WO2006132287A1 - Fluorocopolymere, son procede de fabrication, et composition de resist le contenant - Google Patents

Fluorocopolymere, son procede de fabrication, et composition de resist le contenant Download PDF

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Publication number
WO2006132287A1
WO2006132287A1 PCT/JP2006/311451 JP2006311451W WO2006132287A1 WO 2006132287 A1 WO2006132287 A1 WO 2006132287A1 JP 2006311451 W JP2006311451 W JP 2006311451W WO 2006132287 A1 WO2006132287 A1 WO 2006132287A1
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Prior art keywords
group
fluorine
alkyl group
carbon atoms
formula
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PCT/JP2006/311451
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English (en)
Japanese (ja)
Inventor
Osamu Yokokoji
Takashi Sasaki
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Asahi Glass Company, Limited
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Priority claimed from JP2006012128A external-priority patent/JP2008214362A/ja
Application filed by Asahi Glass Company, Limited filed Critical Asahi Glass Company, Limited
Publication of WO2006132287A1 publication Critical patent/WO2006132287A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • C08F214/186—Monomers containing fluorine with non-fluorinated comonomers
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain

Definitions

  • Fluorine-containing copolymer, method for producing the same, and resist composition containing the same Fluorine-containing copolymer, method for producing the same, and resist composition containing the same
  • the present invention relates to a novel fluorine-containing copolymer, a method for producing the same, and a resist composition.
  • fluorine-containing polymers used in fluorine-based ion exchange membranes and curable fluorine resin coatings are known as fluorine-containing polymers having a functional group, but these all have a basic skeleton. It is a chain polymer, and is obtained by copolymerization of fluoroolefin represented by tetrafluoroethylene and a monomer having a functional group.
  • Polymers containing a functional group and having a fluorinated alicyclic structure in the main chain are also known, and a method for introducing a functional group into a polymer having a fluorinated alicyclic structure in the main chain is known.
  • the method uses end groups of the polymer obtained by polymerization, treats the polymer at a high temperature to oxidatively decompose the side chains or ends of the polymer to form functional groups, and combines monomers having functional groups.
  • a method of polymerizing and introducing by treatment such as hydrolysis as necessary (for example, see Patent Documents 1, 2, 3, and 4;).
  • Patent Document 1 Japanese Patent Laid-Open No. 4 189880
  • Patent Document 2 Japanese Patent Laid-Open No. 4-226177
  • Patent Document 3 JP-A-6-220232
  • Patent Document 4 International Publication No.02Z064648 Pamphlet
  • the problem to be solved by the present invention is that the concentration of the functional group is high and sufficient functional group characteristics can be obtained.
  • the fluorine-containing polymer is wide and has a high transparency in the wavelength region, and the fluoropolymer. Providing a manufacturing method, and further using this fluorine-containing polymer as a chemically amplified resist, in particular far ultraviolet rays such as KrF and ArF excimer lasers and vacuum such as F excimer lasers.
  • An object of the present invention is to provide a resist composition that provides a resist pattern that is excellent in transparency to ultraviolet rays and dry etching properties, and further excellent in sensitivity, resolution, dissolution rate, flatness, heat resistance, and the like.
  • the present invention firstly includes a unit derived from a monomer unit obtained by cyclopolymerization of a fluorine-containing phenine represented by the following formula (1): Derived from a unit derived from a monomer unit obtained by polymerization of an acryl monomer represented by (2) and from a monomer unit obtained by polymerization of an acrylic monomer represented by the following formula (3) And a fluorine-containing copolymer (A).
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 12 or less carbon atoms.
  • R 3 represents a hydrogen atom, an alkyl group having 20 or less carbon atoms, or a carbon group having 15 or less carbon atoms.
  • Alkoxycarbo group or CH R 4 R 4 is an alkoxy carbo having 15 or less carbon atoms.
  • the alkyl group, alkoxycarbo group and R 4 constituting R 3 have an etheric oxygen atom in which some or all of the hydrogen atoms may be substituted with fluorine atoms. May be.
  • n represents an integer of 0 to 2.
  • R 5 represents a hydrogen atom, a fluorine atom, an alkyl group having 3 or less carbon atoms, or a fluoroalkyl group having 3 or less carbon atoms.
  • R 6 is a force that can be replaced by a hydrogen atom by an acid. a blocking group to form a.
  • R 6 a good tool R 6 may be substituted with a fluorine atom or a hydroxyl group part of hydrogen atoms in the alkyl group to be configured to represent an alkyl group having 20 or less carbon atoms
  • the alkyl group may have an etheric oxygen atom or an ester group.
  • R 7 is a blocking group of a carboxyl group that is not substituted with a hydrogen atom by an acid, and has 20 or less carbon atoms. A part of the hydrogen atoms in the alkyl group constituting R 7 may be substituted with a fluorine atom or a hydroxyl group.
  • the alkyl group constituting R 7 is an etheric oxygen atom or It may have an ester group.
  • the acrylic monomer represented by the formula (2) is preferably one selected from the (meth) acrylic acid ester power represented by the following formula. ,.
  • the acrylic monomer represented by the formula (3) is one selected from the (meth) acrylate ester power represented by the following formula: U prefer.
