WO2004024787A1 - Procede de production de fluoropolymeres pour reserve - Google Patents

Procede de production de fluoropolymeres pour reserve Download PDF

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Publication number
WO2004024787A1
WO2004024787A1 PCT/JP2003/011605 JP0311605W WO2004024787A1 WO 2004024787 A1 WO2004024787 A1 WO 2004024787A1 JP 0311605 W JP0311605 W JP 0311605W WO 2004024787 A1 WO2004024787 A1 WO 2004024787A1
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Prior art keywords
group
acid
monomer
polymer
fluorine
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PCT/JP2003/011605
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English (en)
Japanese (ja)
Inventor
Takayuki Araki
Takuji Ishikawa
Meiten Koh
Minoru Toriumi
Tamio Yamazaki
Takamitsu Furukawa
Toshiro Itani
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Daikin Industries, Ltd.
Semiconductor Leading Edge Technologies, Inc.
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Application filed by Daikin Industries, Ltd., Semiconductor Leading Edge Technologies, Inc. filed Critical Daikin Industries, Ltd.
Priority to JP2004535941A priority Critical patent/JPWO2004024787A1/ja
Priority to AU2003262070A priority patent/AU2003262070A1/en
Publication of WO2004024787A1 publication Critical patent/WO2004024787A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine

Definitions

  • the present invention relates to a method for producing a fluorine-containing polymer for a resist which is transparent in a vacuum ultraviolet region, in particular, F 2 laser (157 nm) light.
  • these conventional resist polymers have strong absorption in the vacuum ultraviolet wavelength range, and are transparent to a single F2 laser at a wavelength of 157 nm, which is being considered for use as a process for ultra-fine patterning. Is low. (The number is large). Therefore, in order to expose with an F2 laser, the thickness of the resist must be extremely thin, and it is practically difficult to use it as a single-layer F2 resist.
  • fluoropolymers obtained by copolymerizing fluoroolefins having 2 or 3 carbon atoms represented by tetrafluoroethylene and the like, and fluoropolymers having a ring structure in the main chain or the main chain have transparency and It is preferable from both aspects of dry etching resistance, and is useful as a resist polymer.
  • copolymers of fluoroolefins represented by tetrafluoroethylene and alicyclic monomers represented by norpolene (or norbornene derivative) are specifically described.
  • the method involves radical polymerization of fluororefin and an alicyclic monomer with a polymerization initiator such as a hydrocarbon-based peroxide.
  • the present inventors have conducted intensive studies in view of these problems, and have conducted radical (co) polymerization of fluorinated olefins and monomers that form a ring structure in the main chain, including those for resists having an acid-reactive group.
  • radical (co) polymerization is performed using a specific radical polymerization initiator, so that a fluoropolymer for resist can be efficiently obtained, and the fluoropolymer is transparent to F 2 laser light. sex was found to improve dramatically.
  • a first object of the present invention is to provide an F 2 laser beam by radically (co) polymerizing a monomer that forms a ring structure in a fluoroolefin or a main chain using a specific radical polymerization initiator.
  • An object of the present invention is to provide a method for producing a fluoropolymer for resist having excellent transparency in the above.
  • a second object of the present invention is to provide a composition for a resist, particularly an F2 resist, containing a fluoropolymer having excellent transparency in vacuum ultraviolet light obtained by such a production method.
  • a third object of the present invention is to provide a novel polymer comprising tetrafluoroethylene and a norpolenene derivative, which is excellent in transparency and has a CF 3 group introduced into the polymer terminal at a high ratio. Disclosure of the invention
  • the first aspect of the present invention is that a repeating unit (Ml) derived from a fluorine-containing ethylenic monomer (ml) having 2 or 3 carbon atoms and having at least one fluorine atom, and And / or has a repeating unit (M 2) derived from a monomer (m 2) which may contain a fluorine atom capable of giving an aliphatic ring structure to the polymer main chain, and the polymer contains an acid.
  • Ml a repeating unit derived from a fluorine-containing ethylenic monomer (ml) having 2 or 3 carbon atoms and having at least one fluorine atom
  • M 2 derived from a monomer (m 2) which may contain a fluorine atom capable of giving an aliphatic ring structure to the polymer main chain, and the polymer contains an acid.
  • the reaction is acid-reactive group Y 1 or an acid-reactive group Y 1 can be converted into groups (hereinafter referred to as "acid-reactive group conversion group") in obtaining the fluorine-containing polymer having a Y 2, fluorine-containing ethylenic Vacuum ultraviolet, characterized by radically polymerizing a monomer (ml) and Z or a monomer (m 2) capable of giving an aliphatic ring structure to the polymer main chain using a polymerization initiator having a fluorine atom.
  • the present invention relates to a method for producing a fluoropolymer for resist having excellent light transparency.
  • the polymerization reaction proceed promptly to increase the molecular weight, but also the resulting fluoropolymer can be treated with light in the vacuum ultraviolet region. Excellent transparency to lines.
  • the second aspect of the present invention is (A-1) an acid dissociable functional group that can be converted to a ⁇ H group by an acid, a COOH group, or an acid that can be dissociated into a COOH group by an acid. containing fluorine polymer having an acid-reactive group Y 1 of at least one sexual functional groups,
  • a fluororesin composition wherein the fluoropolymer (A-1) is a polymer obtained by the production method according to the first aspect of the present invention.
  • Such a photoresist composition provides a resist film having excellent vacuum ultraviolet light transparency, and is particularly useful when used in an ultrafine processing process.
  • the third aspect of the present invention comprises, as essential components, a repeating unit (M1A) derived from tetrafluoroethylene and a repeating unit (M2A) derived from a norbornene derivative (m2a) which may contain a fluorine atom.
  • M1A a repeating unit derived from tetrafluoroethylene
  • M2A a repeating unit derived from a norbornene derivative (m2a) which may contain a fluorine atom.
  • a polymer containing at least one CF 3 group at one end of the polymer main chain and being detected by 19 F-NMR analysis. Assuming that the intensity of one CF 3 signal at the end of the main chain is H (terminal CF 3 ) and the intensity of the main chain—CF 2 —signal is H (—CF 2 —), equation (1):
  • the present invention relates to a fluoropolymer satisfying the relational expression (1).
  • Such a fluoropolymer can more effectively improve transparency, is useful as the above-mentioned resist, and is a polymer useful not only for the resist but also for other optical uses.
  • the fluorine-containing polymer produced by the production method of the present invention includes a repeating unit (Ml) derived from a fluorinated ethylene monomer (ml) and a fluorine atom capable of giving an aliphatic ring structure to the polymer main chain.
  • M2 repeating unit derived from a fluorinated ethylene monomer
  • Y acid-reactive group converting group Y 2
  • it may further include an optional repeating unit ( ⁇ ⁇ ⁇ ).
  • the fluorine atom in the fluoropolymer obtained in the present invention is not always derived from the monomer (m1) or the monomer (m2), but may be derived from any other comonomer. It may be derived.
  • the production method of the present invention is characterized in that, when the above-mentioned fluoropolymer having the acid-reactive functional group Y is obtained, radical polymerization is carried out using a polymerization initiator containing a fluorine atom.
  • the radical polymerization reactivity of the fluorine-based monomer is improved, and the initiator residue at the terminal of the polymer also becomes a fluorine-containing terminal, and transparency in the vacuum ultraviolet region is obtained. Is further improved.
  • the polymerization initiator having a fluorine atom can be used as long as it is a compound that generates a radical by temperature (eg, heat) or light. Among them, a fluorine-containing organic peroxide is preferred.
