含氮化合物（α)、含氮化 -58- 200934755 合物（β)、含氮雜環式化合物、具有酸解離性基之含氮 有機化合物等。上述酸擴散控制劑可單獨使用或混合兩種 以上使用。 ^ 酸擴散控制劑之搭配量，相對於含酸解離性基之樹脂 或鹼可溶性樹脂1 〇〇質量份，較好爲1 5質量份以下，更 好爲0.0 01〜10質量份，最好爲0.005〜5質量份。該情況下 ，藉由使酸擴散控制劑之搭配量在0.001質量份以上，可 φ 抑制隨製程條件之圖型形狀或尺寸忠實度之下降，又藉由 成爲15質量份以下，可更提升作爲光阻劑之感度或鹼現 像性。 本發明之正型敏輻射線性樹脂組成物及負型敏輻射線 性樹脂組成物，可搭配具有藉由酸之作用對於鹼顯像液之 溶解性增高之性質之溶解控制劑。 該等溶解控制劑可列舉爲例如具有酚性羥基、羧基、 磺酸基等酸性官能基之化合物，或該化合物中之酸性官能 G 基之氫原子經酸解離性基取代之化合物等。 溶解控制劑可爲低分子化合物亦可爲高分子化合物， 負型敏輻射線性樹脂組成物中之高分子溶解控制劑可使用 例如正型敏輻射線性樹脂組成物中之含酸解離性基之樹脂 。上述溶解控制劑可單獨使用或混合兩種以上使用。 溶解控制劑之搭配量相對於敏輻射線性樹脂組成物中 之全部樹脂成分100質量份，通常爲50質量份以下，較 好爲2G質量份以下。 本發明之正型敏輻射線性樹脂組成物及負型敏輻射線 -59- 200934755 性樹脂組成物，可搭配顯示改良敏輻射線性樹脂組成物之 塗佈性、條紋現象'顯像性等作用之界面活性劑。 該等界面活性劑可使用陰離子系、.陽離子系、非離子 系或兩性界面活性劑之任一種’但較好爲非離子系界面活 性劑。 上述非離子系界面活性劑可列舉爲例如聚氧乙烯高級 烷醚類、聚氧乙烯高級烷基苯基醚類、聚乙二醇之高級脂 0 肪酸二酯類以及以下列商品名「KP」（信越化學工業公司 製造）、「POLYFLOW」（共榮公司化學公司製造）、「 F TOP」 （JEMC0公司製造）、「MEGAFACE」（大日本 油墨化學工業公司製造）、「FLU0RAD」（住友3M公司 製造）、「ASAHIGUARD」及「SURFLON」（旭硝子公 司製造）等各種系列等。上述界面活性劑可單獨使用或混 合兩種以上使用。 界面活性劑之搭配量，相對於敏輻射線性樹脂組成物 〇 中之全部樹脂成分1〇〇質量份，界面活性劑之有效成分通 常爲2質量份以下，較好爲1.5質量份以下。 本發明之正型敏輻射線性樹脂組成物及負型敏輻射線 性樹脂組成物可搭配具有吸收輻射線之能量、將該能量傳 達到敏輻射線性酸產生劑、藉此增加酸之生成量之作用且 可提高敏輻射線性樹脂組成物之外觀感度之增感劑。該等 增感劑可列舉爲例如苯乙酮類、二苯甲酮類、萘類、雙乙 醯、曙紅、玫瑰紅、芘類、蒽類、吩噻嗪類等。該等增感 劑可單獨使用或混合兩種以上使用。 -60- 200934755 增感劑之搭配量相對於敏輻射線性樹脂組成物中之全 部樹脂成分100質量份，通常爲50質量份以下，較好爲 3 0質量份以下。 再者，本發明之正型敏輻射線性樹脂組成物及負型敏 輻射線性樹脂組成物在不妨礙本發明效果之範圍內，可依 據需要搭配除上述以外之添加劑，例如染料、顏料、接著 助劑、光暈防止劑、儲存安定劑 '消泡劑、形狀改良劑等 〇 ，具體而言爲4-羥基-4’-甲基查爾酮等。該情況下，藉由 搭配染料或顏料，使曝光部分之潛像可見化，可緩和曝光 時光暈之影響，另外藉由搭配接著助劑，可改善與基板之 接著性。 組成物溶液之調製： 本發明之正型敏輻射線性樹脂組成物及負型敏輻射線 性樹脂組成物通常在使用時將各種成分溶解於溶劑中成爲 Ο 均勻溶液，隨後依據需要通過例如孔徑〇.2μπι左右之過濾 器等過濾，而調製成組成物溶液。 上述溶劑可列舉爲例如醚類、酯類、醚酯類、酮類、 酮酯類、醯胺類、醯胺酯類、內醯胺類、（鹵化）烴類等 。更具體而言可列舉爲例如乙二醇單烷基醚類、二乙二醇 二烷基醚類、丙二醇單烷基醚類、丙二醇二烷基醚類、乙 二醇單烷基醚乙酸酯類、丙二醇單烷基醚乙酸酯類、非環 式或環式酮類、乙酸酯類、羥基乙酸酯類、烷氧基乙酸酯 類、乙醯乙酸酯類、丙酸酯類、乳酸酯類、其他取代之丙 -61 - 200934755 酸酯類、（取代）之丁酸酯類、丙酮酸酯類、N，N_二院基 甲醯胺類、ν，ν·二烷基乙醯胺類、Ν·烷基啦略院嗣類、（ 鹵化）脂肪族烴類、（鹵化）芳香族烴類等―。 上述溶劑之具體例可列舉爲乙二醇單甲基醚、乙二醇 單乙基醚、乙二醇單正丙基醚、乙二醇單正丁基醚、二乙 二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二正丙基醚 、二乙二醇二正丁基醚、乙二醇單甲基醚乙酸酯、乙二醇 〇 單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基 醚乙酸酯、丙二醇單正丙基醚乙酸酯、甲基乙基酮、2-庚 酮、3-庚酮、4-庚酮、環己酮、乙酸乙酯、乙酸正丙酯、 乙酸正丁酯、異丙烯基乙酸酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、羥基乙酸乙酯、乙氧基乙酸乙 酯、乙醯基乙酸甲酯、乙醯基乙酸乙酯、異丙烯基丙酸酯 、3 -甲基-3-甲氧基丁基丙酸酯、乳酸甲酯、乳酸乙酯、乳 酸正丙酯' 乳酸異丙酯、3-甲氧基丙酸甲酯、3_甲氧基丙 ❹ 酸乙酯、3-乙氧基丙酸甲酯、3_乙氧基丙酸乙酯、3_甲基_ 3 -甲氧基丁基丁酸酯、2-羥基-3-甲基丁酸甲酯、2_經基_2_ 甲基丙酸乙酯、Ν，Ν-二甲基甲醯胺、Ν，Ν_:甲基乙醯胺、 Ν-甲基吡咯烷酮、甲苯、二甲苯等。 該等溶劑中’丙二醇單烷基醚乙酸酯類、非環式或環 式酮類、乳酸酯類、3-烷氧基丙酸酯類等，就確保塗佈時 良好膜面均句性之觀點而言，爲較佳。上述溶劑可單獨使 用或混合兩種以上使用。 另外可依據需要，與上述溶劑一起使用其他溶劑，例 -62- 200934755 如苄基乙基醚、二正己基醚、二乙二醇單甲基醚、二乙二 醇單乙基醚、乙醯基丙酮、異佛爾酮、己酸、辛酸、卜辛 醇、1-壬醇、苄基醇、乙酸苄酯、苯甲酸乙酯、草酸二乙 醋、馬來酸二乙酯、γ-丁內酯、碳酸乙烯酯、碳酸丙烯酯 '乙一醇單苯基醚乙酸酯等高沸點溶劑等。該等其他溶劑 中，以γ-丁內酯較佳。 上述其他溶劑可單獨使用或混合兩種以上使用。其他 〇 溶劑之使用比例相對於全部溶劑通常爲5 0質量％以下，更 好爲3 0質量％以下。 溶劑之合計使用量爲使組成物溶液之總固形成分濃度 通常爲5~50質量％，較好爲1 〇〜5〇質量％，更好爲i 〇~4〇 質量％ ’最好爲1〇~30質量％，尤其成爲10〜25質量％之量 。藉由使溶液之總固形成分濃度在該範圍內，可確保塗佈 時之良好膜面內均勻性。 φ 光阻圖型之形成： 自本發明之正型敏輻射線性樹脂組成物及負型敏輻射 線性樹脂組成物形成光阻圖型時，藉由旋轉塗佈、澆鑄塗 佈、輥塗佈等適宜之塗佈方法將如上述般調製之組成物溶 液塗佈在例如矽晶圓、經鋁被覆之晶圓等基板上，形成光 阻被膜。隨後，依狀況經預先加熱處理（以下稱爲「PB」 )後，通過特定之光罩對該光阻被膜曝光。(14-4) 47- 200934755 The above resin may be obtained by (co)polymerizing one or more decane compounds having an acid dissociable group or introducing one or more acid dissociable groups on a previously synthesized organopolyoxane. Manufacturing. When the decane compound having an acid-dissociable group is (co)polymerized, an acidic catalyst is preferably used as a catalyst. In particular, after the decane compound is polycondensed in the presence of an acidic catalyst, it is preferred to add a basic catalyst and then carry out the reaction. . Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, boric acid Q, phosphoric acid, titanium tetrachloride, zinc chloride, and aluminum chloride; formic acid, acetic acid, n-propionic acid, butyric acid, valeric acid, and oxalic acid. , malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, phthalic acid, terephthalic acid, acetic anhydride, maleic anhydride, citric acid 'benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonate Organic acids such as acids. Among the acidic catalysts, 'hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, acetic anhydride, maleic anhydride or the like is preferred. Further, examples of the basic catalyst include inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, and potassium carbonate; Organic bases such as triethylamine, tri-n-propylamine, tri-n-butylamine, and pyridine. When the resin containing an acid-dissociable group is polymerized by a polymerizable unsaturated monomer or produced by the polymerization, the resin can be introduced into a unit derived from a polyfunctional monomer having two or more polymerizable unsaturated bonds and/or A branched structure of an acetal crosslinkable group. By introducing the branched structure as described above, the heat resistance of the resin containing the acid-dispersible group can be improved. In this case, the introduction ratio of the branched structure in the acid-dissociable group-containing resin can be appropriately selected by the branching structure or the kind of the resin into which the structure is introduced -48-200934755, but it is preferably 1 with respect to all the repeating units. 0% or less. The molecular weight of the acid-dissociable group-containing resin is not particularly limited and may be appropriately selected, but it is converted into a weight molecular weight of polystyrene by gel permeation chromatography (GPC) (hereinafter referred to as "Mw"), and is usually 1,000~ 500,000, preferably 2,000 to 400,000, more preferably 3,000 to 300,000. Further, the Mw of the acid-dissociable group-containing resin having no branched structure is preferably from 1,000 to 150,000, more preferably from 3,000 to 100, Å, and Mw having the acid-dissociable group-containing resin (B) having a branched structure of 0 It is preferably from 5,000 to 500,000, more preferably from 8,000 to 300,000. The obtained photoresist is excellent in alkali developability by using an acid-dissociable group-containing resin having Mw in the above range. In addition, the ratio (Mw/Mn) of the Mw of the resin containing the acid-dissociable group to the number average molecular weight (hereinafter referred to as "Μη") measured by GPC and converted into polystyrene is not particularly limited and may be appropriately selected. It is usually 1 to 10, preferably 1 to 8, more preferably 1 to 5. By using a resin having an acid dissociable group having such a range of φ Mw / Mn, the resulting photoresist has excellent resolution. In the positive-type radiation-sensitive linear resin composition of the present invention, the acid-dissociable group-containing resin may be used singly or in combination of two or more. The method for producing the acid-dissociable group-containing resin is not particularly limited, and for example, a method of introducing one or more acid-dissociable groups into an acidic functional group in a previously prepared alkali-soluble resin can be used; A method in which one or more polymerizable unsaturated monomers are polymerized together with one or more other polymerizable unsaturated monomers, and one or more polycondensable components having an acid dissociable group are condensed with other polycondensable components as the case may be. Method, etc. -49- 200934755 and manufactured. The polymerization of the polymerizable unsaturated monomer in the production of the above alkali-soluble resin and the polymerization of the polymerizable unsaturated monomer having the above-described acid-dissociable group are appropriately selected depending on the type of the polymerizable unsaturated monomer or the reaction medium to be used. Selective polymerization initiators, anionic polymerization catalysts, coordination anionic polymerization catalysts, cationic polymerization catalysts, and the like, polymerization initiators or polymerization catalysts, which can be bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization, suspension Polymerization, 块 block-suspension polymerization, and the like are carried out in a suitable polymerization form. Further, the polycondensation of the polycondensable component having the above acid-cleavable group is preferably carried out in an aqueous medium or a mixed medium of water and a hydrophilic solvent in the presence of an acidic catalyst. In the positive type sensitive radiation linear resin composition of the present invention, the amount of the sensitive radiation linear acid generator can be variously selected according to the desired characteristics of the photoresist, but 1 part by mass relative to the resin containing the acid dissociable group. It is preferably from 0.001 to 70 parts by mass, more preferably from 0.01 to 50 parts by mass, most preferably from 0.1 to 20 parts by mass. In this case, when the amount of the sensitive radiation-based linear acid generator is 0.001 parts by mass or more, the sensitivity and the resolution can be suppressed from being lowered, and by 70 parts by mass or less, the photoresist coating property and pattern can be suppressed. The shape is reduced. [Alkali-Soluble Resin] The negative-sensitive radiation-linear resin composition of the present invention has one or more functional groups which exhibit affinity with an alkaline developing solution, for example, an oxygen-containing functional group such as a phenolic hydroxyl group, an alcoholic hydroxyl group or a carboxyl group. Base, can also be used in the alkali imaging solution with -50-200934755 soluble alkali soluble resin. The alkali-soluble resin may, for example, have a repeating unit (hereinafter referred to as "repeating unit, repeating unit represented by the following general formula (16) (hereinafter referred to as position (16))") selected from (15) and The at least one type of resin or the like of the group consisting of "repetition unit (17)") is represented by the formula (17). (In the general formula (15) and the general formula (16), R23 and R25 are each a hydrogen atom or a methyl group, and R24 is a hydroxyl group, a carboxyl group, -R OR26COOH, -OCOR26COOH or -COOR26COOH (independent of each other) 〖). - 'e is an integer from 1 to 4.) The alkali-soluble resin may also be composed only of repeating units (15), 16) or repeating units (17), but as long as the resulting tree is in the developing liquid, There may be more than one other repetition. Other repeating units may be, for example, the same units as the other repeating units containing the above-described acid dissociation property. The repeating unit (15) in the alkali-soluble resin is repeated with the following general formula (15)") as "repeated single unit (additional aggregation of the following species: 3 3) R23u R25u ρ 十 十 P 十 / Η Η, 4c —c+ 〇=? 1 io=cc=o OH | | OH OH ^24 :15) (16) (17) Independent of each other, Table 26COOH, ·, each R26 repeat unit (lipid soluble in alkali units. The total content of the units (1 6 ) -51 - 200934755 and the repeating unit (1 7 ) in the resin may not be specified as the number of other repeating units included, but preferably 10 to 100. The molar %, more preferably 20 to 100% by mole. The alkali-soluble resin may also be used in the case of a repeating unit having a carbon-carbon unsaturated bond as in the repeating unit (15). The hydrogenation rate is usually 70% or less, preferably 50% or less, more preferably 40% or less, in the carbon-carbon unsaturated bond contained in the repeating unit. In this case, when the hydrogenation rate exceeds 70% There is a case where the alkali-developing property of the alkali-soluble resin is lowered. The alkali-soluble resin in the present invention is especially poly(4-hydroxyl). A resin which is a main component such as styrene), 4-hydroxystyrene/4-hydroxy-α-methylstyrene copolymer, 4-hydroxystyrene/styrene copolymer, etc. The Mw of the alkali-soluble resin is based on negative The type of the sensitive radiation linear resin composition varies depending on the desired properties, but is usually 1,000 to 1 50,000, preferably 3,000 to 1 Torr, and is the base of the negative-sensitive radiation-linear resin composition of the present invention. The soluble resin may be used alone or in combination of two or more. [Crosslinking Agent] The negative-sensitive radiation-linear resin composition of the present invention may be compounded with a compound capable of crosslinking an alkali-soluble resin in the presence of an acid (hereinafter referred to as The cross-linking agent is, for example, a compound containing one or more functional groups (hereinafter referred to as "crosslinkable functional groups") having cross-linking reactivity with an alkali-soluble resin. -52- 200934755 The crosslinkable functional group may, for example, be a glycidyl ester group, a glycidylamine group, a methoxymethyl group, an oxymethyl group, an ethoxymethyl group, a benzhydryloxyethyl group or a vinyl group. Isopropenyl, (dimethyl Aminoamino)methyl, (dihydroxymethylamino)methyl, (methyl, morpholinylmethyl, etc.) The crosslinking agent may, for example, be bisphenol A-based epoxidized Φ epoxy compound, bisphenol S-based epoxy compound, phenolic compound, resole resin-based epoxy styrene) epoxy compound, hydroxymethyl-containing hydroxymethyl-containing benzoguanamine compound, hydroxymethyl group-containing a hydroxymethyl phenol compound, an alkoxyalkyl-containing tripolyalkoxyalkyl benzoguanamine compound, an alkoxy group-containing, alkoxyalkyl group-containing phenol compound, carboxyl group-containing methyl ester, a benzomethylamine resin of a carboxymethyl group, a phenol resin containing a carboxyl group, a phenol resin containing a carboxy group, a benzoguanamine compound containing a carboxy group containing a carboxymethyl group, a phenol compound containing a carboxyl group and a carboxyl group containing a methyl group Wait. Among these crosslinking agents, a melamine compound containing a hydroxymethyl group, a glycerol compound containing a methoxymethylmethoxymethyl group, and a methoxymethyl group containing an ethoxy group are preferable. a methyl phenol compound, more preferably a dicyandiamide-containing compound (for example, a hexamethoxymethyl melamine methyl glycoluril compound, a methoxymethyl group-containing urea glyceryl ether group, a glycidyl ethoxymethyl group, a benzyl group) Base, formazan, methyl, (diethylenedihydroxyethylamino), bisphenol F varnish resin epoxy, poly(hydroxylamine compound, urea compound, cyanamide compound, A urethane resin containing a urethane compound, a melamine resin, a urethane compound, a urea compound compound, a methoxyl compound, a urea compound, and an oxymethyl group, etc. An oxy compound or the like. The melamine compound containing methyl-53-200934755 oxymethyl group is sold under the trade names of CYMEL 300, CYMEL 301, CYMEL 303, CYMEL 305 (manufactured by Mitsui Cyanamide Co., Ltd.), etc. It is sold under the trade name of CYMEL 1174 (manufactured by Mitsui Cyanamide Co., Ltd.), and the urea compound containing methoxymethyl group is sold under the trade name of MX 290 (manufactured by Sanwa Chemical Co., Ltd.). Further, by substituting the above-mentioned crosslinkable functional group for the hydrogen atom of the φ oxygen-containing functional group in the above alkali-soluble resin, a resin having a crosslinking property can be suitably used as a crosslinking agent. In this case, the introduction ratio of the crosslinkable functional group may not be defined depending on the type of the crosslinkable functional group and the alkali-soluble resin into which the group is introduced, but is relative to all the oxygen-containing functional groups in the alkali-soluble resin. , usually 5 to 60% by mole, preferably 10 to 50% by mole, more preferably 1 to 5 to 40% by mole. In this case, when the introduction rate of the crosslinkable functional group is less than 5 mol%, the residual film ratio is lowered, and there is a tendency that the pattern is meandering or swelling, and the other side is more than 60% by mole. There is a tendency for the alkali imaging to decline. The crosslinking agent in the present invention is preferably a compound containing a methoxymethyl group, more specifically, dimethoxymethyl urea, tetramethoxymethyl glycoluril or the like. In the negative-sensitive radiation linear resin composition of the present invention, the crosslinking agent may be used singly or in combination of two or more. In the negative-sensitive radiation linear resin composition of the present invention, the amount of the radiation-sensitive linear acid generator is preferably from 0.01 to 70 parts by mass, more preferably from 0.1 to 50 parts by mass, per 100 parts by mass of the alkali-soluble tree. It is preferably 5 to 20 parts by mass. In this case, the amount of the sensitive radiation linear acid generator is -54-200934755. If it is less than 0.01 parts by mass, if the sensitivity and the resolution are more than 70 parts by mass, the coating of the photoresist may be easily deteriorated. The tendency. Further, the amount of the crosslinking agent used is preferably from 5 to 95 parts by mass, more preferably from 15 to 85 parts by mass, from 20 to 75 parts by mass, based on the alkali solubility. In this case, if the amount of the crosslinking agent is used, the residual film ratio is likely to be lowered, and the pattern is meandering and swelling. On the other hand, if it exceeds 95 parts by mass, there is alkali development [other additive]. The sensitive radiation linear resin composition and the resin composition are preferably matched with an acid diffusion which controls an undesired chemical reaction in the exposed region of the diffusion of the acid generated by the exposure acid generator in the photoresist film. The acid diffusion control agent can improve the linear storage stability of the sensitive radiation and further improve the resolution. In addition, the result can be obtained by changing the lead width of the change in the standing time (PED) before the treatment, and the resin composition excellent in process stability can be obtained. As for the acid diffusion controlling agent, it is preferred that the alkalinity is not changed by exposure or heat treatment in the photoresist. The above-mentioned nitrogen-containing organic compound may, for example, be a compound represented by) (hereinafter referred to as "the tendency of the nitrogen-containing compound to fall, and the additional or the shape-shaped tree is made up of 100 parts by mass, preferably not more than 5 parts by mass. The tendency to run, etc., the tendency to decline in the negative sensitive radiation and self-sensitive radiation image, and to suppress the non-control agent. By the inhibition of the resin composition exposure to the visible radiation pattern of the sensitive radiation pattern Forming a step nitrogen organic compound having the following formula (18 (a)"), the same as -55-200934755, a diamine compound having two nitrogen atoms in one molecule (hereinafter referred to as "nitrogen-containing compound (β)"), having a polyamine compound or a polymer of three or more nitrogen atoms (hereinafter referred to as "nitrogen-containing compound (γ)"), a guanamine-containing compound, a urea compound, a nitrogen-containing heterocyclic compound, etc. [Chem. 3 4] R27 R27_N_R27 〇(18) (In the formula (18), each R 2 7 is independent of each other and represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and each of these groups may be substituted.) Formula (1 8 ) The alkyl group which may be substituted by R27 may, for example, be a carbon number of 1 to 15 'preferably from 1 to 10, specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 丨-methylpropyl, tert-butyl, positive Pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-ethylhexyl, n-decyl, n-decyl, hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, etc. The aryl group which may be substituted by R27 may, for example, be a carbon number of 6 to 12, specifically, a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group or a 2,3-dimethylphenyl group. , 2,4-xylyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-xylyl, 3,5-dimethylphenyl, cumyl, i-naphthyl Further, the above-mentioned aralkyl group which may be substituted by R2 7 may, for example, be a carbon number of 7 to 19', preferably 7 to 13 'specifically, a benzyl group, a cardamoyl group, a phenethyl group, and 1 -naphthylmethyl, etc. -56- 200934755 The nitrogen-containing compound (α) may, for example, be a monoalkylamine such as n-hexylamine, n-heptylamine, n-octylamine, n-decylamine or n-decylamine. Di-n-butylamine, di-n-pentylamine, di-n-hexylJ-an, di-n-heptylamine, a dialkylamine such as n-octylamine, di-n-decylamine or di-n-decylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, Trialkylamines such as tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, tri-n-decylamine; alkanolamines such as ethanolamine, diethanolamine, triethanolamine; aniline, φ N-methyl Aniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, 1-naphthylamine An aromatic amine or the like. The nitrogen-containing compound (P) can be exemplified by, for example, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediene Amine, n, n, n', n'-肆 (2-hydroxyethyl) ethylenediamine, hydrazine, hydrazine, hydrazine, Ν'-肆 (2-hydroxypropyl) ethylenediamine, 4, 4' -diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2, 2'-bis(4_Q-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propene, 2-(4-aminophenyl)-2 - (3-hydroxyl Propionyl, 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane, 1,4-bis[1-(4-aminophenyl)-1-methylethyl Benzene, anthracene, 3·bis π-(4-aminophenyl)-1·methylethyl]benzene, and the like. The nitrogen-containing compound (γ) may, for example, be a polymer of a mercaptoamine group, such as a polymer of a polyethylenimine, a polyallylamine or a fluorenyl-(2-dimethylaminoethyl) acrylamide. For example, it can be exemplified by, for example, amarylamine, Ν-methylformamide, hydrazine, hydrazine-dimethyl dimethylamine, ethanoamine, hydrazine-methyl acetamide, -57-200934755 N,N-dimethyl ethane Amidoxime, acrylamide, benzamide, pyrrolidone, N-methylpyrrolidone, etc. The above urea compound can be exemplified by urea, methyl urea, hydrazine, 1 dimethyl urea, ι, 3 - 2 Methyl urea, 1, hydrazine, 3,3-tetramethyl urea, 1,3-diphenyl urea, tri-n-butyl sulphide, and the like. The above nitrogen-containing heterocyclic compound may, for example, be imipenem, benzimidazole, 2-methylimidazole, 4-methylimidazole, 1,2-dimethylimidazole, 2-phenylimidazolium φ, 4-phenylimidazole , 4-methyl-2-phenylimidazole, 2-phenylbenzimidazole, and the like; pyridine, 2-methylpyridine, 4-methyl oxime, U-denier, 2-ethyl oxime ratio D, 4 _ ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinic acid decylamine, sputum, 8- oxyquine Pyridines such as porphyrin and aziridine are also listed as pyrazine, pyrazole, pyridazine, quinoxaline, indole, pyrrolidine, piperidine, 1-piperidineethanol, 2-piperidineethanol, morpholine, 4- Methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, and the like. Further, a compound having an acid dissociable group can be used as the above nitrogen-containing organic compound. As the nitrogen-containing organic compound having an acid-dissociable group, for example, N-(t-butoxycarbonyl)piperidine, N-(third-butoxycarbonyl)imidazole, and N-(third-butoxycarbonyl) may be mentioned. Benzimidazole, N-(t-butoxycarbonyl)-2-phenylbenzimidazole, N-(t-butoxycarbonyl)di-n-octylamine, N-(t-butoxycarbonyl) Diethanolamine, N-(t-butoxycarbonyl)dicyclohexylamine, N-(t-butoxycarbonyl)diphenylamine, tert-butyl-4-hydroxy-1-piperidinecarboxylate, etc. . The nitrogen-containing organic substance is preferably a nitrogen-containing compound (α), a nitrogen-containing compound -58-200934755 (β), a nitrogen-containing heterocyclic compound, a nitrogen-containing organic compound having an acid-cleavable group, or the like. The above acid diffusion controlling agents may be used singly or in combination of two or more. The amount of the acid diffusion controlling agent is preferably 15 parts by mass or less, more preferably 0.01 to 10 parts by mass, based on 1 part by mass of the acid-dissociable group-containing resin or the alkali-soluble resin. 0.005 to 5 parts by mass. In this case, by setting the amount of the acid diffusion controlling agent to 0.001 part by mass or more, it is possible to suppress the decrease in the shape shape or the degree of faithfulness of the pattern depending on the process conditions, and to increase the amount by 15 parts by mass or less. Sensitivity of the photoresist or alkali appearance. The positive-type radiation-sensitive linear resin composition and the negative-type radiation-sensitive resin composition of the present invention can be combined with a dissolution controlling agent having a property of increasing solubility in an alkali developing solution by an action of an acid. The dissolution controlling agent may, for example, be a compound having an acidic functional group such as a phenolic hydroxyl group, a carboxyl group or a sulfonic acid group, or a compound in which the hydrogen atom of the acidic functional group G in the compound is substituted with an acid dissociable group. The dissolution controlling agent may be a low molecular compound or a high molecular compound, and the polymer dissolution controlling agent in the negative sensitive radiation linear resin composition may use, for example, an acid dissociable group-containing resin in a positive sensitive radiation linear resin composition. . The above dissolution controlling agents may be used singly or in combination of two or more. The amount of the dissolution controlling agent is usually 50 parts by mass or less, preferably 2 parts by mass or less, based on 100 parts by mass of all the resin components in the radiation-sensitive linear resin composition. The positive-type sensitive radiation linear resin composition of the present invention and the negative-type sensitive radiation-59-200934755 resin composition can be used together with the coating property of the modified sensitive radiation linear resin composition, the streaking phenomenon, and the like. Surfactant. As the surfactant, any of an anionic, cationic, nonionic or amphoteric surfactant can be used, but a nonionic surfactant is preferred. The nonionic surfactant may, for example, be a polyoxyethylene higher alkyl ether, a polyoxyethylene higher alkylphenyl ether or a higher aliphatic fatty acid diester of polyethylene glycol, and the following trade name "KP" (made by Shin-Etsu Chemical Co., Ltd.), "POLYFLOW" (manufactured by Kyoei Chemical Co., Ltd.), "F TOP" (manufactured by JEMC0), "MEGAFACE" (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), "FLU0RAD" (Sumitomo 3M) Various types of products, such as ASAHIGUARD and SURFLON (made by Asahi Glass Co., Ltd.). The above surfactants may be used singly or in combination of two or more. The amount of the surfactant to be used is usually 2 parts by mass or less, preferably 1.5 parts by mass or less, based on 1 part by mass of the total resin component in the sensitive radiation linear resin composition 〇. The positive-type sensitive radiation linear resin composition and the negative-type sensitive radiation linear resin composition of the present invention can be combined with the energy of absorbing radiation, and the energy is transmitted to the sensitive radiation linear acid generator, thereby increasing the amount of acid generated. Further, the sensitizer for improving the appearance sensitivity of the radiation-sensitive linear resin composition can be improved. Examples of such sensitizers include acetophenones, benzophenones, naphthalenes, dithizone, eosin, rose beng, anthraquinones, anthracenes, and phenothiazines. These sensitizers may be used singly or in combination of two or more. -60-200934755 The amount of the sensitizer is usually 50 parts by mass or less, preferably 30 parts by mass or less, based on 100 parts by mass of the total resin component in the radiation-sensitive linear resin composition. Furthermore, the positive-type radiation-sensitive linear resin composition and the negative-type radiation-sensitive linear resin composition of the present invention may be combined with additives other than the above, such as dyes, pigments, and subsequent aids, as needed within the range not impeding the effects of the present invention. An agent, a halo preventing agent, a storage stabilizer, an antifoaming agent, a shape improving agent, etc., specifically, 4-hydroxy-4'-methylchalcone or the like. In this case, by matching the dye or the pigment to visualize the latent image of the exposed portion, the influence of the halation during exposure can be alleviated, and the adhesion to the substrate can be improved by using the auxiliary agent. Modulation of the composition solution: The positive-type radiation-sensitive linear resin composition of the present invention and the negative-type radiation-sensitive linear resin composition usually dissolve various components in a solvent into a homogeneous solution at the time of use, and then pass through, for example, an aperture 〇 as needed. A filter of about 2 μπι or the like is filtered to prepare a composition solution. The solvent may, for example, be an ether, an ester, an ether ester, a ketone, a ketoester, a guanamine, a guanamine ester, an indoleamine or a (halogenated) hydrocarbon. More specifically, for example, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates , propylene glycol monoalkyl ether acetates, acyclic or cyclic ketones, acetates, glycolic esters, alkoxy acetates, acetamidine acetates, propionates, lactates , other substituted C-61 - 200934755 acid esters, (substituted) butyrate, pyruvate, N, N_ two-yard carbamide, ν, ν · dialkyl acetamide , Ν 烷基 烷基 烷基 嗣 嗣 嗣 、, (halogenated) aliphatic hydrocarbons, (halogenated) aromatic hydrocarbons, etc. Specific examples of the above solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol dimethyl ether. , diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol oxime monoethyl ether Acid ester, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-glycol Ketone, cyclohexanone, ethyl acetate, n-propyl acetate, n-butyl acetate, isopropenyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Acetate, ethyl hydroxyacetate, ethyl ethoxyacetate, methyl acetoxyacetate, ethyl acetoxyacetate, isopropenyl propionate, 3-methyl-3-methoxybutylpropane Acid ester, methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Ester, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutene Ethyl ester, methyl 2-hydroxy-3-methylbutanoate, ethyl 2-hydrazino-2-methylpropanoate, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine _: methyl acetamide, Ν-methylpyrrolidone, toluene, xylene, and the like. Among these solvents, 'propylene glycol monoalkyl ether acetates, acyclic or cyclic ketones, lactic acid esters, 3-alkoxypropionates, etc., ensure good film surface uniformity during coating. In terms of opinion, it is preferred. The above solvents may be used singly or in combination of two or more. In addition, other solvents may be used together with the above solvents as needed, for example, -62-200934755 such as benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetamidine Acetone, isophorone, caproic acid, caprylic acid, octanoicol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, oxalic acid diethyl acetonate, diethyl maleate, γ-butyl A high boiling point solvent such as lactone, ethylene carbonate or propylene carbonate 'ethyl ketone monophenyl ether acetate. Among these other solvents, γ-butyrolactone is preferred. The above other solvents may be used singly or in combination of two or more. The use ratio of the other 〇 solvent is usually 50% by mass or less, more preferably 30% by mass or less based on the total of the solvent. The total amount of the solvent used is such that the total solid content concentration of the composition solution is usually 5 to 50% by mass, preferably 1 〇 to 5 〇 mass%, more preferably i 〇 to 4 〇 mass%, preferably 1 〇. ~30% by mass, especially in an amount of 10 to 25% by mass. By making the total solid content concentration of the solution within this range, good in-plane uniformity of the film at the time of coating can be ensured. Formation of φ photoresist pattern: When forming a photoresist pattern from the positive-type sensitive radiation linear resin composition and the negative-type sensitive radiation linear resin composition of the present invention, by spin coating, casting coating, roll coating, etc. A suitable coating method is to apply a composition solution prepared as described above to a substrate such as a tantalum wafer or an aluminum-coated wafer to form a photoresist film. Subsequently, after the preheating treatment (hereinafter referred to as "PB"), the photoresist film is exposed through a specific mask.

