TW200408649A - Process for preparing a fluorine-containing polymer for resist - Google Patents

Abstract

A process for preparing a fluorine-containing polymer for resist which is excellent in transparency in vacuum ultraviolet region and can form an ultra fine pattern for a photoresist, particularly for F2 resist. The process is used to obtain a fluorine-containing polymer which has a recurring unit (M1) derived from a fluorine-containing ethylenic monomer (m1) having 2 or 3 carbon atoms and at least one fluorine atom and/or a recurring unit (M2) derived from a monomer (m2) which can give an aliphatic ring structure to a trunk chain of the polymer and may contain fluorine atom, and has an acid-reactive group Y1 reacting by an acid or a group Y2 which can be converted to the acid-reactive group Y1. The process is characterized by carrying out radical polymerization of the fluorine-containing ethylenic monomer (m1) and/or the monomer (m2) which can give an aliphatic ring structure to a trunk chain of the polymer, by using a polymerization initiator having fluorine atom.

Description

200408649 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for producing a fluoropolymer for transparent photoresist under the vacuum ultraviolet field ', especially under an F 2 laser (). [Previous technology] As the large-scale integrated circuit (LSI) improves the high integration, photolithography technology requires micro-processing technology. Therefore, 'taste far ultraviolet rays longer than the current g-line (wavelength 4 3 6 nm) and i-line (wavelength 3 65 nm), KrF laser (wavelength 24 8nm)' ArF laser 1 93 nm) as the exposure light source, and Practical. Also, when reviewing the ultra-fine processing technology steps using F2 laser (15 nm) in the vacuum ultraviolet field recently, it was found that it has a promising post-technical section goal of 0.07 μm exposure technology. The current photoresist resins used for photolithography, such as a part or all of the hydroxyl groups of phenol are protected by a protective group such as acetal or ketal, and the carboxyl group of a methacrylic resin is introduced into an acid dissociated product (ArF photo Resistance) and so on. However, the current photoresist polymers are absorbing in the vacuum ultraviolet wavelength range, and have a fundamental problem of low transparency (large absorption coefficient) for the wavelength 1 F2 laser used in the ultra-fine patterning step. The thickness of the photoresist film used for F2 laser exposure needs to be extremely thin, but in fact it is not a single layer of F2 photoresist. Therefore, we began to review the use of fluoropolymer with high transparency for F2 laser 1 5 7 nm. The necessity of using a shorter wave (wavelength (wavelength becomes the substance of today's resin (sexual ester group will have a strong 5 7 nm). Therefore, it is easy to use的 光 -5- (2) (2) 200408649. Among them, in terms of transparency and dry corrosion resistance, a fluoropolymer copolymerized with a fluoroolefin having a carbon number of 2 or 3 represented by tetrafluoroethylene and the like and / or A fluorine-containing polymer having a ring structure in the main chain is preferred. 'Suitable as a photoresist polymer.' The proposed fluorine-based photoresist is, for example, a fluorine-containing polymer for photoresist having a functional group using an acid reaction, and a photoresist using the same. Composition (for example, refer to International Publication No. 00/17712, International Publication No. 00/67072, International Publication No. 01/7 4 9 16). The above-mentioned patent documents have specifically described the tetrafluoroethylene A copolymer of a representative fluorohydrocarbon and an alicyclic monomer represented by norbornene (or a norbornene derivative), and the production method is to use a polymerization initiator such as a hydrocarbon peroxide to make the fluoroolefin and The alicyclic monomer is radically polymerized. In view of this, after intensive research, the inventors have discovered that the fluoroolefin and the monomer that forms a ring structure in the main chain are radically (co) polymerized to obtain When a fluoropolymer for photoresist having an acid-reactive group is used, radical (co) polymerization using a specific radical polymerization initiator can efficiently obtain the fluoropolymer for photoresistance, and can leapfrog the fluoropolymer. Transparency to F2 laser. A first object of the present invention is to provide a free radical (co) polymerization of a fluoroolefin and a monomer forming a ring structure with a main chain by using a specific radical polymerization initiator to obtain an F 2 laser device. A method for producing a fluoropolymer for photoresistance with excellent transparency. A second object of the present invention is to provide a fluoropolymer containing the above-mentioned production method. (6) (3) (3) 200408649 Excellent transparency to vacuum ultraviolet light Photoresist for fluoropolymers, especially F2 * resist composition. A third object of the present invention is to provide a tetrafluoroethane fired from CF 3 groups with excellent transparency and polymer terminal introduction at a high ratio. Scum The novel polymer formed. [Summary of the Invention] [Disclosure of the Invention] The first series of the present invention is related to the production of a fluorine-containing ethylenic compound having at least one fluorine atom in an ethylenic monomer having 2 or 3 carbon atoms. The repeating unit (M 1) of the monomer (π 1), and / or the repeating unit (M2) derived from the monomer (m2) capable of forming an aliphatic ring structure of the polymer and containing a fluorine atom, and the polymer has For acid-reactive acid-reactive groups Υ1 or groups which can be converted into acid-reactive groups Υ1 (hereinafter referred to as "acid-reactive group conversion groups") Υ2 fluoropolymers, use polymerization initiators with fluorine atoms Fluorine-containing photoresist for photoresist having excellent transparency to vacuum ultraviolet light by radically polymerizing a fluorine-containing ethylenic monomer (m 1) and / or a monomer (m2) capable of forming an aliphatic ring structure of a polymer main chain物 的 制造 方法 The manufacturing method of the object. In addition to the rapid polymerization reaction and high molecular weight of the manufacturing method of the present invention, the obtained fluoropolymer has excellent transparency to light in the vacuum ultraviolet field in particular. The second system of the present invention relates to an acid-dissociative functional group having an OH group of (0-1), which can be converted to an OH group by an acid, a COOH group, or an acid-dissociation property that can be changed to a C Ο OH group by acid dissociation. An acid-reactive group of at least one of the functional groups (4) (4) 200408649 Y1 fluoropolymer, (B) a photoacid generator and (C) a solvent composed of 'the fluoropolymer (A- 1) A photoresist composition for a polymer obtained by the production method described in the first aspect of the present invention. The photoresist composition is a photoresist composition capable of forming a photoresist film 'having excellent transparency to vacuum ultraviolet light, and is particularly suitable for ultrafine processing steps. The third aspect of the present invention relates to a fluorine-containing polymer in which a repeating unit (M1A) derived from tetrafluoroethylene and a repeating unit (M2A) derived from a norbornene derivative (m2a) which may contain a fluorine atom are necessary components. , At least one of the ends of the polymer main chain contains a polymer molecule having a -CF3 group, and the -Cf3 signal strength η (terminal CF3) of the end of the polymer main chain measured by 19F-NMR analysis, and _Cf2-Signal intensity H (-CF2-) is a fluoropolymer that conforms to the formula (1): 0.3 (terminal CF3) / H (-CF2-) g. 0.01 formula (1). The fluoropolymer can more effectively improve the transparency, and is suitable for the above-mentioned photoresist. In addition, the polymer is suitable for other optical applications in addition to the photoresist application. [Embodiment] [Best Mode for Implementing the Invention] The fluoropolymer obtained by the production method of the present invention has a repeating unit (M 1) derived from a fluorinated ethylenic monomer (m 1) and a polymer Either or both of the repeating units (M2) of the monomer (m2) in which the main chain forms an aliphatic ring structure and may contain a fluorine atom, and the polymer has an acid inversion (5) (5) 200408649 reactive group Y 1 or A fluorine-containing polymer of an acid-reactive group conversion group Y2 (hereinafter also referred to as "acid-reactive functional group Y"). Furthermore, it may contain arbitrary repeating units (N). In the fluoropolymer obtained in the present invention, the fluorine atom is not limited to a substance derived from a monomer (ml) or a monomer (m2), and may be derived from other arbitrary monomers. The detailed method for introducing the acid-reactive functional group Y into the polymer is described later, but it may be as follows. (I) The monomer (ml) and / or the monomer (m2) having a monomer having the acid-reactive functional group Y is copolymerized. (II) a method of copolymerizing a monomer (nl) having an acid-reactive functional group Y other than the monomers (ml) and (m2). First, the fluorine-containing radical polymerization initiator will be described first, and then each monomer of the radical polymerization will be specifically described. The production method of the present invention is characterized in that, when a fluoropolymer having the above-mentioned acid-reactive functional group Y is produced, radical polymerization is performed using a fluorine atom-containing polymerization initiator. The use of the fluorine-containing polymerization initiator can improve the radical polymerization reactivity of the fluorine-based monomer, and make the initiator end of the polymer terminal be a fluorine-containing terminal, and further improve the transparency in the vacuum ultraviolet field. The fluorine atom-containing polymerization initiator used may be a compound capable of generating radicals by using temperature (heat, etc.) and light. Among them, fluorine-containing organic peroxides are preferred. The fluorine-containing organic peroxide is preferably, for example, a fluorine-containing difluorenyl peroxide, a fluorine-containing peroxydicarbonate, a fluorine-containing peroxyester, or a fluorine-containing dialkyl peroxide-9- (6) (6 ) 200408649 One or more selected from the oxides. Among them, fluorine-containing difluorenyl peroxides which can promote the radical polymerization reactivity 'and further improve the transparency of the obtained polymer to the vacuum ultraviolet field are preferred. This fluorine-containing organic peroxide is a fluorine-free hydrogenated carbon-based peroxide skeleton in which a part or all of a hydrogen atom such as an alkyl group and an aryl group is substituted with a fluorine atom. For example, peroxides having a fluorine-containing alkyl group, a fluorine-containing aryl group, a fluorine-containing alkyl group having an ether bond, a fluorine-containing alkyl group (ie, a fluorine-containing aralkyl group) substituted with a fluorine-containing aryl group, and the like in the skeleton. Among them, an organic peroxide having a fluorine-containing alkyl group and a fluorine-containing alkyl group having an ether bond is more preferable for improving the transparency. The fluorine-containing alkyl group and the fluorine-containing alkyl group having an ether bond may be linear or branched. In addition, the effect of improving the transparency is particularly preferably a fluorine-containing alkyl group and a fluorine-containing alkyl group having an ether bond. The perfluoroalkyl group or a part of the fluorine atom is substituted by a hydrogen atom, a chlorine atom, a bromine atom and the like, and a substituted perfluoroalkane base. The fluorine-containing difluorenyl peroxides are preferably of the formula: 〇 〇

II II R f 3— 01010—C—R ί4 (where Rf3 and Rf4 may be the same or different and may have an ether bond, a fluorine-containing alkyl group having 1 to 40 carbon atoms, and a carbon number of 6 to 40 Fluorinated aryl group or fluorinated aromatic group having 7 to 40 carbon atoms), which is further represented by the formula: • 10- (7) 200408649 〇〇

II II

F ^ C-〇-〇 ~ C-tCF2i-vX (where m and n are the same or different integers from 1 to 20; X and X1 are the same or different F, C1, or H) A fluorofluorenyl) peroxide is preferred. Specific examples are preferred, such as 〇

II

[H (CF2CF2) nCO] 2 (wherein II is an integer of 1 to 5), 〇 [Cl (CF2CF2) nl: 10] 2 (wherein, η is an integer of 1 to 5), 〇