  • fluorinated organic peroxide one or more selected from fluorinated dihydroxy peroxides, fluorinated veroxydicarboxylic acids, fluorinated peroxide esters, and fluorinated dialkyl peroxides are preferable. .
  • fluorinated disilvoxides are preferred because they can promote radical polymerization reactivity and can further improve the transparency of the obtained polymer in the vacuum ultraviolet region.
  • fluorine-containing organic peroxides are obtained by substituting part or all of the hydrogen atoms of a hydrocarbon group such as an alkyl group or an aryl group in a fluorine-free hydrogen-based peroxide skeleton with a fluorine atom. It was done.
  • an organic peroxide having a fluorinated alkyl group or a fluorinated alkyl group having an ether bond is preferred from the viewpoint of improving the transparency.
  • Fluorinated alkyl group The fluorinated alkyl group having a polyester bond may be linear or branched.
  • the fluorinated alkyl group or the fluorinated alkyl group having an ether bond is a perfluoroalkyl group or a substituted perfluoroalkyl group in which a part of a fluorine atom is substituted with a halogen atom such as a hydrogen atom, a chlorine atom, or a bromine atom.
  • Alkyl groups are preferred because they are particularly excellent in the effect of improving transparency.
  • R f 3 and R f 4 are the same or different and each may have an ether bond, a fluorinated alkyl group having 1 to 40 carbon atoms, a fluorinated aryl group having 6 to 40 carbon atoms or a carbon number. And a fluorinated aralkyl group of 7 to 40).
  • n are the same or different and are integers from 1 to 20; X and X 'are the same or different and F (C1 or H)) is preferred.
  • n 0 or an integer from 1 to 5
  • n 0 or an integer from 1 to 5
  • n 0 or an integer of 1 to 5
  • the monomer (ml) that gives the repeating unit (Ml) to the fluorinated polymer is a polymerizable, especially a radically polymerizable, fluorinated ethylene having 2 or 3 carbon atoms having one carbon-carbon double bond. It is a monomer having at least one fluorine atom.
  • Such a fluorine-containing ethylenic monomer (ml) is a monoene compound having one polymerizable carbon-carbon double bond, and does not form a repeating unit having a ring structure in the main chain even by polymerization.
  • the fluorinated ethylenic monomer (ml) may or may not have an acid-reactive functional group Y in the monomer, but usually has an acid-reactive functional group. It is preferable to use a monomer which is not used, since the radical polymerization reactivity is good and the transparency can be more effectively improved.
  • Preferred fluorine-containing ethylenic monomers (ml) include those in which at least one hydrogen atom of ethylene or propylene is substituted with a fluorine atom.
  • Other hydrogen atoms may be substituted by halogen atoms other than fluorine atoms.
  • a monomer in which a fluorine atom is bonded to at least one carbon atom constituting a carbon-carbon double bond is preferable.
  • a fluorine atom can be introduced into the repeating unit (Ml), that is, into the polymer main chain, and a fluorine-containing polymer giving particularly excellent transparency in the vacuum ultraviolet region can be effectively obtained.
  • At least one monomer selected from tetrafluoroethylene, chlorofluoroethylene, vinylidene fluoride, vinyl fluoride, trifluoroethylene, hexafluoropropylene, and CH 2 CFCF 3
  • the body is preferred.
  • At least one or a mixture of two or more of tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride or hexafluoropropylene is particularly preferable in terms of transparency. Fluoroethylene and / or chlorotrifluoroethylene are preferred.
  • a monomer (m 2) which may have a fluorine atom and which can give a repeating unit (M 2) having an aliphatic ring structure in the polymer main chain will be described.
  • the monomer (m2) may be one selected from unsaturated cyclic compounds having a radically polymerizable carbon-carbon unsaturated bond in a ring structure, or may be a main chain obtained by cyclopolymerization of a jelly conjugate.
  • the compound may be selected from non-conjugated gen compounds that can form a ring structure.
  • the monomer (m2) may or may not have the acid-reactive functional group Y in the monomer.
  • the first preferable monomer (m2) is a monocyclic monomer having a radically polymerizable carbon-carbon unsaturated bond in its ring structure and having no acid-reactive functional group Y.
  • (m2-1) is preferably an aliphatic unsaturated hydrocarbon compound having a 3- to 8-membered ring structure which may contain an ether bond in the ring structure.
  • a monomer in which part or all of the hydrogen atoms of these monomers (m 2-1) are substituted with a fluorine atom may be used.
  • the second preferable monomer (m2) is a monomer (m2_2) having a monocyclic aliphatic unsaturated hydrocarbon compound having an acid-reactive functional group Y, and having an ether bond in the ring structure. It is preferably an unsaturated hydrocarbon compound having a 3- to 8-membered ring structure which may be contained.
  • the monomer (m2-2) may be a monomer in which part or all of the hydrogen atoms have been substituted with fluorine atoms.
  • the monocyclic monomer (m2-2) having an acid-reactive functional group Y is, specifically,
  • the third preferred of the monomer (m2) is to provide a structural unit having an aliphatic bicyclic structure in the polymer main chain, and to have an aliphatic bicyclic structure having no force or acid-reactive functional group Y. It is a monomer (m 2-3).
  • Preferred monomer (m2-3) is norbo It is a renene derivative.
  • the monomer having an aliphatic bicyclic structure not having the acid-reactive functional group Y (m 2 13) is specifically,
  • the above-mentioned exemplified norponenes may be those obtained by introducing a fluorine atom into the ring structure.
  • a fluorine atom By introducing a fluorine atom, the transparency can be improved without lowering the dry etching resistance.
  • A, B, D and D ' are the same or different, and all are H, F, an alkyl group having 1 to 10 carbon atoms or a fluorine-containing alkyl group having 1 to 10 carbon atoms.
  • M is an integer from 0 to 3; Provided that any one of A, B, D, and D contains a fluorine atom).
  • Fluorine-containing norpolene represented by X or the like is obtained.
  • a preferred fourth of the monomer (m2) is a monomer having a structural unit having an aliphatic bicyclic structure in the polymer main chain and containing an aliphatic bicyclic structure having an acid-reactive functional group Y.
  • Body (m2-4) The preferred monomer (m2-4) is a norpolene derivative.
  • the monomer (m2-4) containing an aliphatic bicyclic structure having an acid-reactive functional group Y is specifically, (m: integer from 0 to 3)
  • a monomer (m 2-4) containing an aliphatic bicyclic structure having an acid-reactive functional group Y is obtained by substituting some or all of the hydrogen atoms bonded to the ring structure with fluorine atoms. This is preferable because it can impart further transparency to the polymer.
  • A, B and D are the same or different, and all may include H, F, an alkyl group having 1 to 10 carbon atoms or an ether bond having 1 to 10 carbon atoms.
  • R is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorinated alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group having an ether bond having 2 to 100 carbon atoms; a Is an integer of 0 to 5; b is 0 or 1. However, when b is 0 or R does not contain a fluorine atom, any one of A, B and D has a fluorine atom or an ether bond.
  • any of A, B, and D is a fluorine atom, or when A, B, and D do not contain a fluorine atom, the fluorine content of R is 60% by weight. It is preferably the above, and more preferably a perfluoroalkylene group, from the viewpoint of imparting transparency to the polymer.
  • R is a divalent hydrocarbon group having 1 to 20 carbon atoms, a fluorinated alkylene group having 1 to 20 carbon atoms or a fluorinated alkylene group having an ether bond having 2 to 100 carbon atoms; An integer of from 5 to 5; b represents a fluorine-containing norportene derivative represented by 0 or 1).