曝光時可使用之輻射線依據使用之敏輻射線性酸產生 劑而定，可列舉爲水銀燈亮線光譜（波長254nm ) 、KrF -63- 200934755 準分子雷射（波長248nm ) 、ArF準分子雷射（ 193nm) 、F2準分子雷射（波長l57nm) 、EUV ( 13nm)等遠紫外線，或同步輻射線等X射線，零子 帶電粒子束等’較好爲遠紫外線及帶電粒子束，最 KrF準分子雷射（波長248nm) 、ArF準分子雷射（ 193nm) 、F2準分子雷射（波長i57nm)及電子束。 另外’輻射線等曝光條件係依據正型敏輻射線性 〇 組成物及負型敏輻射線性樹脂組成物之搭配組成、添 之種類等適當選擇。又’光阻圖型形成時，就提升光 外觀感度之觀點而言，較好進行曝光後之加熱處理（ 稱爲「PEB」）。PEB之加熱條件係依據敏輻射線性 組成物之搭配組成、添加劑之種類等而變，通 3 0~2 0 0°C，較好爲 50~150°C。 隨後，藉由使經曝光之光阻被膜在鹼顯像液中顯 形成特定之正型或負型光阻圖型。 ❹ 上述鹼顯像液係使用例如溶解鹼金屬氫氧化物、 、烷基胺類、烷醇胺類、雜環式胺類、四烷基氫氧化 、膽鹼、1，8-二氮雜雙環[5.4.0]-7-十一烷烯、1，5-二 雙環[4.3 ·0]-5-壬烯等鹼性化合物之一種以上之鹼性水 ，最佳之鹼性顯像液爲四烷基氫氧化銨類之水溶液。 上述鹼性水溶液之濃度較好爲1 〇質量％以下，更 1 ~ 1 0質量％，最好爲2~5質量％。該情況下，由於鹼 溶液之濃度在1 0質量％以下，因此可抑制未曝光部分 型之情況）或曝光部分（負型之情況）於鹼性顯像液 波長 波長 束等 好爲 波長 樹脂 加劑 阻劑 以下 樹脂 常爲 像， 氨水 銨類 氮雜 溶液 好爲 性水 (正 中之 -64- 200934755 溶解。 又’由上述鹼性水溶液構成之顯像液中，較好添加適 量之界面活性劑等，藉此可提高鹼顯像液對於光阻被膜之 潤濕性。而且，在以由上述鹼性水溶液構成之顯像液顯像 後，通常以水洗淨並乾燥。 【實施方式】 © [實施例] 以下根據實施例具體說明本發明，但本發明並不受該 等實施例之限制。 [實施例1]: 將下述通式（19)所示之化合物、1，1,2,2-四氟丁烷-1 -磺酸鈉，藉由以下方法進行合成。The radiation that can be used during exposure depends on the sensitive linear acid generator used, which can be listed as the bright line spectrum of mercury lamp (wavelength 254nm), KrF-63-200934755 excimer laser (wavelength 248nm), ArF excimer laser (193nm), F2 excimer laser (wavelength l57nm), EUV (13nm) and other far-ultraviolet rays, or X-rays such as synchrotron radiation, zero-charged particle beam, etc., preferably far ultraviolet and charged particle beams, the most KrF Molecular laser (wavelength 248 nm), ArF excimer laser (193 nm), F2 excimer laser (wavelength i57 nm) and electron beam. Further, the exposure conditions such as radiation are appropriately selected depending on the composition of the positive-type sensitive radiation linear 〇 composition and the negative-type sensitive radiation linear resin composition, and the type of addition. Further, in the case of forming a photoresist pattern, it is preferable to perform heat treatment after exposure (referred to as "PEB") from the viewpoint of enhancing the appearance sensitivity of light. The heating condition of the PEB is changed according to the composition of the linear composition of the sensitive radiation, the type of the additive, and the like, and is 30 to 200 ° C, preferably 50 to 150 ° C. Subsequently, a specific positive or negative photoresist pattern is formed by exposing the exposed photoresist film to an alkali developing solution. ❹ The above alkali developing solution is, for example, dissolved alkali metal hydroxide, alkylamine, alkanolamine, heterocyclic amine, tetraalkyl hydroxide, choline, 1,8-diazabicyclo ring [5.4.0] One or more alkaline waters of a basic compound such as -7-undecene and 1,5-dibicyclo[4.3 ·0]-5-decene, and the most preferred alkaline imaging solution is An aqueous solution of tetraalkylammonium hydroxide. The concentration of the above aqueous alkaline solution is preferably 1% by mass or less, more preferably 1 to 10% by mass, most preferably 2 to 5% by mass. In this case, since the concentration of the alkali solution is 10% by mass or less, it is possible to suppress the unexposed portion type) or the exposed portion (in the case of the negative type) in the wavelength of the alkaline developing solution wavelength wave, etc. The following resins are often used as the agent, and the ammonia-ammonium-based aza solution is good for water (the medium-64-200934755 is dissolved. Also, in the imaging solution composed of the above alkaline aqueous solution, it is preferred to add an appropriate amount of surfactant. In this way, the wettability of the alkali developing solution to the resist film can be improved. Further, after developing with the developing liquid composed of the above alkaline aqueous solution, it is usually washed with water and dried. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by the examples. [Example 1]: A compound represented by the following formula (19), 1, 1, 2 , 2-tetrafluorobutane-1 -sulfonic acid sodium, synthesized by the following method.