  • the present invention secondly represents a fluorine-containing gen represented by the above formula (1) and the above formula (2).
  • the present invention thirdly provides a resist composition comprising the above-mentioned fluorine-containing copolymer (A), an acid-generating compound that generates an acid upon irradiation with light, and an organic solvent. .
  • a fluorinated copolymer (A) having an aliphatic ring structure in the main chain and a functional group in the side chain can be produced.
  • the fluorine-containing copolymer (A) of the present invention has high chemical stability and heat resistance. Since a functional group is introduced into the ring side chain, sufficient functional group characteristics can be expressed without lowering Tg, which has been difficult to achieve with conventional fluorine-containing polymers. Furthermore, it has high transparency in a wide wavelength region.
  • the resist composition of the present invention can be used as a chemically amplified resist, and is particularly transparent to far ultraviolet rays such as KrF and ArF excimer lasers and vacuum ultraviolet rays such as F excimer lasers.
  • the fluoropolymer (A) of the present invention is also useful as a resist resin for immersion ArF lithography when water is used as the immersion medium, taking advantage of its water repellency. Since a conventional resist resin has a high possibility of swelling when it comes into contact with water, it is necessary to cover the resist resin film with a top coat when water is used as the immersion medium. Since the fluorine-containing copolymer (A) of the present invention has water repellency, it can be expected to be used as a resist resin for immersion ArF lithography without being covered with a top coat.
  • FIG. 1 is a graph showing the discrimination curves of resist films obtained in Examples 15 and 16 and Comparative Example 3.
  • FIG. 2 is a graph showing the disclination curves of resist films obtained in Examples 17 and 18 and Comparative Example 3.
  • FIG. 3 is a graph showing the discrimination curves of resist films obtained in Examples 19 to 21 and Comparative Example 3.
  • FIG. 4 is a graph showing the relationship between the exposure intensity and the residual film thickness of the resin for the resin thin films obtained in Examples 28 to 29 and Comparative Example 4.
  • a unit derived from a monomer unit obtained by cyclopolymerization of a fluorinated gen represented by the following formula (1) (hereinafter referred to as fluorinated gen (1)), and the following formula ( A unit derived from a monomer unit obtained by polymerization of an acryl monomer represented by 2) (hereinafter referred to as monomer (2)), and an acrylic compound represented by the following formula (3):
  • a fluorine-containing copolymer (A) having a unit derived from a monomer unit obtained by polymerizing a monomer hereinafter referred to as monomer (3)
  • the “unit derived from a monomer unit” means the monomer unit itself and the monomer unit in which a functional group in the monomer unit is chemically converted by functional group conversion or the like after polymerization.
  • CF CFCH CH (C (CF) (OR 3 )) (CH) CR ⁇ CHR 2 (1)
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 12 or less carbon atoms.
  • the alkyl group having 12 or less carbon atoms may be a cyclic hydrocarbon group having only a linear or branched aliphatic hydrocarbon group or a hydrocarbon group having a cyclic hydrocarbon group.
  • the cyclic hydrocarbon group refers to a group in which the cyclic hydrocarbon group is directly bonded to the remaining part of the formula (1).
  • a hydrocarbon group having a cyclic hydrocarbon group refers to a group in which the cyclic hydrocarbon group is bonded to the remaining part of the formula (1) via another hydrocarbon group such as an alkyl group.
  • cyclic hydrocarbon group a hydrocarbon group having at least one cyclic structure is preferred.
  • Monocyclic saturated hydrocarbon groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group and the like as shown below, -Cyclocyclic saturated hydrocarbon group such as cyclohexyl cyclohexyl group, bridged ring such as polycyclic saturated hydrocarbon group such as 1 decahydronaphthyl group or 2-decahydronaphthyl group, 1 norbornyl group, 1-adamantyl group
  • Formulas include saturated hydrocarbon groups and spiro hydrocarbon groups such as spiro [3.4] octyl groups.
  • R 2 is preferably a hydrogen atom, a methyl group, or a cyclic aliphatic hydrocarbon group having 6 or less carbon atoms, and particularly preferably a hydrogen atom or a methyl group. Most preferably, R ⁇ R 2 is simultaneously a hydrogen atom.
  • R 3 represents a hydrogen atom, an alkyl group having 20 or less carbon atoms, an alkoxy carbo group having 15 or less carbon atoms, or CH R 4 (R 4 is an alkoxy carbo group having 15 or less carbon atoms).
  • the constituting alkyl group, alkoxycarbonyl group and R 4 may have an etheric oxygen atom in which part or all of the hydrogen atoms may be substituted with fluorine atoms.
  • the alkyl group having 20 or less carbon atoms which may have an etheric oxygen atom is a linear or branched fatty acid. It may be a hydrocarbon group having a cyclic hydrocarbon group or a cyclic hydrocarbon group consisting only of an aliphatic hydrocarbon group.
  • the cyclic hydrocarbon group the same groups as described above can be used, and the ring structure may have an etheric oxygen atom. Specific examples include methyl group, trifluoromethyl group, t C H, CH OCH, CH OC H, CH OCH.
  • the carbon number 15 or less alkoxycarbonyl - le group, CH R 4 are, COOR 8, respectively, C
  • R 8 is an alkyl group having 14 or less carbon atoms. Specifically, COO (t
  • 2-AdM represents a 2-methyladamantyl-2-yl group.