  • Norpolene derivatives such as (n: 0 to: LO) are preferred.
  • a monomer (m2-4) containing an aliphatic bicyclic structure having an acid-reactive functional group Y is preferably represented by the following formula:
  • R f R f 2 are the same or different and each is a fluorine-containing alkyl group having 1 to 10 carbon atoms or a fluorine-containing alkyl group having an ether bond;
  • B and D are The same or different, each of which is H, F, C1, an alkyl group having 1 to 10 carbon atoms or a fluorinated alkyl group which may contain an ether bond having 1 to 10 carbon atoms;
  • R is H or 1 carbon atom;
  • To 10 alkyl groups; n is an integer of 0 to 5).
  • exemplified monomers (m2-3) and (m2-4) each having an aliphatic bicyclic structure are particularly preferable as a raw material for a resist polymer, since they can impart dry etch resistance to the polymer.
  • the production method of the present invention is also preferable in that a polymer can be efficiently produced by a radical polymerization method and transparency can be effectively improved.
  • Lenorpartene derivatives containing a fluorine atom in a bicyclic structure are particularly preferable. It is preferable in terms of transparency, and is also preferable in that a polymer can be efficiently produced by a radical polymerization method and the transparency can be effectively improved by the production method of the present invention.
  • a norpolenene derivative (m2-4) having an acid-reactive functional group Y is preferable because a functional group necessary for resist application can be efficiently introduced into a polymer, and as a result, transparency and dry etching resistance are advantageous. .
  • a fifth preferred monomer (m2) is a non-conjugated diene compound (m2-5) which may have a fluorine atom and can form an aliphatic ring structure by polymerization.
  • the non-conjugated diene compound (m2-5) can efficiently give a polymer having a repeating unit having a ring structure in the main chain, and can improve the transparency in the vacuum ultraviolet region as described above.
  • non-conjugated diene compound (m2-5) for example, a specific divinyl compound which gives a monocyclic structure to the main chain by cyclopolymerization is preferable.
  • Z 1 and Z 2 are the same or different, and are a hydrogen atom, a fluorine atom, a carbon number: a hydrocarbon group which may have an ether bond of 5 to 5, an ether bond of 1 to 5 carbon atoms, A fluorine-containing alkyl group which may have a).
  • tau zeta 2 are as defined above
  • a fluoropolymer having a cyclic structure can be efficiently obtained by using the above-mentioned fluoropolymerization initiator, and as described above, the transparency in the vacuum ultraviolet region can also be improved. It is.
  • the acid-reactive functional group ⁇ will be described.
  • a convertible acid reactive group conversion group gamma 2 generic acid reactive groups gamma 1 and the acid-reactive group gamma 1.
  • Acid-reactive group gamma 1 in the present invention refers to the acid-labile or acid-decomposable functional groups functional groups Contact and acid condensate compatibility.
  • 1Acid dissociable or acid decomposable functional group
  • An acid-labile or acid-decomposable functional group is a functional group that is insoluble or hardly soluble in Al-rikari before reacting with an acid, but can be solubilized in Al-lili by the action of acid. . This change in solubility in alkali makes it usable as a base polymer for a positive resist.
  • the acid-dissociable or acid-decomposable functional group is, specifically,
  • R 7 R 8 R 9 R 10 R 11 , R 12 R 14 R 18 R 19 20 , R 21 R 22 R 24 R 25 R 26 R 27 R 28 R 29 are the same or different and have the same number of carbon atoms.
  • R 13 R 15 R 16 are the same or different; H or C 1 10 hydrocarbon groups;
  • R 17 R 23 are the same or different; C 2 10 divalent carbon Hydrogen group
  • R 3 ° is an alkyl group having 1 to 10 carbon atoms
  • the acid-condensation-reactive functional group is soluble in an alkaline developer (or other developing solvent) before reacting with the acid, but the acid itself causes the polymer itself to be dissolved in an alkaline developer (or It is a functional group that can be made insoluble in other developing solvents.
  • a self-condensation, polycondensation by the action of an acid or a cation, or a functional group that causes a condensation reaction or a polycondensation reaction with a cross-linking agent by the action of an acid in the presence of a crosslinking agent, or a rearrangement reaction by an acid-cation (For example, pinacol rearrangement, carbinol rearrangement), etc., which cause a polarity change, and as a result, the polymer itself is insoluble in an alkaline developer (or other developing solvent). It becomes.
  • Acid condensable functional groups include — ⁇ H, one C ⁇ OH, one CN, -SO3H, Those selected from epoxy groups and the like are preferred specific examples.
  • the crosslinking agent is not particularly limited, and may be arbitrarily selected from those conventionally used as a crosslinking agent for a negative resist.
  • Preferred specific examples of the crosslinking agent include N-methylolated melamine, N-alkoxymethylated melamine compound, urea compound, epoxy compound and isocyanate compound.
  • acid-reactive group Y 1 OH groups, acid labile functional group which can be converted to OH group with an acid, COOH groups, acid labile functional group that dissociates to can be changed to CO OH group with an acid At least one is preferred.
  • Acid dissociable functional groups that can be converted to 0H groups with an acid include:
  • R 31 , R 32 , R 33 and R 34 are the same or different and each is an alkyl group having 1 to 5 carbon atoms).
  • OCH 2 OC 2 H 5 is preferable, and _ ⁇ C (CH 3 ) 3 , —OCH 2 ⁇ CH 3 , and one OCH 2 OC 2 H 5 are more preferable in terms of good transparency.
  • Acid dissociable functional groups that can be converted to one C ⁇ H group with an acid include:
  • R 35 , R 36 , R 37 , R 38 , R 39 , R 4 , R 41 , R 42 , R 46 , R 47 , R 48 are the same or different, and each has 1 to 10 carbon atoms.
  • R 43 and R 44 are the same or different, and each is H or a hydrocarbon group having 1 to 10 carbon atoms; 1 45 is a divalent hydrocarbon group having 2 to 10 carbon atoms).
  • These acid-reactive group Y 1 can usually be introduced monomer having an acid-reactive group Y 1 to the polymer by accordance connexion polymerization to the preparation of the present invention.
  • the monomer having an acidic group-converting group (ester group) Y 2 ) is copolymerized with m 1 and / or m 2 by the production method of the present invention to obtain a fluorine-containing polymer having an acid-reactive group converting group Y 2 manufacture, and a method of converting the obtained fluorine-containing polymer of acid-reactive group conversion group Y 2 to ⁇ _H group by causing alkaline hydrolysis (acid-reactive group Y 1) and the like.
  • the present invention also includes a method for producing a fluoropolymer that having a acid-reactive group Y 1 via the process of polymer reaction.
  • a fluoropolymer having an acid-reactive group Y 1 can be efficiently obtained, and transparency in the vacuum ultraviolet region can be improved.
  • the fluorine-containing polymer having the acid-reactive functional group Y is a monomer having the acid-reactive functional group Y among the above-mentioned monomers (ml), or a monomer capable of providing an aliphatic ring structure.
  • a monomer (m2-2) or (m2_4) having a reactive functional group Y or a cyclopolymerizable divinyl compound (m2-5) having an acid-reactive functional group Y It can be obtained by radical polymerization of at least one kind using a fluorine-containing polymerization initiator.