II

[CF3CF2 (CF2CF2) nCH2CO] 2 (where η is an integer of 0 or 1 to 5),

〇

II

[CF3 (CF2CF2) nCH2CO] 2 (where η is an integer of 0 or 1 to 5), 〇

II

[(cf3) 2chc〇] 2, -11-(8) (8) 200408649

II

[(cf3) 3cc〇] 2, CF3 CF3 〇

I I II

[C3F7〇 (CFCF2〇) nCF —C〇] 2. (Where n is an integer of 0 or 1 to 5), 〇 _

II

[C3F7〇 (CF2CF2CF2〇) nCF2CF2C〇] 2 φ (where n is an integer of 0 or 1 to 5), 〇

II

[cf3〇cf2cf2c〇] 2, 〇

II

[cf3cf2c〇] 2 〇

II

[cf3cf2cf2c〇] 2 etc. Next, each monomer for radical polymerization using the above-mentioned fluorine-containing polymerization initiator will be described. β The monomer (m 1) imparting a repeating unit (M1) of a fluoropolymer is a fluorinated ethylenic polymer having a carbon number of 2 · or 3 having a polymerizability, particularly a radical polymerizable carbon-carbon double bond. A monomer having at least one fluorine atom in the monomer. This fluorinated ethylenic monomer (m 1) is a single compound having one polymerizable carbon-carbon double bond. Therefore, even when polymerized, it does not form a repeating unit having a ring structure in the main chain. -12- (9) (9) 200408649 The monomer of fluorine-containing ethylenic monomer (m 1) may or may not contain an acid-reactive functional group, but in general, a monomer containing no acid-reactive functional group is generally used. It is better to obtain good radical polymerization reactivity and improve transparency more effectively. The fluorine-containing ethylenic monomer (m 1) is preferably, for example, at least one hydrogen atom of ethylene or propylene substituted with a fluorine atom. Further, other hydrogen atoms may be substituted by halogen atoms other than fluorine atoms. Among them, a monomer having at least one fluorine atom bonded to a carbon atom constituting a carbon-carbon double bond is preferred. In this way, a fluorine atom can be introduced into the repeating unit (M 1) ', that is, the polymer main chain', and a fluoropolymer having particularly excellent transparency in the vacuum ultraviolet field can be effectively produced. Specific examples are preferred. At least one selected from tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, ethylene fluoride, difluoroethylene, hexafluoropropylene, and CH2 = CFCF3. Among them, particularly good transparency is a mixture of at least one or more of tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, or hexafluoropropylene, and most preferably tetrafluoroethylene and / or chlorotrifluoroethylene . Next, the fluorine atom-containing monomer (m2) which gives the repeating unit (M2) of the aliphatic ring structure of the polymer main chain will be described. This monomer (m2) can be used to introduce a repeating unit (M2) of an aliphatic ring structure capable of improving dry corrosion resistance when used as a photoresist, into a polymer main chain. This effect is matched with the above-mentioned effect of improving transparency in the vacuum ultraviolet field, and the gas-containing polymer having an aliphatic ring structure in the main key obtained by the method of the present invention is particularly suitable as a photoresist for F2 lasers. -13- (10) (10) 200408649 The monomer (m 2) is selected from unsaturated cyclic compounds having free-radically polymerizable carbon-carbon unsaturated bonds in the ring structure, or using diene compounds. Cyclic polymerization is selected from non-conjugated diene compounds in which the main chain forms a ring structure. The monomer (m2) may or may not have an acid-reactive functional group Y in the monomer. By copolymerizing the monomer (2), a polymer having an aliphatic ring structural unit having a monocyclic structure or a complex ring structure in the main chain can be obtained. The first monomer (2) is preferably a monocyclic monomer (m2-l) having a free-radically polymerizable carbon-carbon unsaturated bond in the ring structure and not having an acid-reactive functional group Y. The structure is preferably an aliphatic unsaturated hydrocarbon compound having a 3-membered to 8-membered ring structure having an ether bond. Specific examples of the monomer (m2-l),

In addition, it may be a monomer in which a part or all of the hydrogen atoms of the monomer (m2-l) is replaced by a fluorine atom, preferably, for example,

-14- (11) (11) 200408649, etc. The second monomer (m 2) is preferably a monomer (m 2-2) having an acid-reactive functional group Y in a monocyclic aliphatic unsaturated hydrocarbon compound, and 3 which may contain an ether bond in the ring structure. Unsaturated hydrocarbon compounds having a member ring to 8 member ring structure are preferred. Also, the monomers in which some or all of the hydrogen atoms of the monomer (m2-2) may be replaced by fluorine atoms are the same. -Specific examples of the monocyclic monomer (m2-2) having an acid-reactive functional group Y For example, CF3 ·

And other monomers. The third monomer (m2) is preferably a monomer (m2-3) having an aliphatic multiple ring structure in the polymer main chain and having an aliphatic multiple ring structure having no acid-reactive functional group Y. The monomer (m2-3) is more preferably -15- (12) (12) 200408649 derivative. Specific examples of the monomer (m2-3) having an aliphatic multiple ring structure having no acid-reactive functional group γ, for example,

The above norbornene ring structure can introduce a fluorine atom, and when a fluorine atom is introduced, the transparency can be improved without reducing the dry melt resistance. For example, the formula:

(In the formula, A, B, D, and EΓ are the same or different H, F, an alkyl group having 1 to 10 carbon atoms or a fluorine-containing alkyl group having 1 to 10 carbon atoms, and m is an integer of 0 to 3. However, any of A, B, D, and D 'contains a fluorine atom.) The fluorine-containing norbornene shown in the above is a specific example. -16- (13) 200408649

ffff, fffcf3, ff, (cf2 # X,

(CF is also X (n: 1 ~ 10, X: H, F, Cl) and other fluorine-containing norbornene as shown. Others such as,

(Eight, eight, zero, and zero 'are norbornene derivatives such as "^ 卩, alkyl or fluorine-containing alkyl having 1 to 10 carbon atoms". The fourth monomer (m2) is preferably a monomer (m2-4) having an aliphatic multiple ring structure in the polymer main chain and containing an aliphatic multiple ring structure having an acid-reactive functional group Y. The monomer (m2-4) is preferably a norbornene derivative. Specific examples of the monomer (m2-4) containing an aliphatic multiple ring structure having an acid-reactive functional group Y, for example, -17- (14) 200408649

In addition, the monomer 4) containing an acid-reactive functional group γ aliphatic multiple ring structure may be a substance in which part or all of the hydrogen atoms bonded to the ring structure are replaced by fluorine atoms, and this substance can give the polymer more excellent transparency. Sex is better. For example,

A B (R) fY

(Wherein A, B and D are the same or different H and F, an alkyl group having 1 to 10 carbon atoms or a fluorine-containing alkyl group having an ether bond having 1 to 10 carbon atoms; R is 1 to 10 carbon atoms 20 divalent hydrocarbon group, a fluorine-containing alkylene group having 1 to 20 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms; a is an integer of 0 to 5, and b is 0 or 1. However, b is 0 or -18- (15) 200408649 When R does not contain a fluorine atom, any of A, B, and D is a fluorine-containing alkyl group which may have a fluorine atom or an ether bond. Among them, when any of A, B, or D is a fluorine atom, or when A, B, or D does not contain a fluorine atom, the fluorine content of R is 60% by weight or more. Fluoroalkylene. Carcass, for example,

F

CF, X n: 0 ~ l0, X: F or CF3) -19- (16) 200408649

The norbornene derivatives are shown in Etc. Another example,

F F

(Where A, B, and D are the same or different H and F, a group having 1 to 10 carbons or a fluorine-containing alkyl group having an ether bond with 1 to 10 carbons; R is 1 to 2 carbons Divalent hydrocarbon group, fluorine-containing alkylene group having 1 to 20 carbon atoms or fluorine-containing alkylene group having 2 to 100 carbon atoms; is an integer of 0 to 5, b is 0 or 1) Olefin derivative. Specific examples are preferred, for example, alkane 2 0 ether -20- (17) 200408649

F F F F

F F

CF20 (CFCF20) nCF-Y I I cf3 cf3

F F

I I cf3 cf3 (n: 0 to 10) and other norbornene derivatives. In addition, the -21-(18) 200408649 monomer (m2-4) containing an aliphatic multiple ring structure having an acid-reactive functional group Y is preferably of formula:

(In the formula, Rf1 and Rf2 are the same or different fluorine-containing alkyl groups having 1 to 10 carbon atoms or fluorine-containing alkyl groups having ether bonds; A, B, and D are the same or different H, F, and C1, C1-C10 alkyl group or C1-C10 fluorine-containing alkyl group which may have an ether bond; R is fluorene or C1-C10 alkyl group; η is an integer from 0 to 5) Flunorbene derivatives. For example, -22- (19) 200408649

Or Cl; m = 1 to 10).

-23- (20) 200408649 Also, specific examples are better,

(m = l ~ 10)

24- (21) (21) 200408649

(In the formula, Rf1 and Rf2 are the same or different fluorine-containing alkyl groups having 1 to 10 carbon atoms or fluorine-containing alkyl groups having ether bonds; B and D are the same or different H, F, C1, and carbon numbers. 1 to 10 alkyl groups or carbon numbers 丨 to ... fluorine-containing alkyl groups that may have an ether bond; R is H or an alkyl group having 1 to 1 carbon number; η is an integer from 0 to 5) derivative. In the above examples, the monomers (m 2 _ 3) and (m2-4) containing an aliphatic multiple ring structure can impart polymerizable dry corrosion resistance, and are therefore particularly suitable as raw materials for photoresist polymers. In addition, since the polymer can be efficiently produced by radical polymerization using the production method of the present invention, transparency can be effectively improved. In particular, the norbornene derivative having a fluorine atom containing a double-ring structure is advantageous for transparency, and the production method of the present invention can efficiently produce a polymer by a radical polymerization method, and effectively improve transparency. Also, the norbornene derivative (m2-4) with an acid-reactive functional group Y can efficiently introduce the functional group required for photoresist applications into the polymer, so it is beneficial to the transparency and dry-resistance of the result. good. The fifth monomer (m2) is preferably a non-conjugated diene compound (m 2-5) having a fluorine atom that can be formed by polymerization to form an aliphatic ring. The non-conjugated diene compound (m 2-5) can efficiently produce a polymer having a repeating unit of a ring structure in the main chain, and can improve the transparency in the vacuum ultraviolet field as described above. The non-conjugated diene compound (m2-5) is preferably a specific diethylene compound capable of cyclizing a main chain having a monocyclic structure. For example, the formula that can have a fluorine atom or an acid-reactive functional group Y is: (22) 200408649 ch2 = chch2 —c-ch2ch = ch2 / \ Y 21 or ch2 = chch2-c-ch2ch = ch2 / \ z1 z2 (formula Among them, z1 and z2 are the same or different hydrogen atom and fluorine atom, a hydrocarbon group having an ether bond with a carbon number of 1 β to 5, and a fluorine-containing alkyl group having an ether bond with a carbon number of 1 to 5- Allyl compound. This diallyl compound can be polymerized in the main chain by radical cyclization to form the following