  • the blocked acidic group is preferably a blocked acidic group obtained by substituting a hydrogen atom of an acidic hydroxyl group with an ether group having an alkyl group, an alkoxycarbo yl group, an acyl group or a cyclic aliphatic hydrocarbon group.
  • an ether group having an alkyl group, an alkoxycarbo yl group, an acyl group or a cyclic aliphatic hydrocarbon group.
  • a blocking agent such as alkanol can be reacted to replace the hydrogen atom of the acidic group with an alkyl group to form a blocked acidic group.
  • R 3 as the blocked acidic group include a methoxymethyl group and an ethoxymethyl group.
  • n represents an integer of 0 to 2. n is preferably 1.
  • fluorine-containing gene (1) in the present invention include the following forces, but are not limited thereto.
  • CF 2 CFCH r (
  • H-CF CH 2 C (CF 3 ) 20H C (CF 3 ) 2 OH
  • CF 2 CFCH 2- (
  • H-CH 2 C3 ⁇ 4CH CH
  • the fluorine-containing polymer (A) of the present invention has a monomer unit formed by cyclopolymerizing the above-mentioned fluorine-containing gene (1).
  • the fluorine-containing polymer (A) of the present invention it is considered that the following monomer units (a) to (f) are formed by cyclopolymerization of the fluorine-containing gene (1).
  • the fluorine-containing polymer (A) is a polymer having a structure containing the monomer unit (a) or the monomer unit (b). It is conceivable that.
  • (A) is considered to be a polymer having a structure containing the monomer unit (c), the monomer unit (d), or the monomer unit (e).
  • the main chain means a carbon chain composed of four carbon atoms constituting a polymerizable unsaturated bond.
  • the fluorinated copolymer (A) of the present invention obtained by copolymerizing the fluorinated gen (1), the monomer (2), and the monomer (3), the fluorinated gen (1) Is cyclopolymerized and is considered to exist as any of the monomer units represented by the above formulas (a) to (f).
  • the acidic groups in these monomer units may be blocked to form blocked acidic groups.
  • the proportion of units derived from the monomer unit obtained by cyclization polymerization of the fluorine-containing gene (1) in the fluorine-containing copolymer (A) is preferably 5 mol% to 95 mol%. Mashi 10 mol 0 /. To 90 mol 0/0 is more preferred tool 10 mol 0 /. The most preferred! / ... is to 40 mol 0/0
  • R 5 represents a hydrogen atom, a fluorine atom, an alkyl group having 3 or less carbon atoms or a fluoroalkyl group having 3 or less carbon atoms, and since it is particularly easily available, a hydrogen atom, a fluorine atom, or a methyl group It is preferably a trifluoromethyl group.
  • R 6 is a carboxyl-blocking group substituted with a hydrogen atom by an acid, and represents an alkyl group having 20 or less carbon atoms. Specific examples of R 6 include alkyl groups having 20 or less carbon atoms, and the carbon atom bonded to the oxygen atom of the carboxyl group is a tertiary carbon. However, even if the carbon atom bonded to the oxygen atom of the carboxyl group is a tertiary carbon alkyl group, the tertiary carbon reacts with the acid. Those with no bond (non-detachable tertiary carbon) do not correspond to R 6 .
  • the tertiary carbon is a carbon atom forming a skeleton of a cyclic structure of an alicyclic hydrocarbon such as adamantane, and the tertiary carbon power Bonding force S-carboxyl group is used for bonding with oxygen atom and bonding with cyclic structure, and has a bond capable of reacting with acid.
  • a part of hydrogen atoms in the alkyl group constituting R 6 may be substituted with a fluorine atom or a hydroxyl group.
  • the alkyl group constituting R 6 may have an etheric oxygen atom or an ester group. .
  • acrylic monomer (2) include the following (meth) acrylic acid esters.
  • the cyclic hydrocarbon groups shown in [Chemical Formula 14] and [Chemical Formula 15] are preferred for dry etching resistance during wafer processing, and those having 7 to 15 carbon atoms are preferred. Furthermore, it is preferable that the (meth) acrylic acid ester power represented by the following formula is selected. [Chemical 16]
  • R 5 is the same as described for formula (2).
  • R 7 is a carboxyl group-blocking group that is not substituted with a hydrogen atom by an acid, and represents an alkyl group having 20 or less carbon atoms. Specific examples of R 7 include an alkyl group having 20 or less carbon atoms, wherein the carbon atom bonded to the oxygen atom of the strong lpoxyl group is a primary carbon or a secondary carbon. In addition, the carbon atom bonded to the oxygen atom of the carboxyl group described in [0035] is a non-leaving tertiary carbon.
  • a part of the hydrogen atoms in the alkyl group constituting R 7 may be substituted with a fluorine atom or a hydroxyl group.
  • the alkyl group constituting R 7 may have an etheric oxygen atom or an ester group. .
  • acrylic monomer (3) examples include the following (meth) acrylic acid esters.
  • Monomers (2) or monomers (3) having various structures can be easily synthesized.
  • the monomer unit obtained by polymerizing the monomer (2) is a plurality of types of monomer units in which either one or both of R 5 and R 6 are different. May exist.