  • the monomer (nl) having the acid-reactive functional group Y is converted into a monomer (ml) ) And (m2), may be copolymerized, and a third repeating unit (N1) having an acid-reactive functional group Y may be introduced in addition to the repeating units (Ml) and Z or (M2).
  • an ethylenic monomer having a copolymerizable acid-reactive functional group Y is preferable.
  • an acrylic monomer having an acid-reactive functional group Y, a fluorinated acryl-based monomer having an acid-reactive functional group Y, and an aryl ether-based monomer having an acid-reactive functional group Y are preferred. More specifically,
  • R f is a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having an ether bond having 2 to 100 carbon atoms
  • A is 0 or an integer of 1 to 3
  • b is a fluorine-containing ethylenic monomer represented by 0 or 1);
  • CH 2 CF-CF 2 0-R f -Y
  • CH 2 CFCF 2 OCF-Y
  • CH 2 CFCF 2 OCFCF 2 OCF- Y
  • CH, CFCF 2 OCF 2 CF 2 OCF 2 -Y
  • CH 2 CFCF 20 (CF 2 CF 20 ) 2 CF 2 -Y
  • CF 2 CFOCF 2 CFOCF 2 CF 2 CH 2 -Y
  • CF 2 CFOCF 2 CF 2 OCF 2 -Y
  • CF 2 CFOCF 2 CF 2 OCF 2 CH 2 -Y
  • CF 2 CFOCF 2 CF 2 CH 2 OCF 2 CF 2 -Y
  • CF 2 CFOCF 2 CF 2 CH 2 OCF 2 CF 2 CH 2 -Y
  • CF 2 CF ⁇ CF 2 CF ⁇ CF 2 CF 2 CH 2 — Y
  • Fluorinated Pinirue one ether compound such as CF 3 and the like.
  • fluorine-containing ethylenic monomers containing an acid-reactive functional group Y include:
  • CF 2 CFCF 2 OCF 2 CF 2 CF 2 -Y
  • CF 2 CFCF 2 OCF 2 CF 2 CF 2 CH 2 -Y
  • CF 2 CFCF 2 -Y
  • CF 2 CFCF 2 CH 2 -Y
  • CH 2 CHCF 2 CF 2 CH 2 CH 2 -Y
  • CH 2 CHCF 2 CF 2 -.Y
  • CH 2 CHO-CH 2 CF 2 CF 2 -Y
  • CH 2 CHOCH 2 CF 2 CF 2 CH 2 — Y, and the like.
  • Such an optional monomer (n) is selected from those which can be copolymerized with a monomer for constituting another structural unit.
  • Acrylic monomer (excluding the monomer described in n1):
  • CH 2 CH ⁇ R
  • CH 2 CHOC—R
  • R is an alkyl group having 1 to 20 carbon atoms which may be substituted by fluorine
  • an ethylenic monomer having 2 or 3 carbon atoms and having at least one fluorine atom (ml), or an aliphatic ring structure can be provided in the polymer main chain.
  • Comonomers (n) containing monomers (m 2-1) to (m 2-5) and, if necessary, an ethylenic monomer (n 1) having an acid-reactive functional group, (Co) polymerization is performed by various known methods using a radical polymerization initiator containing a fluorine atom.
  • Polymerization methods include solution polymerization in an organic solvent that dissolves monomers, suspension polymerization in an aqueous medium in the presence or absence of a suitable organic solvent, and addition of an emulsifier to an aqueous medium.
  • an emulsion polymerization method carried out, a park polymerization method carried out without a solvent, and the like can be used.
  • solution polymerization using organic solvents 00 Hire 1605
  • the polymerization solvent is not particularly limited, but a hydrocarbon solvent, a fluorine solvent (fluorocarbon), a chlorine solvent, an alcohol solvent, a ketone solvent, an ester acetate solvent, an ether solvent, or the like is preferably used. .
  • fluorine-based solvents and chlorine-based solvents are preferred in that they have good solubility of monomers and initiators, and that they can promote the polymerization reaction well.
  • the polymerization is initiated by contacting the fluorinated radical polymerization initiator with a monomer and applying heat (at a temperature specific to the initiator) or irradiating active energy rays such as light or ionizing radiation.
  • composition of the resulting copolymer can be controlled by the composition of the monomers to be charged.
  • the molecular weight can be controlled by the concentration of the monomer used for the 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 to be used with respect to the monomer to be used is from 0.05 to 10 parts by weight, preferably from 0.01 to 5 parts by weight, per 100 parts by weight of the monomer. Preferably it is 0.1 to 1 part by weight. From another viewpoint, the fluorine-containing radical polymerization initiator is contained in an amount of 0.01 to 10 mol%, preferably 0.05 to 5 mol%, more preferably 0 to 10 mol% based on the molar amount of the monomer used. 1 to 2 mol%.
  • the amount of the fluorinated radical polymerization initiator is too small, the polymerization reaction hardly proceeds sufficiently, unreacted monomers remain, or oligomer components are formed, which is not preferable because the coloring and transparency of the polymer decrease. If the amount of the fluorine-containing radical polymerization initiator is too large, the molecular weight of the polymer is reduced, and the transparency is reduced or unreacted. This is not preferable because the polymerization initiator remains and causes the coloring of the polymer and the decrease in transparency.
  • the reaction temperature in the polymerization using the fluorinated organic peroxide as the radical polymerization initiator depends on the respective 10-hour half-life temperature of the fluorinated organic peroxide to be used, and further according to the target reaction time. Although it can be appropriately selected, it is generally 0 to 150 ° (: preferably 5 to 120 ° C, more preferably 10 to 100 ° C.
  • composition of the monomers to be copolymerized may be selected in accordance with the polymerization reactivity of each monomer, the copolymerization reaction ratio, and the properties imparted to the obtained fluoropolymer.
  • the properties that each monomer can give to the fluoropolymer are as described above. More specifically, it will be described later.
  • the fluoropolymer obtained by the production method of the present invention has high transparency with respect to light in the vacuum ultraviolet region having a wavelength of 20 O nm or less. Therefore, the Ar F excimer laser (193 nm) and F 2 It is a resist polymer that is particularly useful for photolithographic processes using a laser (157 nm).
  • the present invention further provides
  • the present invention relates to a photoresist composition, wherein the fluoropolymer (A-1) is a polymer obtained by the above-mentioned production method of the present invention.
  • the acid-reactive functional group Y is dissociated with an OH group, an acid-dissociable functional group that can be converted to a ⁇ H group with an acid, Fluoropolymer having a specific acid-reactive group Y 1 called at least one acid labile functional group which can be converted to a COOH group (A- 1) to use.
  • the acid dissociable functional group that can be converted to an OH group with an acid and the acid dissociable functional group that can be converted to a COOH group with an acid those described above can be employed.
  • fluorine-containing polymer (A- 1) having a specific acid-reactive group Y 1 one technique of polymers are preferred.
  • Ml is a structural unit derived from a monomer (m 1) which is an ethylenic monomer having 2 or 3 carbon atoms and has at least one fluorine atom; M 2-2 is a monocyclic aliphatic fluorine-containing polymer Ru indicated in the structural unit) derived from which may monomer have a fluorine atom (the M2-2 a) having an acid-reactive group Y 1 in the unsaturated hydrocarbon compound.
  • composition ratio of the structural units (Ml) and (M2-2) is usually 80 20 to 20/80 mol% ratio, preferably 70/30 to 30/70 mol% ratio, particularly preferably 60 Z 40 to 40 mol%.
  • the ratio is 60 mol%.
  • acid-reactive functional group Y is an acid reactive group Y 1 of the embodiment of the monomer (m2_2) monomer described above (ml) It can be preferably exemplified.