(Wherein, Z1 and Z2 are the same as described above). When the above-mentioned fluorinated polymerization initiator is used in the cyclized radical polymerization, a fluorinated polymer having a cyclic structure can be efficiently produced, and the transparency in the ultraviolet field can be improved in the same manner as in the above. The acid-reactive functional group Y will be described below. As described above, the acid-reactive functional group γ-based acid-reactive group Y1 and the acid-reactive group conversion group Υ2 which can be converted into the acid-reactive group γ1 are collectively referred to. The acid-reactive group Υ1 in the present invention means an acid-dissociable or acid-decomposable functional group and an acid-condensable functional group. ① Acid-dissociable or acid-decomposable functional group: The acid-dissociable or acid-decomposable functional group is a functional group that is insoluble or hardly soluble in alkali before reacting with acid, but can be dissolved in alkali by the action of acid. In addition, using this change in the solubility of alkali, it can be used as a basic polymer for positive photoresist. Specifically, it has the ability to change to -0Η group, · COOH group, -S03H group, etc. under the action of acid or cation. And the fluoropolymer itself is alkali soluble. Specific examples of the acid-dissociable or acid-decomposable functional group are preferably R7, R10, R13, Ri6, / 11, 10C, R8 —〇CH2C〇〇C —R11 —〇C, 10R14 —〇C —〇 R1

R 12 17y -CHjC 〇 I R 15

H-CH2 〇

R27 / -OS i -R28 \ R29 R18 / one 〇C〇C — R19 II \ 〇R20 R24 / one C〇C-R25 \ R26 -27- (24) 200408649 (where R7, R8, R9, R1., Rll, R12, R14, R18, Rl9, R20, R21, R22, R24, R25, R26, r28, r29 are the same or different hydrocarbon groups of 1 to 10 carbons; R 13, R 1 5 And R 16 are the same or different fluorene or a hydrocarbon group of 1 to 10 carbons; R17 and R23 are the same or different carbon groups of 2 to 10 carbon atoms) Also, specific examples are preferably, such as 10ch 2 〇ch3, 〇ch2〇c2h5, 〇c (ch3) 3, 〇ch2c〇〇c (ch3)

/ η3 〇c〇c-ch3 II \ 〇 ch3 • -OCHOR30 I ch3 〇 / 〇c

ch ^ chch2 〇 〇

ch3 ch3

1 CH

2CH CH:

ch ^ chch2 〇 〇

— C〇〇C (CH3) 3, 〇S i (CH3) 3

(r3 () is an alkyl group having 1 to 10 carbons) and the like. ②Acid condensation reactive functional group: The acid condensation reactive functional group is soluble in _ _ image solution (or other imaging solvents) before reaction with acid, but the polymer itself is not g to alkali reaction under the action of acid Functional group of imaging liquid (or other imaging solvents). Specifically, it can be self-condensed or polycondensed under the action of an acid or a cation, and there is a functional group that can cause a condensation reaction with the cross-linking agent due to the action of an acid under the presence of a crosslinking agent. , Or the use of acid or cation rearrangement reactions (such as pinacol rearrangement, methanol rearrangement), etc., to produce polar functional groups, but in any way, the result is that the polymer itself is not soluble in the alkali imaging solution (or Other imaging solvents). This insolubilization can be used as a base polymer for positive photoresist. Specific examples of the acid-condensable functional group are preferably selected ones such as —OH, —COOH—CN, —S03H, and epoxy groups. The cross-linking agent used is not particularly limited, and can be freely selected from cross-linking agents conventionally used in negative photoresists. Specific examples of the crosslinking agent include N-methylolated melamine, N-alkoxymethylated melamine compounds, urea compounds, epoxy compounds, isocyanate compounds, and the like. Among the above acid-reactive groups Y1, at least one of the acid-dissociative functional group which is converted into OH group by using OH group and COOH group, and the acid-dissociable functional group which can be changed to C 0 0 OH group by acid dissociation. 1 species. The acid-dissociable functional group which can be converted into a thiol group by an acid is preferably, for example, 10CH2R32, 10COC (R33)

-OC (R31) 3-10CH〇R34

I CH3, (wherein R31, r32, R33 and R34 are the same or different alkyl groups having 1 to 5 carbon atoms). Preferred specific examples are ’-29- (26) 200408649 〇c (ch3) 3, 〇ch2och3, 〇ch2〇c2h5,

〇c〇c (ch3) 3, 〇ch〇c2h5, -〇

II I 〇ch3 Among them, better acid reactivity is better, 〇c (ch3) 3, 〇c〇c (ch3) 3, och2〇ch3, · 〇-och2oc2h5, better transparency,- OC (CH3) 3, -OCH2OCH3, -OCH2OC2H5. An acid-dissociable functional group which can be converted to -CO Η by an acid is preferably,

R31

-COOC-R26

—〇CH2C〇〇C-R29 R27

One COC — 〇R32II I 〇R33 R34 R36

-C0C-〇II ^) 〇R35-COCOC — R37 II II \ 〇〇R38 (where R35, R36, R37, R38, R39, R4. ,, R42, R46, R47, R48 are the same or the same phase Different hydrocarbon groups of 1 to 10 carbons; r43 and r44 are -30-200408649 identical or different fluorene or carbon groups of 1 to] 0 hydrocarbon groups; R45 is a bivalent hydrocarbon group of 2 to [0] carbon atoms) etc. The best specific examples are:-COOC (CH3) 3, -OCH2COOC (CH3) 3,

^ U CH3, o CH3, o (R32 is the same as above), etc. In general, the acid-reactive group Y1 can be used to polymerize a monomer having the acid-reactive group Υ1 by the production method of the present invention and introduce it into a polymer. Also, after using the production method of the present invention to polymerize a monomer having an acid-reactive group conversion group Υ2 which can be converted to the acid-reactive group Υ1 and introduce the polymer, the polymer reaction can be used to convert the acid-reactive group γ to the purpose.] . The method for introducing the acid-reactive group γ 1 for the purpose of polymer reaction conversion is, for example, using the manufacturing method of the present invention to formula:

CX5X6 = CX7 — OCR (where X, X is Η or F, X7 is h, CH3 or CF3, and R is a radical or fluorine-containing radical of 1 to 5 carbon atoms) The vinyl ester compound shown (with acid reaction The mono-31-(28) (28) 200408649 body of the conversion group (ester group) γ2 is copolymerized with m 1 and / or m 2 to obtain the acid-reactive group conversion group Y 2 and the obtained fluorine-containing group A method for converting an acid-reactive group conversion group γ 2 of a polymer into a 0-fluorenyl group (acid-reactive group γ 1) by hydrolysis and the like. The present invention also includes a method for producing a fluoropolymer having an acid-reactive group Υ1 by using a polymer reaction step. Either way, by using the manufacturing method of the present invention, a fluorine-containing polymer having an acid-reactive group fluorene 1 can be efficiently produced, and the transparency in the vacuum ultraviolet field can be improved. The fluorine-containing polymer having an acid-reactive group Υ 1 can use a fluorine-containing polymerization initiator to combine the monomer having an acid-reactive functional group γ among the monomers (m 1) into the monomer capable of imparting an aliphatic ring structure. At least one of the monomer (m2-2) or (m2-4) having an acid-reactive functional group Y and the cyclizable polymerizable dienyl compound (m 2-5) having an acid-reactive functional group Y Base polymerization. When monomers (m 1) and (m 2) having no acid-reactive functional group Y are used, the monomer (η 1) having acid-reactive functional group Y and the monomers (ml) and ( 2) Copolymerize and introduce a third type of repeating unit (N1) having an acid-reactive functional group γ other than the repeating units (M1) and / or (M2). The monomer (η 1) capable of introducing the acid-reactive functional group Υ into an arbitrary structural unit (N 1) is preferably an ethylenic monomer having an acid-reactive functional group 共 which can be copolymerized. Specifically, a propylene-based monomer having an acid-reactive functional group Υ, a fluorine-containing propylene-based monomer having an acid-reactive functional group Υ, and an allyl ether-based monomer having an acid-reactive functional group 较佳Fluorine-32- (29) (29) 200408649 with acid-reactive functional group Υ, vinyl ether-based monomer with acid-reactive functional group γ, acid-reactive functional group Fluorine-containing vinyl ether monomers and the like. More specifically, (meth) propane;) ¾ acid, fluoropropionic acid, α-dioxin I methylpropionic acid, t-butyl (meth) propionic acid vinegar, t.] Yl fluoride Acrylate, t-butyl-α-trifluoromethacrylate, ch2 = chch2y, ch2 = chch2〇ch2ch2y, cf3 ch2 = chch2c-y, ®

I cf3 formula:

CX1X2 = CX3 ~ (CX42) -f4〇) -tR fY (where x1 and x2 are the same or different H or F; X3 is H, F, CH3 or CF3; X4 is H, F or CF3, Rf It is a fluorine-containing alkylene group having 1 to 40 carbon atoms or a fluorine-containing alkylene group having an ether bond having 2 to 100 carbon atoms; a is an integer of 0 or 1 to 3; b is 0 or 1) Fluorine shown in Φ Ethylene monomer. Among them, a fluorine-containing allyl ether compound represented by CH2 = CF—CF2〇—R—Y * (where Rf is the same as the above) is preferred. Specific examples are preferred, such as -33, (30) (30) 200408649 CH2 = CFCF2〇CF-Y, CH2 = CFCF2〇CFCF2〇CF-Y,

I I I CF3 C F 3 C F 3 CH2 = CFCF2〇 (CFCF2〇) 2CF — Y,

I I cf3 cf3 ch2 = cfcf2〇ch2cf2-_y, CH2 = CFCF2〇CH2CF2CF2〇CF-Y, '

I cf3 · CH2 = CFCF2〇CF2CF2〇CF2 — Y,

CH2 = CFCF2〇 (CF2CF2〇) 2CF2-Y and other fluorine-containing allyl ether compounds. Also, the preferred formula is:

CF2-C F-O-R f ~ Y (wherein Rf is the same as above) represented by a fluorine-containing vinyl ether compound. Specific examples thereof are: '-34- (31) 200408649 CF2 = CF〇CF2CF〇CF2CF2CH2 —Y, cf3 CF2 = CF〇 (CF2 " HY, CF2 = CF〇 ^ CFfHCH2 —Y, CF2 = CF〇CF2CF2〇CF2 — Y ,

CF2 = CF, CF2, CF2, CF2CH2 — Y, CF2 = CF, CF2CF2CH2, CF2CF2 — Y, CF2 = CF, CF2CF2CH2, CF2CF2CH2 — Y, CF2 = CF, CF2CF, CF2CF2CH2, Y, cf3 and other fluorine-containing vinyl ether compounds. Other fluorine-containing ethylenic monomers having an acid-reactive functional group Y are, for example, CF2 = CF-CF2〇-Rf-Υ, CF2 = CF —Rf—Y,

CH2 = CH-R f -Y, CH2 = CH — 〇-Rf-Y (Rf is the same as above) and other monomers, and specific examples thereof are cf2 = cfcf2〇cf2cf2cf2-y,

CF2 = CFCF2〇CF2CF2CF2CH2—Y, CF2 = CFCF2〇CF2CF —: Y, CF2 = CFCF2〇CF2CF —ch2-y,

II cf3 cf3 cf2 = cfcf2-y, cf2 = cfcf2ch2—y, CH2 = CHCF2CF2CH2CH2-Y > ch2 = chcf2cf2-: y, CH2 = CHCF2CF2CH2- Y, ch2 = chcf2cf2cf2cf2cf2—y, ch2 = chcf2ch2cf2cf2cf2cf2cf2 A ch2cf2cf2-y, CH2 = CH0CH2CF2CF2CH2-Y, -35- (32) 200408649, etc. In the manufacturing method of the present invention, in order to improve, for example, mechanical strength, coatability, etc., a random monomer having a characteristic different from that of a fluorinated copolymer having a radical polymerizable monomer (η) can be copolymerized. The optional monomer (η) can be selected from those which can be copolymerized with monomers constituting other structural units. For example, propylene-based monomers (other than the monomers described in η 1): ch2 = cxc〇〇h, ch2 = cxc〇ch2chch2, ο CH2 = CXC〇〇CH2CH2〇H, ch2 = cxc〇〇 一 < ^),

ch2 = cxcoo ch2 = cxcoo- < ^) (X: H, CH3, F, CF3 selected) Styrene monomer: -36- 200408649

CH〇 = CH (33)-< 0 > > CH2 = CH ^ f

OH

CF? = CF

CF〇 = CF CH〇 = CH

(CH2 ^ -nC-〇H

F

〇H, CF. CH2 = CH · (n: integer from 0 to 2) Vinyl monomer: CH2 = CH2, CH2 = CHCH3, CH2, CHC1, etc. Maleic acid monomer:

CH = CH CH = CH / \ II should

〇 = C C = 〇, HOOC C〇〇H, W

~ Q

CH = CH CH = CH

I I C〇〇R, COOH.