【化3 5】 F2 \^C^S03Na (19) 在反應燒瓶內，加入連二亞硫酸鈉6.96g、及碳酸鈉 6·64§後，加入離子交換水30ml並攪拌30分鐘。接著， 於此混合溶液中花15分鐘滴下預先溶於乙腈30ml的1-漠·1，1，2,2-四氟丁烷4.18g後，邊攪拌邊加熱3.5小時（ 內溫60°C )。使反應溶液以減壓除去，經濃縮乾燥而得到 1，1，2,2-四氟丁烷-丨_亞磺酸鈉的粗純化物i〇.8g。不再純化 -65- 200934755 1,1,2,2-四氟丁烷-1-亞磺酸鈉而用於接下來的反應。 於反應燒瓶內，於1,1,2,2-四氟丁烷-1-亞磺酸鈉之粗 純化物l〇.8g中，加入離子交換水20mL、碳酸鈉3.325、 鎢酸鈉〇.27g，並攪拌30分鐘。接著於此反應混合溶液中 花30分鐘滴下30wt%過氧化氫水20ml後，在60°C攪拌3 小時。接著將反應溶劑以減壓除去，以50mL純水洗淨3 次，以二氯甲烷50mL進行萃取。藉由將有機層減壓除去 〇 ，而得到1,1，2,2 -四氟丁烷-1-磺酸鈉之白色固體4.lg。 又，關於1，1，2,2-四氟丁烷-1-磺酸鈉，使用 W-NMR (商品名：JNM-EX270，日本電子公司製造）分析之結果 ’獲得之化學位移爲 W-NMRCappnUDMSO): 1.10( 3H，t ，J = 7.36Hz ) 、2.12-2.24 ( 3H > m) ] ' 19F-NMR[appm ( DMSO) ： 44.93-44.97 ( 2F > m ) 、4 8.4 2 - 4 8.5 6 ( 2 F，m ) ]，確認爲目的化合物（又，19F-NMR係以六氟苯之峰値 爲Oppm (內部標準））。純度92wt% (以1H-NMR測定 © ) [實施例2]: 將下述通式（B-a)所示之化合物、三苯基锍^,2,2-四氟丁烷-1-磺酸鹽，藉由以下方法進行合成。[Chemical Formula 3 5] F2 \^C^S03Na (19) After adding 6.96 g of sodium dithionite and sodium carbonate 6·64 § in the reaction flask, 30 ml of ion-exchanged water was added and stirred for 30 minutes. Then, 4.18 g of 1-di-1,1,2,2-tetrafluorobutane previously dissolved in 30 ml of acetonitrile was added dropwise to the mixed solution for 15 minutes, and then heated while stirring for 3.5 hours (internal temperature 60 ° C). . The reaction solution was removed under reduced pressure and concentrated to dryness to give a crude product of <RTIgt;1,2,2-tetrafluorobutane-indole-sulphonic acid. No longer purified -65- 200934755 1,1,2,2-tetrafluorobutane-1-sulfinate sodium for use in the next reaction. In the reaction flask, in the crude purified product of 1,1,2,2-tetrafluorobutane-1-sulfinate sodium, 8 g, ion exchange water 20 mL, sodium carbonate 3.325, sodium tungstate ruthenium. 27g and stirred for 30 minutes. Then, 20 ml of 30 wt% hydrogen peroxide water was added dropwise to the reaction mixture for 30 minutes, and the mixture was stirred at 60 ° C for 3 hours. Then, the reaction solvent was removed under reduced pressure, washed three times with 50 mL of purified water, and extracted with 50 mL of dichloromethane. The white solid of 1,1,2,2-tetrafluorobutane-1-sulfonic acid sodium was obtained by removing hydrazine under reduced pressure. Further, regarding the sodium 1,1,2,2-tetrafluorobutane-1-sulfonate, the chemical shift obtained by W-NMR (trade name: JNM-EX270, manufactured by JEOL Ltd.) was obtained as W- NMRCappnUDMSO): 1.10 (3H, t, J = 7.36 Hz), 2.12-2.24 (3H > m) ] '19F-NMR[appm (DMSO): 44.93-44.97 (2F > m ) , 4 8.4 2 - 4 8.5 6 ( 2 F,m ) ], which was confirmed to be the objective compound (further, 19F-NMR was a peak of hexafluorobenzene of 0 ppm (internal standard)). Purity: 92% by weight (determined by 1H-NMR) [Example 2]: A compound represented by the following formula (Ba), triphenylsulfonium, 2,2-tetrafluorobutane-1-sulfonate The synthesis was carried out by the following method.