  • the monomer unit formed by polymerizing the monomer (3) may include a plurality of types of monomer units in which one or both of R 5 and R 7 are different.
  • the proportion of units derived from mono mer units the monomers in the fluorine-containing copolymer (A) (2) is formed by polymerization, preferably 5 mol% to 90 mol 0/0 device 10 More preferred is mol% to 80 mol%, and most preferred is 30 mol% to 70 mol%.
  • the proportion of the unit derived from the monomer unit obtained by polymerizing the monomer (3) in the fluorine-containing copolymer (A) is 5 mol 0 /.
  • To 90 mol 0/0 is preferred tool 10 mol 0 /.
  • To 80 mol 0/0 and more preferably tool particularly 10 mol% to 40 mol% is most preferred.
  • the ratio of the monomer unit obtained by polymerizing the monomer (2) and the unit derived from the monomer unit obtained by polymerizing the monomer (3) is the total. 5 mol% to 95 mol 0/0 preferably fixture 50 mole% to 95 mole 0/0 force Ri preferred instrument particularly 60 mol% to 90 mol% is most preferred.
  • the fluorine-containing copolymer (A) of the present invention includes a unit derived from a monomer unit obtained by cyclopolymerizing the fluorine-containing gene (1), and a monomer unit obtained by polymerizing the monomer (2). And a unit derived from a monomer unit obtained by polymerizing the monomer (3) as an essential component.
  • monomer units derived from other radical polymerizable monomers hereinafter referred to as other monomers
  • the proportion of other monomer units is preferably 50 mol% or less, more preferably 15 mol% or less.
  • Examples of other monomers that may be mentioned include a- olefins such as ethylene, propylene, and isobutylene, and fluorine-containing olefins such as tetrafluoroethylene and hexafluoropropylene.
  • the fluorinated copolymer (A) of the present invention can be obtained by radical copolymerization of the fluorinated gen (1), the monomer (2) and the monomer (3) under a polymerization initiation source.
  • the polymerization initiating source is not particularly limited as long as the polymerization reaction proceeds radically, and examples thereof include a radical generator, light, and ionizing radiation. Particularly preferred are radical generators.
  • peroxides azo compounds, persulfates and the like, and radical generators containing fluorine atoms in the molecule are more preferred.
  • radical generator include azoisobisbutyro-tolyl, benzoyl peroxide, diisopropyl peroxydicarbonate, di-t-butyl peroxydicarbonate, t-butyl peroxypivalate, perfluorobutyryl peroxide, Perfluorobenzoyl peroxide is preferred. Of these, the peroxides listed below are preferred.
  • C H is a phenyl group
  • C F is a pentafluorophenyl group
  • C H is a cyclohexyl group
  • the method of radical polymerization is not particularly limited, so-called Balta polymerization in which a monomer is directly subjected to polymerization, fluorinated hydrocarbon, chlorinated hydrocarbon, fluorinated chlorohydrocarbon, alcohol, hydrocarbon dissolving the monomer.
  • Examples include solution polymerization performed in other organic solvents, suspension polymerization performed in the presence or absence of a suitable organic solvent in an aqueous medium, and emulsion polymerization performed by adding an emulsifier to an aqueous medium.
  • any solvent that dissolves monomers, initiators, and the like can be selected in consideration of the molecular weight, polymerization temperature, etc. of the target fluorine-containing copolymer, regardless of the type of solvent.
  • the organic solvent used as a solvent in the solution polymerization is not limited to one type, and may be used as a mixed solvent of a plurality of types of organic solvents.
  • aliphatic hydrocarbons heptane such as pentane, hexane, to, methanol, ethanol, n-propanol, hydrocarbon alcohols such as isopropanol, t chromatography butanol, acetone, Mechiruechiruketo emissions, methyl isobutyl ketone, cyclo Hydrocarbon ketones such as hexanone, hydrocarbon ethers such as dimethyl ethereol, jetinoreethenole, methinoleethinoleenotenole, methinore tertinotinatenore, ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether , Cycloaliphatic hydrocarbon ethers such as tetrahydrofuran and 1,4 dio
  • the temperature and pressure at which the polymerization is carried out are not particularly limited, but are preferably set appropriately in consideration of various factors such as the boiling point of the monomer, the heating source used, and the removal of the polymerization heat.
  • a suitable temperature can be set between 0 ° C and 200 ° C, and a practically suitable temperature can be set at room temperature to about 100 ° C.
  • the polymerization pressure can be reduced or increased. Practically, a suitable polymerization can be carried out even if the pressure is about lkPa to 100 MPa, further about 10 kPa to 10 MPa.
  • the present invention includes a fluorine-containing copolymer (A) (hereinafter also collectively referred to as a fluorine-containing copolymer), an acid-generating compound that generates an acid upon irradiation with light, and an organic solvent.
  • a resist composition is also provided.
  • the acid generating compound that generates an acid upon irradiation with light in the present invention is a compound that decomposes upon irradiation with light, more specifically, irradiation with actinic rays to generate an acid.
  • Part or all of the blocked acidic groups present in the fluorine-containing copolymer are cleaved (deblocked) by the acid generated by irradiation with this actinic ray.