CO〇RC〇〇R (R is a nicotinyl group having 1 to 20 carbon atoms) Allyl monomer: CH2 = CHCH2C1, ch2 = chch2〇h, ch2 = chch2c〇H, CH2 = CHCH2B r, etc. -37 -(34) 200408649 Allyl ether-based monomer: CH2 = CH CH2OR λ CH2 = CHCH2 〇C H2 (CF2hrX, (R: hydrocarbon group of 1 to 20 carbons) (η: 1 to 10, X: H, C 1.F) ch2 = chch2oCH2CH2COOH, CH2 = CHCH2OCH2CHCH2, CH2 = CHCH2OCH2CHCH2

\ / I I

〇 OH OH

Other monomers: ch2 = cho ~ r, CH2 = CH〇C—R,

II 〇

(R is an alkyl group having 1 to 20 carbon atoms which can be substituted by fluorine), for example, ch2 = = CHO-4CH2 ^ H, ch2 = cho- < ^^, ch2: = CH〇 《^), CH2 = CH〇C4CH2-nH, 〇ch2 = CH〇i- < 0 >, CH2 = CHOCh ^ H ^ 〇〇ch2 = ch〇4chch2 〇MCH2VH, -38 ·

X (35) (35) 200 408 649 (n: 1 to 20, n ': 0 to 5, X: I ^ cH3), and the like. The present invention uses the above-mentioned fluorine atom-containing radical polymerization initiator to make a polymer having at least one fluorine atom (m 1) in an ethylenic monomer having 2 to 3 carbon atoms by various known methods. The monomers (m2-l) to (m2_5) with an aliphatic ring structure in the main chain and the comonomer (η) (co-monomer) of the ethylenic monomer (n 丨) containing an acid-reactive functional group used when necessary )polymerization. The polymerization methods used are, for example, a solution polymerization method in which monomers are dissolved in an organic solvent, a suspension polymerization method in the presence or absence of an appropriate organic solvent in an aqueous medium, and an emulsion polymerization method in which an emulsifier is added to an aqueous medium. 'Bulk polymerization method without solvent, etc. Among them, solution polymerization using an organic solvent, suspension polymerization is preferred. The polymerization solvent to be used is not particularly limited, but a hydrocarbon-based solvent, a fluorine-based solvent (furan-based), a chlorine-based solvent, an alcohol-based solvent, a ketone-based solvent, an acetate-based solvent, an ether-based solvent, and the like are preferred. Among them, a fluorine-based solvent and a chlorine-based solvent have good solubility for monomers and initiators, and it is preferred that the polymerization reaction proceeds smoothly. Specifically, for example, one type or two or more types are selected from hydrofluorocarbons, hydrochlorocarbons, chlorofluorocarbons, and hydrochlorofluorocarbons. During the polymerization, the above-mentioned fluorine-containing radical polymerization initiator is brought into contact with a monomer and heated (using the temperature unique to the initiator), or is irradiated with active energy rays such as light or ionizing radiation to start polymerization. The composition of the resulting copolymer can be controlled by the monomer components added. (39) (36) (36) 200408649 The molecular weight can be controlled by the concentration of the monomer for polymerization, the concentration of the polymerization initiator, the concentration of the chain transfer agent, and the temperature. The amount of the fluorine-containing radical polymerization initiator used for the monomer is 0.005 to 10 parts by weight, preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 1 part by weight based on 100 parts by weight of the monomer. . From another point of view, the fluorine-containing radical polymerization initiator is 0.01 to 10 mole%, preferably 0.0 5 to 5 mole%, and more preferably 0.1 to 1 mole% of the monomers used. 2 mole%. When the amount of the fluorine-containing radical polymerization initiator is too small, it will be difficult to sufficiently polymerize the reaction and leave unreacted monomers, and it will reduce the coloration and transparency of the polymer forming the oligomer, which is unfavorable. Too many fluorine-containing radical polymerization initiators will decrease the molecular weight and transparency, and the residual polymerization initiator will reduce the polymer coloration and transparency, which is not suitable. When using fluorine-containing organic peroxide as a radical polymerization initiator for polymerization, the reaction temperature can be appropriately selected according to the 10-hour half-life temperature of each fluorine-containing organic peroxide used and the target reaction time, but generally It is 0 to 150 ° C, preferably 5 to 120 ° C, and more preferably 10 to 100 ° C. The monomer composition during the copolymerization can be selected according to the polymerization reactivity of each monomer, the copolymerization reaction ratio, and the characteristics imparted to the obtained fluoropolymer. The characteristics imparted to the fluoropolymer by each monomer are as described above, and more specific characteristics are described later. The fluorine-containing polymer obtained by the manufacturing method of the present invention has high transparency to the vacuum ultraviolet light field with a wavelength of less than 200 nm, and is therefore particularly suitable for the photolithographic technical steps using ArF laser (193 nm) and F2 laser (1 57 nm). In addition, the present invention relates to -40- (37) (37) 200408649 (Al) having an OH group, an acid dissociable functional group that can be converted to an OH group by an acid, a COOH group, or an acid that can be changed to a COOH group by an acid The fluorine-containing polymer of the acidic reactive group Y 1 of at least one of the dissociable functional groups, (B) the photo-acid generator (C) solvent, the fluorine-containing polymer (A-1) is The invention provides a photoresist composition for a polymer obtained by the above manufacturing method. The photoresist composition of the present invention uses an OH group having an acid-reactive functional group Y, an acid dissociable functional group that can be converted to an OH group by an acid, a COOH group, or an acid dissociable functional group that can change a COOH group by an acid. A fluorine-containing polymer (A-1) having at least one of the specific acid-reactive groups Y1. The acid-dissociable functional group which can be converted to OH group by using an acid and the acid-dissociable functional group which can be changed to C 0 0 by using an acid can be the above-mentioned. Fluorine containing a specific acid-reactive group Υ 1 The polymer (A-1) is preferably the following polymer. (I) Formula: One (Ml) — (M2 — 2) — (where M1 is a structural unit of at least one of the vinyl monomers having 2 or 3 carbon atoms derived from a fluorine atom-containing monomer (m 1) ; M 2-2 is a structural unit derived from a monocyclic aliphatic unsaturated hydrocarbon compound having an acid-reactive group fluorene-containing monomer (m2-2a) -41-(38) (38) 200408649 Fluoropolymer shown. The structural unit (Ml) and the composition ratio with (M2-2) are generally 80/20 to 20/80 mole% ratio, preferably 70/30 to 30/70 mole% ratio, Extraordinary is from 60/40 to 40/60 Mor. / ◎ ratio. Specific examples of the monomer are preferably the above-mentioned specific examples of the monomer (m; [), and among the specific examples of the monomer (m2-2), the acid-reactive functional group γ is an acid-reactive group γΐ. (II) Formula:-(Ml)-(M2-4)-(In the formula, Ml is the same as above; (M2-4) is an aliphatic complex ring-containing monomer (m) having the above-mentioned acid-reactive group Y 1 (m 2-4 a), especially the structural unit of norbornene derivatives). The composition ratio of the structural units (Ml) and (M2-4) is generally 80/20 to 20/80% mole ratio, preferably 70/30 to 30/70% mole ratio, especially The ratio is preferably 60/40 to 40/60 mole%. Specific examples of the monomer are preferably, for example, the specific examples of the monomer (m1) described above, and the specific examples of the monomer (m2-4). The acid-reactive functional group Y is an example of the acid-reactive group Y1. The fluorinated polymers of (I) and (II) are excellent in themselves and have excellent transparency and resistance to dryness. Furthermore, the use of the manufacturing method of the present invention using a fluorinated polymerization initiator can further improve the transparency in the vacuum ultraviolet field. . -42- (39) (39) 200408649 (III) Formula: — (Μ 1)-(Μ 2 — 1) — (N 1) — (In the formula, MI is the same as above; M2-1 is from the ring structure and has Structural unit of polymerizable carbon-carbon unsaturated bond III monocyclic monomer (m2-1) without acid-reactive functional group Y; N 1 is a copolymerizable ethylenic monomer derived from acid-reactive group Y 1 (Η 1 a) Structural unit) The fluoropolymer shown. The composition ratio of the structural units (Ml), (M2-1) and (N1) is (

Ml) + (M2-1) + (N1) = 100 mole% ?, (Ml) + (M2- 1) / (Nl)-generally 90/10 to 2 0/8 0 mole% ratio, compared with The molar ratio is preferably 80/20 to 30/70 0, and the molar ratio is particularly preferably 70/3/3 to 40/6 0. Specific monomers are preferred, such as the above monomers (ml) and (m2) -1) Specific examples, specific examples of the monomer (η-1) are examples in which the acid-reactive functional group Y is the acid-reactive group Υ1. (IV) Formula:-(Ml)-(M2-3)-(N 1)-(where M1 and N1 are the same as above; M2-3 is derived from monomers without aliphatic multiple ring structure (m2-3), In particular, the constituent units of norbornene derivatives) are fluoropolymers. • 43- (40) (40) 200408649 The composition ratio of structural units (Ml), (M2-3) and (N1) is (

Ml) + (M2-3) + (N1) is 100 mole%, (Ml) + (M9 · 3) / (N1)-generally 90/10 to 20/80 mole% ratio, preferably Molar% ratio of 80/20 to 30/70%, particularly preferably 70/3/40 to 40 / 6mol% ratio. Specific examples of monomers are preferred. For example, the above monomers (m 1) And (⑺? _ 3), a specific example of the monomer (η 1), and an example of the acid-reactive functional group γ as the acid-reactive group Υ 1. (V) Formula:-(M2-5)-(N 1)-(In the formula, N1 is the same as above; M2-5 is a ring structure of the polymer main chain obtained by cyclization polymerization of non-conjugated divinyl compound. Construction unit) shown fluoropolymer. The composition ratio of the structural unit (M2-5) to (N1) is generally 80/2/20 to 20/80 mole%, preferably 70/30 to 30/70 mole%. The ratio is particularly preferably 60/40 to 40/60 mole%. Specific examples of the monomer are preferably, for example, specific examples of the monomer (m2-5) described above, and specific examples of the monomer (η 1) are examples in which the acid-reactive functional group Y is an acid-reactive group Y 1. The (III), (IV), and (V) fluoropolymers themselves are excellent and have excellent dry corrosion resistance. Moreover, the use of the manufacturing method of the present invention using a fluoropolymerization initiator can further improve the transparency to the vacuum ultraviolet field. Sex. -44- (41) (41) 200408649 In addition, the acid-reactive group γ 1 containing (I) to (V) is ignited by water η and contains the residue of the interception polymerization initiator, which is different from the current light Fluorinated polymer for resistance, especially having excellent transparency in the vacuum ultraviolet field. In the photoresist composition of the present invention, the fluorinated polymer (A-1) having an acid-reactive group Υ 1 is 15 7 nm. The wavelength has excellent transparency. Among them, those with a light absorption coefficient of 2 · 7 μπΓ1 or less at 15 7nm are more preferable, those with 1.5 μ πΓ 1 or less are more preferable, and those with 1 · 0μ πτ 1 or less are most preferable. It is preferably 0.5 μm -1 or less, and when the thing with the lowest absorption coefficient at the wavelength of 15 7 nm is used in the F2 photographic photoresist composition, a good photoresist pattern can be formed. Examples of the photoacid generator (B) used in the inventive photoresist composition are preferably examples of the photoacid generator (B) described in International Publication No. 0 1/949 1 6. Specifically, compounds that generate acids or cations by light irradiation, such as organic halogen compounds, sulfonates, and iron salts (especially fluoroalkylphosphonium salts whose central elements are iodine, sulfur, selenium, tellurium, nitrogen, or phosphorus Etc.), ferrous diazonium salts, ferric compounds, master diazides or mixtures thereof. Specific examples are as follows. (1) TPS series: -45- (42) (42) 200408649