-66- 200934755 於反應燒瓶中加入1，1，2,2-四氟丁烷-1-磺酸鈉53.2g 與三苯基锍溴化物54.9g，並加入離子交換水5 00ml、二 氯甲烷500ml，在室溫進行1小時間攪拌。使有機層分離 後’使此有機層以離子交換水500ml洗淨5次。之後，藉 由除去溶劑而得到三苯基銃1,1,2,2 -四氟丁烷-1-磺酸鹽 78.1g。又，關於三苯基毓l,l，2,2 -四氟丁烷-1·磺酸鹽，使 ❺ 用 h-NMR (商品名：JNM-EX270、日本電子公司製）， 令測定溶劑爲重水所分析之結果，所得化學位移爲1H-NMR[appm(CDCl3) : 1.10 ( 3H > t ^ J = 7.36Hz ) ' 2.12- 2.24 ( 3H，m) ' 7.76-7.89 ( 1 5H > m ) j , 19F-NMR[oppm (CDC13) ： 44.93-44.97 ( 2F ^ m)，4 8.4 2-4 8.5 6 ( 2 F - m )]’確認爲目的化合物（又’ 19F-NMR係令六氟苯的峰 値爲Oppm)。純度99wt%以上。 ❹ [實施例3] 與上述實施例 2同樣地， 得：到下述之化合物 (B-b) [化3 7】-66- 200934755 Add 53.2 g of sodium 1,1,2,2-tetrafluorobutane-1-sulfonate and 54.9 g of triphenylsulfonium bromide to the reaction flask, and add 500 ml of ion-exchanged water, dichloromethane. 500 ml, stirred at room temperature for 1 hour. After the organic layer was separated, the organic layer was washed 5 times with 500 ml of ion-exchanged water. Thereafter, 78.1 g of triphenylsulfonium 1,1,2,2-tetrafluorobutane-1-sulfonate was obtained by removing the solvent. Further, regarding triphenylsulfonium 1,1,2,2-tetrafluorobutane-1·sulfonate, h-NMR (trade name: JNM-EX270, manufactured by JEOL Ltd.) was used, and the measurement solvent was As a result of analysis by heavy water, the obtained chemical shift was 1H-NMR [appm(CDCl3): 1.10 (3H > t ^ J = 7.36 Hz ) ' 2.12- 2.24 ( 3H,m) ' 7.76-7.89 ( 1 5H > m j , 19F-NMR [oppm (CDC13) : 44.93-44.97 ( 2F ^ m), 4 8.4 2-4 8.5 6 ( 2 F - m )] 'confirmed as the target compound (also '19F-NMR system hexafluoride The peak of benzene is Oppm). The purity is 99% by weight or more.实施 [Example 3] In the same manner as in the above Example 2, the following compound (B-b) was obtained: [Chem. 3 7]