  • the exposed portion of the resist film becomes readily soluble in an alkaline developer, and a positive resist pattern is formed by the alkaline developer.
  • Examples of the acid generating compound used in the resist composition of the present invention include photoinitiators for photopower thione polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, and ultraviolet light.
  • photoinitiators for photopower thione polymerization include photoinitiators for photopower thione polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, and ultraviolet light.
  • Acid generator compounds used in acid generators and the like used in micro-photoresist that generate acid by active light rays such as vacuum ultraviolet rays such as laser beam, electron beam, X-ray, molecular beam, ion beam, etc. .
  • an acid generating compound that generates an acid upon irradiation with actinic rays having a wavelength of 250 nm or less, more preferably 200 nm or less is preferable. .
  • actinic rays are used in a broad concept including radiation.
  • Examples of the acid generating compound include an onium salt, a halogen-containing compound, a diazoketone compound, a sulfone compound, and a sulfonic acid compound. Examples of these acid generating compounds include the following.
  • Examples of the onium salt include a odonium salt, a sulfonium salt, a phosphonium salt, a diazo salt, a pyridinium salt, and the like.
  • Specific examples of preferred salt Diphenyl rhododonium triflate, diphenyl rhododrom piransnorephonate, diphenyl rhododoxy hexafluoroantimonate, diphenyl rhododonium decylbenzenesulfonate, bis (4 — Tert-butylphenol) iodine triflate, bis (4-tert-butylphenol) iodine decylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonylnonate, triphenylenoles Norepho-perfluorooctane sulfonate, triphenyls
  • halogen-containing compound examples include a haloalkyl group-containing hydrocarbon compound, a haloalkyl group-containing heterocyclic compound, and the like.
  • Specific examples include (trichloromethyl) -s triazine derivatives such as phenyl-bis (trichloromethyl) s triazine, methoxyphenyl bis (trichloromethyl) s-triazine, naphthyl bis (trichloromethyl) s triazine, and 1 , 1-bis (4 black mouth file) 1, 2, 2, 2 trichrome mouth ethane.
  • sulfone compounds include 13-ketosulfone, 13 sulfonylsulfone, diazo compounds of these compounds, and the like. Specific examples include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenolsulfol) methane, and the like.
  • sulfonic acid compound examples include alkyl sulfonic acid ester and alkyl sulfone. And acid imides, haloalkyl sulfonates, aryl sulfonates, iminosulfonates, and the like. Specific examples include benzoin tosylate, 1,8-naphthalenedicarboxylic acid imide triflate, and the like.
  • Diazodisulfones diazoketosulfones, iminosulfonates, disulfones, and the like are also preferred as the acid-generating compound.
  • the acid generating compound include polymer compounds having a group capable of generating an acid upon irradiation with actinic rays in the main chain or side chain of the polymer.
  • polymer compound examples include, as a group that generates an acid upon irradiation with actinic rays, an aliphatic alkylsulfo group having a 2-oxocyclohexyl group or an N-hydro group.
  • a polymer compound having a xylsuccinimide sulfonate group and the like is preferably exemplified.
  • the organic solvent sufficiently dissolves the fluorinated copolymer and the acid-generating compound, and the solution is subjected to methods such as spin coating, flow coating, roll coating, and the like.
  • the organic solvent is not particularly limited as long as it is an organic solvent that can be applied with the above method to form a uniform coating film.
  • organic solvents examples include alcohols such as methyl alcohol, ethyl alcohol, diacetone alcohol, and ketones such as acetone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, N-methylpyrrolidone, and ⁇ -butyrolatathone.
  • alcohols such as methyl alcohol, ethyl alcohol, diacetone alcohol
  • ketones such as acetone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, N-methylpyrrolidone, and ⁇ -butyrolatathone.
  • organic solvent those exemplified above may be used alone or in combination of two or more.
  • the amount of moisture is small.
  • each component in the resist composition of the present invention is suitably 0.1 to 20 parts by weight of an acid generating compound and 50 to 2000 parts by weight of an organic solvent with respect to 100 parts by weight of the fluorinated copolymer.
  • the acid generating compound is 0.1 to 100 parts by mass of the fluorine-containing copolymer. ⁇ 10 parts by mass and organic solvent 100 ⁇ : L000 parts by mass.
  • the amount of the acid-generating compound used is 0.1 parts by mass or more, sufficient sensitivity and developability can be provided, and when it is 10 parts by mass or less, transparency to radiation is sufficiently maintained, A more accurate resist pattern can be obtained.
  • the resist composition of the present invention includes an acid-cleavable additive for improving pattern contrast, a surfactant for improving coating properties, a nitrogen-containing basic compound for adjusting an acid generation pattern, and a substrate.
  • an adhesion assistant, a storage stabilizer, etc. can be appropriately blended depending on the purpose in order to improve the storage stability of the composition.
  • the resist composition of the present invention is preferably used after each component is uniformly mixed and filtered through a 0.1 to 2 m filter.
  • a resist film is formed by applying and drying the resist composition of the present invention on a substrate such as a silicone wafer.
  • a substrate such as a silicone wafer.
  • the coating method spin coating, flow coating, roll coating or the like is adopted.