(Where X_ is PF6 ·, SbF6 ·, CF3S03 ·, C4F9S03-, etc .; Rla, Rib, Ric are the same or different ch30, H, t-Bu, CH3, OH, etc.) (2) DPI system :

(Where χ- is CF3S03, C4F9Sor, CH3-0-S03, SbF6-, etc .; R2a and R26 are the same or different H, OH, CH3, CH30, t-Bu Etc.) • 46-200408649

Etc.) (4) Sulfonate series: 〇 //

C

〇II N — 〇S — R4a or

C II 〇

N-0-S-R 4 a where 1143 is -47- (44) (44) 200408649

Etc.) In the photographic photoresist composition of the present invention, the content of the photoacid generator with respect to the acid-containing gas-containing polymer (A-1) having a base Y of 100 is preferably 0.1 to 30 parts by weight, more It is preferably 0.2 to 20 parts by weight, and most preferably 0.5 to 10 parts by weight. When the content of the photoacid generator is less than 0.1 parts by weight, the sensitivity is lowered, and when it exceeds 30 parts by weight, the light absorption of the photoacid generator is increased, so that light cannot reach the substrate and the resolution is easily reduced. The photographic photoresist composition of the present invention may contain an organic base having an alkali action on the acid generated by the photoacid generator. The organic base used may be the same as that described in International Publication No. 0 1/74 9 16. Specifically, organic amine compounds selected from nitrogen-containing compounds, such as pyridine compounds, pyrimidine compounds, amines substituted with hydroxyalkyl groups having 1 to 4 carbon atoms, aminophenols, etc., are particularly preferred. Hydroxylamines. Specific examples are preferably butylamine, dibutylamine, tributylamine, triethylamine, tripropylamine, tripentylamine, pyridine and the like. The content of the organic base to the content of the photoacid generator in the photographic photoresist composition of the present invention is preferably from 0.1 to 100 mole%, more preferably from 1 to 50 mole%. When the content is less than 0.1 mol%, the resolution is lowered and when it exceeds 100 mol -48- (45) (45) 200408649%, the sensitivity tends to be low. The photographic photoresist composition of the present invention may contain additives described in International Publication No. 0 1/74 9 1 6 as necessary, such as a dissolution inhibitor, a sensitizer, a dye, an adhesive improver, a water-retaining agent, and the like. Various additives commonly used in the field. The solvent (C) used in the photographic photoresist composition of the present invention may be the same as the solvent (C) described in International Publication No. 0 1/749 16.

Specific examples include a cellosolve-based solvent, an ester-based solvent, a propylene glycol-based solvent, a ketone-based solvent, an aromatic hydrocarbon-based solvent, or a mixed solvent thereof. In order to improve the solubility of the fluorinated polymer (A-1), a fluorinated hydrocarbon-based solvent such as CH3CCl2FCHCFO 1 4 16) or a fluorinated solvent such as a fluoroalcohol may be used. The content of the solvent (C) can be selected according to the type of the solid component for dissolution, the coating substrate, the target film thickness, and the like, but the ease of coating is preferably such that the concentration of the entire solid content of the photoresist composition can be 0.5 to 70% by weight, preferably 1 to 50% by weight. The photoresist composition of the present invention is used in a photoresist pattern forming method of the current photoresist technology. Especially when used in the photoresist pattern formation method, 'the photoresist composition solution is first coated on a support such as a silicon plate by a rotation method, etc., and a photosensitive layer is formed after drying, and then a reduction projection exposure device is used. Hopefully, the mask method is irradiated with ultraviolet rays, deep-UV, laser light, X-rays, or drawing and heating with electron beams. Thereafter, a developing solution such as an alkaline aqueous solution such as an aqueous solution of 1 to 10% by weight of a tetramethylammonium hydroxide compound is used for developing processing. This method of forming can obtain a faithful image of a mask pattern. -49-(46) (46) 200408649 When using the photoresist composition of the present invention, a highly transparent photoresist film (photosensitive layer) can be formed even in the vacuum ultraviolet field. Therefore, it is suitable for the photolithography technology using F 2 laser (1 57 nm wavelength) with a goal of 〇 7 μm in the future development. The method of applying the photoresist of the present invention to form a film is to coat the photoresist composition on a support such as a silicon plate and then dry it by a coating method such as spin coating, and the film contains an acid-reactive group. Solid components such as fluoropolymer (A-1), photoacid generator (B) and other additives. The formed photoresist film is generally a thin film having a thickness of 1.0 μm or less, preferably a film having a thickness of 0.01 to 0.5 μm, and more preferably 0.05 to 0.5 μm. In addition, the film obtained by coating the photographic photoresist composition of the present invention is preferably one having high transparency in the vacuum ultraviolet field, specifically, an absorption coefficient at a wavelength of 15 7 nm is 2.5 μπΓ1 or less, more preferably 2.0 μπΓ1 or less, particularly preferably 1.50 μπΓ1 or less, and most preferably 1.0 μηΓ1 or less. This coating can be effectively used in the lithography process of F2 laser (157nm) light. The substrate used for forming the photoresist film can be the same as various substrates currently used for photoresist. For example, a silicon plate, a silicon plate provided with an organic or inorganic antireflection film, a glass substrate, etc., especially a silicon plate provided with an organic antireflection film, can obtain good sensitivity and contour shapes. In addition, the present inventors proposed a review of the structure of the main chain terminal of the fluoropolymer, and found that the polymerization of the specific fluoropolymer obtained by introducing CF3 groups into tetrafluoroethylene and norbornene at a high ratio of specific fluorene or more At the end, the obtained polymer can more effectively improve the transparency, especially the transparency to vacuum ultraviolet light represented by 15 nm. -50- (47) (47) 200408649 Specific examples of the novel polymer of the present invention are: (1) ·-(M1A)-(M2A)-(N1A)-(where MIA is derived from tetrafluoroethylene The structural unit, M2A is a structural unit derived from a norbornene derivative (m2a) which can contain a fluorine atom. MIA is derived from a monomer (η 1 a) which can be copolymerized with tetrafluoroethylene and a norbornene derivative (m2a). The structural unit) shows that the structural unit M 1 A contains 12 to 70 mol%, the structural unit M2A content is 12 to 70 mol%, and the structural unit N1A content is 0 to 60 mol. /. And (MIA) + (M2A) = 100, in the fluoropolymer having a molar ratio of (MIA) / (M2A) of 3 0/70 to 7 0/3 0 and an average molecular weight of 1,000 to 50,000 At least one side of the polymer terminal contains a polymer molecule with a cf3 group, and the -CF 3 signal strength of the polymer main chain terminal obtained by 19f-nmr analysis is Η (terminal (F 3) 'forming the main chain -When the CF2-signal intensity is H (-CF2-), the fluoropolymer conforms to the formula (1): 0.3g (terminal CF3) / H (-CF2-) 20.01 formula (1). The above-mentioned fluoropolymer based on a high ratio of CF3 polymer terminals is a novel compound that has not been described in patents, literatures, etc. More specifically, the fluoropolymer of the present invention may be (i) CF3 polymerized at both terminals. Biomolecules, (ii) single-terminal CF3 polymer molecules, (iii) polymer molecules without CF3 groups at the ends -51-(48) (48) 200408649, a mixture of three polymer molecules, and may be At least one of the ends of the polymer main chain contains-CF3 based polymer molecules (the polymer molecules of the above (0 and / or (H))), which is in accordance with the formula (1) The analysis of the _ CF 3 group at the polymer terminal can be performed by using various types of machines such as IR analysis and NMR analysis. However, NMR analysis is preferred for accuracy. As in the examples described below, As for the F atom signal, the signal of the CF3 group at the end of the polymer main chain can be separated independently when the signal is _80 to -84PPm (trifluorochloromethane standard), so it is particularly preferably 19F-NMR. In the fluoropolymer of the present invention 'The formula (1) (terminal cf3) / H (-CF2-)' refers to the ratio of the CF3 group at the terminal of the polymer main chain to -CF2- (for example, a substance derived from tetrafluoroethylene) of the polymer main chain ' It may vary depending on the molecular weight of the fluoropolymer, but it is better to use a larger number in the above range. The specific formula (1) is preferably, the formula (丨 -1): 0.32H (terminal CF3) / H (-CF2-) 20.02 Equation (1-1) is more preferably, Equation (1-2): 0 · 25 ^ Η (terminal CF3) / H (-CF2-) 20.03 Equation (1 -2) Particularly preferably, the formula (1-3): 0.22H (terminal CF3) / H (-CF2-) 20.05 The formula (1-3). The fluorine-containing polymer of the present invention may vary depending on the molecular weight, But specifically, it is preferably 40% of all the ends of the polymer main chain. % Or more is CF3 group, more preferably 50% or more, particularly preferably 70% or more, and most preferably 90% or more of the polymer into which CF3 group is introduced at the end. -52- (49) (49) 200408649 This can be improved more effectively Transparency. In the fluorinated polymer represented by formula (1) of the present invention, the hypoxic derivative (m 2 a) constituting the structural unit M 2 A is preferably 'monomer (m 2) Norbornene derivatives in the examples ° Specific examples are preferably the above monomers (m 2-3) without acid-reactive functional group Y, and monomers (m 2-4) with acid-reactive functional group Y In the example described in 〇, the fluoropolymer shown in (1) of the present invention, the structural unit N1A is an optional component, and is a structural unit derived from a copolymerizable monomer other than tetrafluoroethylene and norbornene derivatives. As a specific example, the monomer (η 1) capable of introducing an acid-reactive functional group Y into the above-mentioned method for producing a fluoropolymer, and an arbitrary early body (η) are preferred. In the fluorinated polymer represented by formula (1) of the present invention, when the existence ratio of the structural units M1A, M2A, and N1A is M1A + M2A = 100, M1A / M2A is 8 0/20 to 20/80 Molar% ratio, A molar ratio of 70/3/3 to 30/70 is preferred, and a molar ratio of 60/40 to 40/60 is more preferred. The presence ratio of the optional component N1 Α to all structural units is 60 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, and particularly preferably 10 mol% or less, the most preferable Is 0 mole%. Therefore, the existence ratio of specific structural units M1 A, M2 A and N1 A is: structural units M1A: 12 to 70 mole%, M2A: 12 to 70 mole%, N1A: 0 to 60 mole%, preferably Structural unit M1 A: 21 to 70 mole%, M2A: 21 to 70 mole%, N1A: 0 to 30 mole%, more preferably structural unit M1A ·· 24 to 70 mole Ear%, ^ 42 VIII: 24 to 70 mole%, N1A: 0-53 · (50) (50) 200 408 649 to 20 mole% 'Extremely good is the structural unit M 1 A: 2 7 to 7 〇 ° / 〇 'M2A: 27 to 70 mol%, N1A: 〇 to 10 mol%, most preferably the structural unit M1A: 30 to 70 mol%, 1 ^ 12 eight: 30 to 70 mol. / q, N1A: 0 mole% c The molecular weight of the fluoropolymer represented by formula (1) of the present invention is a number average molecular weight of 1,000 or more, preferably 2000 or more, more preferably 2500 or more, and 50,000 or less. It is preferably 30,000 or less, and more preferably 10,000 or less. Even if the fluorinated polymer represented by the formula (1) of the present invention is a low-molecular-weight substance, it can have excellent transparency due to the effect of the cf3 group at the terminal, so it is preferable. The method for producing a fluoropolymer having a cf3 group at the end of the polymer main chain of the present invention can be variously selected, for example, (1) a method for producing a polymer using a polymerization initiator capable of introducing a CF3 group at the end, (2) using A method for producing a polymer by introducing a CF3 group into a terminal chain transfer agent, (3) a method for converting a prepared fluoropolymer terminal into a CF 3 group by using a polymer reaction, etc. The method (1) of the polymer, and the method (2) of producing the polymer by using a chain transfer agent, preferably introduce a CF3 group into the terminal, which is preferable. The method (1) for manufacturing a polymer by using a polymerization initiator is preferably to select a polymerization initiator having a CF3 group among the fluorine atom-containing polymerization initiators shown in the above-mentioned fluoropolymer manufacturing method, for example, the above-mentioned di (fluoro A fluorenyl) peroxide is exemplified by a CF3 group peroxide. -54- (51) 200408649 The present invention will be described below by way of examples and the like, but the present invention is not limited to the examples and the like. [Embodiment] Example 1 (Synthesis of OH-containing fluorinated norbornene (NB-1) copolymers such as TFE) A nitrogen-filled 500ml partial pressure cooker equipped with a valve, a pressure gauge, a stirrer and a thermometer was replaced with nitrogen several times. After vacuum, put -OH-containing fluorine-containing norccan (NB-1):