-67- 200934755 4-n-丁氧基-1 —萘基四氫噻吩鎗1，1，2,2-四氟丁烷-1-磺酸 鹽 ^-NMRtoppmCCDCh) ： 1 · 〇 4 ( 3 Η，t，J = 7 _ 3 6 Hz )、 1.10 ( 3H，t，J = 7.36Hz ) 、1.56- 1.63 ( 5H，m)、l_91--67- 200934755 4-n-butoxy-1 -naphthyltetrahydrothiophene gun 1,1,2,2-tetrafluorobutane-1-sulfonate ^-NMRtoppmCCDCh) : 1 · 〇4 ( 3 Η ,t,J = 7 _ 3 6 Hz ), 1.10 ( 3H,t,J = 7.36Hz ) , 1.56- 1.63 ( 5H,m), l_91-

1-95 ( 2H，m) 、2 · 1 2 - 2.2 4 ( 3 H，m ) 、2 · 6 1 - 2 · 6 7 ( 4 H， m ) ' 3.67-3.71 ( 2H > m ) 、4.2 2 - 4.2 5 ( 4 H，m ) ' 7.05 (1H，d，J = 8.56Hz ) 、7.65-7.80 ( 2H，m ) 、7.94 ( 1H1-95 ( 2H,m) , 2 · 1 2 - 2.2 4 ( 3 H,m ) , 2 · 6 1 - 2 · 6 7 ( 4 H, m ) ' 3.67-3.71 ( 2H > m ) , 4.2 2 - 4.2 5 ( 4 H,m ) ' 7.05 (1H,d,J = 8.56Hz ) , 7.65-7.80 ( 2H,m ) , 7.94 ( 1H