  • composition ratio of the structural units (Ml) and (M2-4) is usually 80Z20-20 / 80 mol% ratio, preferably 70 / 30-30 / 70 mol% ratio, especially Preferably, the ratio is 60/40 to 40/60 mol%.
  • fluorine-containing polymers (I) and (II) are excellent in transparency and resistance to drying in themselves, and are further produced in a vacuum ultraviolet region by the production method of the present invention using a fluorine-containing polymerization initiator. Can improve transparency.
  • M1 1 (Ml) 1 (M2-1)-(N1)-(wherein, M1 is the same as above; M2_1 has a polymerizable carbon-carbon unsaturated bond in a ring structure and has an acid-reactive function.
  • the monomer include the above-mentioned specific examples of the monomers (ml) and (m2 ⁇ l) and the specific examples of the monomer (n1), in which the acid-reactive functional group Y is acid-reactive.
  • group Y 1 it can be preferably exemplified.
  • M2-3 has an acid-reactive functional group Y and has a structure derived from an aliphatic bicyclic structure-containing monomer (m2-3), particularly a norpolenene derivative.
  • a fluoropolymer represented by the following formula: The composition ratio of the structural units (Ml), (M2-3), and (N1) is (Ml) + (M2-1) + (N1) 100 mol%, and (Ml) + (M2- 1) / (N 1) is usually a 90/10 to 20/80 mol% ratio, preferably an 80/20 to 30/70 mol% ratio, particularly preferably a 70Z30 to 40/60 mol% ratio.
  • the monomer include the above-mentioned specific examples of the monomers (ml) and (m2-3) and the specific examples of the monomer (nl), wherein the acid-reactive functional group Y is an acid-reactive group.
  • Y 1 it can be preferably exemplified.
  • composition ratio of the structural units (M2-5) and (N1) is usually 80/20 to 20/80 mol% ratio, preferably 70Z30 to 30Z70 mol% ratio, particularly preferably 60 to 40 to 40 to 60 mol. % Ratio.
  • the monomer include the specific examples of the aforementioned monomer (m 2-5) and the specific examples of the monomer (nl), wherein the acid-reactive functional group Y is an acid-reactive group Y 1 Some of them are preferably exemplified.
  • fluorine-containing polymers (III), (IV) and (V) are excellent in dry etching resistance themselves, and are further evacuated by the production method of the present invention using a fluorine-containing polymerization initiator.
  • the transparency in the ultraviolet region can be improved.
  • the acid reactive group Y 1 fluorine-containing polymer (I) ⁇ (V) is different from the conventional Regis Bok for fluorinated polymers in that it has a fluorine-containing polymerization initiator residue in the polymerization initiation terminal Excellent in transparency especially in the vacuum ultraviolet region.
  • the nitrogen polymer (A-1) has excellent transparency at a wavelength of 157 nm, and has an extinction coefficient at 157 nm of 2.0 im- 1 or less, preferably 1.5 m- 1.
  • the photoacid generator (B) those similar to the photoacid generator (B) described in WO01 / 74916 pamphlet can be similarly preferably exemplified, The present invention can also be used effectively.
  • it is a compound that generates an acid or a cation by irradiating light, and is, for example, an organic halogen compound, a sulfonate, or an ionic salt (in particular, the central element is iodine, io, selenium, tellurium) , A nitrogen or phosphorus fluoroalkylonium salt), a diazonium salt, a disulfone compound, a sulfonediazide, and the like, or a mixture thereof.
  • an organic halogen compound in particular, the central element is iodine, io, selenium, tellurium
  • a nitrogen or phosphorus fluoroalkylonium salt A nitrogen or phosphorus fluoroalkylonium salt
  • a diazonium salt a disulfone compound, a sulfonediazide, and the like, or a mixture thereof.
  • X- is PF 6 one, SbF 6 -, CF 3 S0 3 -, C 4 F 9 S0 3 - , etc.; R la, R lb, Ric are the same or different, CH 3 ⁇ , H, t one Bu, CH 3,
  • R 2a , R 2b are the same or different, H, OH, CH 3 , CH 30 .t-Bu, etc.
  • the content of the photoacid generator in the photoresist composition of the present invention, the fluorine-containing polymer having an acid-reactive group Y 1 (A- 1) is preferably 0.1 to 30 parts by weight per 100 parts by weight, Further, the amount is preferably 0.2 to 20 parts by weight, and most preferably 0.5 to 10 parts by weight.
  • the content of the photoacid generator is less than 0.1 part by weight, the sensitivity is lowered.
  • the content is more than 30 parts by weight, the amount of the photoacid generator absorbing light increases, and the light does not reach the substrate sufficiently. Resolution is likely to be reduced.
  • the photoresist composition of the present invention may contain an organic base capable of acting as a base with respect to the acid generated from the photoacid generator.
  • organic base those similar to those described in WO 01/74916 pamphlet can be preferably exemplified, and can be effectively used in the present invention.
  • it is an organic amine compound selected from nitrogen-containing compounds, for example, pyridine compounds, pyrimidine compounds, amines substituted with a hydroxyalkyl group having 1 to 4 carbon atoms, aminophenols, and the like. , Particularly, hydroxyl group-containing amines are preferable.
  • Specific examples include preferably butylamine, dibutylamine, triptylamine, triethylamine, tripropylamine, triamylamine, pyridine and the like.
  • the content of the organic base in the photoresist composition of the present invention is preferably from 0.1 to 100 mol%, more preferably from 1 to 50 mol%, based on the content of the photoacid generator. If it is less than 0.1 mol%, the resolution tends to be low, and if it is more than 100 mol%, the sensitivity tends to be low.
  • additives described in WO 01/74916 pamphlet such as dissolution inhibitors, sensitizers, dyes, adhesion improvers, and water retention agents may be added to the photoresist composition of the present invention.
  • various additives commonly used in this field can be contained.
  • the solvent (C) is preferably the same as the solvent (C) described in WO 01/74916 pamphlet, and can be effectively used in the present invention. .
  • a cellosolve solvent, an ester solvent, a propylene glycol solvent, a ketone solvent, an aromatic hydrocarbon solvent, or a mixed solvent thereof is preferable.
  • a solvent may be used in combination.
  • the amount of these solvents (C) is selected depending on the type of solid content to be dissolved, the substrate to be coated, the target film thickness, etc., but from the viewpoint of ease of application, the total solid content of the photoresist composition is high. It is preferable to use such that the partial concentration is 0.5 to 70% by weight, preferably 1 to 50% by weight.
  • the photoresist composition of the present invention is used in a conventional method of forming a resist pattern in a photoresist technique.
  • a solution of the photoresist composition is coated on a support such as silicon A8 using a spinner or the like, and dried to form a photosensitive layer. Irradiation with ultraviolet rays, deep-UV, excimer laser, or X-rays through a desired mask pattern or drawing with an electron beam and heating. Then add this to the developer, for example: Develop using an aqueous alkaline solution such as a 10% by weight aqueous solution of tetramethylammonium hydroxide. With this forming method, an image faithful to the mask pattern can be obtained.
  • a highly transparent resist film (photosensitive layer) can be formed even in the vacuum ultraviolet region by using the photoresist composition of the present invention.
  • it can be used favorably in the photolithography process using an F 2 laser (157 nm wavelength), which is being developed with the aim of 0.07 xm technology in the future.
  • the coating film coated with the photoresist of the present invention is formed by applying the above-described photoresist composition on a support such as a silicon wafer by a coating method such as spin coating, and drying the coating. It contains solid components such as a fluoropolymer having an acid-reactive group (A-1), a photoacid generator (B), and other additives.
  • A-1 a fluoropolymer having an acid-reactive group
  • B photoacid generator
  • the thickness of the resist film to be formed is usually a thin film of 1.0 // m or less, preferably a thin film of 0.01 to 0.5 m, more preferably 0.05 to 0.5 m. .
  • the coating film coated with the photoresist composition of the present invention preferably has high transparency in the vacuum ultraviolet region, and specifically has an absorption coefficient at a wavelength of 157 nm of 2.5 m- 1 or less. Is preferably 2.0 m- 1 or less, particularly preferably 1.50 m- 1 or less, and further preferably 1.0 m- 1 or less.
  • This coating is lithographic using an F 2 laser (157 nm). It can be used effectively for roughing processes.
  • the substrate on which the resist coating is applied various types of substrates to which a conventional resist is applied can be similarly used.
  • it may be a silicon wafer, a silicon wafer provided with an organic or inorganic antireflection film, a glass substrate, or the like.
  • the sensitivity and the profile shape on a silicon wafer provided with an organic antireflection film are good.
  • the present inventors conducted a study by focusing on the structure of the main chain terminal of the fluoropolymer, and found that in a specific fluoropolymer obtained by polymerizing tetrafluoroethylene and a norportene derivative. It has been found that a polymer in which CF 3 groups are introduced at a high ratio exceeding a specific value at the polymer terminal can more effectively improve the transparency, particularly the transparency in vacuum ultraviolet light represented by 157 nm.
  • novel polymer of the present invention has the formula (1):
  • Ml A is a structural unit derived from tetrafluoroethylene
  • M2 A is a structural unit derived from a norpornene derivative (m2a) which may contain a fluorine atom
  • N 1 A is tetrafluoroethylene
  • a monomer (n1a) -derived structural unit copolymerizable with a norpoleneene derivative (m2a) and the structural unit MlA is 12 to 70 mol% and the structural unit M2A is 12 to 70 mol%.
  • Fluoropolymer polymer terminal is CF 3 at a high ratio as described above, patent, are novel compounds not described in literature.
  • the fluoropolymer of the present invention is
  • the value of H (terminal CF 3 ) / H (—CF 2 —) in the mathematical formula (1) is based on —CF 2 — (for example, derived from tetrafluoroethylene) in the polymer main chain. It represents the ratio of three main chain terminal CFs of the polymer to the above, and varies depending on the molecular weight of the fluoropolymer, but is preferably a large value in the above numerical range.
  • Equation (1) is replaced by Equation (1-1):
  • the fluorine-containing polymer of the present invention varies depending on the molecular weight, specifically, at least 40% of all terminals of the polymer main chain are preferably CF 3 groups, more preferably at least 50%, Is preferably a polymer having a CF 3 group introduced at the terminal of 70% or more, particularly 90% or more.
  • the norponene derivative (m2a) constituting the structural unit M 2 A in the fluoropolymer represented by the formula (1) of the present invention is a monomer (m2) of the monomer (m2) described in the above-mentioned method for producing a fluoropolymer. From the examples, those which are norpolene derivatives are also preferably selected.
  • the same monomers as those described above for the monomer having no acid-reactive functional group Y (m2-3) and the monomer having an acid-reactive functional group Y (m2-4) are preferable. Available.
  • the structural unit NLA in the fluoropolymer represented by the formula (1) of the present invention is an optional component, and is a structural unit derived from a copolymerizable monomer other than tetrafluoroethylene and a norpolenene derivative.
  • a monomer (n1) capable of introducing an acid-reactive functional group Y described in the above-mentioned method for producing a fluoropolymer, and those similar to those described for the optional monomer (n) can be used. It can be used preferably.
  • M1AZM2A is 80/20 to 2080 mol. % Ratio, preferably 70Z 30 3030/70 mol% ratio, more preferably 60 6040/40/60 mol% ratio.
  • the content ratio of the optional component N 1 A to all structural units is 60 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, further 10 mol% or less, and most preferably 0 mol%. It is.
  • the specific proportions of the structural units M 1 A, M 2 A and N 1 A are, specifically, 12 to 70 mol% of the structural unit M 1 A, 12 to 70 mol% of the M 2 A, and Nl A 0 to 60 mol%, preferably 21 to 70 mol% of the structural unit MlA, 21 to 70 mol% of the M2A, 0 to 30 mol% of the structural unit Ml A, more preferably 24 to 30 mol% of the structural unit Ml A ⁇ 70 mol%, M2A is 24 ⁇ 70 mol%, N1A is 0 ⁇ 20 mol%, and the structural unit MlA is 27 ⁇ 70 mol%, M2A is 27 ⁇ 70 mol%, 1 ⁇ 1 8 to 10 mol%, most preferably 30 to 70 mol% of the structural unit M1A, 30 to 70 mol% of M2A, and 0 mol% of N1A.
  • the molecular weight of the fluoropolymer represented by the formula (1) of the present invention is 1000 or more in number average molecular weight, preferably 2000 or more, more preferably 2500 or more, 50,000 or less, preferably 30,000 or less, more preferably 10,000 or less. is there.
  • the fluorine-containing polymer of the present invention represented by the formula (1) is preferable because it has excellent transparency due to the effect of the terminal CF 3 group even if it is a low molecular weight polymer.
  • Various methods for obtaining a fluoropolymer having a main chain terminal CF 3 group of the polymer of the present invention can be selected variously,
  • the method of producing a polymer using a polymerization initiator (1) and the method of producing a polymer using a chain transfer agent (2) can selectively introduce CF 3 groups into the terminal. It is preferred in that respect.
  • a polymerization initiator having a CF 3 group is selected from the polymerization initiators containing a fluorine atom exemplified in the method of producing a fluorine-containing polymer.
  • An agent is selected.
  • the polymerization solution was taken out, concentrated and then reprecipitated with hexane to separate the copolymer. Vacuum drying was performed until a constant weight was obtained, and 3.5 g of a copolymer was obtained.
  • the copolymer had a copolymer weight ratio of TFE / the ⁇ H group-containing fluorinated norportene derivative (NB-1) of 50/50 mol%. It was united.
  • Example 1 in place of the fluorinated norbornene derivative containing 1 OH group (NB-1), a fluorinated norpoleneene derivative containing _OCH 2 OC 2 H 5 group (NB-1 (1)):
  • the polymerization solution was taken out, concentrated, and reprecipitated with methanol / water (1: 1) to separate the copolymer. Vacuum drying was performed until a constant weight was obtained to obtain 2.5 g of a copolymer.
  • composition ratio of this copolymer is ⁇ Chromatography NMR and 19 F- from the results of NMR analysis, Ding £ / the chromatography 0 (: ⁇ 0_Rei 2 11 5 group-containing fluorine-norbornene derived
  • the copolymer (NB-1 (1)) was a 50Z50 mol% copolymer.
  • GPC analysis revealed a number average molecular weight of 3,800.
  • composition ratio of this copolymer was determined to be T FEZ—OH group-containing fluorinated norportene derivative (NB—1) / one OCH 2 ⁇ C 2 H 5 group
  • the content of the fluorine-containing norportene derivative (NB-1 (1)) was 50/40/10 mol%.
  • the reaction was carried out in the same manner as in Example 2 except that 66.0 g of 51 was used, followed by separation and purification to obtain 2.0 g of a copolymer.