Η F3? F3 c—c 丨 c (ΝΒ-1) 49.0g and HCFC- 1 4 1 6 25 0 ml. Thereafter, Atfe 80〇§ and 7H-dodecafluoroheptane peroxide (formula) were added using a valve: I-1 OMMC 3 [H (CF2CF2) 8 · 0% by weight perfluorohexane solution 2 6 · 0 g, the reaction was stirred at 20 ° C for 4 hours. After releasing the unreacted monomer, the polymerization solution was taken out, and after concentrating, the source was re-sinked with hexane to isolate the copolymer. After reaching a constant amount, vacuum drying was performed to obtain 3.5 g of copolymer. -55- (52) (52) 200408649 The composition ratio of the copolymer was analyzed by 1H-NMR and 19F-NMR. As a result, the TFE / the above-mentioned OH-containing fluorine-containing norbornene derivative (NB-1) was 50 to 5 0 mole% copolymer. The number average molecular weight obtained by G PC analysis was 4 1 0 0. Example 2 (Synthesis of butadiene? Copolymer with -0 (: 1120 (: 2) ^ 5 group fluorine-containing norbornene derivative (NB-1 (l))) In addition to -0CH2OC2H5 group containing fluorine Norbornene derivatives (NB-1 (1

Except for 59.0 g of substituted OH-containing fluorine-containing norbornene derivative (NB-1), and 52.0 g of a 8.0% by weight perfluorohexane solution of 7H-dodecafluoroheptane peroxide Perform the reaction. After releasing the unreacted monomer, the polymerization solution was taken out, and after concentrating, it was reprecipitated with methanol / water (1: 1) to isolate the copolymer. After reaching a constant amount, vacuum drying was performed to obtain 2.5 g of a copolymer. The composition ratio of the copolymer was analyzed by 1H-NMR and 19F-NMR. As a result, the copolymerization of TFE / the above-containing OCH2OC2H5 group-containing fluorine-containing norbornene derivative (NB-1 (1) was 50/50 mole% copolymerization The number average molecular weight obtained by GPC analysis is 3 800. -56- (53) 200408649 Example 3 (Synthesis of TFE and -OH-containing fluorine-containing norbornene derivative (NB-1) and -OCH2OC2H5 group Fluorine-containing norbornene derivative (NB-1 (1) copolymer) In addition to using 80.0 g of TFE, 39.0 g of -OH-group-containing fluorine-containing norbornene derivative (NB-1) and the examples are used 2 Except for 12.0 g of fluorine-containing norbornene derivative (NB-1 (1)) containing -0CH2OC2H5 group, the reaction was carried out in the same manner as in Example 2. After the unreacted monomer was discharged, it was separated and purified in the same manner as in the Example. 5.2 g of copolymer was obtained. The composition ratio of the copolymer was analyzed by 1H-NMR and 19F-NMR, and the result was TFE / -OH group-containing fluorine-containing norbornene derivative (NB-1) /-OCH2OC2H5 group-containing fluorine The norbornene derivative (NB-1 (1)) is a copolymer of 50/4 0/1 10 mol%. The number average molecular weight obtained by GPC analysis is 43 00. Example 4 (Synthesis of TFE with -0 ( C = 0) OC (CH3) 3-based fluorine Derivative (NB-1 (2)) of the copolymer) containing addition-square (〇0) OC (CH3) 3 group fluorine norbornene derivatives (N B -1 (2)):

(NB — 1 (2)) -57- (54) (54) 200 408 649 66.0 g Substituted fluorine-containing norbornene derivative 1 B-1 (9) containing -〇CH2OC2H5 group, the same as in Example 2 The reaction was performed, and 2.0 g of a long-term copolymer was separated and purified. 1h-nmr and 19f-nmr were used to analyze the composition ratio of the copolymer, and the fruit was TFE / the above-mentioned 0-containing (C = 0) 0C (CH3) 3-based fluorine-containing dazzling burner. Biology (NB-2) It is a copolymer of 50 to 50 mole%. The number average molecular weight obtained by GPC analysis was 3,700. Example 5 (Synthesis of TFE / (NB-1) / (NB-1 (2)) Copolymer) In addition to using TFE 8 0 · 0 g, the fluorene-containing norbornene containing -0 fluorenyl group used in Example 1 was used. Derivative (NB-1) 39.0 g and _0 (C = 0) OC (CH3) 3-based fluorine-containing norbornene derivative (NB-1 (2)) 1 3.2 g used in Example 4, The other reactions were carried out in the same manner as in Example 2. After releasing the unreacted monomer, it was separated and purified in the same manner as in Example 1 to obtain 5.2 g of a copolymer. φ The composition ratio of the copolymer was analyzed by 1H-NMR and 19F_NMR, and the result was TFE / fluorine-containing norbornene derivative (NB_ι) containing -OH group / OC (CH3) 3-group fluorine-containing A norbornene derivative (NB-1 (2)) is a copolymer of 50 * / 4 1/9 mole%. The number average molecular weight obtained by GPC analysis was 4,400. Example 6 (Synthesis of TFE and OH-containing fluorinated norbornene (NB-2)) -58- (55) 200408649 Except for -OH-containing fluorinated norbornene (NB-2)

(NB-2) The reaction was carried out in the same manner as in Example 2 except that 55.0 g of the substituted -OCH2OC2H5 group-containing fluorine-containing norbornene derivative (NB-1 (1)) was used. After releasing the unreacted monomer, it was separated and purified in the same manner as in Example 1 to obtain 4.3 g of a copolymer. The composition ratio of the copolymer was analyzed by iH-NMR and 19F-NMR, and the result was a copolymer in which TFE / the above-OH group-containing fluorine-containing norbornene derivative (NB-2) was 50/50 mole%. The number average molecular weight obtained by GPC analysis was 2200. Example 7 (Synthesis of copolymer of TFE and -OCH2OC2H5 group-containing fluorine-containing norbornene derivative (NB-2 (1))) A -OCH2OC2H5 group-containing fluorine-containing norbornene derivative (NB-2 (1))

(NB — 2 (1)) och2och2ch3 -59- (56) (56) 200408649 14.〇g, HCFC-1416 50ml and 7H-dodecafluoroheptane peroxide 8.0% by weight perfluorohexane solution]. .4 g is placed in a 1000m1 autoclave equipped with a valve, pressure gauge, stirrer and thermometer, and then fully replaced with nitrogen while cooling with dry ice / methanol solution. Next, add 5.0 g of TFE I from the valve, and shake at room temperature for 18 hours. During the reaction, the gauge pressure was reduced from 0.96 M PaG (9.7 kgf / cm2G) before the reaction to 0.91 MPaG (9.2 kgf / cm2G). Then, it was separated and purified in the same manner as in Example 2 to obtain 1.0 g of a copolymer. The composition ratio of the copolymer was analyzed by iH-NMR and 19F-NMR. As a result, TFE / the above-mentioned -0CH20C2H5 group-containing fluorine-containing norbornene derivative (NB-2 (1)) was 50/50 moles. / 〇 的 copolymer. The number average molecular weight obtained by GPC analysis was 2,300. Example 8 (Synthesis of a copolymer of tetrafluoroethylene / (NB-2) / (NB-2 (1))) In addition to using 80.0 g of TFE, the fluorine-containing norbornene derivative containing -OH group used in Example 6 was used. (NB-2) I8.3g and -OCH2OC2H5-containing fluorine-containing norbornene derivative (NB-2 (1)) used in Example 7 except for 14.8g, the other reactions were carried out in Example 2, and the same were performed thereafter. Example 1 was isolated and purified to obtain 4.7 g of a copolymer. The composition ratio of the copolymer was analyzed by 1H-NMR and 9F-NMR. The results were TFE / -OH group-containing fluorine-containing norbornene derivative (NB-2) /-OCH2OC2H5 group-containing fluorine-containing norbornene derivative ( NB-2 (1)) is a 50/39/11 mole% copolymer. The number average molecular weight obtained by GPC analysis was 2400. -60- (57) (57) 200 408 649 Example 9 (Synthesis of TFE / -OH-containing fluorine-containing dilute dilute (NB-1) co-amplifier) Replaced with nitrogen several times equipped with a valve, pressure gauge, After the stirrer and a 500ml autoclave with a temperature of § ten, put in a vacuum a solution containing 39.0g of a 0H-based fluorine-containing antipyrene (NB-1) and 250ml of a solution of HCFC-1416. Next, 58.0 g of D-FE was added through a valve, and then pentafluoropropane peroxide: (CF3CF2COO) 2 of a 10 · 0% by weight perfluorohexane solution 10 · 5 g, and the reaction was stirred at 3 ° C. 3 hour. After the unreacted monomer was discharged, the polymerization solution was taken out, and after concentrating, it was reprecipitated with hexane to isolate the copolymer. After reaching a constant amount, vacuum drying was performed to obtain 3.5 g of a copolymer. The composition ratio of the copolymer was analyzed by 1H-NMR and 19F-NMR. As a result, the copolymer having a TFE / the above-OH group-containing fluorine-containing norbornene derivative (NB-1) of 50/50 mole% was obtained. The number average molecular weight obtained by GPC analysis was 3,700. Example 10 (Synthesis of a TFE / -OH-containing fluorinated norbornene (NB-1) copolymer) After replacing a 500 ml autoclave equipped with a valve, a pressure gauge, a stirrer, and a thermometer several times with nitrogen, the mixture was placed under vacuum. Put 39.0 g of -OH-containing fluorine-containing norbornene (NB-1) and 260 ml of HCFC-1416 solution. Next, 58.0 g of TFE was added using a valve, and then pentafluoropropane peroxide: (CF3CF2CF2COO) 2 0.0% by weight of a perfluorohexane solution 17 · 0g, and the reaction was stirred for 3 hours at 35 t. -61-(58) 200408649 After releasing the unreacted monomer, the polymerization solution was taken out and the precipitate was concentrated to isolate the copolymer. After reaching a constant amount, it was dried in vacuum at 3.4 g. The copolymer was analyzed by 1 TF-NMR and 1 9 F-NMR. The copolymer was TF Ε / the above-mentioned fluorene-containing norbornene-derived burdock 5-0 / 5 0 mole. % Copolymer. The number average molecular weight obtained by GPC analysis was 3800 °. Comparative Example 1 Except the substitution of 6.5 g of bis (4-t-butylcyclohexyl) peroxide 2) 7H-dodecafluoroheptane peroxide as a self-agent, and the use of -OH group fluorine-containing norbornene (NB-1) 30 except for the reaction in the same manner as in Example 丨 to obtain 5.0 g of a copolymer of TFE and the aforementioned norbornene derivative (NB-1). The copolymer was analyzed by 1H-NMR and 19F-NMR. The result was a copolymer of 50% by mole of TFE / the above-mentioned OH group-containing fluorine-containing norbornene derivative.