❹ ，d，J = 8.60Hz) 、8.26 ( 1H，d，J = 8.56Hz ) 、 8.42 ( 1H ，d、J = 8.56Hz ) ]、19F-NMR[appm ( CDC13 ) ： 44.92- 44.97 ( 2F，m) 、4 8 · 42-48 · 5 5 ( 2F，m )]。純度 98wt% 以 上。 「樹脂合成」 (實施例3 ) 準備將21.17克（25莫耳％)之下述化合物（3-1)、 〇 27.21克（25莫耳％)下述化合物（S-4) 、51.62克（50 莫耳％)之下述化合物（S-5)溶解於200克2·丁酮中， 接著注入3.81克二甲基2,2’-偶氮雙（2-甲基丙酸酯）之 單體溶液。以氮氣沖洗加入有1〇〇克2-丁酮之1000毫升 三口燒瓶30分鐘，經氮氣沖洗後，攪拌反應釜且加熱至 80 °C，使用滴加漏斗在3小時內滴加事先準備之上述單體 溶液。以滴加開始作爲聚合起始時間，進行聚合反應歷時 6小時。聚合結束後，以水冷使聚合溶液冷卻至3 (TC以下 ，投入至2000克甲醇中之後，過濾所析出之白色粉末。 -68- 200934755 使過濾之白色粉末於400克甲醇中分散成獎料狀，洗淨兩 次後進行過據操作兩次，隨後’在5 0 °C下乾燥1 7小時， 獲得白色粉末狀共聚物（樹脂（A) ) (74克，產率74% )。該共聚物之 Mw 爲 6180，Mw/Mn=1.717，Uc nmr 分 析之結果，爲以化合物（S-1)、化合物（s-4)、化合物 (S-5)表示之各重複單位之含有率爲24.5· 24.2: 51.3( 莫耳％)之共聚物。該共聚物稱爲聚合物（Α·1)。❹, d, J = 8.60 Hz), 8.26 (1H, d, J = 8.56 Hz), 8.42 (1H, d, J = 8.56 Hz)], 19F-NMR [appm (CDC13): 44.92- 44.97 (2F, m) , 4 8 · 42-48 · 5 5 ( 2F, m )]. The purity is above 98% by weight. "Resin Synthesis" (Example 3) 21.17 g (25 mol%) of the following compound (3-1), 〇27.21 g (25 mol%) of the following compound (S-4), 51.62 g ( 50 mole %) of the following compound (S-5) was dissolved in 200 g of 2-butanone, followed by injection of 3.81 g of dimethyl 2,2'-azobis(2-methylpropionate) Body solution. The 1000 ml three-necked flask containing 1 g of 2-butanone was added with nitrogen for 30 minutes, and after flushing with nitrogen, the reaction vessel was stirred and heated to 80 ° C, and the above-prepared preparation was added dropwise over 3 hours using a dropping funnel. Monomer solution. The polymerization was carried out for 6 hours starting from the start of the dropwise addition as the polymerization initiation time. After the completion of the polymerization, the polymerization solution was cooled to 3 (TC or less) by water cooling, and then poured into 2000 g of methanol, and the precipitated white powder was filtered. -68- 200934755 The filtered white powder was dispersed in 400 g of methanol into a prize-like shape. After washing twice, it was subjected to two operations, followed by 'drying at 50 ° C for 17 hours to obtain a white powdery copolymer (resin (A)) (74 g, yield 74%). The Mw of the material was 6180, and Mw/Mn was 1.17. As a result of Uc nmr analysis, the content of each repeating unit represented by the compound (S-1), the compound (s-4), and the compound (S-5) was 24.5. · 24.2: Copolymer of 51.3 (mol%). This copolymer is called a polymer (Α·1).

各實施例及比較例中之各種測定•評估係以下述之要 領進行。 (感度） 使用在晶圓表面上形成膜厚7 80埃之ARC29 ( BreWer Science公司製造）膜之矽晶圓（ArC29)，且以旋轉塗 佈將各組成物溶液塗佈在基板上，在加熱板上，在表1中 所示之溫度下進行PB歷時60秒，形成膜厚0.12μιη之光 阻被膜上’使用Nikon公司製之ArF準分子雷射曝光裝置 (開口數0.78 )，通過光罩圖型曝光。隨後，在表1中所 -69- 200934755 示之溫度下進行PEB歷時60秒後，以2.38質量％之四甲 基氫氧化銨水溶液在25。(：下顯像30秒，經水洗、乾燥’ 形成正型光阻圖型。此時，以1對1之線寬形成線寬 9 0nm之線與空間圖型（1L1S)之曝光量作爲最適曝光量 ’且以該最適曝光量作爲感度。 (密集線焦點深度） φ 在90nmlL/l S光罩圖型中經解像的圖型尺寸係令成爲 光罩設計尺寸的± 1 0%以內的焦點振幅作爲密集線焦點深度 〇 (孤立線焦點深度） 在140nmL/1400nmP之光罩圖型中經解像的 90nmL/ 1 400nmP圖型尺寸，係使成爲81〜99nmlL/1400nmP範圍 內時之焦點振幅作爲孤立線焦點深度。 (LWR ) 在最適曝光量解像之90nmlL/lS圖型之觀測中，以日 立公司製造之測長SEM : S 9220由圖型上部觀察時，以任 意之觀測1 〇點線寬，以3 Σ表示該測量偏差之値作爲 LWR。 (最小崩壞前尺寸） 在 9 0nml L/l S光罩圖型中，從最適曝光量每調高 -70- 200934755 lmJ/cm2的曝光量， τι圖型朋壞前的前—階段曝光量之圖 型尺寸作爲爲最小崩壞前尺寸。 >份、下述敏輻射線性酸 份、及下述酸擴散控制劑 混合所得聚合物（Α-1) 1〇〇 產生劑（酸產生劑）（B-1 )7.5- (C ) 0.7份，得到敏輻射線性樹脂組成物。混合下述溶劑 (D-1) 1500份、下述溶劑（D_2) 65〇份、及下述溶劑（ D - 3 ) 3 0份後製作混合溶劑’於此混合溶劑中，將所得敏 〇 輻射線性樹脂組成物溶解而得到敏輻射線性樹脂組成物溶 液。又，各溶劑之搭配量以相對於聚合物（A_ i ) 1 00份 的質量比（質量份）表示。使用所得敏輻射線性樹脂組成 物溶液，進行上述各測定。測定結果如表2。 敏輻射線性酸產生劑（B )： B-l: 1-(4-正丁氧基萘基）四氫噻吩鎗九氟正丁烷磺 酸鹽 Q B-2 :三苯基锍2-雙環[2.2.1]庚-2-基-1,1,2,2-四氟乙 烷磺酸鹽 B-3:三苯基毓全氟正丁烷磺酸鹽 B-4: 4-正丁氧基-1-萘基四氫噻吩鑰2-雙環[2.2.1]庚-2-基-1,1,2,2-四氟乙烷磺酸鹽 B-5: 4-正丁氧基-1-萘基四氫噻吩鎗九氟丁烷磺酸鹽 B-6 ·· 4-環己基苯基-二苯基锍九氟正丁烷磺酸鹽 上述敏輻射線性酸產生劑（B -1 )〜（B - 6 )分別對應 之化學式爲以下所不之式（B_1)〜式（B-6)。 -71 - 200934755The various measurements and evaluations in the respective examples and comparative examples were carried out in the following manner. (sensitivity) A ruthenium wafer (ArC29) of ARC29 (manufactured by BreWer Science Co., Ltd.) having a film thickness of 70 angstroms was formed on the surface of the wafer, and each composition solution was applied onto the substrate by spin coating, and heated. On the board, PB was subjected to PB for 60 seconds at a temperature shown in Table 1, and a photoresist film having a film thickness of 0.12 μm was formed on the film by using an ArF excimer laser exposure apparatus (number of openings: 0.78) manufactured by Nikon Co., Ltd., through a mask. Graphic exposure. Subsequently, PEB was subjected to a temperature of -69 to 200934755 in Table 1 for 60 seconds, and then a 2.38 mass% aqueous solution of tetramethylammonium hydroxide was used at 25. (: 30 seconds under the image, washed and dried to form a positive photoresist pattern. At this time, the line width of the line width of 90 nm and the exposure of the space pattern (1L1S) are optimized as line widths of 1 to 1. Exposure amount 'and the optimum exposure amount as the sensitivity. (Dense line focus depth) φ The resolution of the image size in the 90nmlL/l S mask pattern is within ± 10% of the mask design size. Focus amplitude as dense line focus depth 孤立 (isolated line focus depth) The 90nmL / 1 400nmP pattern size resolved in the 140nmL/1400nmP reticle pattern is the focal amplitude when it is in the range of 81~99nmlL/1400nmP As the depth of the isolated line focus (LWR) In the observation of the 90nmlL/lS pattern of the optimum exposure image, the length of the SEM: S 9220 manufactured by Hitachi is observed from the upper part of the pattern, and 1 point is observed arbitrarily. Line width, 3 Σ indicates the measurement deviation as LWR. (Minimum before collapse) In the 90 nml L/l S mask pattern, the optimum exposure is increased by -70-200934755 lmJ/cm2 The amount of exposure, the pattern size of the pre-stage exposure before the τι pattern is broken The size before the minimum collapse. > parts, the following linear radiation of sensitive radiation, and the following acid diffusion control agent mixed polymer (Α-1) 1〇〇 generator (acid generator) (B-1) 7.5 - (C) 0.7 parts, to obtain a radiation sensitive linear resin composition, mixing 1500 parts of the following solvent (D-1), 65 parts of the following solvent (D_2), and the following solvent (D - 3 ) 30 parts Preparing a mixed solvent in the mixed solvent, and dissolving the obtained linear radiation-sensitive resin composition to obtain a solution of the radiation-sensitive linear resin composition. Further, the amount of each solvent is 10,000 parts relative to the polymer (A_i). The mass ratio (parts by mass) is expressed by using the obtained sensitive radiation linear resin composition solution, and the above respective measurements are performed. The measurement results are shown in Table 2. The sensitive radiation linear acid generator (B): Bl: 1-(4-n-butoxy group) Naphthyl)tetrahydrothiophene gun nonafluoro-n-butane sulfonate Q B-2 : triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane Sulfonic acid salt B-3: triphenylsulfonium perfluoro-n-butane sulfonate B-4: 4-n-butoxy-1-naphthyltetrahydrothiophene key 2-bicyclo[2.2.1]heptan-2- Base-1,1,2,2-tetrafluoroethane sulfonate B-5: 4-n-butoxy-1-naphthyltetrahydrothiophene gun nonafluorobutane sulfonate B-6 ·· 4-cyclohexylphenyl-diphenylfluorene nonafluorobutane sulfonate The acid generators (B -1 ) to (B - 6 ) respectively correspond to the following formula (B_1) to formula (B-6). -71 - 200934755

【化3 9】[化3 9]

【0 2 2 9】 【化4 0】[0 2 2 9] [Chemical 4 0]

(B-3)(B-3)

(B-4)(B-4)

C4F9SO3 (Β-6) 酸擴散控制劑（C ) (C) ••第三丁基-4-羥基-1-哌啶羧酸酯 上述酸擴散控制劑（C )相對應之化學式（C )如下。 -72- 200934755 【化4 1】C4F9SO3 (Β-6) Acid Diffusion Controlling Agent (C) (C) ••T-butyl-4-hydroxy-1-piperidinecarboxylic acid ester The above acid diffusion controlling agent (C) corresponds to the chemical formula (C) as follows . -72- 200934755 【化4 1】

溶劑（D ): (D-1):丙二醇單甲基醚乙 0 ( D-2) ··環己酮 (D-3 ) : γ·丁內酯 上述溶劑（D-1 )〜（D-3 ) ^ 所示之式（D-1)〜（D-3)。 酸酯 別對應之化學式爲以下 ❹ 【化4 2】Solvent (D): (D-1): propylene glycol monomethyl ether E (D-2) · · cyclohexanone (D-3): γ · butyrolactone The above solvent (D-1) ~ (D- 3) ^ The equations (D-1) to (D-3) are shown. The chemical formula corresponding to the acid ester is the following ❹ [Chemical 4 2]

(D-1) Ο(D-1) Ο

(D-2) 0(D-2) 0

(D-3) 除了將化合物（S-1)等之赛 物（樹脂（Α))」所示之各莫ϊ (A ) ) ( A-2〜4 )，所得聚合物 輻射線性酸產生劑（B )及上述酸 中所示之比率混合以外，其餘如j 性樹脂組成物（實施例2〜1 〇，比 輻射線性樹脂組成物溶解於表i 述溶劑（D)而成之混合溶齊υφ , ^耳比作成於下述「共聚 Ϊ比，製作聚合物（樹脂 (Α-2~4 )分別與上述敏 擴散控制劑（C )以表1 t施例1般製作敏輻射線 較例1 ~ 1 3 )。將所得敏 中所示之混合比率混合上 1獲得敏輻射線性樹脂組 -73- 200934755 成物溶液。表1中，「樹脂j爲「共聚物（樹脂（A)) 」。使用所得敏輻射線性樹脂組成溶液進行上述各種測定 ，測定結果如表2。 【化4 3](D-3) The obtained polymer radiation linear acid generator is obtained by using each of the compounds (S-1) and the like (resin (Α)) as shown in (A-2 to 4). (B), in addition to the ratio shown in the above-mentioned acid, the remaining resin composition (Examples 2 to 1) is more soluble than the radiation-linear resin composition dissolved in the solvent (D). Υφ , ^ ear ratio is made in the following "copolymerization ratio", the production of polymer (resin (Α-2~4) and the above-mentioned sensitive diffusion control agent (C), respectively, as shown in Table 1 t Example 1 1 ~ 1 3 ). The mixing ratio shown in the obtained sensitivity is mixed with 1 to obtain a solution of the radiation sensitive linear resin group -73-200934755. In Table 1, "resin j is "copolymer (resin (A))" The above various measurements were carried out using the obtained sensitive radiation linear resin composition solution, and the measurement results are shown in Table 2. [Chemical 4 3]

共聚合物（樹脂（A))； A-2 ： ( S-l ) 25/ ( S-3) 25/ ( S-5 ) 5 0 = 23.5/20.6/55.9 (莫耳比）、Mw = 5768，Mw/Mn= 1.698 A-3 : ( S-2 ) 25/ ( S-4) 25/ ( S-5 ) 5 0 = 2 3.1 /24.1 /52.8 (莫耳比）、Mw = 6491，Mw/Mn= 1.601 ❹ A-4 ： ( S-2 ) 25/ ( S-3) 25/ ( S-6 ) 5 0 = 23.9/20.3/55.8 (莫耳比）、Mw = 6811，Mw/Mn=1.348 A-5 : ( S-l ) 50/ ( S-5 ) 50 = 46.4/53.6 (莫耳比）、Copolymer (Resin (A)); A-2 : ( Sl ) 25/ ( S-3) 25/ ( S-5 ) 5 0 = 23.5/20.6/55.9 (Morby), Mw = 5768, Mw /Mn= 1.698 A-3 : ( S-2 ) 25/ ( S-4) 25/ ( S-5 ) 5 0 = 2 3.1 /24.1 /52.8 (Morby), Mw = 6491, Mw/Mn= 1.601 ❹ A-4 : ( S-2 ) 25/ ( S-3) 25/ ( S-6 ) 5 0 = 23.9/20.3/55.8 (Morby), Mw = 6811, Mw/Mn=1.348 A- 5 : ( Sl ) 50/ ( S-5 ) 50 = 46.4/53.6 (Morby),

Mw = 63 3 2，Mw/Mn=l .623 A-6 ： (S-2) 50/ (S-5) 50 = 45.8/54.2 (莫耳比）、 M w = 62 53 > Mw/Mn= 1.648 -74 200934755Mw = 63 3 2, Mw / Mn = l .623 A-6 : (S-2) 50 / (S-5) 50 = 45.8/54.2 (Mohr ratio), M w = 62 53 > Mw / Mn = 1.648 -74 200934755