  • Example 2 single 0 CH 2 ⁇ C 2 H 5 group containing norbornene derivative conductor (NB- 1 (1)) in place of one OH group-containing fluorine-norbornene (NB 2):
  • the reaction was carried out in the same manner as in Example 2 except that 55 g of Og 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 this copolymer was such that TFE / the OH-containing fluorine-containing norportene derivative (NB-2) was 50 to 50 mol%. .
  • GPC analysis revealed a number average molecular weight of 2,200.
  • composition ratio of this copolymer was as follows: from the results of —NMR and 19 F—NMR analyses, it was found that TFE / the above-mentioned fluorinated norpolenene derivative (NB—2 (1)) containing a CH 2 —C 2 H 5 group contained 50Z50 It was a mole% copolymer.
  • composition ratio of this copolymer is based on the results of —NMR and 19 F—NMR analyses. From the results of TFE / —OH group-containing fluorinated norportene derivative (NB—2) / — OCH 2 ⁇ C 2 H 5 group-containing fluorinated norpolenene
  • the derivative (NB-2 (1)) was a copolymer of 50Z39 / 11 mol%.
  • the polymerization solution was taken out, concentrated and then reprecipitated with hexane to separate the copolymer. Vacuum drying was performed until a constant weight was obtained to obtain 3.5 g of a copolymer.
  • composition ratio of this copolymer was determined by T-NMR and 19 F-NMR analysis to be that the TFE / the above-mentioned mono-OH group-containing fluorinated norponene derivative (NB-1) was 50/50 mol%.
  • the polymerization solution was taken out, concentrated and then reprecipitated with hexane to separate the copolymer. Vacuum drying was performed until a constant weight was obtained, to obtain 3.4 g of a copolymer.
  • the copolymer had a composition of TFE / the above-mentioned mono-OH group-containing fluorinated norportene derivative (NB-1) having a molar ratio of 50Z50 mol%.
  • GPC analysis revealed a number average molecular weight of 3,800.
  • Example 1 6.5 g of bis (4-tert-butylcyclohexyl) peroxydicarbonate (TCP) as a radical polymerization initiator in place of 7H-dodecafluoroheptanyl peroxide was used. And the same operation as in Example 1 was carried out except that the reaction was carried out at 40 ° C. using 30.6 g of fluorine-containing norportene (NB-1) containing 1H group. 5.0 g of a copolymer of a fluorine norportene derivative (NB-1) was obtained.
  • TCP bis (4-tert-butylcyclohexyl) peroxydicarbonate
  • NB-1 fluorine-containing norportene
  • NB-1 a copolymer of a fluorine norportene derivative
  • TF-containing fluorine-containing norportene derivative (NB-1) was a copolymer of 50Z and 50 mol% in T FEZ.
  • Example 2 instead of 7H-dodecafluoroheptanyl peroxide, 6.5 (bis- (4-tert-butylcyclohexyl)) peroxydiponic acid (TCP) was used as a radical polymerization initiator.
  • TCP bis- (4-tert-butylcyclohexyl) peroxydiponic acid
  • ⁇ 1 2 hundred 2 H 5 group-containing fluorine-norbornene (NB 1 (1) in use Les 401 37. 0 g) of non-reacted performs the same operation as in example 2, TF 6.0 g of a copolymer of E and the _OCH 2 OC 2 H 5 group-containing fluorinated norponene derivative (NB-1 (1)) was obtained.
  • the composition ratio of the copolymer was such that 50/50 mol% of TFEZ-containing fluorine-containing norportene derivative (NB-1 (1)) containing 50% CH 2 OC 2 H 5 was used. It was a copolymer.
  • Example 3 6.5 g of bis (4-tert-butylcyclohexyl) peroxide-ponate (TCP) was used as the radical polymerization initiator in place of 7H-dodecafluoroheptanyl peroxide.
  • TCP bis (4-tert-butylcyclohexyl) peroxide-ponate
  • Example 2 39.0 g of OH-containing fluorinated norportene (NB-1) and 12.O g of the ⁇ CH 2 ⁇ C 2 H 5- group-containing fluorinated norpolene (NB-1 (1)) used in Example 2
  • the reaction was carried out in the same manner as in Example 3 except that the reaction was carried out at 40 ° C. using TFE, and the TFE, the fluorine-containing norponene derivative containing 1H group (NB-1), and the OCH 2 OC 2 H 5 5.2 g of a terpolymer of a group-containing fluorinated norportene derivative (NB-1 (1)) was obtained.
  • T FEZ- ⁇ _H fluorine-containing norbornene derivative (NB 1) / one OCH 2 OC 2 H 5 group-containing fluorine-norbornene derivative ( NB-1 (1)) was a copolymer of 50 / 40Z10 mol%.
  • Example 4 6.5 g of bis (4-tert-butylcyclohexyl) hydroxyl-ponate (TCP) as a radical polymerization initiator instead of 7H-dodecafluoroheptanyl peroxide was used.
  • TCP bis (4-tert-butylcyclohexyl) hydroxyl-ponate
  • Example 6 6.5 g of bis (4-t-butylcyclohexyl) peroxydicarbonate (TCP) as a radical polymerization initiator in place of 7 H-dodecafluoroheptanyl peroxide and —
  • TCP bis (4-t-butylcyclohexyl) peroxydicarbonate
  • NB-2 bis (4-t-butylcyclohexyl) peroxydicarbonate
  • GPC analysis revealed a number average molecular weight of 2,100.
  • Example 7 1.3 g of bis (4_t-butylcyclohexyl) peroxydicarbonate (TCP) as a radical polymerization initiator in place of 7 H-dodecafluoroheptanyl peroxide and 1 OCH 2 ⁇ C 2 PC listening ⁇
  • Example 7 The same operation as in Example 7 was carried out except that 9.3 g of the fluorine-containing norpolenene derivative containing H 5 group (NB-2 (1)) was reacted at 40 ° C. 1.0 g of a copolymer of a fluorinated norpoleneene derivative (NB-2 (1)) containing a CH 2 ⁇ C 2 H 5 group was obtained.
  • composition ratio of the copolymer was found to be TZ50 / 50 mol% (50-2% by mole) TFE / the above-mentioned fluorinated norponene derivative containing a CH 2 OC 2 H 5 group (NB-2 (1)).
  • GPC analysis revealed a number average molecular weight of 2,200.
  • Example 8 6.5 g of bis (4_t-butylcyclohexyl) peroxydicarbonate (TCP) was used as a radical polymerization initiator in place of 7H-dodecafluoroheptanyl peroxide, and with 8. 2 g of 27.
  • composition ratio of the copolymer as a result of the analysis TFE / - OH group-containing fluorine-nor bornene derivatives (NB- 2) Z- ⁇ _CH 2 OC 2 H 5 group-containing fluorine-Norupo Runen derivative (NB- 2 (1 )) Is a 50/40/10 mol% copolymer.
  • the solution was applied to a C a F 2 on the substrate, and dried at 1 10 ° C, to prepare a film thickness of about 90 to 200 nm of the coating.
  • the absorbance at 157 nm was measured with the above-mentioned spectrophotometer using a C a F 2 substrate coated with each fluoropolymer film, and the extinction coefficient was calculated from the film thickness of each film.
  • Example 11 In the same manner as in Example 11 except that the fluorinated polymer obtained in Comparative Examples 1 to 8 was used instead of the fluorinated polymer obtained in Examples 1 to 10, preparation of a coating film at 157 nm Transparency measurements were taken.
  • Example 11 Comparative Example 9 Fluorinated polymer 157 nm extinction coefficient Fluorinated polymer 157 nm extinction coefficient
  • Example 1 0.40 Comparative Example 1 0.93 Example 2 0.61 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 90 . 39
  • Example 10 0.38
  • Example 12 Measurement of solubility in developer
  • the dissolution rate was measured by the quartz oscillator method (QCM method) as described below.
  • a composition was prepared.
  • the photosensitive composition is applied on a silicon wafer coated with an anti-reflection film (manufactured by SHI PLEY, AR 19) to a thickness of 80 nm using a spin coater, dried at 110 ° C for 90 seconds, and dried to a thickness of 150 A nm resist film was formed.
  • this resist film was subjected to frame exposure on a spot of 1 cm X 1 cm square (1 cm 2 ).
  • TMAH tetramethylammonium hydroxide
  • Example 14 Example 14
  • a photosensitive composition was prepared in the same manner as in Example 13 except that the fluorinated copolymer obtained in Example 5 was used instead of the fluorinated copolymer obtained in Example 3, and a resist film was prepared. It was formed and subjected to frame exposure, heating, and development using a single F2 laser beam.
  • Example 13 patterning evaluation was performed using a reduction projection exposure apparatus using an F2 laser as a light source. As a result, a fine pattern of 80 nm and 1: 1 LZS could be produced with an exposure amount of 12 mJ / cm 2 . From this, the fluororesin obtained in Example 5 can function as a positive resist. It turned out that it has resolution.
  • a photosensitive composition was prepared in the same manner as in Example 13 except that the fluorinated copolymer obtained in Example 8 was used instead of the fluorinated copolymer obtained in Example 3, and a resist film was prepared. It was formed and subjected to frame exposure, heating, and development with F2 laser light.
  • Example 13 patterning evaluation was performed using a reduction projection exposure apparatus using an F2 laser as a light source. As a result, a fine pattern of 80 nm and 1: 1 L / S could be produced with an exposure amount of 27 mJ / cm 2 . From this, it was found that the fluororesin obtained in Example 8 had a resolution capable of functioning as a positive resist.
  • Example 9 10 and the fluorine-containing polymer obtained respectively in Comparative Example 1 was measured terminal CF 3 content as follows.
  • the fluoropolymer powder was dissolved in deuterated acetone at 0.1 to 10% by weight, and it was confirmed that it was completely dissolved.
  • NMR Appatus: AC-300, manufactured by BRUKER
  • Op pm chemical shift standard
  • the integrated value (area value) of the signal at the polymer terminal CF 3 shown in Table 3 was defined as H (terminal CF 3 ).
  • the signal of CF 2 in the polymer main chain is shown in Table 3.
  • a broad peak was obtained in such a wide chemical shift range, and the sum of the integrated values (area values) of the broad peak was defined as H (—CF 2 —).
  • Table 4 shows the value of H (terminal CF 3 ) / H (one CF 2 —) from the calculated H (terminal CF 3 ) and H (—CF 2 —).
  • the production method of the present invention it is possible to produce a fluoropolymer having excellent transparency in a vacuum ultraviolet region and capable of forming an ultrafine pattern for a photoresist, particularly for an F 2 resist.

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Abstract

L'invention concerne un procédé permettant de préparer des fluoropolymères pour réserve, lesquels présentent une excellente transparence dans la région de l'ultraviolet extrême et sont utiles en tant que photorésines (en particulier la réserve F2) pour former des motifs ultra-fins. Ces fluoropolymères comprennent chacun des unités récurrentes (M1) provenant d'un monomère éthylénique fluoré (m1) comprenant de deux à trois atomes de carbone et au moins un atome de fluor et/ou des unités récurrentes (M2) provenant d'un monomère (m2) éventuellement fluoré capable de conférer une structure alicyclique à la chaîne principale du polymère et comprenant, dans le polymère, des groupes réagissant à l'acide (Y1) ou des groupes (Y2) transformables en groupes réagissant à l'acide (Y1). Le procédé décrit dans cette invention se caractérise en ce que le monomère (m1) et/ou le monomère (m2) sont polymérisés par radicaux au moyen d'un déclencheur de polymérisation contenant du fluor.
PCT/JP2003/011605 2002-09-13 2003-09-11 Procede de production de fluoropolymeres pour reserve WO2004024787A1 (fr)

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JP2006023538A (ja) * 2004-07-08 2006-01-26 Fuji Photo Film Co Ltd 液浸露光用保護膜形成組成物及びそれを用いたパターン形成方法
JP2006085081A (ja) * 2004-09-17 2006-03-30 Daikin Ind Ltd 微細パターン形成方法およびそれに用いるレジスト組成物
JP2009280774A (ja) * 2008-05-26 2009-12-03 Asahi Glass Co Ltd 含フッ素弾性共重合体、その製造方法および架橋ゴム
WO2010137724A1 (fr) * 2009-05-29 2010-12-02 日産化学工業株式会社 Polymère fluoré fortement ramifié et composition de résine contenant celui-ci

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JPS62223210A (ja) * 1986-03-25 1987-10-01 Asahi Glass Co Ltd 耐熱性樹脂の製造法
WO2001074916A1 (fr) * 2000-04-04 2001-10-11 Daikin Industries, Ltd. Fluoropolymere renfermant un groupe qui reagit aux acides et composition photoresist a amplification chimique contenant ledit fluoropolymere
JP2003255540A (ja) * 2002-03-04 2003-09-10 Asahi Glass Co Ltd レジスト組成物

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JP4551704B2 (ja) * 2004-07-08 2010-09-29 富士フイルム株式会社 液浸露光用保護膜形成組成物及びそれを用いたパターン形成方法
JP2006085081A (ja) * 2004-09-17 2006-03-30 Daikin Ind Ltd 微細パターン形成方法およびそれに用いるレジスト組成物
JP2009280774A (ja) * 2008-05-26 2009-12-03 Asahi Glass Co Ltd 含フッ素弾性共重合体、その製造方法および架橋ゴム
US20120135206A1 (en) * 2009-05-29 2012-05-31 Nissan Chemical Industries, Ltd. Fluorine-containing highly branched poymer and resin composition containing the same
CN102449005A (zh) * 2009-05-29 2012-05-09 日产化学工业株式会社 含氟高支化聚合物和包含该聚合物的树脂组合物
WO2010137724A1 (fr) * 2009-05-29 2010-12-02 日産化学工業株式会社 Polymère fluoré fortement ramifié et composition de résine contenant celui-ci
JP5751425B2 (ja) * 2009-05-29 2015-07-22 日産化学工業株式会社 含フッ素高分岐ポリマー及びそれを含む樹脂組成物
TWI510507B (zh) * 2009-05-29 2015-12-01 Nissan Chemical Ind Ltd 含氟高分支化聚合物及含有該聚合物之樹脂組成物
CN102449005B (zh) * 2009-05-29 2016-01-20 日产化学工业株式会社 含氟高支化聚合物和包含该聚合物的树脂组合物
US9410006B2 (en) 2009-05-29 2016-08-09 Nissan Chemical Industries, Ltd. Fluorine-containing highly branched polymer and resin composition containing the same
US20160264739A1 (en) * 2009-05-29 2016-09-15 Nissan Chemical Industries, Ltd. Fluorine-containing highly branched polymer and resin composition containing the same
US10227457B2 (en) 2009-05-29 2019-03-12 Nissan Chemical Industries, Ltd. Fluorine-containing highly branched polymer and resin composition containing the same

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