The number average molecular weight obtained by GpC analysis was 4,700. Comparative Example 2 Except that 6.5 g of bis (4-t-butylcyclohexyl) peroxide was substituted for 6.5 g of 7H-dodecafluoroheptane peroxide as a self-agent 'and a fluorine-containing norbornene containing -OCH20C2h5 (A 7 · Q g ^ 40 ° C except for the reaction, the others were the same as in Example 1 and then mulberry was used to obtain the composition ratio of the copolymer. (NB-1) was carbonate (TCP polymerization Initiation. 6g contains -OH group and fluorine composition ratio at 40 ° C, and the knot 1 (NB-1) is carbonate (TCP initiated by radical polymerization NB-1 (1)). TFE and -62- ( 59) (59) 200408649 The aforementioned copolymer containing -OCH2OC2H5 group fluorine-containing norbornene derivative (NB-1 (1)) 6.0 g. The composition ratio of the copolymer was analyzed by 1H-NMR and I9F-NMR, and the result was TFE / The above-mentioned fluorinated norbornene derivative (NB-1 (1)) containing -0CH2OC2H5 is a copolymer of 50/50 mole%. The number average molecular weight obtained by GPC analysis is 4,600. Comparative Example 3 Except As a radical polymerization initiator, 6.5 g of bis (4-t-butylcyclohexyl) peroxydicarbonate (TCP) was used in place of 7H-dodecylfluoroheptane peroxide, and the content containing- OH-based fluorinated norbornene (NB-1 (1)) 39.0g In Example 2, 12.0 g of -OCH2OC2H5 group-containing fluorine-containing norbornene (NB-1 (1)) was reacted at 40 t, and the others were carried out in the same manner as in Example 3 to obtain TFE and the -OH group-containing fluorine-containing norbrene Terpolymer of ene derivative (NB-1) with the aforementioned -oCH2OC2H5 group fluorine-containing norbornene derivative (NB-1 (1) 5.2 g. The copolymer was analyzed by 1H-NMR and 19F-NMR The composition ratio showed that TFE / the above-OH group-containing fluorine-containing norbornene derivative (NB-1) / the above-OCH2OC2H5 group-containing fluorine-containing norbornene derivative (NB-1 (1)) was 50/40 / 10 ear% copolymer. The number average molecular weight obtained by GPC analysis is 4000. Comparative Example 4

In addition to using bis (4-t-butylcyclohexyl) peroxydicarbonate (TCP -63- (60) (60) 200408649) 6_5g instead of 7H-dodecylfluoroheptane peroxide as a radical polymerization initiator ' And using 41.6 g of fluorinated fluorinated derivatives (NB-i (Nb-1 (2))) containing _〇 (C = 0) OC (CH3) 3 group at 40 t, the others are the same as in Example 4 The process was performed to obtain 6.0 g of a copolymer of τ FE and the aforementioned-(C = 0) 0 C (C Η 3) 3 group fluorine-containing norbornene derivative (NB-1 (2)). The composition ratio was TFE / the above-containing (-) (c = 0) 〇C (CH3) 3-group fluorine-containing norbornene derivative (NB-1 (NB-1 (2)) was 50/50 mole % Copolymer. The number-average molecular weight obtained by GPC analysis is 3300. Comparative Example 5 Except for 6-5 g of bis (4-t-butylcyclohexyl) peroxydicarbonate (TCP) in place of 7H-dodecafluoroheptane Peroxide was used as a radical polymerization initiator, and 30.6 g of a fluorine-containing norbornene derivative (NB-1) containing -OH group and-〇 (C = 〇) OC (CH3) 3 group fluorine-containing norbornene were used. 8.3 g of derivative (NB-1 (2)) was reacted at 40 ° C, and the other examples were carried out to obtain TFE and the -OH group containing Terpolymer of fluoronorbornene derivative (NB-1) and the aforementioned -0 (C = 0) 〇C (CH3) 3-group fluoronorbornene derivative (NB-1 (2)) terpolymer The composition ratio of the copolymer was analyzed, and the result was TFE / -OH group-containing fluorine-containing norbornene derivative (NB-1) /--((C = 0) 0C (CH3) 3 group fluorine-containing norbornene derivative The compound (NB-1 (2)) is a copolymer of 5 0/3 9/1 1 mol%. The number average molecular weight obtained by GPC analysis is 2900. -64- (61) (61) 200408649 Comparative Example 6 6.5 g of bis (4-butylcyclohexyl) peroxydicarbonate (TCP) substituted 7H-dodecylfluoroheptane peroxide as a radical polymerization initiator, and a fluorine-containing norbornene derivative containing -0 fluorenyl group (NB-2) 3 4.6 g was reacted at 40 ° C, and the others were carried out in the same manner as in Example 6 to obtain 4.5 g of a copolymer of TFE and the aforementioned -OH group-containing fluorine-containing norbornene derivative (NB-2). The composition ratio of the copolymer was analyzed, and the result was a copolymer in which the TFE / the above-mentioned _ 0 H group-containing fluorine-containing norbornene derivative (NB-2) was 50/50 mole%. The number average molecular weight obtained by GPC analysis It is 2100. Comparative Example 7 Except for bis (4-t-butylcyclohexyl) peroxydicarbonate (TCP) 1.3 g of 7H-dodecafluoroheptane peroxide. Was used as a radical polymerization initiator, and 9.3 g of a fluorine-containing norbornene derivative (NB-2 (1)) containing -0CH2OC2H5 was used. Except for the reaction at 40 ° C, the other was carried out in the same manner as in Example 7 to obtain 1.0 g of a copolymer of TFE and the aforementioned fluorine-containing norbornene derivative (NB-2 (1) containing -0CH2OC2H5 group. When the composition ratio of the copolymer was analyzed, it was found that the copolymer of TFE / the above-containing -0CH2C2H5 group fluorine-containing norbornene derivative (NB-2 (1)) was 50/50 mole:%. The number average molecular weight obtained by GPC analysis was 2200. Comparative Example 8 Except using 6.5 g of bis (4-t-butylcyclohexyl) peroxydicarbonate (TCp (62) (62) 200408649) instead of 7H-dodecylfluoroheptane peroxide as a radical polymerization initiator And using 27.7 g of fluorine-containing norbornene derivative (NB-2) containing -OH group and 8.2 g of fluorine-containing norbornene derivative (NB-2 (1)) containing-OCH2 0c2H5 group at 40 t The reaction was carried out in the same manner as in Example 8 to obtain butylene FE and the aforementioned -OH group-containing fluorine-containing norbornene derivative (NB-2) and the aforementioned -OHCH2OC2H5-based fluorine-containing norbornene derivative (NB- 2 (1)) copolymer 5.2g. The composition ratio of the copolymer was analyzed, and the result was TFE / the above-H group-containing fluorine-containing norbornene derivative (NB-2) / the above-mentioned -0CH2OC2H5 group-containing fluorine-containing norbornene derivative (NB-2 ( 1)) is 50/4 0/1 10 mole% copolymer. The number average molecular weight obtained by GPC analysis was 2,300. Example 11 1 (Measurement of transparency at 157 nm) (Measuring device) VU-201 type vacuum ultraviolet spectrometer (manufactured by a spectrometer) made of a fluoropolymer film (producing a fluoropolymer film) The fluoropolymers obtained in Examples 1 to 10 were polymerized The material was dissolved in PGMEA and prepared as a 10% solution. The solution was coated on a CaF 2 substrate using a spin coater and dried at 110 ° C to obtain a film having a film thickness of about 90 to 200 nm. (Measurement of transparency) The above-mentioned spectrophotometer was used to measure the absorbance of CaF2 substrates each provided with a fluoropolymer film at 157 nm ', and the light absorption coefficient was calculated from the film thickness of each film. The results are shown in Table 1. -66- (63) 200408649 Comparative Example 9 (Measurement of Transparency at 157 nm) Except for replacing the fluoropolymer obtained in Examples 1 to 10 with the fluoropolymer obtained in Comparative Examples 1 to 8, the same procedure as in Example 11 A film was produced and the transparency was measured at 5 7 nm. The results are shown in Table 1. Table 1 __ Fluoropolymer Example 1 1 1 5 7nm Absorption Coefficient (μπΓ 1) -------------- ^ Fluoropolymer Comparative Example 9 1 5 7 nm Absorption Coefficient (μπΓ1) Implementation Example 1 0.40 Comparative Example 1 0.93 Example 2 0.6 1 Comparative Example 2 1.00 Example 3 0.38 Comparative Example 3 0.76 Example 4 2.40 Comparative Example 4 3.00 Example 5 1.00 Comparative Example 5 1.96 Example 6 0.60 Comparative Example 6 1.80 Example 7 0.80 Comparative Example 7 1.90 Example 8 0.70 Comparative Example 8 1.70 Example 9 0.39 Example 1 〇0.3 8 Example 2 (Measurement of solubility in imaging solution) Obtained using Example 1 or Example 6 For the fluoropolymer, the dissolution rate (1) was measured by the following crystal vibrator method (QCM method). Preparation samples: -67 · (64) (64) 200408649 obtained from Example 1 (or Example 6) containing fluorine The solution obtained by dissolving the polymer in p GMEA was coated on a 1-inch-diameter crystal vibrator plate coated with gold to obtain a film of about 100 nm. (2) Measurement of dissolution rate: The film pressure is measured by converting the vibration number of the crystal vibrator. The fluoropolymer-coated crystal vibrator plate was immersed in a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution, and the change in the film thickness of the film over time was measured using the vibration plate change. Dissolution rate per unit time (nm / sec). The results are shown in Table 2. Table 2 Solubility (nm / s) of fluoropolymer Example 1 23 6 Example 6 3 14 Example 1 3 5 parts by weight of triphenylphosphonium perfluorobutylsulfonate was added to the fluorine-containing compound obtained in Example 3. In 100 parts by weight of the polymer, a photosensitive composition capable of being dissolved in PGME A was obtained. This photosensitive composition was coated on a silicon plate coated with an 80-nm anti-reflection film (AR19 manufactured by Shipley Co., Ltd.) using a spin coater, and dried at 110 ° C. for 90 seconds to obtain a thickness of 50 nm. . An F2 excimer laser (wavelength 157 nm) was used for flame exposure of the photoresist film at a point of lcni χ lcm angle (lcm2). After exposure, it was heated at 110 ° C. for 90 seconds using a hot plate, and then developed with a tetramethylammonium hydroxide (TMAH) aqueous solution having a concentration of 2.38% by weight. -68- (65) (65) 200408649 The exposure of the F2 laser was changed from 0.1 lmJ / cm2 to 10011 ^ / (: 1: 1). The flame exposure, heating, and development processing described above were performed, and the result was 2.5. The point of 1 cm2 is completely dissolved at an exposure amount of mj / cm2 or more. Therefore, it is known that the fluorinated copolymer obtained in Example 3 has a positive photoresist function and has sensitivity. A shrinkage projection exposure device using an F2 laser as a light source ( 157nm micro-stepper manufactured by Yagesi Corporation: Levenson Mask, NA / σ = 0.85 /0.30 Conv.) For mapping evaluation. As a result, an exposure of i5mJ / cm2 can be used to produce 8 5 nm, 1: 1 L / S Fine pattern. Therefore, it is known that the fluororesin obtained in Example 3 has a positive photoresist function and has resolvability. Example 1 4 In addition to replacing the fluorine-containing copolymer obtained in Example 3 with the fluorine-containing copolymer obtained in Example 5 Except for the copolymer, others were the same as in Example 13. 3, the photosensitive composition was prepared, a photoresist film was prepared, and F2 laser was used for flame exposure, heating, and development processing. Results 1.3 cm at an exposure amount of 1 cm or more The point 2 is completely dissolved. Therefore, it is known that the fluorinated copolymer obtained in Example 5 has positive light. Function and sensitivity. Same as in Example 13 and 3, using a reduced projection exposure device using a holmium laser as a light source for drawing evaluation. As a result, a fine map of 80 nm and 1: 1 L / S can be obtained at an exposure of 12 mJ / cm2. Therefore, it is known that the fluororesin obtained in Example 5 has a positive photoresist function and has resolvability. Example 15 In addition to replacing the -69- obtained in Example 3 with the fluorinated copolymer obtained in Example 8 66) (66) 200408649 Except for the fluorinated copolymer, the same as in Example 13 was used to modulate the photosensitive composition, make a photoresist film, and use F2 laser for flame exposure, heating, and development processing. The result is an exposure amount of 1.6 / cm2 or more It can completely dissolve the point of 1 cm2. Therefore, it is known that the fluorinated copolymer obtained in Example 8 has a positive photoresist function and has sensitivity. The same as in Example 1 3, the reduction projection exposure device using F2 laser light source is used for drawing evaluation. As a result, a fine pattern of 8 nm and 1: 1 L / S can be obtained at an exposure of 27 mJ / cm2. Therefore, it is known that the fluororesin obtained in Example 8 has a positive photoresist function and has resolvability. Example 1 6 (Analyze CF3 of fluoropolymer) The terminal cf3 content of the fluoropolymer obtained in each of Examples 1, 9, 10, and Comparative Example 1 was measured in the following manner. The powder of the fluoropolymer was dissolved in deuterated acetone in an amount of 0.1 to 10% by weight and confirmed. Completely dissolve. The polymer solution was analyzed by NMR (device: AC-3 00 manufactured by BRUKER Corporation) using trichlorofluoromethane as a chemical shift standard (Oppm) at room temperature to obtain an I9F-NMR4 modulation chart. Using the 19 F-N M R data map, the signal of each part of the polymer can be detected from the position of the chemical shift as shown in Table 3. The integral 値 (area 値) of the polymer terminal C F 3 signal shown in Table 3 is Η (terminal C F 3). In addition, as shown in Table 3, the signal of the polymer main chain CF2 under a wide chemical shift range is a broad peak, so the total integration 値 (area 値) of all the broad peaks is H (-CF2-). -70- (67) (67) 200408649 Table 4 shows the Η (terminal CF3) / Η (-CF2-) 由 obtained from the calculated 末端 (terminal CF3) and-(-CF2-). table 3