[表1] 測旨(份) 酸產生劑(份） 酸擴散控制劑(份) 溶劑(份） 1 A-l(lOO) B-a(7.1) C(l.l) D-1 (1700),D-2(700),D-3(30) 2 A-l(lOO) B-a(5) C(0.7) D-l(1350),D-2(580) 3 A-2(100) B-a(7.1) C(l.l) D-l(1700),D-2(700),D-3(30) 4 A-3(100) B-a(7.1) C(1.1) D-1 (1700),D-2(700),D-3(30) 實施例 5 A-4(100) B-a(7.1) C(l.l) D-l (1700),D-2(700),D-3(30) 6 A-5(100) B-a(7.1) C(l.l) D-l(1700),D-2(700),D-3(30) 7 A-6(100) B-a(7.1) C(l.l) D-1 (1700),D-2(700),D-3 (3 0) 8 A-l(lOO) B-a(6) B-b(2) C(1.0) D-1 (1700),D-2(700),D-3(30) 1 A-l(lOO) B-3(7.1) C(l.l) D-1 (1700),D-2(700),D-3 (3 0) 2 A-l(lOO) B-3(5) C(0.7) D-l(1350),D-2(580) 3 A-l(lOO) B-2(7.1) C(l.l) D-l(1700),D-2(700),D-3(30) 4 A-l(lOO) B-l(7.1) C(l.l) D-1(1700),D-2(700),D-3(30) 5 A-2(100) B-3(7.1) C(l.l) D-l(1700),D-2(700),D-3(30) 比較例 6 A-3(100) B-3(7.1) C(l.l) D-1(1700),D-2(700),D-3(30) 7 A-4(100) B-3(7.1) C(l.l) D-l(1700),D-2(700),D-3(30) 8 A-5(100) B-3(7.1) C(l.l) D-1 (1700),D-2(700),D-3 (3 0) 9 A-6(100) B-3(7.1) C(l.l) D-l(1700),D-2(700),D-3(30) 10 A-l(lOO) B-3(6) B-4(2) C(1.0) D-l(1700),D-2(700),D-3(30) -75- 200934755 [表2] SB (°c ) PEB (°C ) 感度 (mJ/cm ) 密集圖型 DOF(Mm) Ml?圖型 DOF(p m) 最小崩壞 前尺寸(nm) LWR 實施例 1 100 105 35.0 0.45 0.25 42.3 6.8 2 100 105 34.0 0.40 0.15 45.1 7.1 3 100 105 33.0 0.45 0.20 43.1 6.6 4 100 105 39.0 0.45 0.20 42.6 6.9 5 100 100 34.0 0.45 0.25 39.7 6.4 6 100 100 35.0 0.45 0.15 42.1 6.0 7 100 100 41.0 0.45 0.15 39.9 6.1 8 100 105 33.0 0.45 0.20 40.8 6.3 比較例 1 100 105 34.0 0.35 0.15 45.8 8.1 2 100 105 33.5 0.25 0.05 50.3 10.5 3 100 105 46.0 0.35 0.15 46.3 7.8 4 100 105 41.0 0.40 0.15 47.1 7.3 5 100 105 32.0 0.35 0.15 46.6 8.1 6 100 105 38.0 0.35 0.15 45.7 8.0 7 100 100 33.0 0.35 0.20 45.1 7.9 8 100 100 34.0 0.35 0.05 45.5 7.6 9 100 100 40.0 0.35 0.05 45.4 7.7 10 100 105 32.0 0.35 0.15 45.1 7.5 ❿ [產業上利用可能性] 本發明極適用作爲化學增幅型光阻劑有用之敏輻射線 性樹脂組成物中之敏輻射線性酸產生劑。 -76-[Table 1] Test purpose (parts) Acid generator (parts) Acid diffusion control agent (parts) Solvent (parts) 1 Al(lOO) Ba(7.1) C(ll) D-1 (1700), D-2 ( 700), D-3(30) 2 Al(lOO) Ba(5) C(0.7) Dl(1350), D-2(580) 3 A-2(100) Ba(7.1) C(ll) Dl( 1700), D-2 (700), D-3 (30) 4 A-3 (100) Ba (7.1) C (1.1) D-1 (1700), D-2 (700), D-3 (30 Example 5 A-4(100) Ba(7.1) C(ll) Dl (1700), D-2(700), D-3(30) 6 A-5(100) Ba(7.1) C(ll ) Dl (1700), D-2 (700), D-3 (30) 7 A-6 (100) Ba (7.1) C (ll) D-1 (1700), D-2 (700), D- 3 (3 0) 8 Al(lOO) Ba(6) Bb(2) C(1.0) D-1 (1700), D-2(700), D-3(30) 1 Al(lOO) B-3 (7.1) C(ll) D-1 (1700), D-2(700), D-3 (3 0) 2 Al(lOO) B-3(5) C(0.7) Dl(1350), D- 2(580) 3 Al(lOO) B-2(7.1) C(ll) Dl(1700), D-2(700), D-3(30) 4 Al(lOO) Bl(7.1) C(ll) D-1 (1700), D-2 (700), D-3 (30) 5 A-2 (100) B-3 (7.1) C (ll) Dl (1700), D-2 (700), D -3(30) Comparative Example 6 A-3(100) B-3(7.1) C(ll) D-1(1700), D-2(700), D-3(30) 7 A-4(100 B-3(7.1) C(ll) Dl(1700), D-2(700), D-3(30) 8 A-5(100) B-3(7.1) C(ll) D-1 ( 1700), D-2 (700), D-3 (3 0) 9 A-6 ( 100) B-3(7.1) C(ll) Dl(1700), D-2(700), D-3(30) 10 Al(lOO) B-3(6) B-4(2) C(1.0 ) Dl (1700), D-2 (700), D-3 (30) -75- 200934755 [Table 2] SB (°c) PEB (°C) Sensitivity (mJ/cm) Dense pattern DOF (Mm) Ml? pattern DOF (pm) minimum collapse size (nm) LWR Example 1 100 105 35.0 0.45 0.25 42.3 6.8 2 100 105 34.0 0.40 0.15 45.1 7.1 3 100 105 33.0 0.45 0.20 43.1 6.6 4 100 105 39.0 0.45 0.20 42.6 6.9 5 100 100 34.0 0.45 0.25 39.7 6.4 6 100 100 35.0 0.45 0.15 42.1 6.0 7 100 100 41.0 0.45 0.15 39.9 6.1 8 100 105 33.0 0.45 0.20 40.8 6.3 Comparative Example 1 100 105 34.0 0.35 0.15 45.8 8.1 2 100 105 33.5 0.25 0.05 50.3 10.5 3 100 105 46.0 0.35 0.15 46.3 7.8 4 100 105 41.0 0.40 0.15 47.1 7.3 5 100 105 32.0 0.35 0.15 46.6 8.1 6 100 105 38.0 0.35 0.15 45.7 8.0 7 100 100 33.0 0.35 0.20 45.1 7.9 8 100 100 34.0 0.35 0.05 45.5 7.6 9 100 100 40.0 0.35 0.05 45.4 7.7 10 100 105 32.0 0.35 0.15 45.1 7.5 ❿ [Industrial Applicability] The present invention is highly suitable as a sensitive radiation linear tree useful as a chemically amplified photoresist. Radiation-sensitive compositions in a linear acid generator. -76-

Claims (1)

200934755 十、申請專利範圍 i —種磺酸鹽，其特徵係以下述通式（1)所表示， 【化1】200934755 X. Patent application scope i - a kind of sulfonate, characterized by the following general formula (1), [Chemical 1] (^^各自獨立，表示氟原子或碳數1〜3之全氟烷基，R1 表示碳數1〜8之直鏈或分支之烷基，R2各自獨立，表示 氫原子、氟原子、或可以氟原子取代之碳數1〜8之直鏈 或分支之烷基，m爲0〜3之整數，η爲1〜3之整數，Mk + 表示k價的陽離子，k表示1〜4之整數）。 2. 如申請專利範圍第1項之磺酸鹽，其中，R2爲氫 原子或碳數1〜8之直鏈或分支之垸基。 3. 如申請專利範圍第1項之磺酸鹽，其中，R2係氫 原子，Rf係氟原子。 4. 如申請專利範圍第1項之磺酸鹽，其中，陽離子 爲錡陽離子或碘鑰陽離子。 5. —種敏輻射線性樹脂組成物，其特徵係含有申請 專利範圍第1〜4項中任一項之磺酸鹽及含酸解離性基之 樹脂。 6. 如申請專利範圍第5項之敏輻射線性樹脂組成物 -77- 200934755 ，其中，上述含酸解離性基之樹脂係含下述通式（8)所 表示之重複單位， 【化2】 ⑻ (R15)d (OH)c (通式（8)中，R15爲氫原子或1價之有機基，複數存在 之R15可互爲相同或相異，c及d分別爲1〜3之整數）。 7.如申請專利範圍第5項之敏輻射線性樹脂組成物 ，其中，上述含酸解離性基之樹脂係包含下述通式（9) 所表示之重複單位及下述通式（10)所表示之重複單位之 至少一種、與下述通式（11)所表示之重複單位，(^^ is independently independent and represents a fluorine atom or a perfluoroalkyl group having a carbon number of 1 to 3, and R1 represents a linear or branched alkyl group having a carbon number of 1 to 8, and R2 is independently represented by a hydrogen atom, a fluorine atom, or a linear or branched alkyl group having a carbon number of 1 to 8 substituted by a fluorine atom, m is an integer of 0 to 3, η is an integer of 1 to 3, Mk + represents a k-valent cation, and k represents an integer of 1 to 4) . 2. The sulfonate of claim 1, wherein R2 is a hydrogen atom or a linear or branched fluorenyl group having 1 to 8 carbon atoms. 3. The sulfonate of claim 1, wherein R2 is a hydrogen atom and Rf is a fluorine atom. 4. The sulfonate of claim 1, wherein the cation is a phosphonium cation or an iodine cation. A sensitizing radiation linear resin composition comprising the sulfonate salt of any one of claims 1 to 4 and a resin containing an acid dissociable group. 6. The sensitive radiation linear resin composition of claim 5, wherein the resin containing the acid dissociable group contains a repeating unit represented by the following formula (8), [Chemical 2] (8) (R15)d (OH)c (In the formula (8), R15 is a hydrogen atom or a monovalent organic group, and the plural R15s may be the same or different from each other, and c and d are each an integer of 1 to 3; ). 7. The radiation-sensitive linear resin composition according to claim 5, wherein the acid-dissociable group-containing resin comprises a repeating unit represented by the following formula (9) and a formula (10) At least one of the repeating units indicated, and a repeating unit represented by the following general formula (11), (9) (1〇) (11) -78- 200934755 (通式（9)、通式（10)及通式（11)中，R16、R18及 R19相互獨立，表示氫原子或甲基，通式（9)中，各R17 相互獨立，表示氫原子、羥基、氰基或-COOR21 (惟’ R21 爲氫原子、碳數1〜4之直鏈狀或分支狀之烷基或碳數3〜 20之環烷基），通式（11)中，各R20相互獨立，表示碳 數4〜20之1價之脂環式烴基或其衍生物或碳數1〜4之 直鏈狀或分支狀之烷基，且r2G之至少一個係該脂環式烴 基或其衍生物，或任兩個之r2()相互鍵結，與各自鍵結的 碳原子共同形成碳數4〜20之2價之脂環式烴基或其衍生 物，其餘的R2()表示碳數1〜4之直鏈狀或分支狀之烷基 或碳數4〜20之1價之脂環式烴基或其衍生物）。(9) (1) (11) -78- 200934755 (In the formula (9), the formula (10) and the formula (11), R16, R18 and R19 are independent of each other and represent a hydrogen atom or a methyl group. In the formula (9), each R17 is independent of each other and represents a hydrogen atom, a hydroxyl group, a cyano group or -COOR21 (only 'R21 is a hydrogen atom, a linear or branched alkyl group having a carbon number of 1 to 4 or a carbon number of 3~ 20 cycloalkyl), in the formula (11), each R20 is independent of each other, and represents a monovalent alicyclic hydrocarbon group having a carbon number of 4 to 20 or a derivative thereof or a linear or branched carbon number of 1 to 4. An alkyl group, and at least one of r2G is an alicyclic hydrocarbon group or a derivative thereof, or any two of r2 () are bonded to each other, and together with the carbon atom to which they are bonded, form a carbon number of 4 to 20 The alicyclic hydrocarbon group or a derivative thereof, and the remaining R2 () represents a linear or branched alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof). -79- 200934755 七、指定代表圖： (一） 、本案指定代表圖為：無 (二） 、本代表圖之元件代表符號簡單說明：無-79- 200934755 VII. Designated representative map: (1) The designated representative figure of this case is: None (2), the representative symbol of the representative figure is simple Explanation: None 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無 ❹8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: no ❹
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