  • Actinic ray irradiation is performed on the formed resist film through a mask on which a pattern is drawn, and then development processing is performed to form a pattern.
  • Actinic rays to be irradiated include ultraviolet rays such as g-rays with a wavelength of 436 nm, i-rays with a wavelength of 365 nm, KrF excimer laser light with a wavelength of 248 nm, ArF excimer laser light with a wavelength of 193 nm, and F excimer laser light with a wavelength of 157 nm.
  • Vacuum ultraviolet rays such as
  • the resist composition of the present invention has ultraviolet light with a wavelength of 250 nm or less, particularly far ultraviolet light (ArF excimer laser light) or vacuum ultraviolet light (F excimer laser light) with a wavelength of 200 nm or less.
  • resist composition useful for an application used as a light source.
  • Resist that can be used for exposure using the so-called immersion technology, which improves resolution by utilizing the refractive index of water, organic compounds, organic compounds containing fluorine atoms, etc. It is a composition.
  • the resist composition of the present invention is capable of forming a finer pattern.
  • alkaline aqueous solutions are applied as the developing solution.
  • alkali include sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide.
  • examples thereof include xide and triethylamine.
  • the conventional resist resin has a high possibility of swelling when it comes into contact with water, when water is used as the immersion medium, it is necessary to cover the resist resin film with a top coat. Since the fluorine-containing copolymer obtained in the present invention has water repellency, it can be expected to be used as a resist resin for immersion ArF lithography without being covered with a top coat.
  • THF Tetrahydrofuran
  • PGMEA Propylene glycol methyl ether acetate
  • AIBN Azobisisobuty-tolyl
  • BPO Benzylperoxide
  • PSt Polystyrene
  • R225 Dichloropentafluoropropane
  • PFB Perfluorobutyryl perio Xid
  • PFBPO Perfluorobenzoyl peroxide
  • IPP Diisopropyl peroxide dicarbonate.
  • a glass pressure-resistant reactor with 10 g of monomer 1, 12.53 g of 2-ethyl-2-adamantyl methacrylate, 5.86 g of ⁇ -trifluoromethyl-2-hydroxy-1-adamantyl acrylate and 66 g of R2 25 in an internal volume of lOOmL was charged.
  • 12.78 g of IPP was added as a polymerization initiator.
  • the system was frozen and degassed, sealed, and polymerized in a constant temperature shaking tank (40 ° C) for 18 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, followed by vacuum drying at 80 ° C. for 24 hours.
  • polymer 1A 16.34 g of an amorphous polymer having a fluorine-containing ring structure in the main chain was obtained (hereinafter referred to as polymer 1A).
  • the obtained polymer was soluble in acetone, THF, ethyl acetate, and methanol.
  • polymer 2A 14.9 g of an amorphous polymer having a fluorine-containing ring structure in the main chain was obtained (hereinafter referred to as polymer 2A).
  • polymer 3A 3.5 g of an amorphous polymer having a fluorine-containing ring structure in the main chain was obtained (hereinafter referred to as polymer 3A).
  • the polymer yarn calculated by 1 9 F-NMR and 1 H-NMR measurement is the repeating unit consisting of monomer 1 Z2-ethyl 2-adamantyl metatalylate repeating unit / 2 hydroxy-1 1 adamantyl
  • the repeating unit consisting of metatalylate 15/55/3 0 mol%.
  • polymer 4A 3.3 g of an amorphous polymer having a fluorine-containing ring structure in the main chain was obtained (hereinafter referred to as polymer 4A).
  • the resulting polymer was soluble in THF.
  • polymer 5A an amorphous polymer having a fluorine-containing ring structure in the main chain was obtained (hereinafter referred to as polymer 5A).
  • the obtained polymer was soluble in THF and cyclopentanone.
  • polymer 6A 2.2 g of an amorphous polymer having a fluorinated ring structure in the main chain was obtained (hereinafter referred to as polymer 6A).
  • the obtained polymer was soluble in THF and cyclopentanone.
  • polymer 7A 2.85 g of an amorphous polymer having a fluorine-containing ring structure in the main chain was obtained (hereinafter referred to as polymer 7A).
  • the obtained polymer was soluble in THF and cyclopentanone.
  • polymer B lg of an amorphous polymer was obtained (hereinafter referred to as polymer B).
  • the obtained polymer was soluble in acetone, THF, ethyl acetate, and methanol.
  • a PTFE filter having a pore size of 0.2 m was prepared by dissolving 0.5 g of each of the polymers 1A to 7A synthesized in Examples 1 to 7 and Comparative Example 1 and 4.5 g of PGMEA. And filtered.
  • the above-mentioned resin solution was spin-coated on a silicon substrate or a synthetic quartz substrate, followed by heat treatment at 90 ° C. for 90 seconds to form a resin thin film having a thickness of 0.21 m.
  • the static contact angle with respect to water was measured using the thus obtained coagulated thin film.
  • a contact angle meter CA-X manufactured by Kyowa Interface Science Co., Ltd. was used for the measurement of the static contact angle.
  • the volume of the water droplet used is 2.
  • the extinction coefficient was measured with a transmittance measuring device (KV-201AD extreme ultraviolet spectroscopy system, manufactured by Spectrometer Co., Ltd.). The above physical properties are shown in Table 1.
  • Polymers 1A to 7A and Polymer B synthesized in Examples 1 to 7 and Comparative Example 1 were dissolved in lg and 0.05 g of trisulfol-sulfur triflate in 45 g of PGMEA, respectively.
  • the resist compositions 1AR to 7AR and BR were produced by filtration using a PTFE filter.
  • the above resist composition was spin-coated on a silicon substrate, followed by heat treatment at 100 ° C. for 90 seconds to form a resist film having a thickness of 0.21 m.
  • the lithography characteristics (discrimination curve) of the resist film thus obtained were evaluated.
  • VUVES-4500 manufactured by RISOTEC Japan
  • RDA-800 manufactured by RISOTEC Japan
  • a glass pressure-resistant reactor containing 9.7 g of monomer 1, 12. Og of 2-ethylyl-2-adamantyl atylate, 3.5 g of y-butylate rataton methacrylate, and 50 g of methyl ethyl ketone with an internal volume of lOOmL was charged.
  • 16.8 g of a 50 mass% solution of IPP R225 was added as a polymerization initiator.
  • the system was frozen and degassed, sealed, and polymerized in a constant temperature shaking tank (40 ° C) for 18 hours. After the polymerization, the reaction solution was dropped into hexane to reprecipitate the polymer, followed by vacuum drying at 80 ° C. for 24 hours.
  • polymer 8A 13.9 g of an amorphous polymer having a fluorine-containing ring structure in the main chain was obtained (hereinafter referred to as polymer 8A).
  • the polymer composition calculated by 19 F-NMR and 1 H-NMR measurements is based on the repeating unit Z 2 -ethyl-2-adamantyl acrylate consisting of monomer 1 The repeating unit was 12 60 Z28 mol%.
  • the resulting polymer was soluble in acetone, THF, cyclopentanone and PGMEA
  • polymer 9A 18 g of an amorphous polymer having a fluorine-containing ring structure in the main chain was obtained (hereinafter referred to as polymer 9A).
  • the polymer yarn calculated by 19 F-NMR and 1 H-NMR measurements is from the repeating unit consisting of monomer 1 Z2-methyl-2-adamantyl metallate, and from the repeating unit Z ⁇ —petit-mouth rataton metatalylate. The repeating unit was 20 ⁇ 55 ⁇ 25 mol%.
  • the obtained polymer was soluble in acetone, THF, cyclopentanone, and PGMEA.
  • polymer 10A 11.3 g of an amorphous polymer having a fluorine-containing ring structure in the main chain was obtained (hereinafter referred to as polymer 10A).
  • the obtained polymer was soluble in acetone, THF, toluene, cyclopentanone, and PGMEA.
  • Examples 25 to 27 The extinction coefficient of each thin resin film obtained by treating in the same manner as in Example 8 using the polymers 8A, 9A, and 10A was measured with a transmittance measuring device. The physical property values are shown in Table 5.
  • the above resin solution was spin-coated on a BARC-treated silicon substrate, followed by heat treatment at 100 ° C. for 90 seconds to form a resin film having a film thickness of 0.25 / zm.
  • the resin thin film thus obtained was exposed to a 193 nm laser beam (BraggStar200 ArF manufactured by TUI Laser) through a pinhole with a diameter of 3 mm while changing the exposure intensity from 0 mjZcm 2 to 10 mjZcm 2 . After exposure, heat treatment was performed at 100 ° C. for 90 seconds, and then alkali development was performed for 60 seconds. After development, the film thickness of the exposed part was measured, and the relationship between the exposure intensity (Exposure dose) and the residual film thickness (normalized thickness) of the resin was determined. The results are shown in Fig. 4.
  • Etching was performed for 60 seconds under the condition of W.
  • the ratio (etching rate ratio) was measured. The results are shown in Table 6.
  • polymer 11A 0.9 g of an amorphous polymer having a fluorine-containing ring structure in the main chain was obtained (hereinafter referred to as polymer 11A).
  • the obtained polymer was soluble in THF, cyclopentanone, and PGMEA.
  • the above-mentioned resin solution was spin-coated on a silicon substrate, followed by heat treatment at 90 ° C. for 90 seconds to form a 0.2 m-thick resin film.
  • the static contact angle and the falling angle with respect to water were measured using the thus obtained greaves thin film.
  • Kyowakai for static contact angle measurement A contact angle meter CA-X manufactured by Surface Science Co., Ltd. was used.
  • a falling angle meter SA-20 manufactured by Kyowa Interface Science Co., Ltd. was used.
  • the volume of water droplets used is a contact angle of 2 and a rolling angle of 50 L. The results are shown in Table 7.
  • polymer 12A 1.75 g of an amorphous polymer having a fluorine-containing ring structure in the main chain was obtained (hereinafter referred to as polymer 12A).
  • the obtained polymer was soluble in THF, PGMEA, cyclopentanone, and methyl amyl ketone.
  • polymer 13A 1.86 g of an amorphous polymer having a fluorine-containing ring structure in the main chain was obtained (hereinafter referred to as polymer 13A).
  • the polymer composition calculated by 19 F—NMR, H—NMR measurement and FT—IR measurement is: repeat unit consisting of monomer 2 / repeat unit consisting of 2-ethyl 2-adamantyl methacrylate Z
  • the repeating unit consisting of tonmetatalylate Z2—the repeating unit consisting of hydroxy-1-adamantylmetatalylate 15Z35Z30Z2 was 0 mol%.
  • the obtained polymer was soluble in THF, PGMEA, cyclopentanone, and methyl amyl ketone.
  • Example 38 Each of the polymers 12A, 13A and 13B synthesized in Example 38, Example 39 and Comparative Example 1 was dissolved in 9 g of PGMEA and filtered using a PTFE filter having a pore size of 0.2 m. .
  • a PTFE filter having a pore size of 0.2 m.
  • the above-mentioned resin solution is spin-coated, and after the coating, heat treatment is performed at 100 ° C for 90 seconds, and the film thickness is 0.3 ⁇ m. A thin oil film was formed. Using the thus obtained coagulated thin film, the static contact angle and dynamic contact angle with respect to water were measured. The results are shown in Table 8.
  • a contact angle meter DM-700 manufactured by Kyowa Interface Science Co., Ltd. was used for measurement of the contact angle.
  • the volume of the water droplet used is 2 L for the static contact angle, and 50 / z L for the dynamic falling angle and dynamic receding angle.
  • the unit of static contact angle, dynamic falling angle and dynamic receding angle is an angle (°).
  • the fluorine-containing copolymer of the present invention includes, for example, an ion exchange resin, an ion exchange membrane, a fuel cell, various battery materials, an optical fiber, an electronic member, a transparent film material, a thick film.
  • ArF excimer laser light or F excimer laser which can be used for film, adhesive, fiber material, weather-resistant paint, etc.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un fluoropolymère ayant une concentration en groupes fonctionnels élevée, et une grande transparence dans une large région de longueurs d'onde. Le fluorocopolymère comporte des unités monomères résultant de la cyclopolymérisation d'un diène fluoré représenté par la formule (1) suivante, et des unités monomères résultant de la polymérisation d'un monomère acrylique ayant une structure spécifique. CF2=CFCH2CH(C(CF3)2(OR3))(CH2)nCR1=CHR2 (1) Dans la formule (1), R1 et R2 représentent chacun indépendamment l'hydrogène ou un groupe en C12 ou un groupe alkyle inférieur ; R3 représente l'hydrogène, un groupe en C20 ou un groupe alkyle inférieur, un groupe en C15 ou un groupe alcoxycarbonyle inférieur, ou CH2R4 (R4 est un groupe en C15 ou un alcoxycarbonyle inférieur), sous réserve que tout ou partie des atomes d'hydrogène des groupes alkyle, alcoxycarbonyle, et R4 constituant R3 puissent avoir été remplacés par un atome de fluor, et que les groupes alkyle, alcoxycarbonyle, et R4 puissent comporter un atome d'oxygène éthérique ; et n est un entier compris entre 0 et 2.
PCT/JP2006/311451 2005-06-08 2006-06-07 Fluorocopolymere, son procede de fabrication, et composition de resist le contenant WO2006132287A1 (fr)

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JP2005-168148 2005-06-08
JP2006012128A JP2008214362A (ja) 2005-06-08 2006-01-20 含フッ素共重合体とその製造方法およびそれを含むレジスト組成物
JP2006-012128 2006-01-20

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002065212A1 (fr) * 2001-02-09 2002-08-22 Asahi Glass Company, Limited Composition de reserve
JP2003255540A (ja) * 2002-03-04 2003-09-10 Asahi Glass Co Ltd レジスト組成物
WO2005012372A1 (fr) * 2003-07-31 2005-02-10 Asahi Glass Company, Limited Compose fluore, polymere fluore, methode de production et composition de resine contenant ces composes
WO2005019284A1 (fr) * 2003-08-21 2005-03-03 Asahi Glass Company, Limited Fluorocopolymere, procede de production associe et composition de reserve contenant ce fluorocopolymere
WO2005042453A1 (fr) * 2003-10-31 2005-05-12 Asahi Glass Company, Limited Compose de fluor, fluoropolymere et son procede de production
WO2005108446A1 (fr) * 2004-05-07 2005-11-17 Asahi Glass Company, Limited Copolymère contenant de la fluorine, sa méthode de production et composition résistante le contenant

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002065212A1 (fr) * 2001-02-09 2002-08-22 Asahi Glass Company, Limited Composition de reserve
JP2003255540A (ja) * 2002-03-04 2003-09-10 Asahi Glass Co Ltd レジスト組成物
WO2005012372A1 (fr) * 2003-07-31 2005-02-10 Asahi Glass Company, Limited Compose fluore, polymere fluore, methode de production et composition de resine contenant ces composes
WO2005019284A1 (fr) * 2003-08-21 2005-03-03 Asahi Glass Company, Limited Fluorocopolymere, procede de production associe et composition de reserve contenant ce fluorocopolymere
WO2005042453A1 (fr) * 2003-10-31 2005-05-12 Asahi Glass Company, Limited Compose de fluor, fluoropolymere et son procede de production
WO2005108446A1 (fr) * 2004-05-07 2005-11-17 Asahi Glass Company, Limited Copolymère contenant de la fluorine, sa méthode de production et composition résistante le contenant

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