Remarks on chemical shift of the site (ppm) CF3 at the end of the polymer -8 0 ～ -8 4 cf2 at the polymer main chain -95 ~ -130 CFs from the CF2 side chain of TFE -70 ~ -76 of norbornene derivatives CF? CF in side chain -139 ~ -172 norbornene derivatives Table 4 Fluoropolymer fluorene (terminal CF: 0 / H (-CF2-) Example 9 0.155 Example 1 〇0.142 Example 1 0 Comparative Example 1 0 Industrial application possibilities By using the manufacturing method of the present invention, a photoresist having excellent transparency in the vacuum ultraviolet field can be obtained, especially a fluoropolymer capable of forming an ultrafine pattern when used for F2 photoresist. .

Claims (1)

(1) (1) 200,408,649, patent application scope 1 · -Production method of fluoropolymer for photoresist with excellent transparency to vacuum ultraviolet light 'characterized in that it has a carbon number of 2 or 3 The repeating unit (M 1) of the fluorine-containing ethylenic monomer (m 1) having at least one fluorine atom in the ethylenic monomer and / or derived from a fluorine-containing atom capable of giving the polymer main chain an aliphatic ring structure When the repeating unit (M2) of the monomer (m2) and the polymer has an acid-reactive group γ 1 or a Y 2 group which can be converted to the acid-reactive group γ 1 in the polymer, A fluorine atom polymerization initiator radically polymerizes the fluorine-containing ethylenic monomer (m 丨) and / or the monomer (m2) capable of making the polymer main chain have an aliphatic ring structure. 2. The manufacturing method according to item 1 of the scope of patent application, wherein the repeating unit (Ml) from the above-mentioned fluorofluoroethylene monomer (ml) is from tetrafluoroethylene, chlorodifluoroethane, fluorinated A structural unit of at least one selected from vinylene, fluorinated ethylene, and hexafluoropropylene. 3. The manufacturing method according to item 1 or 2 of the scope of patent application, wherein the repeating unit (M2) derived from the monomer (m 2) capable of giving the polymer main chain an aliphatic ring structure is derived from a fluorine-containing atom A repeating unit of norbornene derivatives. 4 · The manufacturing method according to any one of claims 1 to 3, wherein the fluorine-containing ethylenic monomer (ml) and / or the monomer (m2) capable of giving the polymer main chain an aliphatic ring structure ) Is a group Y2 which has an acid-reactive group γ1 or can be converted into an acid-reactive group Y1. 5 · The manufacturing method of any one of items 1 to 4 of the scope of patent application, wherein the repeating unit (M1) and (M2) contained in the fluoropolymer are repeating -72 · (2) (2) 200408649 units In the formula, a repeating unit (N1) containing a monomer (η 1) derived from an acid-reactive group Y 1 or a group Υ 2 which can be converted into an acid-reactive group Υ1, and in addition to the above-mentioned fluorine-containing ethyl-bridged monomer (m 1) and / or a monomer (m 2) capable of giving the polymer main chain an aliphatic ring structure, and an acid-reactive group γ 1 or a monomer Y 2 which can be converted into an acid-reactive group Y 1 ( nl) radical polymerization. 6 · The manufacturing method according to item 4 or 5 of the scope of patent application, which is obtained by using a polymer reaction method to radically polymerize a polymerization initiator having a fluorine atom, and has a base that can be converted into an acid-reactive group Y 1 The fluoropolymer of Y2 is converted into an acid-reactive group Y1. 7 · The manufacturing method according to any of items 1 to 6 of the scope of the patent application, wherein the acid-reactive group Y 1 of the fluorinated polymer is a 0Η group, and an acid dissociable functional group which can be converted into a 0Η group by an acid At least one of a COOH group or an acid dissociable functional group that can be changed to a COOH group by acid dissociation. 8. The manufacturing method according to any one of claims 1 to 7 of the patent application § wherein the radical polymerization initiator having a fluorine atom is a fluorinated (fluorenyl) peroxide. 9. The manufacturing method according to item 8 of the scope of the patent application, wherein the di (distillate) peroxide is a formula: 〇〇II || (where m and n are the same or different integers from 1 to 20乂 and χ are the same or different F, C1, or Η) -73- (3) (3) 200408649 di (fluorofluorenyl) peroxide. 10. The manufacturing method according to item 9 of the scope of the patent application, wherein the di (fluorenyl) peroxide is a formula: (CF3C F2C〇) 2 pentafluoropropionamidine peroxide. 11. The manufacturing method according to item 9 of the scope of patent application, wherein the di (fluorenyl) peroxide is a formula: (CF3CF2CF2C〇) 2 heptafluorobutyrazine peroxide. 1 2. —A photoresist composition for forming a photoresist film having excellent transparency to vacuum ultraviolet light, which is (A -1) an acid dissociability having an OH group and which can be converted into an η group by an acid. A fluorine-containing polymer having at least one acid-reactive group γ 1 of a functional group, a C 〇 OH group or an acid-dissociable functional group that can be changed to a C 〇 OH group by acid dissociation, (B) a photoacid generator (C) In a composition composed of a solvent, the fluorinated polymer (A-1) is a polymer obtained by using the manufacturing method according to any one of claims 1 to 11 in the patent application scope. · The photoresist composition according to item 12 of the patent application, wherein the fluoropolymer (A-1) is a polymer having an absorption coefficient at 157 nm and a wavelength of ι.0 μιη-ι or less. I4. A fluoropolymer having the formula (1):-(Μ 1 A)-(M2 A)-(Ν 1 Α)-(1) -74- (4) 200408649 (where ΙΑ is Structural units derived from tetrafluoroethylene; M2A is a structural unit derived from a norbornene derivative (m 2 a) which can contain a fluorine atom, and N 1 A is derived from a copolymer that can co-operate with tetrafluoroethylene and norbornene derivatives (m2a) Structural unit of polymerized monomer (nla)) As shown, the structural unit M1A is 12 to 70 mole%, the structural unit M2A is 12 to 70 mole%, and the structural unit N1A is 0 to 60 moles. /. And (M1A) + (M2A) = 100, (M1A) / (M2A) is 30/70 to 70/30 moles 〇 /. In the fluorine-containing polymer having an average molecular weight of 1,000 to 5000, at least one of the ends of the polymer main chain contains a polymer molecule having a -CF3 group, and the polymer main body obtained by 19F-NMR analysis When the signal strength of -CF3 at the end of the chain is Η (terminal CF3), the signal strength of -CF2- forming the main chain is H (-CF2-), which meets the formula (1): 03- Η (terminal CF3) / H ( -CF2-) g 0.0 1 The relational expression of formula (1). • 75- 200408649 柒, (a) (two), the designated representative picture in this case is: None, the component representative symbols of this representative picture are simply explained: None, if there is a chemical formula in this case, please reveal the chemical formula that can best show the characteristics of the invention: